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WO2020066871A1 - Curable composition, cured film, method for forming pattern, optical filter and photosensor - Google Patents

Curable composition, cured film, method for forming pattern, optical filter and photosensor Download PDF

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Publication number
WO2020066871A1
WO2020066871A1 PCT/JP2019/036905 JP2019036905W WO2020066871A1 WO 2020066871 A1 WO2020066871 A1 WO 2020066871A1 JP 2019036905 W JP2019036905 W JP 2019036905W WO 2020066871 A1 WO2020066871 A1 WO 2020066871A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
curable composition
group
mass
photopolymerization initiator
Prior art date
Application number
PCT/JP2019/036905
Other languages
French (fr)
Japanese (ja)
Inventor
全弘 森
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2020549105A priority Critical patent/JP7059387B2/en
Priority to KR1020217004975A priority patent/KR102527570B1/en
Publication of WO2020066871A1 publication Critical patent/WO2020066871A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/0325—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polysaccharides, e.g. cellulose
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking

Definitions

  • the present invention relates to a curable composition, a cured film, a method for forming a pattern, an optical filter, and an optical sensor.
  • Patent Literature 1 discloses a color filter array having a semiconductor substrate, a color filter array having two or more color filter layers, and a separation wall separating at least a color filter layer of a different color between the semiconductor substrate and the color filter array. And a light-collecting unit disposed in the solid-state imaging device.
  • optical sensors that sense near infrared rays have been studied. Near-infrared rays have a longer wavelength than visible rays, so they are not easily scattered, and can be used for distance measurement, three-dimensional measurement, and the like. In addition, since near-infrared light is invisible to humans and animals, even when illuminating the subject with near-infrared light at night, the subject is not noticed, and it stimulates the opponent as an application for shooting nocturnal wildlife and security. It can also be used to shoot without. As described above, the optical sensor that senses near-infrared rays can be developed for various uses. In such an optical sensor, a filter having a transmission band in a near-infrared region such as a near-infrared transmission filter is used (for example, see Patent Documents 2 and 3).
  • the above-described color filter and near-infrared transmission filter form a film using a curable composition containing a coloring material, a polymerizable compound, and a photopolymerization initiator, and cure the film by heating or the like. It is manufactured by doing.
  • Patent Document 4 discloses that a color filter is manufactured using a curable composition using an oxime ester-based photopolymerization initiator containing a fluorine atom as a photopolymerization initiator.
  • non-Si-based materials such as organic materials, quantum dots, and InGaAs (indium gallium arsenide) have been used in solid-state imaging devices in place of Si-based materials from the viewpoints of high resolution, high sensitivity, power saving and miniaturization. It has been studied to carry out photoelectric conversion using. Since the non-Si-based material as described above is weaker to heat than the Si-based material, it is desired that the heating temperature at the time of curing the curable composition be less than 200 ° C.
  • the present invention has been made in view of the above demands, and has as its object to provide a curable composition capable of forming a cured film having excellent adhesion at a low temperature.
  • the above problem was solved by using two types of photopolymerization initiators having predetermined light absorption characteristics different from each other in a curable composition having a low transmittance for light having a wavelength of 365 nm. Specifically, the above problem was solved by the following means ⁇ 1>, preferably by ⁇ 2> to ⁇ 20>.
  • the photopolymerization initiator A1 has an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at a wavelength of 365 nm, and the photopolymerization initiator A1 has an extinction coefficient of 1.0 ⁇ 10 3 in methanol at a wavelength of 365 nm.
  • the photopolymerization initiator A1 is an oxime compound, The curable composition according to ⁇ 1>.
  • the oxime compound is a compound containing a fluorine atom, The curable composition according to ⁇ 2>.
  • the photopolymerization initiator A2 is a hydroxyalkylphenone compound, The curable composition according to any one of ⁇ 1> to ⁇ 3>.
  • the photopolymerization initiator A2 is a compound represented by the following formula (A2-1): The curable composition according to any one of ⁇ 1> to ⁇ 3>; Formula (A2-1): In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may combine with each other to form a ring. , M represents an integer of 0 to 5.
  • the photopolymerization initiator A2 contains 50 to 200 parts by mass with respect to 100 parts by mass of the photopolymerization initiator A1.
  • the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the curable composition is 5 to 15% by mass;
  • the polymerizable compound is a compound containing three or more ethylenically unsaturated groups, The curable composition according to any one of ⁇ 1> to ⁇ 7>.
  • the polymerizable compound is a compound containing an ethylenically unsaturated group and an alkyleneoxy group
  • the polymerizable compound is contained in an amount of 170 to 345 parts by mass based on 100 parts by mass of the photopolymerization initiator A1 and the photopolymerization initiator A2 in total.
  • the content of the polymerizable compound in the total solid content of the curable composition is 17.5 to 27.5% by mass;
  • the coloring material is a black coloring material containing at least one of a bisbenzofuranone compound, a perylene compound, and an azo compound.
  • the colorant comprises at least three compounds, The curable composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> Further, a compound having a cyclic ether structure, and a curing accelerator for a compound having a cyclic ether structure, The curable composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> Further containing resin, The curable composition according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 16> A cured film obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 17> Forming a curable composition layer on a support using the curable composition according to any one of ⁇ 1> to ⁇ 15>; A first exposure step of irradiating the curable composition layer with light having a wavelength of more than 350 nm and not more than 380 nm, and exposing in a pattern; A developing step of developing the curable composition layer, A second exposure step of irradiating the curable composition layer with light having a wavelength of 254 to 350 nm after the development step.
  • ⁇ 18> A step of heating the curable composition layer at a temperature of less than 200 ° C.
  • the curable composition of the present invention enables a cured film having excellent adhesion to be formed at a low temperature.
  • the curable composition of the present invention can provide the cured film, the pattern forming method, the optical filter, and the optical sensor of the present invention.
  • the numerical range represented by the symbol “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit, respectively.
  • step is meant to include not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended operation of the step can be achieved.
  • the notation of not indicating substituted or unsubstituted includes not only those having no substituent but also those having a substituent.
  • alkyl group when the term “alkyl group” is simply used, this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Meaning.
  • (meth) acrylate means both or “acrylate” and “methacrylate”
  • (meth) acryl means both “acryl” and “methacryl”
  • (Meth) acryloyl” means both or both “acryloyl” and “methacryloyl”.
  • the concentration of the total solids in a composition is represented by the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
  • the temperature is 23 ° C. unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined, for example, using HLC-8220 (manufactured by Tosoh Corporation) and using a guard column HZ-L, TSKgel @ Super @ HZM-M, TSKgel @ Super @ HZ4000, TSKgel. It can be determined by using Super @ HZ3000 and TSKgel @ Super @ HZ2000 (manufactured by Tosoh Corporation).
  • each layer constituting the laminate when the positional relationship of each layer constituting the laminate is described as “up” or “down”, other layers may be placed above or below a reference layer among a plurality of layers of interest. If there is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
  • the direction in which the layers are stacked on the substrate is referred to as “up”, or, if there is a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as “up”.
  • the opposite direction is referred to as "down”. Note that such setting in the vertical direction is for convenience in the present specification, and in an actual embodiment, the “up” direction in the present specification may be different from the vertical upward.
  • the curable composition of the present invention contains a coloring material, a polymerizable compound, and a photopolymerization initiator. And in the curable composition of this invention, content of a coloring material is 30 mass% or more with respect to the total solid content of a composition. Furthermore, the photopolymerization initiator A1 has an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at 365 nm in wavelength, and the photopolymerization initiator has an extinction coefficient of 1.0 nm in methanol at 365 nm in wavelength.
  • a photopolymerization initiator A2 having an absorption coefficient of not more than ⁇ 10 2 mL / gcm and an absorption coefficient at a wavelength of 254 nm of not less than 1.0 ⁇ 10 3 mL / gcm. Further, the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more.
  • the curable composition of the present invention has spectral characteristics that easily absorb visible light and easily transmit near infrared rays. Therefore, for example, it is used for manufacturing a near-infrared transmission filter.
  • near infrared refers to the vicinity of a wavelength range of 700 to 2500 nm.
  • the transmittance for light having a wavelength of 365 nm is relatively low due to the influence of the bottom of the absorption characteristics in the visible light region.
  • a cured film having excellent adhesion can be formed at a low temperature.
  • the effect is considered as follows.
  • the curable composition contains the photopolymerization initiator A1 and the photopolymerization initiator A2, exposure using light having a wavelength of more than 350 nm and not more than 380 nm (for example, 365 nm) (first exposure) ) And exposure using light having a wavelength of 254 to 350 nm (for example, 254 nm) (second exposure) is performed to achieve sufficient curing at a low temperature of less than 200 ° C.
  • the term "light” is used for convenience for electromagnetic waves other than the visible region, and the meaning of "light” is the same as “electromagnetic wave” for electromagnetic waves other than the visible region.
  • the second exposure is performed.
  • the composition can be sufficiently cured by heat treatment. That is, the curable composition of the present invention can be used in a method in which exposure is performed in one step, in addition to a method in which exposure is performed in two steps.
  • a photopolymerization initiator that has absorbed light generates active species, and the polymerization of the polymerizable compound is promoted by the active action of the active species.
  • components other than the photopolymerization initiator In particular, the coloring material
  • the coloring material has a property of easily absorbing visible light, and accordingly, light having a wavelength of 365 nm close to the visible light region is also easily absorbed by components other than the photopolymerization initiator.
  • exposure using light having a wavelength of 365 nm (first exposure) is regarded as a step of imparting sufficient strength to the curable composition to withstand development, and after the first exposure and development, The second exposure using the photopolymerization initiator A2 is performed.
  • the pattern has already been cut, and the influence of the diffusion of the excessively generated active species on the pattern size is small, so that the exposure energy can be increased. Therefore, sufficient light can reach the photopolymerization initiator A2 to the deep layer of the curable composition, and the curing of the deep layer can be sufficiently promoted.
  • the present invention since the absorption coefficient of the photopolymerization initiator A2 at a wavelength of 365 nm is relatively low and the consumption of the photopolymerization initiator A2 in the first exposure can be suppressed, the polymerization can be efficiently performed in the second exposure.
  • the polymerization of the hydrophilic compound is promoted.
  • the present invention relates to a composition used in such an application. Especially useful for:
  • the deep portion of the curable composition is sufficiently cured by the second exposure, and By improving the mechanical strength of the deep portion, the adhesion to the base can be improved.
  • the A / B is preferably 5 or more, more preferably 7.5 or more, further preferably 15 or more, and particularly preferably 30 or more. Further, the A / B is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less.
  • the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
  • a ⁇ ⁇ log (T ⁇ / 100) (1)
  • a ⁇ is the absorbance at the wavelength ⁇
  • T ⁇ is the transmittance (%) at the wavelength ⁇ .
  • the value of the absorbance may be a value measured in a state of a solution, or a value of a film formed using a curable composition.
  • a method such as spin coating on a glass substrate
  • Apply the curable composition so that the thickness of the film after drying becomes a predetermined thickness, and use a hot plate.
  • the measurement is preferably performed using a film prepared by drying at 100 ° C. for 120 seconds.
  • the thickness of the film can be measured for the substrate having the film by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC).
  • the absorbance can be measured using a conventionally known spectrophotometer. It is preferable to measure the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 600 nm is adjusted to be 0.1 to 3.0. By measuring the absorbance under such conditions, the measurement error can be reduced. There is no particular limitation on the method for adjusting the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to be 0.1 to 3.0. For example, when measuring the absorbance in the state of a solution, a method of adjusting the optical path length of the sample cell may be used.
  • the absorbance When the absorbance is measured in the state of the film, a method of adjusting the film thickness may be used.
  • the absorbance can be measured using, for example, an ultraviolet-visible-near-infrared spectrophotometer.
  • an ultraviolet-visible-near-infrared spectrophotometer As such an apparatus, for example, U-4100 (manufactured by Hitachi High-Tech) can be used.
  • the curable composition more preferably satisfies any of the following spectral characteristics (1) to (4).
  • Amin1 / Bmax1 which is the ratio of the minimum absorbance Amin1 in the wavelength range of 400 to 640 nm to the maximum absorbance Bmax1 in the wavelength range of 800 to 1300 nm, is 5 or more and 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin1 / Bmax1 is preferably 500 or less, more preferably 400 or less, and still more preferably 300 or less. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 750 nm or less while blocking light having a wavelength in the range of 400 to 640 nm. Such a film preferably has, for example, spectral characteristics in which the maximum value of the transmittance at a wavelength of 400 to 640 nm is 20% and the transmittance at a wavelength of 750 nm is 70% or more.
  • Amin2 / Bmax2 which is the ratio of the minimum absorbance Amin2 in the wavelength range of 400 to 750 nm to the maximum absorbance Bmax2 in the wavelength range of 900 to 1300 nm, is 5 or more and 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin2 / Bmax2 is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 850 nm or less while blocking light having a wavelength of 400 to 750 nm. Such a film preferably has, for example, spectral characteristics in which the maximum value of the transmittance at a wavelength of 400 to 750 nm is 20% and the transmittance at a wavelength of 850 nm is 70% or more.
  • Amin3 / Bmax3 which is the ratio of the minimum absorbance Amin3 in the wavelength range of 400 to 850 nm to the maximum absorbance Bmax3 in the wavelength range of 1000 to 1300 nm, is 5 or more, and is 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin3 / Bmax3 is preferably equal to or less than 500, more preferably equal to or less than 400, and still more preferably equal to or less than 300. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 940 nm or less while blocking light having a wavelength of 400 to 830 nm. Such a film preferably has, for example, spectral characteristics such that the maximum value of the transmittance at a wavelength of 400 to 830 nm is 20% and the transmittance at a wavelength of 940 nm is 70% or more.
  • Amin4 / Bmax4 which is the ratio of the minimum absorbance Amin4 in the wavelength range of 400 to 950 nm to the maximum absorbance Bmax4 in the wavelength range of 1100 to 1300 nm, is 5 or more, and is 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin4 / Bmax4 is preferably equal to or less than 500, more preferably equal to or less than 400, and still more preferably equal to or less than 300. According to this aspect, it is possible to form a film that shields light in the wavelength range of 400 to 950 nm and transmits near infrared rays having a wavelength of 1040 nm or less. For example, such a film preferably has spectral characteristics such that the maximum value of the transmittance at a wavelength of 400 to 950 nm is 20% and the transmittance at a wavelength of 1040 nm is 70% or more.
  • the curable composition of the present invention contains a coloring material.
  • the coloring material is preferably a material that transmits at least a part of light in a near-infrared region and absorbs light in a visible region.
  • the coloring material is preferably a material that absorbs light in a violet to red wavelength region.
  • the coloring material is preferably a material that absorbs light in a wavelength region of 400 to 600 nm.
  • the coloring material is preferably a material that transmits light having a wavelength of 1000 to 1300 nm.
  • the coloring material preferably satisfies at least one of the following requirements (A) and (B).
  • A Two or more chromatic colorants are included, and black is formed by a combination of two or more chromatic colorants.
  • B Contains an organic black colorant.
  • the chromatic colorant means a colorant other than a white colorant and a black colorant.
  • the organic black colorant means a material that absorbs visible light but transmits at least a part of infrared light. Therefore, in the present invention, the organic black colorant does not include a black colorant that absorbs both visible light and infrared light, for example, carbon black and titanium black.
  • the organic black colorant is preferably a colorant having a maximum absorption wavelength in a wavelength range of 400 nm to 700 nm.
  • the color material is, for example, a material in which the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more. Is preferred.
  • the wavelength ⁇ p at which the absorbance (extinction coefficient) in the wavelength range of 400 to 600 nm is maximum is preferably larger than 365 nm by 20 nm or more, more preferably 30 nm or more. When the wavelength ⁇ p satisfies the above requirements, the irradiation light for exposure can be efficiently absorbed by the photopolymerization initiator described below.
  • the above-mentioned spectral characteristics may be satisfied with one kind of material, or may be satisfied with a combination of a plurality of materials.
  • the above-mentioned spectral characteristics are satisfied by combining a plurality of chromatic colorants.
  • the organic black colorant alone may satisfy the above-mentioned spectral characteristics.
  • the above spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.
  • the chromatic colorant is preferably a colorant selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
  • the chromatic colorant may be a pigment or a dye. Preferably, it is a pigment.
  • a material in which an inorganic pigment or an organic-inorganic pigment is partially replaced with an organic chromophore can be used. By partially replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, the hue design can be facilitated.
  • the pigment preferably has an average particle size (r) of 20 nm ⁇ r ⁇ 300 nm, more preferably 25 nm ⁇ r ⁇ 250 nm, and still more preferably 30 nm ⁇ r ⁇ 200 nm.
  • the “average particle size” here means an average particle size of secondary particles in which primary particles of the pigment are aggregated.
  • the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also referred to simply as “particle size distribution”) is such that the secondary particles contained in the range of the average particle size ⁇ 100 nm are 70% by mass or more of the whole. Preferably, it is 80% by mass or more.
  • the particle size distribution of the secondary particles is measured using a scattering intensity distribution.
  • the chromatic colorant used in the present invention preferably contains a pigment. Further, the content of the pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass or more. Is particularly preferred.
  • the chromatic colorant may be a pigment alone. Examples of the pigment include the following.
  • Yellow pigment C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Or more, orange pigment), C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3.
  • a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule.
  • a compound described in CN106909097A, a phthalocyanine compound having a phosphate as a ligand, or the like can also be used.
  • an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment.
  • Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247593 and paragraph 0047 of JP-A-2011-157478.
  • yellow pigment a pigment described in JP-A-2017-201303 and a pigment described in JP-A-2017-197719 can be used.
  • a metal containing at least one anion, two or more metal ions, and a melamine compound selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof: Azo pigments can also be used.
  • the alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, and still more preferably has 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent.
  • the substituent is preferably a halogen atom, a hydroxyl group, an alkoxy group, a cyano group or an amino group.
  • yellow pigment a compound described in JP-A-2018-062644 can also be used. This compound can also be used as a pigment derivative.
  • red pigments diketopyrrolopyrrole-based pigments in which at least one bromine atom is substituted in the structure described in JP-A-2017-2013384, diketopyrrolopyrrole-based pigments described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 Etc. can also be used.
  • red pigment a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is introduced to a diketopyrrolopyrrole skeleton may be used. it can.
  • the dye is not particularly limited, and a known dye can be used.
  • a known dye can be used.
  • thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, azo compounds described in JP-A-2011-145540, and JP-A-2018-012863. Can also be preferably used.
  • yellow dye quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can be used.
  • dyes described in WO 2012/128233 and JP-A-2017-201303 can be used.
  • red colorant dyes described in WO2012 / 102399, WO2012 / 117965 and JP-A-2012-229344 can be used.
  • green colorant a dye described in International Publication No. 2012/102395 can be used.
  • a salt-forming dye described in WO 2011/037195 can be used.
  • the coloring material preferably contains two or more selected from a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent and a green coloring agent. That is, it is preferable that the colorant forms black by a combination of two or more types of colorants selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
  • Preferred combinations include, for example, the following. (1) A combination of a red colorant and a blue colorant. (2) A combination of a red colorant, a blue colorant and a yellow colorant. (3) A combination of a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
  • a combination of a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant (5) A combination of a red colorant, a blue colorant, a yellow colorant and a green colorant. (6) A combination of a red colorant, a blue colorant and a green colorant. (7) A combination of a yellow colorant and a purple colorant.
  • the mass ratio of the red colorant, the blue colorant, the yellow colorant, the purple colorant, and the green colorant is red colorant: blue colorant: yellow colorant: purple colorant: green colorant.
  • Agent 10 to 80:20 to 80: 5 to 40: 5 to 40: 5 to 40, preferably 10 to 60:30 to 80: 5 to 30: 5 to 30: 5 to 30.
  • the ratio is more preferably 10 to 40:40 to 80: 5 to 20: 5 to 20: 5 to 20.
  • C.I. I. Pigment Yellow 139, 150, and 185, and C.I. I. Pigment ⁇ Yellow ⁇ 139,150 is more preferable, and C.I. I. Pigment ⁇ Yellow ⁇ 139 is more preferable.
  • blue colorants include C.I. I. Pigment Blue 15: 6 is preferred.
  • purple colorant include C.I. I. Pigment Violet 23 is preferred.
  • Green colorants include C.I. I. Pigment Green 7, 36, 58, 59 are preferred.
  • the organic black colorant may be a pigment or a dye, and is preferably a pigment.
  • the organic black colorant include a bisbenzofuranone compound (also referred to as a benzodifuranone compound), an azomethine compound, a perylene compound, and an azo compound.
  • the organic black colorant preferably contains at least one of a bisbenzofuranone compound, a perylene compound and an azo compound.
  • the bisbenzofuranone compound include compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, and the like. For example, as “Irgaphor Black” manufactured by BASF Available.
  • perylene compounds examples include C.I. I. Pigment Black 31, 32, and the compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821.
  • examples of the azomethine compound include those described in JP-A-01-170601 and JP-A-02-034664, and for example, it can be obtained as "Chromofine Black A1103" manufactured by Dainichi Seika.
  • the bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent
  • R 3 and R 4 each independently represent a substituent
  • a and b each independently represent an integer of 0 to 4.
  • a plurality of R 3 may be the same or different, and a plurality of R 3 may combine to form a ring
  • a plurality of R 4 s may be the same or different, and a plurality of R 4 s may combine to form a ring.
  • the substituents represented by R 1 to R 4 are a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR 301 , —COR 302 , and —COOR 303 , -OCOR 304 , -NR 305 R 306 , -NHCOR 307 , -CONR 308 R 309 , -NHCONR 310 R 311 , -NHCOOR 312 , -SR 313 , -SO 2 R 314 , -SO 2 OR 315 , -NHSO 2 R 316 or —SO 2 NR 317 represents R 318 , and R 301 to R 318 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroary
  • an organic black colorant when used as a coloring material, it is preferable to use it in combination with a chromatic colorant.
  • a chromatic colorant By using an organic black colorant and a chromatic colorant in combination, it is easy to obtain excellent spectral characteristics.
  • the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more.
  • the mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, per 100 parts by mass of the organic black colorant. preferable.
  • the content of the pigment in the coloring material is preferably 95% by mass or more, more preferably 97% by mass or more, and more preferably 99% by mass or more based on the total amount of the coloring material. preferable.
  • the content of the coloring material is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and more preferably 45% by mass, based on the total solid content of the composition. % Or more is more preferable, and 50% by mass or more is particularly preferable. Further, the content of the coloring material is preferably not more than 80% by mass, more preferably not more than 75% by mass, more preferably not more than 70% by mass based on the total solid content of the composition.
  • the curable composition of the present invention can contain a near infrared absorbing agent.
  • the near-infrared absorbing agent has a role of limiting the light transmitted in the near-infrared region to a longer wavelength side in the spectral characteristics of the composition.
  • the near-infrared absorbing agent a compound having a maximum absorption wavelength in a near-infrared region (preferably, a wavelength exceeding 700 nm and 1,300 nm or less) can be preferably used.
  • the near-infrared absorbing agent may be a pigment or a dye.
  • a near-infrared absorbing compound having a ⁇ -conjugated plane containing a monocyclic or condensed aromatic ring can be preferably used as the near-infrared absorbing agent.
  • the number of atoms other than hydrogen constituting the ⁇ -conjugate plane of the near-infrared absorbing compound is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, and 30 or more. It is particularly preferable that the above is satisfied.
  • the upper limit is, for example, preferably 80 or less, and more preferably 50 or less.
  • the ⁇ -conjugate plane of the near-infrared absorbing compound preferably contains two or more monocyclic or condensed aromatic rings, more preferably contains three or more aromatic rings described above, More preferably, it contains four or more, particularly preferably five or more of the above-mentioned aromatic rings.
  • the upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less.
  • the near-infrared absorbing compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm.
  • “having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm” means a wavelength showing a maximum absorbance in a wavelength range of 700 to 1000 nm in an absorption spectrum of a solution of a near-infrared absorbing compound. Means to have.
  • the measurement solvent used for measuring the absorption spectrum of the near-infrared absorbing compound in a solution includes chloroform, methanol, dimethyl sulfoxide, ethyl acetate, and tetrahydrofuran.
  • chloroform is used as a measuring solvent. If the compound does not dissolve in chloroform, use methanol. If it does not dissolve in either chloroform or methanol, use dimethyl sulfoxide.
  • the near-infrared absorbing compound is a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterylene compound, a merocyanine compound, a croconium compound, an oxonol compound, a diimonium compound, a dithiol compound, a triarylmethane compound, At least one selected from a pyrromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a diimonium compound is more preferable. At least one selected from a pyrrolopyrrole compound, a cyanine compound, a
  • Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraphs 0011 to 0052 of JP-A-2011-068731, and WO 2015/166873. Examples include the compounds described in paragraphs 0010 to 0033, the contents of which are incorporated herein.
  • Examples of the squarylium compound include compounds described in paragraphs 0044 to 0049 of JP-A-2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, and paragraph 0040 of WO 2016/181987.
  • the compounds described in WO 2013/133030, the compounds described in WO 2014/088063, the compounds described in JP-A-2014-126642, and the compounds described in JP-A-2016-146619 Compounds, compounds described in JP-A-2015-176046, compounds described in JP-A-2017-025311, compounds described in International Publication No. WO2016 / 154772, compounds described in Patent No.
  • Patent 6036689 Compounds described in the gazette, No. 5,810,604, compounds described in JP-A-2017-068120, compounds described in JP-A-2017-197439, compounds described in paragraphs 0090 to 0107 of WO2017 / 213047, and the like. And their contents are incorporated herein.
  • Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026 to 0030 of JP-A-2002-194040, and JP-A-2015-172004. And the compounds described in JP-A-2015-172102, the compounds described in JP-A-2008-088426, and the like, the contents of which are incorporated herein.
  • examples of the diimonium compound include the compounds described in JP-T-2008-528706, the contents of which are incorporated herein.
  • examples of the phthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraphs 0013 to 0029 of JP-A-2013-195480. And the contents of which are incorporated herein.
  • examples of the naphthalocyanine compound include the compounds described in paragraph 0093 of JP-A-2012-077153, the contents of which are incorporated herein.
  • the compounds described in paragraphs 0010 to 0081 of JP-A-2010-11117 may be used, the contents of which are incorporated herein. It is.
  • the cyanine compound for example, “Functional Dye, Shin Ogawara / Sen Matsuoka / Teijiro Kitao / Tsunaki Hirashima / Author, Kodansha Scientific” can be referred to, and the contents thereof are incorporated herein.
  • the near-infrared absorbing compound the compounds described in JP-A-2016-146519 can also be used, and the contents thereof are incorporated herein.
  • Examples of the near-infrared absorbing agent include a squarylium compound described in JP-A-2017-197439, a squarylium compound described in paragraphs 0090 to 0107 of WO2017 / 213047, and a paragraph 0019 to JP-A-2018-054760.
  • the near-infrared absorbing compound a commercial product may be used.
  • SDO-C33 manufactured by Arimoto Chemical Industry Co., Ltd.
  • EEX Color IR-14 EEX Color IR-10A
  • EEX Color TX-EX-801B EEX Color TX-EX-805K
  • Shigenox NIA-8041 Shigenox NIA-8042
  • Shigenox NIA-814 Shigenox NIA-820
  • Shigenox NIA-839 Manufactured by Hako Chemical Co., Ltd., Hako Chemical Co., Ltd.
  • Film Co., Ltd. NK-3027, NK-5060 (manufactured by Hayashibara), YKR-3070 (manufactured by Mitsui Chemicals, Inc.) and the like.
  • inorganic particles may be used as the near-infrared absorbing agent.
  • the shape of the inorganic particles is not particularly limited, and may be sheet-like, wire-like, or tube-like regardless of spherical or non-spherical shape.
  • metal oxide particles or metal particles are preferable. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped).
  • tungsten oxide-based compound can be used as the inorganic particles.
  • the tungsten oxide-based compound is preferably cesium tungsten oxide.
  • the content of the near-infrared absorbing agent is preferably 1 to 30% by mass based on the total solid content of the composition.
  • the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the total amount of the near-infrared absorbing agent and the coloring material is preferably 10 to 70% by mass of the total solids of the composition.
  • the lower limit is preferably at least 20% by mass, more preferably at least 25% by mass.
  • the content of the near-infrared absorbing agent in the total amount of the near-infrared absorbing agent and the coloring material is preferably 5 to 40% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably at least 10% by mass, more preferably at least 15% by mass.
  • one kind of the near-infrared absorber may be used alone, or two or more kinds may be used in combination.
  • the total is preferably within the above range.
  • the near-infrared absorbing compound a commercial product may be used.
  • SDO-C33 manufactured by Arimoto Chemical Industry Co., Ltd.
  • EEX Color IR-14 EEX Color IR-10A
  • EEX Color TX-EX-801B EEX Color TX-EX-805K
  • ShigenoxNIA-8041 ShigenoxNIA-8042
  • ShigenoxNIA-814 ShigenoxNIA-820
  • ShigenoxNIA-839 Hakko Chemical Co., Ltd.
  • EpoliteV-63 Epolight3801, made Epolight3036 (EPOLIN, Inc.)
  • PRO-JET825LDI Fluji Film Co., Ltd.
  • NK-3027 NK-5060
  • YKR-3070 manufactured by Mitsui Chemicals, Inc.
  • the content of the near-infrared absorbing agent is preferably 1 to 30% by mass based on the total solid content of the curable composition.
  • the upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less.
  • the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
  • the total amount of the near-infrared absorbing agent and the coloring material is preferably 35 to 80% by mass of the total solid of the curable composition.
  • the lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more.
  • the upper limit is preferably 75% by mass or less, more preferably 70% by mass or less. Further, the content of the near-infrared absorbing agent in the total amount of the near-infrared absorbing agent and the coloring material is preferably 5 to 40% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably at least 10% by mass, more preferably at least 15% by mass.
  • the near-infrared absorbing agent may be used alone or in combination of two or more.
  • the total is preferably within the above range.
  • the curable composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include a compound having an ethylenically unsaturated group.
  • the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound is preferably a compound polymerizable by a radical (radical polymerizable compound).
  • the molecular weight of the polymerizable compound is preferably from 100 to 2,000.
  • the upper limit is preferably 1500 or less, more preferably 1000 or less.
  • the lower limit is more preferably 150 or more, and further preferably 250 or more.
  • the lower limit is preferably at least 3 mmol / g, more preferably at least 4 mmol / g, even more preferably at least 5 mmol / g.
  • the upper limit is preferably at most 12 mmol / g, more preferably at most 10 mmol / g, even more preferably at most 8 mmol / g.
  • the polymerizable compound is preferably a compound containing three or more ethylenically unsaturated groups, and more preferably a compound containing four or more ethylenically unsaturated groups. According to this aspect, the curability of the curable composition upon exposure is good.
  • the upper limit of the number of ethylenically unsaturated groups is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less from the viewpoint of the stability over time of the composition.
  • the polymerizable compound is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 10 functional (meth) acrylate compound. More preferably, it is particularly preferably a tri- to hexafunctional (meth) acrylate compound.
  • the polymerizable compound is also preferably a compound containing an ethylenically unsaturated group and an alkyleneoxy group. Since such a polymerizable compound has high flexibility and the ethylenically unsaturated group is easily moved, the polymerizable compound easily reacts with each other at the time of exposure, and a cured film (pixel) having excellent adhesion to a support or the like. Can be formed. Further, when a hydroxyalkylphenone compound is used as the photopolymerization initiator, the polymerizable compound and the photopolymerization initiator approach each other to generate radicals in the vicinity of the polymerizable compound to more effectively convert the polymerizable compound. It is presumed that they can be reacted, and it is easy to form a cured film (pixel) having better adhesion and solvent resistance.
  • the number of alkyleneoxy groups contained in one molecule of the polymerizable compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
  • the upper limit is preferably 20 or less from the viewpoint of the stability over time of the composition.
  • the SP value (Solubility @Parameter) of the compound containing an ethylenically unsaturated group and an alkyleneoxy group is preferably from 9.0 to 11.0 from the viewpoint of compatibility with other components in the composition.
  • the upper limit is preferably 10.75 or less, more preferably 10.5 or less.
  • the lower limit is preferably 9.25 or more, and more preferably 9.5 or more.
  • the SP value used the calculated value based on the Fedors method.
  • Examples of the compound having an ethylenically unsaturated group and an alkyleneoxy group include a compound represented by the following formula (M-1).
  • a 1 represents an ethylenically unsaturated group
  • L 1 represents a single bond or a divalent linking group
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 30
  • n represents 3
  • L 2 represents an n-valent linking group.
  • Examples of the ethylenically unsaturated group represented by A 1 include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
  • Examples of the divalent linking group represented by L 1 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, and a group combining two or more of these. .
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the carbon number of the alkylene group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2.
  • the alkylene group represented by R 1 is preferably linear or branched, and more preferably linear. Specific examples of the alkylene represented by R 1 include an ethylene group, a linear or branched propylene group, and an ethylene group is preferable.
  • n represents an integer of 3 or more, and preferably an integer of 4 or more.
  • the upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and even more preferably an integer of 6 or less.
  • Examples of the n-valent linking group represented by L 2 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group and a group formed by a combination thereof, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group. Examples include a group formed by combining at least one selected from a ring group and at least one selected from -O-, -CO-, -COO-, -OCO- and -NH-.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched.
  • the carbon number of the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.
  • the heterocyclic group is preferably a 5- or 6-membered ring. Examples of the types of hetero atoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the n-valent linking group represented by L 2 is also preferably a group derived from a polyfunctional alcohol.
  • a compound represented by the following formula (M-2) is more preferable.
  • R 2 represents a hydrogen atom or a methyl group
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 30
  • n represents an integer of 3 or more
  • L 2 represents an n-valent linking group.
  • R 1, L 2, m, n of formula (M-2) is R 1, L 2, m, synonymous with n in formula (M-1), and preferred ranges are also the same.
  • polymerizable compounds having an ethylenically unsaturated group and an alkyleneoxy group include KAYARAD T-1420 (T), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • dipentaerythritol triacrylate (KAYARAD @ D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD @ D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Nippon Kayaku), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD @ D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD @ DPHA; Nippon Kayaku ( NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues.
  • SR commercially available from Sartomer It is may SR
  • ARONIX M-402 a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.).
  • trimethylolpropane tri (meth) acrylate trimethylolpropanepropyleneoxy-modified tri (meth) acrylate, trimethylolpropaneethyleneoxy-modified tri (meth) acrylate, isocyanuric acid ethyleneoxy-modified tri (meth) acrylate
  • a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate.
  • trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • NK ester # A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD @ GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And the like.
  • a polymerizable compound having an acid group As the polymerizable compound.
  • the curable composition layer in an unexposed portion is easily removed at the time of development, and the generation of a development residue can be suppressed.
  • the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable.
  • the polymerizable compound having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate.
  • the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developer is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.
  • the polymerizable compound is also preferably a compound having a caprolactone structure.
  • the polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD @ DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
  • Polymerizable compounds include compounds described in JP-A-2017-048367, JP-A-6057891, and JP-A-6031807, compounds described in JP-A-2017-194662, 8UH-1006, and 8UH. It is also preferable to use -1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like.
  • the content of the polymerizable compound is preferably 5.0 to 35% by mass based on the total solid content of the curable composition.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
  • the curable composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoalkylphenone compounds, hydroxyalkylphenone compounds, phenylglyoxylate compounds, and the like.
  • paragraphs 0265 to 0268 of JP-A-2013-029760 and JP-A-6301489 can be referred to, and the contents thereof are incorporated herein.
  • Phenylglyoxylate compounds include phenylglyoxylic acid methyl ester and the like.
  • Commercially available products include DAROCUR-MBF (manufactured by BASF).
  • aminoalkylphenone compound examples include, for example, an aminoalkylphenone compound described in JP-A-10-291969. Further, as the aminoalkylphenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can also be used.
  • acylphosphine compound examples include the acylphosphine compounds described in Japanese Patent No. 422598. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • acylphosphine compound IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.
  • hydroxyalkylphenone compound examples include a compound represented by the following formula (V).
  • Rv 1 represents a substituent
  • Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent
  • Rv 2 and Rv 3 may combine with each other to form a ring
  • m represents an integer of 0 to 5.
  • Examples of the substituent represented by Rv 1 include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms).
  • the alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear.
  • the alkyl group and the alkoxy group represented by Rv 1 may be unsubstituted or may have a substituent.
  • Examples of the substituent include a hydroxyl group and a group having a hydroxyalkylphenone structure.
  • Examples of the group having a hydroxyalkylphenone structure include a benzene ring to which Rv 1 is bonded in Formula (V) or a group having a structure in which one hydrogen atom is removed from Rv 1 .
  • Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent.
  • an alkyl group preferably an alkyl group having 1 to 10 carbon atoms
  • Rv 2 and Rv 3 may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms).
  • the alkyl group is preferably linear or branched, and more preferably linear.
  • IRGACURE-184 As the hydroxyalkylphenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can also be used.
  • Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, and J.I. C. S. Compounds described in Perkin II (1979, pp. 1653-1660); C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer, Science and and Technology (1995, pp.
  • oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.
  • IRGACURE-OXE01 IRGACURE-OXE02
  • IRGACURE-OXE03 IRGACURE-OXE04
  • TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
  • Adeka Optomer N-1919 (Photopolymerization initiator 2 manufactured by ADEKA Corporation and described in JP-A-2012-014052).
  • Examples of the oxime compound include compounds described in JP-A-2009-519904 in which an oxime is linked to the N-position of a carbazole ring, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds described in JP-A-2010-015025 and US Patent Application Publication No. 2009/0292039 in which a nitro group is introduced into a dye moiety, ketoxime compounds described in WO2009 / 131189, triazine skeletons and oximes A compound described in US Pat. No.
  • the oxime compound is preferably an oxime compound containing a fluorine atom.
  • the oxime compound containing a fluorine atom preferably has an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated alkyl group), and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated group). .
  • fluorinated group examples include -OR F1 , -SR F1 , -COR F1 , -COOR F1 , -OCOR F1 , -NR F1 R F2 , -NHCOR F1 , -CONR F1 R F2 , -NHCONR F1 R F2 , -NHCOOR At least one group selected from F1 , —SO 2 R F1 , —SO 2 OR F1, and —NHSO 2 R F1 is preferable.
  • R F1 represents a fluorine-containing alkyl group
  • R F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group or a heterocyclic group.
  • the fluorine-containing group is preferably -OR F1 .
  • the carbon number of the alkyl group and the fluorine-containing alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4.
  • the alkyl group and the fluorine-containing alkyl group may be linear, branched or cyclic, but are preferably linear or branched.
  • the substitution ratio of fluorine atoms is preferably from 40 to 100%, more preferably from 50 to 100%, even more preferably from 60 to 100%.
  • the substitution rate of a fluorine atom means the ratio (%) of the number of substitution with a fluorine atom to the total number of hydrogen atoms of the alkyl group.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4.
  • the number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and more preferably 3 to 20.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom.
  • the group containing a fluorine atom preferably has a terminal structure represented by the formula (1) or (2). -CHF 2 (1) -CF 3 (2)
  • the total number of fluorine atoms in the fluorine-containing oxime compound is preferably 3 or more, more preferably 4 to 10.
  • the oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1). (OX-1)
  • Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent, and R 1 represents an aryl group having a group containing a fluorine atom. And R 2 and R 3 each independently represent an alkyl group or an aryl group.
  • Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent.
  • the aromatic hydrocarbon ring may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10.
  • a benzene ring and a naphthalene ring are preferable.
  • at least one of Ar 1 and Ar 2 is preferably a benzene ring, and more preferably Ar 1 is a benzene ring.
  • Ar 2 is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.
  • Examples of the substituent which Ar 1 and Ar 2 may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR X1 , —SR X1 , —COR X1 , and —COOR X1. , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 No. R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group as a substituent and the alkyl group represented by R X1 and R X2 preferably have 1 to 30 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • some or all of the hydrogen atoms may be substituted with halogen atoms (preferably, fluorine atoms).
  • part or all of the hydrogen atoms may be substituted with the above substituents.
  • the carbon number of the aryl group as a substituent and the aryl group represented by R X1 and R X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aryl group may be a single ring or a condensed ring. Further, in the aryl group, part or all of the hydrogen atoms may be substituted with the above substituents.
  • the heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably a 5- or 6-membered ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above substituents.
  • the aromatic hydrocarbon ring represented by Ar 1 is preferably unsubstituted.
  • the aromatic hydrocarbon ring represented by Ar 2 may be unsubstituted or may have a substituent. It preferably has a substituent.
  • —COR X1 is preferable.
  • R X1 is preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an aryl group.
  • the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.
  • R 1 represents an aryl group having a group containing a fluorine atom.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the group containing a fluorine atom an alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing a fluorine atom-containing alkyl group (fluorine-containing group) are preferable.
  • the group containing a fluorine atom has the same meaning as the above-mentioned range, and the preferred range is also the same.
  • R 2 represents an alkyl group or an aryl group, and is preferably an alkyl group.
  • the alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have.
  • the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • R 3 represents an alkyl group or an aryl group, and is preferably an alkyl group.
  • the alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have.
  • the number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the aryl group represented by R 3 preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and still more preferably has 6 to 10 carbon atoms.
  • oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471.
  • Compound (C-3) examples include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471.
  • an oxime compound having a fluorene ring can be used as the oxime compound.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
  • an oxime compound having a benzofuran skeleton can be used as the oxime compound.
  • Specific examples include compounds OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can be used.
  • Specific examples of such oxime compounds include the compounds described in WO2013 / 083505.
  • an oxime compound having a nitro group can be used.
  • the oxime compound having a nitro group is preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 of JP-A-2014-137466, and 0070 to 0079, and JP-A-4223071. And the like.
  • a photopolymerization initiator A1 having an absorption coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at a wavelength of 365 nm, and a wavelength of 365 nm in methanol.
  • a photopolymerization initiator A2 having an extinction coefficient of 1.0 ⁇ 10 2 mL / gcm or less and an extinction coefficient at a wavelength of 254 nm of 1.0 ⁇ 10 3 mL / gcm or more.
  • the composition is easily cured sufficiently by exposure, and has excellent adhesion in a low-temperature process (for example, at a temperature of less than 200 ° C., or 150 ° C. or less, and even 120 ° C. or less throughout the entire process), Furthermore, a cured film having excellent solvent resistance, flatness, and rectangularity of the pattern can be formed.
  • a compound having the above-mentioned extinction coefficient is preferably selected from the above-mentioned compounds and used.
  • the extinction coefficient of the photopolymerization initiator at the above-mentioned wavelength is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Carry5000) manufactured by Agilent Technologies, and the wavelength was 365 nm and the wavelength was applied by applying the following formula. The extinction coefficient (mL / gcm) at 254 nm was calculated.
  • ⁇ represents the extinction coefficient (mL / gcm)
  • A represents the absorbance
  • c represents the concentration of the photopolymerization initiator (g / mL)
  • l represents the optical path length (cm).
  • the extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm is 1.0 ⁇ 10 3 mL / gcm or more, preferably 1.0 ⁇ 10 4 mL / gcm or more, and more preferably 1.1 ⁇ 10 4 mL / gcm. It is more preferably at least 10 4 mL / gcm, even more preferably 1.2 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / gcm, and 1.3 ⁇ 10 4 to 5.0 ⁇ 10 4 mL. / Gcm, more preferably 1.5 ⁇ 10 4 to 3.0 ⁇ 10 4 mL / gcm.
  • the extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm in methanol is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / gcm, and 1.5 ⁇ 10 4 to 1.5 ⁇ 10 4 mL / gcm. It is more preferably 9.5 ⁇ 10 4 mL / gcm, and still more preferably 3.0 ⁇ 10 4 to 8.0 ⁇ 10 4 mL / gcm.
  • the photopolymerization initiator A1 is preferably an oxime compound, an aminoalkylphenone compound or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, further preferably an oxime compound, and has compatibility with other components contained in the composition.
  • an oxime compound containing a fluorine atom is particularly preferred.
  • a compound represented by the above formula (OX-1) is preferable.
  • photopolymerization initiator A1 examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (as commercial products, for example, IRGACURE-OXE01, BASF , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (commercially available, for example, IRGACURE- OXE02, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercially available, for example, IRGACURE-819, manufactured by BASF), and specific examples of the above oxime compounds ( C-13) and (C-14).
  • the extinction coefficient of the photopolymerization initiator A2 for light having a wavelength of 365 nm in methanol is 1.0 ⁇ 10 2 mL / gcm or less, preferably 10 to 1.0 ⁇ 10 2 mL / gcm. More preferably, it is about 1.0 ⁇ 10 2 mL / gcm.
  • the difference between the extinction coefficient of photopolymerization initiator A1 at 365 nm in methanol and the extinction coefficient of photopolymerization initiator A2 at 365 nm in methanol is 9.0 ⁇ 10 2 mL.
  • the extinction coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 254 nm in methanol is 1.0 ⁇ 10 3 mL / gcm or more, and 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6 mL / gcm. And more preferably from 5.0 ⁇ 10 3 to 1.0 ⁇ 10 5 mL / gcm.
  • the photopolymerization initiator A2 is preferably a hydroxyalkylphenone compound, a phenylglyoxylate compound, an aminoalkylphenone compound, an acylphosphine compound, more preferably a hydroxyalkylphenone compound and a phenylglyoxylate compound, and further preferably a hydroxyalkylphenone compound.
  • a compound represented by the above formula (V) is preferable.
  • photopolymerization initiator A2 examples include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl 2-hydroxy-2-methyl-1-propan-1-one (commercially available, for example, IRGACURE-2959, manufactured by BASF).
  • the photopolymerization initiator A1 As a combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound is preferable, and the photopolymerization initiator A1 is preferably More preferably, the combination is an oxime compound, wherein the photopolymerization initiator A2 is a compound represented by the above formula (V), wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator A2 is Combinations of the compounds of formula (V) described above are particularly preferred.
  • the content of the photopolymerization initiator A1 is preferably 1.0 to 20.0% by mass based on the total solid content of the curable composition of the present invention.
  • the lower limit of the content of the photopolymerization initiator A1 is preferably 2.0% by mass or more, and more preferably 3.0% by mass or more. More preferably, it is more preferably 4.0% by mass or more.
  • the upper limit of the content of the photopolymerization initiator A1 is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, and 10.0% or less. It is more preferable that the content be not more than mass%.
  • the content of the photopolymerization initiator A2 is preferably 0.5 to 15.0% by mass based on the total solid content of the curable composition of the present invention.
  • the lower limit of the content of the photopolymerization initiator A2 is preferably 1.0% by mass or more, more preferably 1.5% by mass or more. More preferably, it is 0% by mass or more.
  • the upper limit of the content of the photopolymerization initiator A2 is preferably 12.5% by mass or less, more preferably 10.0% by mass or less, and 7.5. It is more preferable that the content be not more than mass%.
  • the curable composition of the present invention preferably contains 50 to 200 parts by mass of the photopolymerization initiator A2 based on 100 parts by mass of the photopolymerization initiator A1.
  • the upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less, from the viewpoint of miniaturization of the pattern after development.
  • the lower limit is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, from the viewpoint of the solvent resistance of the obtained cured film.
  • the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the curable composition of the present invention is preferably 5 to 15% by mass or more.
  • the lower limit is preferably 6% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more.
  • the upper limit is preferably 14.5% by mass or less, more preferably 14.0% by mass or less, and still more preferably 13.0% by mass or less, from the viewpoint of miniaturization of the pattern after development. .
  • the curable composition of the present invention can contain a photopolymerization initiator other than the photopolymerization initiator A1 and the photopolymerization initiator A2 (hereinafter, also referred to as another photopolymerization initiator) as a photopolymerization initiator. It is preferable that other photopolymerization initiators are not substantially contained.
  • the case where the other photopolymerization initiator is not substantially contained means that the content of the other photopolymerization initiator is 1 part by mass with respect to 100 parts by mass in total of the photopolymerization initiator A1 and the photopolymerization initiator A2. It is preferably at most 0.5 part by mass, more preferably at most 0.5 part by mass, even more preferably at most 0.1 part by mass, and even more preferably not containing other photopolymerization initiator.
  • the composition of the present invention can contain a resin.
  • the resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition or for the purpose of a binder.
  • a resin mainly used for dispersing particles such as a pigment is also referred to as a dispersant.
  • a use of the resin is an example, and the resin may be used for a purpose other than the use.
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 3,000 or more, more preferably 5,000 or more.
  • cyclic olefin resin a norbornene resin can be preferably used from the viewpoint of improving heat resistance.
  • Examples of commercially available norbornene resin include ARTON series (for example, ARTON @ F4520) manufactured by JSR Corporation.
  • Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester resin.
  • Epoxy resin glycidylamine-based epoxy resin, epoxy resin obtained by glycidylation of halogenated phenols, condensate of silicon compound with epoxy group and other silicon compound, polymerizable unsaturated compound with epoxy group and other Copolymers with other polymerizable unsaturated compounds and the like can be mentioned. Also, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation) , An epoxy group-containing polymer) and the like.
  • resins described in Examples of International Publication WO 2016/088865, resins described in JP-A-2017-057265, resins described in JP-A-2017-032685, A resin described in JP-A-0-75248 and a resin described in JP-A-2017-066240 can also be used, and the contents thereof are incorporated herein.
  • a resin having a fluorene skeleton can be preferably used.
  • examples of the resin having a fluorene skeleton include a resin having the following structure.
  • A is a residue of a carboxylic acid dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride.
  • M is a phenyl or benzyl group.
  • the resin used in the present invention may have an acid group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group, and a carboxyl group is preferable. These acid groups may be used alone or in combination of two or more.
  • the resin having an acid group can be used as an alkali-soluble resin.
  • a polymer having a carboxyl group in a side chain is preferable.
  • alkali-soluble polymers such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins.
  • examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxyl group.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds.
  • alkyl (meth) acrylate and the aryl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, and cyclohexyl (meth) acrylate include styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydr
  • N-substituted maleimide monomers described in JP-A-10-300922 for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used.
  • the other monomer copolymerizable with the (meth) acrylic acid may be only one kind or two or more kinds.
  • the resin having a diacid group may further have a polymerizable group.
  • the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group.
  • Commercial products include Dianar NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS Resist 106 (all of Osaka Organic Chemicals, Inc.) Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel @ CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Accrecur RD-F8 (Co., Ltd.) Nippon Shokubai).
  • Resins having an acid group include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate.
  • a multi-component copolymer composed of acrylate / (meth) acrylic acid / other monomer can be preferably used.
  • copolymers of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-07-140654.
  • the resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferable that the polymer contains a repeating unit derived from a component.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • RIn the formula (ED2) R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168538 can be referred to.
  • ether dimer for example, paragraph 0317 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated herein.
  • the ether dimer may be only one kind or two or more kinds.
  • the resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a carbon atom having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring.
  • n represents an integer of 1 to 15.
  • the resin having an acid group is described in paragraphs 0558 to 0571 of JP-A-2012-208494 (paragraphs 0885 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) and JP-A-2012-198408. Can be referred to, and the contents thereof are incorporated in the present specification.
  • a commercially available resin can be used as the resin having an acid group.
  • Acrybase FF-426 manufactured by Fujikura Kasei Co., Ltd.
  • the like can be mentioned.
  • the acid value of the resin having an acid group is preferably from 30 to 200 mgKOH / g.
  • the lower limit is preferably at least 50 mgKOH / g, more preferably at least 70 mgKOH / g.
  • the upper limit is preferably equal to or less than 150 mgKOH / g, and more preferably equal to or less than 120 mgKOH / g.
  • Examples of the resin having an acid group include a resin having the following structure.
  • Me represents a methyl group.
  • the composition of the present invention can also contain a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of an acid group is larger than the amount of a basic group.
  • the acid dispersant (acidic resin) is preferably a resin in which the amount of the acid group accounts for 70 mol% or more when the total amount of the acid group and the basic group is 100 mol%. More preferred are resins consisting only of groups.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant is preferably from 40 to 105 mgKOH / g, more preferably from 50 to 105 mgKOH / g, even more preferably from 60 to 105 mgKOH / g.
  • the basic dispersant (basic resin) refers to a resin in which the amount of the basic group is larger than the amount of the acid group.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of the basic group exceeds 50 mol% when the total amount of the acid group and the amount of the basic group is 100 mol%.
  • the basic group of the basic dispersant is preferably an amino group.
  • the resin used as the dispersant preferably contains a repeating unit having an acid group.
  • residues generated on the base of the pixel can be further reduced when a pattern is formed by a photolithography method.
  • the resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for a solvent due to the graft chain, the dispersibility of the pigment and the dispersion stability after aging are excellent.
  • the details of the graft copolymer can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • specific examples of the graft copolymer include the following resins.
  • the following resins are also resins having an acid group (alkali-soluble resins).
  • examples of the graft copolymer include resins described in paragraphs 0072 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain as the resin (dispersant).
  • the oligoimine-based dispersant includes a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain including a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain. Resins having a basic nitrogen atom on at least one side are preferred.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
  • oligoimine-based dispersant the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • a resin having the following structure or a resin described in paragraphs 0168 to 0174 of JP-A-2012-255128 can be used.
  • the dispersant is also available as a commercial product, and specific examples of such a dispersant include Disperbyk-111 (manufactured by BYK Chemie), Solsperse 76500 (manufactured by Nippon Lubrizol Co., Ltd.), and the like. Further, pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated herein. Further, the above-mentioned resin having an acid group can be used as a dispersant.
  • the content of the resin is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less.
  • the content of the resin having an acid group is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less.
  • the composition of the present invention may include only one type of resin, or may include two or more types of resins. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the curable composition of the present invention preferably contains a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound).
  • a furyl group-containing compound a compound containing a furyl group
  • the furyl group and the ethylenically unsaturated group of the polymerizable compound form a bond by the Diels-Alder reaction even at a low temperature of less than 200 ° C., and thus are excellent in low-temperature curing.
  • the structure of the furyl group-containing compound is not particularly limited as long as it contains a furyl group (a group obtained by removing one hydrogen atom from furan).
  • a furyl group a group obtained by removing one hydrogen atom from furan.
  • the furyl group-containing compound the compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used.
  • the difuryl group-containing compound may be a monomer, an oligomer, or a polymer.
  • the polymer is preferably used because it is easy to improve the durability of the obtained film.
  • the weight average molecular weight is preferably from 2000 to 70000.
  • the upper limit is preferably 60,000 or less, more preferably 50,000 or less.
  • the lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more.
  • the weight average molecular weight is preferably less than 2000.
  • the polymer type furyl group-containing compound is a component corresponding to the resin in the curable composition of the present invention, and the monomer type furyl group-containing compound is also a polymerizable compound in the curable composition of the present invention.
  • the corresponding component is a component corresponding to the resin in the curable composition of the present invention, and the monomer type furyl group-containing compound is also a polymerizable compound in the curable composition of the present invention.
  • Examples of the monomer type furyl group-containing compound include compounds represented by the following formula (fur-1). This compound has a polymerizable group in addition to the furyl group.
  • Rf 1 represents a hydrogen atom or a methyl group
  • Rf 2 represents a divalent linking group
  • Examples of the divalent linking group represented by Rf 2 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups.
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group.
  • the furyl group-containing monomer is preferably a compound represented by the following formula (fur-2).
  • Rf 1 represents a hydrogen atom or a methyl group
  • Rf 11 represents —O— or —NH—
  • Rf 12 represents a single bond or a divalent linking group.
  • Examples of the divalent linking group represented by Rf 12 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups.
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group.
  • furyl group-containing monomer examples include a compound having the following structure.
  • Rf 1 represents a hydrogen atom or a methyl group.
  • the polymer type furyl group-containing compound (hereinafter also referred to as a furyl group-containing polymer) is preferably a resin containing a repeating unit containing a furyl group, and is preferably a resin derived from the compound represented by the above formula (fur-1). More preferably, the resin contains units.
  • the concentration of the furyl group in the furyl group-containing polymer is preferably 0.5 to 6.0 mmol, more preferably 1.0 to 4.0 mmol, per 1 g of the furyl group-containing polymer. When the concentration of the furyl group is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form a pixel having excellent solvent resistance and the like. If the concentration of the furyl group is 6.0 mmol or less, preferably 4.0 mmol or less, the curable composition has better stability over time.
  • the furyl group-containing polymer may contain a repeating unit having an acid group and / or a repeating unit having a polymerizable group in addition to the repeating unit having a furyl group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group.
  • the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • its acid value is preferably from 10 to 200 mgKOH / g, more preferably from 40 to 130 mgKOH / g.
  • the furyl group-containing polymer contains a repeating unit having a polymerizable group, it is easy to form a pixel having more excellent solvent resistance and the like.
  • the furyl group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP-A-2017-194662.
  • the content of the furyl group-containing compound is preferably 0.1 to 70% by mass based on the total solid content of the curable composition.
  • the lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and even more preferably 7.5% by mass or more.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content of the furyl group-containing polymer in the resin contained in the curable composition is preferably 0.1 to 100% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more.
  • the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the curable composition of the present invention can further contain a compound having a cyclic ether group.
  • the curable composition of the present invention preferably contains a curing accelerator for the compound having a cyclic ether group.
  • the cyclic ether group is, for example, an epoxy group and an oxetane group, and an epoxy group is preferable.
  • the compound having an epoxy group a compound having two or more epoxy groups in one molecule is preferable.
  • the epoxy group preferably has 2 to 100 epoxy groups in one molecule.
  • the upper limit can be, for example, 10 or less, or 5 or less.
  • the compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (a macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
  • the molecular weight (weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000.
  • the upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.
  • EHPE3150 manufactured by Daicel Corporation
  • EPICLON @ N-695 manufactured by DIC Corporation
  • Marproof G-0150M Marproof G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (both manufactured by NOF Corporation, epoxy group-containing polymer) and the like.
  • the content of the compound is preferably 0.1 to 20% by mass based on the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more.
  • the upper limit is more preferably equal to or less than 15% by mass, and still more preferably equal to or less than 10% by mass.
  • the compound having a cyclic ether group may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
  • a compound generally used as a curing accelerator for an epoxy compound can be used, for example, acid anhydride, Amines, carboxylic acids and alcohols are preferred.
  • Acid anhydrides as curing accelerators include, for example, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, 2,4-diethyl glutaric anhydride, butane tetra Carboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3 4-Tricarboxylic acid-3,4-anhydride and the like are preferred from the viewpoints of light resistance, transparency and workability.
  • the carboxylic acid as a curing accelerator is preferably a di- to hexa-functional carboxylic acid.
  • Such carboxylic acids include, for example, alkyltricarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid and citric acid; Aliphatic cyclic polycarboxylic acids such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid and methylnadic acid; linolenic acid and oleic acid Dimer acids which are multimers of unsaturated fatty acids and their reduced products; linear alkyl diacids such as malic acid and the like are preferable, and hexane di
  • the amine as the curing accelerator is preferably a polyvalent amine, and more preferably a diamine.
  • Such amines are, for example, hexamethylenediamine, triethylenetetramine, polyethyleneimine and the like.
  • Alcohols as curing accelerators are preferably polyhydric alcohols, more preferably diols.
  • Such alcohols are, for example, polyether diol compounds, polyester diol compounds, polycarbonate diol compounds and the like.
  • the content of the curing accelerator is preferably 1 to 30 parts by mass, and more preferably 5 to 25 parts by mass based on 100 parts by mass of the compound having a cyclic ether group. Part by mass, more preferably 10 to 20 parts by mass.
  • the curing accelerators may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
  • the curable composition of the present invention preferably contains a solvent.
  • the solvent include an organic solvent.
  • the solvent is basically not particularly limited as long as the solubility of each component and the coatability of the curable composition are satisfied.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For details thereof, paragraph 0223 of WO 2015/166779 can be referred to, and the contents thereof are incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like.
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • aromatic hydrocarbons for environmental reasons or the like (for example, 50 ppm by mass (parts per part with respect to the total amount of the organic solvent). (million) or less, 10 mass ppm or less, or 1 mass ppm or less).
  • a solvent having a low metal content it is preferable to use a solvent having a low metal content, and it is preferable that the metal content of the solvent be, for example, 10 mass ppb (parts per per billion) or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one isomer may be contained, or a plurality of isomers may be contained.
  • the content of the peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide.
  • the content of the solvent in the curable composition is preferably from 60 to 95% by mass.
  • the upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and even more preferably 85% by mass or less.
  • the lower limit is preferably at least 65% by mass, more preferably at least 70% by mass, even more preferably at least 75% by mass.
  • the curable composition of the present invention does not substantially contain an environmental regulation substance from the viewpoint of environmental regulation.
  • the term "substantially not containing an environmental control substance” means that the content of the environmental control substance in the curable composition is 50 mass ppm or less, and 30 mass ppm or less. It is more preferably at most 10 ppm by mass, particularly preferably at most 1 ppm by mass.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • azeotrope When a small amount of environmentally regulated substances are distilled off, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency.
  • a polymerization inhibitor or the like When a compound having a radical polymerizability is contained, a polymerization inhibitor or the like is added in order to suppress the radical polymerization reaction from proceeding and crosslinking between molecules during the distillation under reduced pressure, followed by distillation under reduced pressure. You may.
  • These distillation methods include a raw material stage, a product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or a curable composition prepared by mixing these compounds. Either stage is possible.
  • the curable composition of the present invention can contain a pigment derivative.
  • the pigment derivative include a compound having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group.
  • the chromophore constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, and a perinone skeleton.
  • quinoline skeleton, benzimidazolone skeleton, diketo A pyrrolopyrrole-based skeleton, an azo-based skeleton, a quinophthalone-based skeleton, an isoindoline-based skeleton, and a phthalocyanine-based skeleton are preferred, and an azo-based skeleton and a benzimidazolone-based skeleton are more preferred.
  • a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable.
  • an amino group is preferable, and a tertiary amino group is more preferable.
  • the description in paragraphs 0162 to 0183 of JP-A-2011-252665 can be referred to, and the contents thereof are incorporated herein.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment.
  • One kind of the pigment derivative may be used alone, or two or more kinds thereof may be used in combination.
  • the curable composition of the present invention may contain a curing accelerator for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature.
  • the curing accelerator include a polyfunctional thiol compound having two or more mercapto groups in a molecule.
  • the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
  • the polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound represented by the formula (T1).
  • n represents an integer of 2 to 4
  • L represents a divalent to tetravalent linking group.
  • the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
  • the curing accelerator examples include a methylol-based compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of JP-A-2005-034963), amines, phosphonium salts, amidine salts, and amide compounds (for example, JP-A-2013-041165, a curing agent described in paragraph 0186), a base generator (for example, an ionic compound described in JP-A-2014-055114), and a cyanate compound (for example, JP-A-2012-150180)
  • Compounds exemplified as acid generators, JP Compounds described in JP-009-180949) or the like can be used.
  • the content of the curing accelerator is preferably 0.3 to 8.9% by mass based on the total solid content of the curable composition, and 0.8 to 6% by mass. 0.4 mass% is more preferred.
  • the curable composition of the present invention can contain a silane coupling agent.
  • a silane coupling agent a silane compound having at least two types of functional groups having different reactivities in one molecule is preferable.
  • the silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureide group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. Is preferred.
  • silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), 3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu) Chemical Industry Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) And KBM-403).
  • the description in paragraphs 0155 to 0158 of JP-A-2013-254407 can be referred to, and the contents thereof are incorporated herein.
  • the content of the silane coupling agent is preferably 0.001 to 20% by mass based on the total solid content of the curable composition, and 0.01 to 10% by mass. % By mass is more preferable, and 0.1 to 5% by mass is particularly preferable.
  • the curable composition of the present invention may include only one type of silane coupling agent, or may include two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the curable composition of the present invention can contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine salts (ammonium salts, cerous salts) and the like.
  • the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the curable composition.
  • the curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the curable composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used.
  • paragraphs 0052 to 0072 of JP-A-2012-208374, paragraphs 0317 to 0334 of JP-A-2013-068814, and paragraphs 0061 to 0080 of JP-A-2016-162946 can be referred to. These contents are incorporated herein.
  • UV absorbers include, for example, UV-503 (manufactured by Daito Chemical Co., Ltd.).
  • benzotriazole compound examples include MYUA series (manufactured by Miyoshi Oil & Fats, Chemical Daily, February 1, 2016).
  • compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as an ultraviolet absorber.
  • the content of the ultraviolet absorber is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the curable composition. Is more preferable, and 0.1 to 3% by mass is particularly preferable.
  • only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the curable composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
  • paragraphs 0238 to 0245 of WO 2015/166779 can be referred to, and the contents thereof are incorporated herein.
  • the surfactant is preferably a fluorinated surfactant.
  • a fluorine-based surfactant in the curable composition, liquid properties (particularly, fluidity) are further improved, and liquid saving properties can be further improved.
  • a film with small thickness unevenness can be formed.
  • the fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of a coating film and liquid saving properties, and has good solubility in a curable composition.
  • fluorinated surfactant examples include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraphs 0060 to 0064 of WO 2014/017669), and JP-A-2011-132503.
  • the surfactants described in paragraphs 0117 to 0132 of the gazette are exemplified, and the contents thereof are incorporated herein.
  • fluorine surfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PolyFox @ PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like. .
  • fluorine-based surfactants have a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off when heat is applied and the fluorine atom is volatilized. It can be suitably used.
  • fluorinated surfactant include Megafac DS series (manufactured by DIC Corporation, Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21.
  • a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant.
  • the description of JP-A-2016-216602 can be referred to for such a fluorine-based surfactant, and the contents thereof are incorporated herein.
  • a block polymer can also be used as the fluorine-based surfactant.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom, and has 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorinated surfactant used in the present invention.
  • the above compound has a weight average molecular weight of preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used.
  • Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Megafac RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation. -72-K and the like.
  • the fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Co., Ltd.), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS ), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fuji
  • silicone-based surfactant examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Inc.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all made by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (all, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (all manufactured by Big Chemie).
  • the content of the surfactant in the total solid content of the curable composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass.
  • the surfactant may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is within the above range.
  • the curable composition of the present invention may optionally contain various additives, for example, a filler, an adhesion promoter, an antioxidant, and an anti-agglomeration agent.
  • additives include those described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein.
  • the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0042 of JP-A-2011-090147), a thioether compound, or the like can be used.
  • antioxidants described in (1) can also be used.
  • One type of antioxidant may be used, or two or more types may be used.
  • the curable composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • a compound in which a protecting group is eliminated to function as an antioxidant can be mentioned.
  • Specific examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP-A-2017-008219.
  • Commercially available products include Adeka Aquel's GPA-5001 (manufactured by ADEKA Corporation).
  • the curable composition of the present invention may be a sensitizer or a light stabilizer described in paragraph 0078 of JP-A-2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of the same, or JP-A-2018-091940.
  • the storage stabilizer described in paragraph No. 0242 of JP-A No. 2-1980 can be contained.
  • the curable composition of the present invention preferably has a content of free metal not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less. Preferably, it is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of a curable component, suppression of conductivity fluctuation due to elution of metal atoms and metal ions, Effects such as improvement of display characteristics can be expected.
  • the types of the above free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Fe, Co, Mg, Al, Ti, Sn, Zn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Bi, and the like.
  • the curable composition of the present invention preferably has a content of free halogen not bound or coordinated with a pigment or the like of 100 mass ppm or less, more preferably 50 mass ppm or less, and 10 mass ppm or less. The content is more preferably not more than ppm by mass, and particularly preferably substantially not contained.
  • Examples of a method for reducing free metals and halogens in the curable composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
  • the curable composition of the present invention contains substantially no terephthalate.
  • substantially free means that the content of the terephthalic acid ester in the solid content of the composition is 1000 mass ppb or less, more preferably 500 mass ppb or less, Particularly preferred is zero.
  • the container for storing the curable composition of the present invention is not particularly limited, and a known container can be used. Further, as a container, for the purpose of suppressing the contamination of impurities into the raw material and the curable composition, a multilayer bottle in which the inner wall of the container is composed of six types of six layers of resin and a six types of resin having a seven layer structure. It is also preferred to use bottles. Examples of such a container include a container described in JP-A-2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel from the viewpoint of preventing metal elution from the inner wall of the container, increasing storage stability of the composition, and suppressing deterioration of components.
  • the curable composition of the present invention can be produced by mixing the above components.
  • the curable composition may be produced by dissolving and / or dispersing all the components in a solvent at the same time.
  • the composition may be manufactured by mixing these at the time of use (at the time of application) as a liquid.
  • the production of the curable composition may include a process of dispersing particles such as pigments.
  • examples of mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion.
  • fine processing of particles may be performed in a salt milling step.
  • the materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin).
  • PTFE polytetrafluoroethylene
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin).
  • PP polypropylene
  • nylon high-density polypropylene
  • nylon are preferred.
  • the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
  • a fibrous filter medium examples include a polypropylene fiber, a nylon fiber, and a glass fiber.
  • Commercially available products include SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno.
  • filters for example, a first filter and a second filter
  • the filtration by each filter may be performed only once or may be performed twice or more.
  • filters having different hole diameters may be combined within the above-described range.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after the other components are mixed, the filtration with the second filter may be performed.
  • the cured film of the present invention can be produced by forming a film of the above-described curable composition of the present invention, drying and curing the film.
  • the cured film of the present invention can be preferably used as a near infrared transmitting filter.
  • the thickness of the cured film can be appropriately adjusted depending on the purpose, and is preferably 100 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the lower limit of the thickness is preferably at least 0.1 ⁇ m, more preferably at least 0.2 ⁇ m, even more preferably at least 0.3 ⁇ m.
  • the maximum value of light transmittance in the thickness direction of the film in a wavelength range of 400 to 600 nm is 20% or less; It is preferable to satisfy the spectral characteristic that the minimum value in the wavelength range of 1000 to 1300 nm is 70% or more.
  • the maximum value in the wavelength range of 400 to 600 nm is preferably 15% or less, more preferably 10% or less.
  • the minimum value in the wavelength range of 1000 to 1300 nm is preferably at least 75%, more preferably at least 80%.
  • the cured film of the present invention more preferably satisfies any of the following spectral characteristics (11) to (14).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 640 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the optical filter of the present invention is, for example, a near-infrared transmitting filter and includes the cured film of the present invention.
  • the optical filter of the present invention may be provided with a protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 on the surface of the cured film.
  • the optical filter of the present invention may include an RGB color filter containing a chromatic colorant. Such a color filter is manufactured using a curable composition containing the same chromatic colorant as the chromatic colorant described in the description of the color material.
  • the pattern forming method of the present invention includes a step of forming a curable composition layer on a support using the curable composition of the present invention, and a step of forming a curable composition layer having a thickness of more than 350 nm to 380 nm or less.
  • a second exposure step of irradiating light having the following.
  • the treatment can be performed at a temperature of less than 200 ° C., preferably at a temperature of 150 ° C. or less throughout all the steps.
  • “the treatment is performed at a temperature of less than 200 ° C. throughout the entire process” means that all of the steps of forming a patterned cured film using the curable composition are performed at a temperature of less than 200 ° C. Means that.
  • a heating step may be further provided after the second exposure step. However, in this case, the heating temperature is lower than 200 ° C.
  • each step will be described in detail.
  • the curable composition of the present invention is applied on a support to form a curable composition layer.
  • the support is, for example, a glass substrate or a resin substrate.
  • the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate.
  • An organic light emitting layer or a photoelectric conversion layer may be formed on these substrates.
  • the substrate may be provided with an undercoat layer for improving adhesion to an upper layer, preventing diffusion of a substance, or planarizing the surface.
  • the undercoat layer may be formed, for example, by applying a curable composition obtained by removing a coloring material from the curable composition of the present invention.
  • a known method can be used as a method for applying the composition.
  • a dropping method drop casting
  • a slit coating method for example, a spraying method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, JP-A-2009-145395).
  • Publications inkjet (eg, on-demand method, piezo method, thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Various printing methods a transfer method using a mold or the like; a nanoimprint method, and the like.
  • the application method in the ink jet is not particularly limited, and for example, a method shown in “Spread and usable ink jets—infinite possibilities seen in patents”, published in February 2005, Sumibe Techno Research (especially from page 115). 133 page), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261828, JP-A-2012-126830, JP-A-2006-169325, and the like. No.
  • the descriptions in WO2017 / 030174 and WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.
  • the cured composition layer formed on the support may be dried (prebaked).
  • the prebaking temperature is preferably 80 ° C or lower, more preferably 70 ° C or lower, still more preferably 60 ° C or lower, and particularly preferably 50 ° C or lower.
  • the lower limit can be, for example, 40 ° C. or higher.
  • the prebake time is preferably from 10 to 3600 seconds. Prebaking can be performed on a hot plate, an oven, or the like.
  • First exposure step light is applied to the curable composition layer in a pattern by irradiating light having a wavelength of more than 350 nm and not more than 380 nm.
  • the curable composition layer can be exposed in a pattern by using an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, the exposed portion of the curable composition layer can be cured.
  • Light that can be used for exposure is light having a wavelength of more than 350 nm and not more than 380 nm, preferably light having a wavelength of 355 to 370 nm, and more preferably i-line (365 nm). This exposure processing may be performed while cutting light having a wavelength shorter than the i-line, as described in KR10201702122130A.
  • the irradiation dose for example, preferably 30 ⁇ 1500mJ / cm 2, more preferably 50 ⁇ 1000mJ / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected.
  • a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free)
  • a high oxygen atmosphere having an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume).
  • the exposure illuminance can be appropriately set and can be selected from a range of usually 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ). .
  • Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the reaction rate of the polymerizable compound in the curable composition layer after exposure is preferably more than 30% and less than 80%. With such a reaction rate, the polymerizable compound can be in a state of being appropriately cured.
  • the reaction rate is preferably set to be higher. Further, in the present invention, the reaction rate is more preferably from 40 to 75%, further preferably from 50 to 70%.
  • the reaction rate of the polymerizable compound refers to a ratio of the reacted polymerizable group among the polymerizable groups included in the polymerizable compound before the first exposure step.
  • the reaction rate of the polymerizable compound can be determined as an average value in the thickness direction of the film by analyzing a peak area near 810 cm -1 by an infrared absorption spectrum method.
  • a pattern (pixel) is formed by developing and removing an unexposed portion of the curable composition layer.
  • the development removal of the unexposed portion of the curable composition layer can be performed using a developer.
  • the curable composition layer in the unexposed portion in the exposure step elutes into the developer, leaving only the photocured portion.
  • the developer include an organic solvent and an alkali developer, and an alkali developer is preferable.
  • the temperature of the developer is preferably, for example, 20 to 30 ° C.
  • the development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • the alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water.
  • the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene
  • Alkaline compounds sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate.
  • the alkali agent a compound having a large molecular weight is preferable in terms of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass.
  • the developer may further contain a surfactant.
  • the surfactant include the surfactants described above, and a nonionic surfactant is preferable.
  • the developer may be once produced as a concentrated solution and diluted to a necessary concentration at the time of use, from the viewpoint of convenience of transportation and storage.
  • the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
  • the rinsing is preferably performed by supplying a rinsing liquid to the curable composition layer after development while rotating the support on which the curable composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the peripheral edge of the support. At this time, when the nozzle is moved from the central portion to the peripheral portion of the support, the nozzle may be moved while gradually lowering the moving speed. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually lowering the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.
  • Second exposure step the curable composition layer is exposed to light having a wavelength of 254 to 350 nm.
  • the light to be irradiated preferably contains light having a wavelength of 300 nm or less, and more preferably contains light having a wavelength of 254 nm.
  • the second exposure step can be performed using, for example, an ultraviolet photoresist curing device. From the ultraviolet photoresist curing device, for example, light having a wavelength of 254 to 350 nm and other light (for example, i-line) may be irradiated.
  • the difference between the wavelength of light used in the above-described exposure before development and the wavelength of light used in the exposure after development (post-exposure) is preferably 200 nm or less, and more preferably 100 to 150 nm.
  • Irradiation dose is preferably 30 ⁇ 4000mJ / cm 2, more preferably 50 ⁇ 3500mJ / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected, similarly to the conditions at the time of the first exposure step.
  • the reaction rate of the polymerizable compound in the curable composition layer after exposure is preferably 60% or more.
  • the upper limit may be set to 100% or less, or may be set to 90% or less.
  • the curable composition layer can be appropriately cured by the first exposure (exposure before development).
  • Exposure 2 exposure after development
  • the curable composition layer is sufficiently cured to form a pattern-like cured film having excellent adhesiveness and excellent solvent resistance, flatness and rectangularity. be able to.
  • the curable composition layer is heated at a predetermined temperature between the developing step and the second exposure step, and at least one of the periods after the second exposure step.
  • a step (post bake) may be performed.
  • the heating temperature of post-baking is preferably lower than 200 ° C., more preferably 150 ° C. or lower, further preferably 120 ° C. or lower. Further, the heating temperature of the post-baking is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 80 ° C. or higher.
  • the heating temperature is preferably 50 to 120 ° C, more preferably 80 to 100 ° C, and 80 to 90 ° C. Is more preferred.
  • the heating time can be appropriately selected and is, for example, 1 to 10 minutes, preferably 2 to 8 minutes, and more preferably 3 to 6 minutes.
  • the post bake may be performed in the air or in a low oxygen atmosphere.
  • the post-baking is preferably performed in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less, and the oxygen concentration is preferably 15% by volume or less. It is more preferably at most 5% by volume, particularly preferably at most 1% by volume (substantially oxygen-free).
  • the post-bake can be performed continuously or batch-wise using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), a high frequency heater or the like.
  • a heating means such as a hot plate, a convection oven (hot air circulation type dryer), a high frequency heater or the like.
  • post-baking may not be performed.
  • the thickness of the patterned cured film after the second exposure step is preferably 0.1 to 5.0 ⁇ m.
  • the lower limit is preferably at least 0.2 ⁇ m, more preferably at least 0.5 ⁇ m.
  • the upper limit is preferably 4.0 ⁇ m or less, more preferably 2.5 ⁇ m or less.
  • the width of the pattern of the cured film is preferably 0.5 to 20.0 ⁇ m.
  • the lower limit is preferably at least 1.0 ⁇ m, more preferably at least 2.0 ⁇ m.
  • the upper limit is preferably 15.0 ⁇ m or less, more preferably 10.0 ⁇ m or less.
  • the patterned cured film preferably has a Young's modulus of 0.5 to 20 GPa, more preferably 2.5 to 15 GPa. The Young's modulus can be measured using, for example, a nanoindentation method.
  • the optical sensor of the present invention includes, for example, a solid-state imaging device constituting a light-receiving element, and a near-infrared transmission filter of the present invention installed on the light-receiving side of the solid-state imaging device. With such a configuration, near infrared rays in a desired wavelength range can be received by the light receiving element.
  • the optical sensor incorporating the near-infrared transmission filter of the present invention can be applied to a CCD (charge coupled device) image sensor, a CMOS (complementary metal oxide semiconductor) image sensor, and the like. It can be preferably used for mobile applications, automobile applications, agricultural applications, medical applications, distance measurement applications, gesture recognition applications, and the like.
  • composition (curable composition) was prepared by mixing the raw materials described in the following table.
  • the numerical values in the following table are parts by mass.
  • IB Irgaphor Black S 0100 CF (manufactured by BASF, compound having the following structure, lactam pigment)
  • PBk32 C.I. I. Pigment Black 32 (compound having the following structure, perylene pigment)
  • PR254 C.I. I. Pigment Red 254
  • PY139 C.I. I. Pigment Yellow 139
  • PB15 6: C.I. I. Pigment Blue 15: 6
  • PB16 C.I. I. Pigment Blue 16 PV23: C.I. I. Pigment Violet 23
  • D1 TMPEOTA (manufactured by Daicel Ornex)
  • D2 Monomer having the following structure.
  • D3 Monomer having the following structure.
  • D4 a mixture of compounds having the following structure (a mixture in which the molar ratio of the left compound (6-functional (meth) acrylate compound) to the right compound (pentafunctional (meth) acrylate compound) is 7: 3)
  • D5 Compound having the following structure (tetrafunctional (meth) acrylate compound having an alkyleneoxy group)
  • I-A1 IRGACURE-OXE02 (manufactured by BASF)
  • I-A2 IRGACURE-OXE03 (manufactured by BASF)
  • I-A3 IRGACURE379 (manufactured by BASF)
  • I-B1 IRGACURE2959 (manufactured by BASF)
  • I-B2 IRGACURE 1173 (manufactured by BASF)
  • Each composition was applied on a glass substrate by spin coating so that the film thickness after the post-baking had the film thickness described in the following table, and after heating and drying at 100 ° C. for 120 seconds using a hot plate, Further, a heat treatment (post-bake) was performed at 200 ° C. for 300 seconds to form a film.
  • the glass substrate on which the film was formed was measured using a UV-visible-near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech) to measure the minimum absorbance A in the wavelength range of 400 to 600 nm and the absorbance in the wavelength range of 1000 to 1300 nm.
  • the maximum value B was measured.
  • CT-4000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on an 8-inch (1 inch is approximately 2.54 cm) silicon wafer by spin coating to form a coating film.
  • the film was treated in an oven at 220 ° C. for 1 hour to cure the applied film and form an undercoat layer.
  • the spinning speed of spin coating was adjusted so that the thickness of the undercoat layer after the heat treatment was about 0.1 ⁇ m.
  • each composition obtained above is applied on an undercoat layer of the silicon wafer using a spin coater so that the film thickness after drying becomes a film thickness described in the following table, and using a hot plate. Dry at 100 ° C. for 120 seconds.
  • the entire glass wafer was irradiated with an exposure amount of 10,000 mJ / cm 2 by using an ultraviolet photoresist curing device (MMA-802-HC-552, manufactured by Ushio Electric Co., Ltd.) to perform a second exposure.
  • an ultraviolet photoresist curing device MMA-802-HC-552, manufactured by Ushio Electric Co., Ltd.
  • a cellophane tape is pressed using a pressure roller (2 kg) for a peeling test, and the tape is peeled off at a speed of 75 mm / sec while tilting the end of the tape at an angle of 45 °.
  • the numbers were evaluated as follows.
  • the adhesion was evaluated using an optical microscope according to the following criteria.
  • compositions of Examples were able to form patterns having excellent adhesion.

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Abstract

A curable composition according to the present invention is configured such that: the content of a colorant is 30% by mass or more relative to the total solid content of the composition; a photopolymerization initiator contains a photopolymerization initiator A1 that has an absorption coefficient of 1.0 × 103 mL/gcm or more at the wavelength of 365 nm in methanol and a photopolymerization initiator A2 that has an absorption coefficient of 1.0 × 102 mL/gcm or less at the wavelength of 365 nm and an absorption coefficient of 1.0 × 103 mL/gcm or more at the wavelength of 245 nm in methanol; and the ratio of the minimum value A of the absorbance of the composition within the wavelength range of 400-600 nm to the maximum value B of the absorbance of the composition within the wavelength range of 1,000-1,300 nm, namely the ratio A/B is 4.5 or more. The present invention also relates to a cured film, a method for forming a pattern, an optical fiter and a photosensor, to each of which this curable composition is applied.

Description

硬化性組成物、硬化膜、パターンの形成方法、光学フィルタおよび光センサCurable composition, cured film, pattern forming method, optical filter, and optical sensor
　本発明は、硬化性組成物、硬化膜、パターンの形成方法、光学フィルタおよび光センサに関する。 The present invention relates to a curable composition, a cured film, a method for forming a pattern, an optical filter, and an optical sensor.
　従来、電荷結合素子（ＣＣＤ）イメージセンサなどの固体撮像素子においては、カラーフィルタを用いて画像のカラー化などの試みが行われている。例えば、特許文献１には、半導体基板と、２色以上のカラーフィルタ層と少なくとも異色のカラーフィルタ層間を隔てて分離する分離壁とを有するカラーフィルタアレイと、半導体基板とカラーフィルタアレイとの間に配置された集光手段と、を備えた固体撮像素子が記載されている。 Conventionally, in a solid-state imaging device such as a charge-coupled device (CCD) image sensor, an attempt has been made to color an image using a color filter. For example, Patent Literature 1 discloses a color filter array having a semiconductor substrate, a color filter array having two or more color filter layers, and a separation wall separating at least a color filter layer of a different color between the semiconductor substrate and the color filter array. And a light-collecting unit disposed in the solid-state imaging device.
　また、近年、近赤外線を感知する光センサについての検討がなされている。近赤外線は可視光線に比べて波長が長いので散乱しにくく、距離計測や、３次元計測などにも活用可能である。また、近赤外線は人間、動物などの目に見えないので、夜間に被写体を近赤外線で照らしても被写体に気付かれることなく、夜行性の野生動物を撮影する用途、防犯用途として相手を刺激せずに撮影することにも使用可能である。このように、近赤外線を感知する光センサは、様々な用途に展開が可能である。このような光センサにおいては、近赤外線透過フィルタなどの近赤外領域に透過帯を有するフィルタなどが用いられている（例えば、特許文献２、３参照）。 近年 In recent years, optical sensors that sense near infrared rays have been studied. Near-infrared rays have a longer wavelength than visible rays, so they are not easily scattered, and can be used for distance measurement, three-dimensional measurement, and the like. In addition, since near-infrared light is invisible to humans and animals, even when illuminating the subject with near-infrared light at night, the subject is not noticed, and it stimulates the opponent as an application for shooting nocturnal wildlife and security. It can also be used to shoot without. As described above, the optical sensor that senses near-infrared rays can be developed for various uses. In such an optical sensor, a filter having a transmission band in a near-infrared region such as a near-infrared transmission filter is used (for example, see Patent Documents 2 and 3).
　通常、上記のようなカラーフィルタおよび近赤外線透過フィルタは、色材と、重合性化合物と、光重合開始剤とを含む硬化性組成物を用いて膜を形成し、加熱などによってこの膜を硬化することにより製造される。例えば、特許文献４には、光重合開始剤としてフッ素原子を含むオキシムエステル系光重合開始剤を用いた硬化性組成物を用いてカラーフィルタを製造することが記載されている。 Usually, the above-described color filter and near-infrared transmission filter form a film using a curable composition containing a coloring material, a polymerizable compound, and a photopolymerization initiator, and cure the film by heating or the like. It is manufactured by doing. For example, Patent Document 4 discloses that a color filter is manufactured using a curable composition using an oxime ester-based photopolymerization initiator containing a fluorine atom as a photopolymerization initiator.
米国特許第９４９６１６４号明細書U.S. Pat. No. 9,496,164 特許第６０３４７９６号公報Japanese Patent No. 6034796 特開２０１７－０５０３２２号公報JP-A-2017-050322 国際公開第２０１６／１５８１１４号International Publication No. WO 2016/158114
　今回、近赤外線透過フィルタ用の組成物を用いて硬化膜を形成する場合には、その分光特性から波長３６５ｎｍの光が透過しにくいため、露光の際に、膜の表層部は硬化するものの深層部は硬化しにくいことが見出された。色材の濃度が高い場合には、組成物の深層部の硬化はさらに難しくなる。したがって、上記硬化性組成物を充分に硬化させ、下地との密着性を向上させるために、２００℃以上の加熱処理をすることが考えられる。
　しかしながら、近年、固体撮像素子において、高解像度、高感度、省電力および小型化などの観点から、Ｓｉ系材料に替えて、有機材料、量子ドットおよびＩｎＧａＡｓ（インジウムガリウム砒素）など、非Ｓｉ系材料を用いて光電変換することが検討されている。上記のような非Ｓｉ系材料は、Ｓｉ系材料に比べ熱に弱いため、硬化性組成物を硬化させる際の加熱温度を２００℃未満とすることが望まれる。 In this case, when a cured film is formed using a composition for a near-infrared transmission filter, light having a wavelength of 365 nm is difficult to transmit due to its spectral characteristics. The part was found to be difficult to cure. When the concentration of the coloring material is high, it is more difficult to cure the deep part of the composition. Therefore, it is conceivable to perform a heat treatment at 200 ° C. or higher in order to sufficiently cure the curable composition and improve the adhesion to the base.
However, in recent years, non-Si-based materials such as organic materials, quantum dots, and InGaAs (indium gallium arsenide) have been used in solid-state imaging devices in place of Si-based materials from the viewpoints of high resolution, high sensitivity, power saving and miniaturization. It has been studied to carry out photoelectric conversion using. Since the non-Si-based material as described above is weaker to heat than the Si-based material, it is desired that the heating temperature at the time of curing the curable composition be less than 200 ° C.
　よって、近年の技術動向を考慮すると、近赤外線透過フィルタ用の組成物を用いて硬化膜を形成する場合にも、低温下でも膜の深層部まで充分に硬化でき、密着性に優れる膜を得られることが望ましい。 Therefore, in consideration of recent technical trends, even when a cured film is formed using a composition for a near-infrared transmission filter, a film that can be sufficiently cured to a deep layer portion even at a low temperature and has excellent adhesion can be obtained. It is desirable that
　本発明は上記要望に鑑みてなされたものであり、密着性に優れる硬化膜を低温で形成することを可能とする硬化性組成物の提供を目的とする。 The present invention has been made in view of the above demands, and has as its object to provide a curable composition capable of forming a cured film having excellent adhesion at a low temperature.
　また、本発明は、上記硬化性組成物を硬化して得られる硬化膜、上記硬化性組成物を用いたパターンの形成方法の提供を目的とする。さらに、本発明は、上記硬化膜を有する光学フィルタおよび光センサの提供を目的とする。 Further, another object of the present invention is to provide a cured film obtained by curing the curable composition, and a method for forming a pattern using the curable composition. Still another object of the present invention is to provide an optical filter and an optical sensor having the above cured film.
　上記課題は、波長３６５ｎｍの光に対する透過率が低い硬化性組成物において、互いに異なる所定の吸光特性を有する２種の光重合開始剤を使用することにより、解決できた。具体的には、以下の手段＜１＞により、好ましくは＜２＞～＜２０＞により、上記課題は解決された。
＜１＞
　色材、重合性化合物、光重合開始剤を含有する硬化性組成物であって、
　色材の含有量が、組成物の全固形分に対して３０質量％以上であり、
　光重合開始剤は、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上である光重合開始剤Ａ１と、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上である光重合開始剤Ａ２とを含み、
　組成物の波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上である、硬化性組成物。
＜２＞
　光重合開始剤Ａ１がオキシム化合物である、
　＜１＞に記載の硬化性組成物。
＜３＞
　オキシム化合物が、フッ素原子を含む化合物である、
　＜２＞に記載の硬化性組成物。
＜４＞
　光重合開始剤Ａ２がヒドロキシアルキルフェノン化合物である、
　＜１＞～＜３＞のいずれか１つに記載の硬化性組成物。
＜５＞
　光重合開始剤Ａ２が下記式（Ａ２－１）で表される化合物である、
　＜１＞～＜３＞のいずれか１つに記載の硬化性組成物；
式（Ａ２－１）：
Figure JPOXMLDOC01-appb-C000002
 　式中Ｒｖ1は、置換基を表し、Ｒｖ2およびＲｖ3は、それぞれ独立して、水素原子または置換基を表し、Ｒｖ2とＲｖ3とが互いに結合して環を形成していてもよく、ｍは０～５の整数を表す。
＜６＞
　光重合開始剤Ａ１の１００質量部に対して、光重合開始剤Ａ２を５０～２００質量部含有する、
　＜１＞～＜５＞のいずれか１つに記載の硬化性組成物。
＜７＞
　硬化性組成物の全固形分中における光重合開始剤Ａ１と光重合開始剤Ａ２の合計の含有量が５～１５質量％である、
　＜１＞～＜６＞のいずれか１つに記載の硬化性組成物。
＜８＞
　重合性化合物がエチレン性不飽和基を３個以上含む化合物である、
　＜１＞～＜７＞のいずれか１つに記載の硬化性組成物。
＜９＞
　重合性化合物がエチレン性不飽和基とアルキレンオキシ基とを含む化合物である、
　＜１＞～＜８＞のいずれか１つに記載の硬化性組成物。
＜１０＞
　光重合開始剤Ａ１と光重合開始剤Ａ２の合計１００質量部に対して、重合性化合物を１７０～３４５質量部含有する、
　＜１＞～＜９＞のいずれか１つに記載の硬化性組成物。
＜１１＞
　硬化性組成物の全固形分中における重合性化合物の含有量が１７．５～２７．５質量％である、
　＜１＞～＜１０＞のいずれか１つに記載の硬化性組成物。
＜１２＞
　色材が、ビスベンゾフラノン化合物、ペリレン化合物およびアゾ化合物の少なくとも１種を含む黒色色材である、
　＜１＞～＜１１＞のいずれか１つに記載の硬化性組成物。
＜１３＞
　色材が少なくとも３種の化合物を含む、
　＜１＞～＜１２＞のいずれか１つに記載の硬化性組成物。
＜１４＞
　さらに、環状エーテル構造を有する化合物と、環状エーテル構造を有する化合物の硬化促進剤とを含む、
　＜１＞～＜１３＞のいずれか１つに記載の硬化性組成物。
＜１５＞
　さらに樹脂を含む、
　＜１＞～＜１４＞のいずれか１つに記載の硬化性組成物。
＜１６＞
　＜１＞～＜１５＞のいずれか１つに記載の硬化性組成物を硬化して得られる硬化膜。
＜１７＞
　＜１＞～＜１５＞のいずれか１つに記載の硬化性組成物を用いて支持体上に硬化性組成物層を形成する工程と、
　硬化性組成物層に対して、３５０ｎｍを超え３８０ｎｍ以下の波長を有する光を照射し、パターン状に露光する第１の露光工程と、
　硬化性組成物層を現像する現像工程と、
　現像工程後に、硬化性組成物層に対して、２５４～３５０ｎｍの波長を有する光を照射する第２の露光工程と、を有するパターンの形成方法。
＜１８＞
　現像工程と第２の露光工程の間、および、第２の露光工程の後の少なくともいずれかの期間に、低酸素雰囲気下、２００℃未満の温度で硬化性組成物層を加熱する工程を有する、
　＜１７＞に記載の方法。
＜１９＞
　＜１６＞に記載の硬化膜を有する光学フィルタ。
＜２０＞
　＜１６＞に記載の硬化膜を有する光センサ。 The above problem was solved by using two types of photopolymerization initiators having predetermined light absorption characteristics different from each other in a curable composition having a low transmittance for light having a wavelength of 365 nm. Specifically, the above problem was solved by the following means <1>, preferably by <2> to <20>.
<1>
A coloring material, a polymerizable compound, a curable composition containing a photopolymerization initiator,
The content of the coloring material is 30% by mass or more based on the total solid content of the composition,
The photopolymerization initiator A1 has an extinction coefficient of 1.0 × 10 3 mL / gcm or more in methanol at a wavelength of 365 nm, and the photopolymerization initiator A1 has an extinction coefficient of 1.0 × 10 3 in methanol at a wavelength of 365 nm. 2 mL / gcm or less, and a photopolymerization initiator A2 having an absorption coefficient at a wavelength of 254 nm of 1.0 × 10 3 mL / gcm or more,
A curable composition wherein the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more.
<2>
The photopolymerization initiator A1 is an oxime compound,
The curable composition according to <1>.
<3>
The oxime compound is a compound containing a fluorine atom,
The curable composition according to <2>.
<4>
The photopolymerization initiator A2 is a hydroxyalkylphenone compound,
The curable composition according to any one of <1> to <3>.
<5>
Wherein the photopolymerization initiator A2 is a compound represented by the following formula (A2-1):
The curable composition according to any one of <1> to <3>;
Formula (A2-1):
Figure JPOXMLDOC01-appb-C000002
 In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may combine with each other to form a ring. , M represents an integer of 0 to 5.
<6>
The photopolymerization initiator A2 contains 50 to 200 parts by mass with respect to 100 parts by mass of the photopolymerization initiator A1.
The curable composition according to any one of <1> to <5>.
<7>
The total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the curable composition is 5 to 15% by mass;
The curable composition according to any one of <1> to <6>.
<8>
The polymerizable compound is a compound containing three or more ethylenically unsaturated groups,
The curable composition according to any one of <1> to <7>.
<9>
The polymerizable compound is a compound containing an ethylenically unsaturated group and an alkyleneoxy group,
The curable composition according to any one of <1> to <8>.
<10>
The polymerizable compound is contained in an amount of 170 to 345 parts by mass based on 100 parts by mass of the photopolymerization initiator A1 and the photopolymerization initiator A2 in total.
The curable composition according to any one of <1> to <9>.
<11>
The content of the polymerizable compound in the total solid content of the curable composition is 17.5 to 27.5% by mass;
The curable composition according to any one of <1> to <10>.
<12>
The coloring material is a black coloring material containing at least one of a bisbenzofuranone compound, a perylene compound, and an azo compound.
The curable composition according to any one of <1> to <11>.
<13>
The colorant comprises at least three compounds,
The curable composition according to any one of <1> to <12>.
<14>
Further, a compound having a cyclic ether structure, and a curing accelerator for a compound having a cyclic ether structure,
The curable composition according to any one of <1> to <13>.
<15>
Further containing resin,
The curable composition according to any one of <1> to <14>.
<16>
A cured film obtained by curing the curable composition according to any one of <1> to <15>.
<17>
Forming a curable composition layer on a support using the curable composition according to any one of <1> to <15>;
A first exposure step of irradiating the curable composition layer with light having a wavelength of more than 350 nm and not more than 380 nm, and exposing in a pattern;
A developing step of developing the curable composition layer,
A second exposure step of irradiating the curable composition layer with light having a wavelength of 254 to 350 nm after the development step.
<18>
A step of heating the curable composition layer at a temperature of less than 200 ° C. in a low-oxygen atmosphere between the developing step and the second exposing step and / or at least any period after the second exposing step. ,
The method according to <17>.
<19>
An optical filter having the cured film according to <16>.
<20>
An optical sensor having the cured film according to <16>.
　本発明の硬化性組成物により、密着性に優れる硬化膜を低温で形成することが可能となる。そして、本発明の硬化性組成物により、本発明の硬化膜、パターンの形成方法、光学フィルタおよび光センサの提供が可能となる。 に よ り The curable composition of the present invention enables a cured film having excellent adhesion to be formed at a low temperature. The curable composition of the present invention can provide the cured film, the pattern forming method, the optical filter, and the optical sensor of the present invention.
　以下、本発明の主要な実施形態について説明する。しかしながら、本発明は、明示した実施形態に限られるものではない。 Hereinafter, main embodiments of the present invention will be described. However, the invention is not limited to the embodiments explicitly described.
　本明細書において「～」という記号を用いて表される数値範囲は、「～」の前後に記載される数値をそれぞれ下限値および上限値として含む範囲を意味する。 に お い て In this specification, the numerical range represented by the symbol “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit, respectively.
　本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。 書 In this specification, the term “step” is meant to include not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended operation of the step can be achieved.
　本明細書における基（原子団）の表記について、置換および無置換を記していない表記は、置換基を有さないものと共に、置換基を有するものをも包含する意味である。例えば、単に「アルキル基」と記載した場合には、これは、置換基を有さないアルキル基（無置換アルキル基）、および、置換基を有するアルキル基（置換アルキル基）の両方を包含する意味である。 基 In the description of the group (atomic group) in the present specification, the notation of not indicating substituted or unsubstituted includes not only those having no substituent but also those having a substituent. For example, when the term “alkyl group” is simply used, this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Meaning.
　本明細書において、「（メタ）アクリレート」は、「アクリレート」および「メタクリレート」の両方、または、いずれかを意味し、「（メタ）アクリル」は、「アクリル」および「メタクリル」の両方、または、いずれかを意味し、「（メタ）アクリロイル」は、「アクリロイル」および「メタクリロイル」の両方、または、いずれかを意味する。 In the present specification, “(meth) acrylate” means both or “acrylate” and “methacrylate”, and “(meth) acryl” means both “acryl” and “methacryl”, or “(Meth) acryloyl” means both or both “acryloyl” and “methacryloyl”.
　本明細書において、組成物中の全固形分の濃度は、その組成物の総質量に対する、溶剤を除く他の成分の質量百分率によって表される。 濃度 As used herein, the concentration of the total solids in a composition is represented by the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
　本明細書において、温度は、特に述べない限り、２３℃とする。 に お い て In this specification, the temperature is 23 ° C. unless otherwise specified.
　本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、特に述べない限り、ゲル浸透クロマトグラフィ（ＧＰＣ測定）に従い、ポリスチレン換算値として示される。この重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００およびＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）を用いることによって求めることができる。また、特に述べない限り、溶離液としてＴＨＦ（テトラヒドロフラン）を用いて測定したものとする。また、特に述べない限り、ＧＰＣ測定における検出には、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用したものとする。 に お い て In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined, for example, using HLC-8220 (manufactured by Tosoh Corporation) and using a guard column HZ-L, TSKgel @ Super @ HZM-M, TSKgel @ Super @ HZ4000, TSKgel. It can be determined by using Super @ HZ3000 and TSKgel @ Super @ HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, it is assumed that the measurement was performed using THF (tetrahydrofuran) as an eluent. Unless otherwise stated, it is assumed that a detector with a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection in GPC measurement.
　本明細書において、積層体を構成する各層の位置関係について、「上」または「下」と記載したときには、注目している複数の層のうち基準となる層の上側または下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、さらに第３の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、または、感光層がある場合には、基材から感光層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。 In this specification, when the positional relationship of each layer constituting the laminate is described as “up” or “down”, other layers may be placed above or below a reference layer among a plurality of layers of interest. If there is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. Also, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as “up”, or, if there is a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as “up”. The opposite direction is referred to as "down". Note that such setting in the vertical direction is for convenience in the present specification, and in an actual embodiment, the “up” direction in the present specification may be different from the vertical upward.
＜硬化性組成物＞
　本発明の硬化性組成物は、色材、重合性化合物、光重合開始剤を含有する。そして、本発明の硬化性組成物において、色材の含有量は、組成物の全固形分に対して３０質量％以上である。さらに、光重合開始剤は、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上である光重合開始剤Ａ１と、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上である光重合開始剤Ａ２とを含む。また、組成物の波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂは４．５以上であり、つまり、本発明の硬化性組成物は、可視光を吸収しやすくかつ近赤外線を透過しやすい分光特性を有する。そのため、例えば、近赤外線透過フィルタの製造に使用される。なお、本明細書において、「近赤外」は、７００～２５００ｎｍの波長域周辺をいう。本発明の硬化性組成物において、上記のような分光特性の結果、可視光域の吸収特性の裾野の影響などにより、波長３６５ｎｍの光に対する透過率も比較的低くなっている。 <Curable composition>
The curable composition of the present invention contains a coloring material, a polymerizable compound, and a photopolymerization initiator. And in the curable composition of this invention, content of a coloring material is 30 mass% or more with respect to the total solid content of a composition. Furthermore, the photopolymerization initiator A1 has an extinction coefficient of 1.0 × 10 3 mL / gcm or more in methanol at 365 nm in wavelength, and the photopolymerization initiator has an extinction coefficient of 1.0 nm in methanol at 365 nm in wavelength. And a photopolymerization initiator A2 having an absorption coefficient of not more than × 10 2 mL / gcm and an absorption coefficient at a wavelength of 254 nm of not less than 1.0 × 10 3 mL / gcm. Further, the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more. The curable composition of the present invention has spectral characteristics that easily absorb visible light and easily transmit near infrared rays. Therefore, for example, it is used for manufacturing a near-infrared transmission filter. In this specification, “near infrared” refers to the vicinity of a wavelength range of 700 to 2500 nm. In the curable composition of the present invention, as a result of the above-described spectral characteristics, the transmittance for light having a wavelength of 365 nm is relatively low due to the influence of the bottom of the absorption characteristics in the visible light region.
　本発明の硬化性組成物を用いることにより、密着性に優れる硬化膜を低温で形成することが可能となる。その作用は次のとおりと考えられる。 用 い る By using the curable composition of the present invention, a cured film having excellent adhesion can be formed at a low temperature. The effect is considered as follows.
　従来、硬化性組成物の露光には、主として波長３６５ｎｍの紫外線（いわゆる、ｉ線）が使用されている。今回、そのような紫外線を用いて露光を行った場合に、本発明の硬化性組成物においては、膜の表層部で紫外線の多くが吸収されてしまい、深層部に充分な光量の紫外線が届かない場合がある問題が見出された。特に、近年、色材の濃度が高くなる傾向にあり、本発明のように、色材の含有量が、組成物の全固形分に対して３０質量％以上という高濃度であるような場合には、上記問題は顕著に表れる。 Conventionally, ultraviolet rays (so-called i-rays) having a wavelength of 365 nm have been mainly used for exposing the curable composition. This time, when exposure is performed using such ultraviolet light, in the curable composition of the present invention, much of the ultraviolet light is absorbed in the surface layer of the film, and a sufficient amount of ultraviolet light reaches the deep layer. A problem that may not be found was found. In particular, in recent years, when the concentration of the coloring material tends to be high and the content of the coloring material is as high as 30% by mass or more based on the total solid content of the composition as in the present invention, In the above, the above problem appears remarkably.
　そこで、本発明において、硬化性組成物が光重合開始剤Ａ１および光重合開始剤Ａ２を含むことにより、３５０ｎｍを超え３８０ｎｍ以下の波長（例えば３６５ｎｍ）を有する光を用いた露光（第１の露光）、および２５４～３５０ｎｍの波長（例えば２５４ｎｍ）を有する光を用いた露光（第２の露光）の２段階で露光を実施し、２００℃未満の低温下で充分な硬化が得られる設計としている。本明細書では、可視領域以外の電磁波についても「光」の用語を便義上使用し、可視領域以外の電磁波に対しては、「光」の意味は「電磁波」と同義とする。なお、上記非Ｓｉ系材料を使用しない固体撮像素子に本発明の硬化性組成物を適用するなど、２００℃未満の低温での硬化が求められていない場合には、上記第２の露光を実施せず、加熱処理で組成物を充分に硬化させることも可能である。つまり、本発明の硬化性組成物は、露光が２段階である方法に使用するほか、露光が１段階である方法に使用することも可能である。 Therefore, in the present invention, since the curable composition contains the photopolymerization initiator A1 and the photopolymerization initiator A2, exposure using light having a wavelength of more than 350 nm and not more than 380 nm (for example, 365 nm) (first exposure) ) And exposure using light having a wavelength of 254 to 350 nm (for example, 254 nm) (second exposure) is performed to achieve sufficient curing at a low temperature of less than 200 ° C. . In this specification, the term "light" is used for convenience for electromagnetic waves other than the visible region, and the meaning of "light" is the same as "electromagnetic wave" for electromagnetic waves other than the visible region. In the case where curing at a low temperature of less than 200 ° C. is not required, such as when the curable composition of the present invention is applied to a solid-state imaging device not using the non-Si-based material, the second exposure is performed. Alternatively, the composition can be sufficiently cured by heat treatment. That is, the curable composition of the present invention can be used in a method in which exposure is performed in one step, in addition to a method in which exposure is performed in two steps.
　具体的には、次のとおりである。通常、露光では、光を吸収した光重合開始剤が活性種を発生させ、その活性種の活性作用により重合性化合物の重合が促進される。しかしながら、本発明の硬化性組成物のように、上記Ａ／Ｂが４．５以上であるような組成物においては、例えばカラーフィルタ用組成物などに比べて、光重合開始剤以外の成分（特に色材）が可視光を吸収しやすい性質を有し、これに付随して、可視光域に近い３６５ｎｍの波長の光も、光重合開始剤以外の成分によって吸収されやすい。このような組成物においては、３６５ｎｍの波長の光を用いて露光を行っても、膜の表層部で光が吸収されて、膜の深層部まで光が届きにくいため、深層部の硬化不良が問題となる。一方、この露光において、深層部まで充分に硬化させようと、露光エネルギーを上げると、表層部で必要以上に発生した活性種が膜中で拡散し、パターンの表層部が目標のサイズより太くなってしまうという別の問題が生じる。 Specifically, it is as follows. Generally, in exposure, a photopolymerization initiator that has absorbed light generates active species, and the polymerization of the polymerizable compound is promoted by the active action of the active species. However, in a composition such as the curable composition of the present invention in which the above A / B is 4.5 or more, for example, components other than the photopolymerization initiator ( In particular, the coloring material) has a property of easily absorbing visible light, and accordingly, light having a wavelength of 365 nm close to the visible light region is also easily absorbed by components other than the photopolymerization initiator. In such a composition, even when exposure is performed using light having a wavelength of 365 nm, light is absorbed at the surface layer of the film, and light hardly reaches the deep layer of the film. It becomes a problem. On the other hand, in this exposure, when the exposure energy is increased to sufficiently cure the deep layer, active species generated more than necessary in the surface layer diffuse in the film, and the surface layer of the pattern becomes thicker than the target size. Another problem arises.
　そこで、本発明では、３６５ｎｍの波長の光を用いた露光（第１の露光）は、現像に耐えうる程度の強度を硬化性組成物に付与する工程と位置づけ、第１の露光および現像後に、光重合開始剤Ａ２を利用した第２の露光を実施する。第２の露光では、すでにパターンが切られており、過剰発生した活性種の拡散によるパターンサイズへの影響は小さいため、露光エネルギーを上げることができる。したがって、硬化性組成物の深層部まで光重合開始剤Ａ２に充分な光を届かせることができ、深層部の硬化を充分に促進することができる。また、本発明においては、光重合開始剤Ａ２の波長３６５ｎｍの吸光係数が相対的に低く、第１の露光における光重合開始剤Ａ２の消費を抑制できるため、第２の露光で、効率よく重合性化合物の重合が促進される。特に、色材の濃度が高く、さらに膜厚が厚い傾向にある近赤外線透過フィルタにおいて、膜の深層部の硬化不良は大きな問題であり、本発明は、そのような用途で使用される組成物に特に有用である。 Therefore, in the present invention, exposure using light having a wavelength of 365 nm (first exposure) is regarded as a step of imparting sufficient strength to the curable composition to withstand development, and after the first exposure and development, The second exposure using the photopolymerization initiator A2 is performed. In the second exposure, the pattern has already been cut, and the influence of the diffusion of the excessively generated active species on the pattern size is small, so that the exposure energy can be increased. Therefore, sufficient light can reach the photopolymerization initiator A2 to the deep layer of the curable composition, and the curing of the deep layer can be sufficiently promoted. In addition, in the present invention, since the absorption coefficient of the photopolymerization initiator A2 at a wavelength of 365 nm is relatively low and the consumption of the photopolymerization initiator A2 in the first exposure can be suppressed, the polymerization can be efficiently performed in the second exposure. The polymerization of the hydrophilic compound is promoted. In particular, in the near-infrared transmission filter in which the concentration of the coloring material is high and the film thickness tends to be large, poor curing of the deep part of the film is a serious problem, and the present invention relates to a composition used in such an application. Especially useful for:
　このような第２の露光の実施により、第１の露光で硬化性組成物の深層部の硬化が不充分であっても、第２の露光で組成物の深層部が充分に硬化し、膜深層部の機械的強度が向上することで、下地との密着性も向上させることができる。特に、波長４００～６００ｎｍの光を遮光し、波長７５０ｎｍ以降の光を透過させる近赤外線透過フィルタや、波長４００～７５０ｎｍの光を遮光し、波長８５０ｎｍ以降の光を透過させる近赤外線透過フィルタの製造に使用する硬化性組成物の場合には、その分光特性に起因して、波長３６５ｎｍの紫外光は、特に、膜の深層部まで届きにくかったため、上記２段階露光による恩恵は従来技術から予測できる範囲を超えている。 By performing such a second exposure, even if the deep portion of the curable composition is insufficiently cured by the first exposure, the deep portion of the composition is sufficiently cured by the second exposure, and By improving the mechanical strength of the deep portion, the adhesion to the base can be improved. Particularly, manufacture of a near-infrared transmission filter that blocks light having a wavelength of 400 to 600 nm and transmits light having a wavelength of 750 nm or less, and a near-infrared transmission filter that blocks light having a wavelength of 400 to 750 nm and transmits light having a wavelength of 850 nm or more. In the case of the curable composition used in the above, ultraviolet light having a wavelength of 365 nm was difficult to reach particularly a deep part of the film due to its spectral characteristics, so that the benefit of the two-step exposure can be predicted from the prior art. Out of range.
　上記Ａ／Ｂは、５以上であることが好ましく、７．５以上であることがより好ましく、１５以上であることがさらに好ましく、３０以上であることが特に好ましい。また、上記Ａ／Ｂは、５００以下であることが好ましく、４００以下であることがより好ましく、３００以下であることがさらに好ましい。
　ある波長λにおける吸光度Ａλは、以下の式（１）により定義される。
Ａλ＝－ｌｏｇ（Ｔλ／１００）　　　・・・（１）
Ａλは、波長λにおける吸光度であり、Ｔλは、波長λにおける透過率（％）である。 The A / B is preferably 5 or more, more preferably 7.5 or more, further preferably 15 or more, and particularly preferably 30 or more. Further, the A / B is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less.
The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).
Aλ = −log (Tλ / 100) (1)
Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.
　本発明において、吸光度の値は、溶液の状態で測定した値であってもよく、硬化性組成物を用いて製膜した膜での値であってもよい。膜の状態で吸光度を測定する場合は、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように硬化性組成物を塗布し、ホットプレートを用いて１００℃、１２０秒間乾燥して調製した膜を用いて測定することが好ましい。膜の厚さは、膜を有する基板について、触針式表面形状測定器（ＵＬＶＡＣ社製　ＤＥＫＴＡＫ１５０）を用いて測定することができる。 に お い て In the present invention, the value of the absorbance may be a value measured in a state of a solution, or a value of a film formed using a curable composition. When measuring the absorbance in the state of the film, by applying a method such as spin coating on a glass substrate, apply the curable composition so that the thickness of the film after drying becomes a predetermined thickness, and use a hot plate. The measurement is preferably performed using a film prepared by drying at 100 ° C. for 120 seconds. The thickness of the film can be measured for the substrate having the film by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC).
　また、吸光度は、従来公知の分光光度計を用いて測定できる。波長４００～６００ｎｍの範囲における吸光度の最小値Ａが、０．１～３．０になるように調整した条件で、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂを測定することが好ましい。このような条件で吸光度を測定することで、測定誤差をより小さくできる。波長４００～６００ｎｍの範囲における吸光度の最小値Ａが、０．１～３．０になるように調整する方法としては、特に限定はない。例えば、溶液の状態で吸光度を測定する場合は、試料セルの光路長を調整する方法が挙げられる。また、膜の状態で吸光度を測定する場合は、膜厚を調整する方法などが挙げられる。吸光度は、例えば、紫外可視近赤外分光光度計を用いて測定できる。そのような装置としては、例えば、Ｕ－４１００（日立ハイテク製）が使用できる。 吸 光 The absorbance can be measured using a conventionally known spectrophotometer. It is preferable to measure the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 600 nm is adjusted to be 0.1 to 3.0. By measuring the absorbance under such conditions, the measurement error can be reduced. There is no particular limitation on the method for adjusting the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to be 0.1 to 3.0. For example, when measuring the absorbance in the state of a solution, a method of adjusting the optical path length of the sample cell may be used. When the absorbance is measured in the state of the film, a method of adjusting the film thickness may be used. The absorbance can be measured using, for example, an ultraviolet-visible-near-infrared spectrophotometer. As such an apparatus, for example, U-4100 (manufactured by Hitachi High-Tech) can be used.
　硬化性組成物は、以下の（１）～（４）のいずれかの分光特性を満たしていることがより好ましい。 The curable composition more preferably satisfies any of the following spectral characteristics (1) to (4).
　（１）：波長４００～６４０ｎｍの範囲における吸光度の最小値Ａｍｉｎ１と、波長８００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ１との比であるＡｍｉｎ１／Ｂｍａｘ１が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。また、上記Ａｍｉｎ１／Ｂｍａｘ１は、５００以下であることが好ましく、４００以下であることがより好ましく、３００以下であることがさらに好ましい。この態様によれば、波長４００～６４０ｎｍの範囲の光を遮光して、波長７５０ｎｍ以降の近赤外線を透過可能な膜を形成することができる。このような膜は、例えば、波長４００～６４０ｎｍにおける透過率の最大値が２０％で、波長７５０ｎｍにおける透過率が７０％以上である分光特性を有することが好ましい。 (1): Amin1 / Bmax1, which is the ratio of the minimum absorbance Amin1 in the wavelength range of 400 to 640 nm to the maximum absorbance Bmax1 in the wavelength range of 800 to 1300 nm, is 5 or more and 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin1 / Bmax1 is preferably 500 or less, more preferably 400 or less, and still more preferably 300 or less. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 750 nm or less while blocking light having a wavelength in the range of 400 to 640 nm. Such a film preferably has, for example, spectral characteristics in which the maximum value of the transmittance at a wavelength of 400 to 640 nm is 20% and the transmittance at a wavelength of 750 nm is 70% or more.
　（２）：波長４００～７５０ｎｍの範囲における吸光度の最小値Ａｍｉｎ２と、波長９００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ２との比であるＡｍｉｎ２／Ｂｍａｘ２が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。また、上記Ａｍｉｎ２／Ｂｍａｘ２は、５００以下であることが好ましく、４００以下であることがより好ましく、３００以下であることがさらに好ましい。この態様によれば、波長４００～７５０ｎｍの範囲の光を遮光して、波長８５０ｎｍ以降の近赤外線を透過可能な膜を形成することができる。このような膜は、例えば、波長４００～７５０ｎｍにおける透過率の最大値が２０％で、波長８５０ｎｍにおける透過率が７０％以上である分光特性を有することが好ましい。 (2): Amin2 / Bmax2, which is the ratio of the minimum absorbance Amin2 in the wavelength range of 400 to 750 nm to the maximum absorbance Bmax2 in the wavelength range of 900 to 1300 nm, is 5 or more and 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin2 / Bmax2 is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 850 nm or less while blocking light having a wavelength of 400 to 750 nm. Such a film preferably has, for example, spectral characteristics in which the maximum value of the transmittance at a wavelength of 400 to 750 nm is 20% and the transmittance at a wavelength of 850 nm is 70% or more.
　（３）：波長４００～８５０ｎｍの範囲における吸光度の最小値Ａｍｉｎ３と、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ３との比であるＡｍｉｎ３／Ｂｍａｘ３が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。また、上記Ａｍｉｎ３／Ｂｍａｘ３は、５００以下であることが好ましく、４００以下であることがより好ましく、３００以下であることがさらに好ましい。この態様によれば、波長４００～８３０ｎｍの範囲の光を遮光して、波長９４０ｎｍ以降の近赤外線を透過可能な膜を形成することができる。このような膜は、例えば、波長４００～８３０ｎｍにおける透過率の最大値が２０％で、波長９４０ｎｍにおける透過率が７０％以上である分光特性を有することが好ましい。 (3): Amin3 / Bmax3, which is the ratio of the minimum absorbance Amin3 in the wavelength range of 400 to 850 nm to the maximum absorbance Bmax3 in the wavelength range of 1000 to 1300 nm, is 5 or more, and is 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin3 / Bmax3 is preferably equal to or less than 500, more preferably equal to or less than 400, and still more preferably equal to or less than 300. According to this aspect, it is possible to form a film capable of transmitting near-infrared light having a wavelength of 940 nm or less while blocking light having a wavelength of 400 to 830 nm. Such a film preferably has, for example, spectral characteristics such that the maximum value of the transmittance at a wavelength of 400 to 830 nm is 20% and the transmittance at a wavelength of 940 nm is 70% or more.
　（４）：波長４００～９５０ｎｍの範囲における吸光度の最小値Ａｍｉｎ４と、波長１１００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ４との比であるＡｍｉｎ４／Ｂｍａｘ４が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。また、上記Ａｍｉｎ４／Ｂｍａｘ４は、５００以下であることが好ましく、４００以下であることがより好ましく、３００以下であることがさらに好ましい。この態様によれば、波長４００～９５０ｎｍの範囲の光を遮光して、波長１０４０ｎｍ以降の近赤外線を透過可能な膜を形成することができる。このような膜は、例えば、波長４００～９５０ｎｍにおける透過率の最大値が２０％で、波長１０４０ｎｍにおける透過率が７０％以上である分光特性を有することが好ましい。 (4): Amin4 / Bmax4, which is the ratio of the minimum absorbance Amin4 in the wavelength range of 400 to 950 nm to the maximum absorbance Bmax4 in the wavelength range of 1100 to 1300 nm, is 5 or more, and is 7.5 or more. Is preferably 15 or more, more preferably 30 or more. Further, Amin4 / Bmax4 is preferably equal to or less than 500, more preferably equal to or less than 400, and still more preferably equal to or less than 300. According to this aspect, it is possible to form a film that shields light in the wavelength range of 400 to 950 nm and transmits near infrared rays having a wavelength of 1040 nm or less. For example, such a film preferably has spectral characteristics such that the maximum value of the transmittance at a wavelength of 400 to 950 nm is 20% and the transmittance at a wavelength of 1040 nm is 70% or more.
　以下、硬化性組成物を構成し得る各成分について説明する。
＜＜色材＞＞
　本発明の硬化性組成物は色材を含有する。本発明において、色材は、近赤外領域の光の少なくとも一部を透過し、かつ、可視領域の光を吸収する材料であることが好ましい。本発明において、色材は、紫色から赤色の波長領域の光を吸収する材料であることが好ましい。また、本発明において、色材は、波長４００～６００ｎｍの波長領域の光を吸収する材料であることが好ましい。また、色材は、波長１０００～１３００ｎｍの光を透過する材料であることが好ましい。本発明において、色材は、以下の（Ａ）および（Ｂ）の少なくとも一方の要件を満たすことが好ましい。
（１）：２種類以上の有彩色着色剤を含み、２種以上の有彩色着色剤の組み合わせで黒色を形成している。
（２）：有機系黒色着色剤を含む。 Hereinafter, each component that can constitute the curable composition will be described.
<< Color materials >>
The curable composition of the present invention contains a coloring material. In the present invention, the coloring material is preferably a material that transmits at least a part of light in a near-infrared region and absorbs light in a visible region. In the present invention, the coloring material is preferably a material that absorbs light in a violet to red wavelength region. In the present invention, the coloring material is preferably a material that absorbs light in a wavelength region of 400 to 600 nm. The coloring material is preferably a material that transmits light having a wavelength of 1000 to 1300 nm. In the present invention, the coloring material preferably satisfies at least one of the following requirements (A) and (B).
(1): Two or more chromatic colorants are included, and black is formed by a combination of two or more chromatic colorants.
(2): Contains an organic black colorant.
　ここで、上記（２）の態様において、更に有彩色着色剤を含有することも好ましい。 Here, in the above embodiment (2), it is also preferable to further include a chromatic colorant.
　なお、本発明において、有彩色着色剤とは、白色着色剤および黒色着色剤以外の着色剤を意味する。また、本発明において、有機系黒色着色剤は、可視光を吸収するが、赤外線の少なくとも一部は透過する材料を意味する。したがって、本発明において、有機系黒色着色剤は、可視光および赤外線の両方を吸収する黒色着色剤、例えば、カーボンブラックやチタンブラックは含まない。有機系黒色着色剤は、波長４００ｎｍ以上７００ｎｍ以下の範囲に極大吸収波長を有する着色剤であることが好ましい。 In the present invention, the chromatic colorant means a colorant other than a white colorant and a black colorant. In the present invention, the organic black colorant means a material that absorbs visible light but transmits at least a part of infrared light. Therefore, in the present invention, the organic black colorant does not include a black colorant that absorbs both visible light and infrared light, for example, carbon black and titanium black. The organic black colorant is preferably a colorant having a maximum absorption wavelength in a wavelength range of 400 nm to 700 nm.
　色材は、例えば、波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上である材料であることが好ましい。また、色材において、波長４００～６００ｎｍの範囲における吸光度（吸光係数）が最大となる波長λｐは、３６５ｎｍよりも２０ｎｍ以上大きいことが好ましく、３０ｎｍ以上大きいことがより好ましい。波長λｐが上記要件を満たすことにより、露光の照射光を効率よく、後述する光重合開始剤に吸収させることができる。 The color material is, for example, a material in which the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more. Is preferred. Further, in the coloring material, the wavelength λp at which the absorbance (extinction coefficient) in the wavelength range of 400 to 600 nm is maximum is preferably larger than 365 nm by 20 nm or more, more preferably 30 nm or more. When the wavelength λp satisfies the above requirements, the irradiation light for exposure can be efficiently absorbed by the photopolymerization initiator described below.
　上記分光特性は、１種類の素材で満たしていてもよく、複数の素材の組み合わせで満たしていてもよい。例えば、上記（１）の態様の場合、複数の有彩色着色剤を組み合わせて上記分光特性を満たしていることが好ましい。また、上記（２）の態様の場合、有機系黒色着色剤が単独で上記分光特性を満たしていてもよい。また、有機系黒色着色剤と有彩色着色剤との組み合わせで上記分光特性を満たしていてもよい。 (4) The above-mentioned spectral characteristics may be satisfied with one kind of material, or may be satisfied with a combination of a plurality of materials. For example, in the case of the above-mentioned embodiment (1), it is preferable that the above-mentioned spectral characteristics are satisfied by combining a plurality of chromatic colorants. Further, in the case of the above embodiment (2), the organic black colorant alone may satisfy the above-mentioned spectral characteristics. Further, the above spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.
＜＜＜有彩色着色剤＞＞＞
　本発明において、有彩色着色剤は、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤およびオレンジ色着色剤から選ばれる着色剤であることが好ましい。本発明において、有彩色着色剤は、顔料であってもよく、染料であってもよい。好ましくは顔料である。また、顔料には、無機顔料または有機‐無機顔料の一部を有機発色団で置換した材料を用いることもできる。無機顔料や有機‐無機顔料の一部を有機発色団で置換することで、色相設計をしやすくできる。顔料は、平均粒径（ｒ）が、２０ｎｍ≦ｒ≦３００ｎｍであることが好ましく、２５ｎｍ≦ｒ≦２５０ｎｍであることがより好ましく、３０ｎｍ≦ｒ≦２００ｎｍであることが更に好ましい。ここでいう「平均粒径」とは、顔料の一次粒子が集合した二次粒子についての平均粒径を意味する。また、使用しうる顔料の二次粒子の粒径分布（以下、単に「粒径分布」ともいう。）は、平均粒径±１００ｎｍの範囲に含まれる二次粒子が全体の７０質量％以上であることが好ましく、８０質量％以上であることがより好ましい。なお、二次粒子の粒径分布は、散乱強度分布を用いて測定される。 <<<< chromatic colorant >>>
In the present invention, the chromatic colorant is preferably a colorant selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. In the present invention, the chromatic colorant may be a pigment or a dye. Preferably, it is a pigment. Further, as the pigment, a material in which an inorganic pigment or an organic-inorganic pigment is partially replaced with an organic chromophore can be used. By partially replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, the hue design can be facilitated. The pigment preferably has an average particle size (r) of 20 nm ≦ r ≦ 300 nm, more preferably 25 nm ≦ r ≦ 250 nm, and still more preferably 30 nm ≦ r ≦ 200 nm. The “average particle size” here means an average particle size of secondary particles in which primary particles of the pigment are aggregated. The particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also referred to simply as “particle size distribution”) is such that the secondary particles contained in the range of the average particle size ± 100 nm are 70% by mass or more of the whole. Preferably, it is 80% by mass or more. The particle size distribution of the secondary particles is measured using a scattering intensity distribution.
　本発明で用いられる有彩色着色剤は、顔料を含むことが好ましい。また、有彩色着色剤中における顔料の含有量は、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることが更に好ましく、９０質量％以上であることが特に好ましい。また、有彩色着色剤は顔料のみであってもよい。顔料としては以下に示すものが挙げられる。 有 The chromatic colorant used in the present invention preferably contains a pigment. Further, the content of the pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass or more. Is particularly preferred. The chromatic colorant may be a pigment alone. Examples of the pigment include the following.
　カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２３１，２３２（メチン／ポリメチン系）等（以上、黄色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４,２７０，２７２，２７９，２９４（キサンテン系、Ｏｒｇａｎｏ　Ｕｌｔｒａｍａｒｉｎｅ、Ｂｌｕｉｓｈ　Ｒｅｄ）等（以上、赤色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，１０，３６，３７，５８，５９，６２，６３等（以上、緑色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１，１９，２３，２７，３２，３７，４２，６０（トリアリールメタン系），６１（キサンテン系）等（以上、紫色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７（モノアゾ系），８８（メチン／ポリメチン系）等（以上、青色顔料）。 Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,231,232 (methine / polymethine system) etc. , Yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Or more, orange pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3. 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (xanthene-based Organo Ultramarine, Bluish Red), etc. (or more, a red pigment),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), etc. (above, purple pigment),
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,29,60,64,66,79,80,87 (monoazo type), 88 (methine / polymethine-based) and the like (all blue pigments).
　また、緑色顔料として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子数が平均８～１２個であり、塩素原子数が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第２０１５／１１８７２０号に記載の化合物が挙げられる。また、緑色顔料としてＣＮ１０６９０９０２７Ａに記載の化合物、リン酸エステルを配位子として有するフタロシアニン化合物などを用いることもできる。 Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule. Can also be used. Specific examples include the compounds described in WO 2015/118720. As the green pigment, a compound described in CN106909097A, a phthalocyanine compound having a phosphate as a ligand, or the like can also be used.
　また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落００２２～００３０、特開２０１１－１５７４７８号公報の段落００４７に記載の化合物が挙げられる。 ア ル ミ ニ ウ ム Also, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247593 and paragraph 0047 of JP-A-2011-157478.
　また、黄色顔料として、特開２０１７－２０１００３号公報に記載されている顔料、特開２０１７－１９７７１９号公報に記載されている顔料を用いることができる。また、黄色顔料として、下記式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料を用いることもできる。 顔料 Further, as the yellow pigment, a pigment described in JP-A-2017-201303 and a pigment described in JP-A-2017-197719 can be used. Further, as a yellow pigment, a metal containing at least one anion, two or more metal ions, and a melamine compound selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof: Azo pigments can also be used.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式中、Ｒ1およびＲ2はそれぞれ独立して、－ＯＨまたは－ＮＲ5Ｒ6であり、Ｒ3およびＲ4はそれぞれ独立して、＝Ｏまたは＝ＮＲ7であり、Ｒ5～Ｒ7はそれぞれ独立して、水素原子またはアルキル基である。Ｒ5～Ｒ7が表すアルキル基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は置換基を有していてもよい。置換基は、ハロゲン原子、ヒドロキシル基、アルコキシ基、シアノ基およびアミノ基が好ましい。 Wherein R 1 and R 2 are each independently —OH or —NR 5 R 6 , R 3 and R 4 are each independently ＝ O or ＮＲNR 7 , and R 5 -R 7 Is each independently a hydrogen atom or an alkyl group. The alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, and still more preferably has 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. The substituent is preferably a halogen atom, a hydroxyl group, an alkoxy group, a cyano group or an amino group.
　上記の金属アゾ顔料については、特開２０１７－１７１９１２号公報の段落００１１～００６２、０１３７～０２７６、特開２０１７－１７１９１３号公報の段落００１０～００６２、０１３８～０２９５、特開２０１７－１７１９１４号公報の段落００１１～００６２、０１３９～０１９０、特開２０１７－１７１９１５号公報の段落００１０～００６５、０１４２～０２２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The metal azo pigments described above are described in paragraphs 0011 to 0062 and 0137 to 0276 of JP-A-2017-171912, paragraphs 0010 to 0062 of JP-A-2017-171913, 0138 to 0295, and JP-A-2017-171914. The descriptions in paragraphs 0011 to 0062 and 0139 to 0190, and paragraphs 0010 to 0065 and 0142 to 0222 in JP-A-2017-171915 can be referred to, and the contents thereof are incorporated herein.
　また、黄色顔料として、特開２０１８－０６２６４４号公報に記載の化合物を用いることもできる。この化合物は顔料誘導体としても使用可能である。 化合物 Further, as the yellow pigment, a compound described in JP-A-2018-062644 can also be used. This compound can also be used as a pigment derivative.
　赤色顔料として、特開２０１７－２０１３８４号公報に記載の構造中に少なくとも１つ臭素原子が置換したジケトピロロピロール系顔料、特許第６２４８８３８号の段落００１６～００２２に記載のジケトピロロピロール系顔料などを用いることもできる。また、赤色顔料として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。 As red pigments, diketopyrrolopyrrole-based pigments in which at least one bromine atom is substituted in the structure described in JP-A-2017-2013384, diketopyrrolopyrrole-based pigments described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 Etc. can also be used. Further, as the red pigment, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is introduced to a diketopyrrolopyrrole skeleton may be used. it can.
　染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が挙げられる。また、特開２０１２－１５８６４９号公報に記載のチアゾール化合物、特開２０１１－１８４４９３号公報に記載のアゾ化合物、特開２０１１－１４５５４０号公報に記載のアゾ化合物、特開２０１８－０１２８６３号公報に記載の分子内イミド型のキサンテン染料も好ましく用いることができる。また、黄色染料として、特開２０１３－０５４３３９号公報の段落００１１～００３４に記載のキノフタロン化合物、特開２０１４－０２６２２８号公報の段落００１３～００５８に記載のキノフタロン化合物などを用いることもできる。 The dye is not particularly limited, and a known dye can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazoleazo, pyridoneazo, cyanine, phenothiazine, pyrrolopyrazoleazomethine, xanthene, Dyes of phthalocyanine type, benzopyran type, indigo type, pyromethene type and the like can be mentioned. Also, thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, azo compounds described in JP-A-2011-145540, and JP-A-2018-012863. Can also be preferably used. Further, as the yellow dye, quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can be used.
　黄色着色剤として、国際公開第２０１２／１２８２３３号、特開２０１７－２０１００３号公報に記載されている色素を用いることができる。また、赤色着色剤として、国際公開第２０１２／１０２３９９号、国際公開第２０１２／１１７９６５号および特開２０１２－２２９３４４号公報に記載されている色素を用いることができる。また、緑色着色剤として、国際公開第２０１２／１０２３９５号に記載されている色素を用いることができる。その他、国際公開第２０１１／０３７１９５号に記載されている造塩型染料を用いることもできる。 色素 As the yellow colorant, dyes described in WO 2012/128233 and JP-A-2017-201303 can be used. As the red colorant, dyes described in WO2012 / 102399, WO2012 / 117965 and JP-A-2012-229344 can be used. Further, as a green colorant, a dye described in International Publication No. 2012/102395 can be used. In addition, a salt-forming dye described in WO 2011/037195 can be used.
　色材は、赤色着色剤、青色着色剤、黄色着色剤、紫色着色剤および緑色着色剤から選ばれる２種以上を含むことが好ましい。すなわち、色材は、赤色着色剤、青色着色剤、黄色着色剤、紫色着色剤および緑色着色剤から選ばれる２種類以上の着色剤の組み合わせで黒色を形成していることが好ましい。好ましい組み合わせとしては、例えば以下が挙げられる。
（１）赤色着色剤および青色着色剤の組み合わせ。
（２）赤色着色剤、青色着色剤および黄色着色剤の組み合わせ。
（３）赤色着色剤、青色着色剤、黄色着色剤および紫色着色剤の組み合わせ。
（４）赤色着色剤、青色着色剤、黄色着色剤、紫色着色剤および緑色着色剤の組み合わせ。
（５）赤色着色剤、青色着色剤、黄色着色剤および緑色着色剤の組み合わせ。
（６）赤色着色剤、青色着色剤および緑色着色剤の組み合わせ。
（７）黄色着色剤および紫色着色剤の組み合わせ。 The coloring material preferably contains two or more selected from a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent and a green coloring agent. That is, it is preferable that the colorant forms black by a combination of two or more types of colorants selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. Preferred combinations include, for example, the following.
(1) A combination of a red colorant and a blue colorant.
(2) A combination of a red colorant, a blue colorant and a yellow colorant.
(3) A combination of a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
(4) A combination of a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
(5) A combination of a red colorant, a blue colorant, a yellow colorant and a green colorant.
(6) A combination of a red colorant, a blue colorant and a green colorant.
(7) A combination of a yellow colorant and a purple colorant.
　上記（１）の態様において、赤色着色剤と青色着色剤との質量比は、赤色着色剤：青色着色剤＝２０～８０：２０～８０であることが好ましく、２０～６０：４０～８０であることがより好ましく、２０～５０：５０～８０であることが更に好ましい。 In the above embodiment (1), the mass ratio of the red colorant to the blue colorant is preferably red colorant: blue colorant = 20 to 80:20 to 80, and 20 to 60:40 to 80. More preferably, it is more preferably 20 to 50:50 to 80.
　上記（２）の態様において、赤色着色剤と青色着色剤と黄色着色剤の質量比は、赤色着色剤：青色着色剤：黄色着色剤＝１０～８０：２０～８０：１０～４０であることが好ましく、１０～６０：３０～８０：１０～３０であることがより好ましく、１０～４０：４０～８０：１０～２０であることが更に好ましい。 In the above embodiment (2), the mass ratio of the red colorant, the blue colorant, and the yellow colorant is red colorant: blue colorant: yellow colorant = 10 to 80:20 to 80:10 to 40. Is preferably 10 to 60:30 to 80:10 to 30, more preferably 10 to 40:40 to 80:10 to 20.
　上記（３）の態様において、赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤との質量比は、赤色着色剤：青色着色剤：黄色着色剤：紫色着色剤＝１０～８０：２０～８０：５～４０：５～４０であることが好ましく、１０～６０：３０～８０：５～３０：５～３０であることがより好ましく、１０～４０：４０～８０：５～２０：５～２０であることが更に好ましい。 In the above embodiment (3), the mass ratio of the red colorant, the blue colorant, the yellow colorant, and the purple colorant is as follows: red colorant: blue colorant: yellow colorant: purple colorant = 10 to 80:20 ８０80: 5 ～ 40: 5 ～ 40, preferably 10 ～ 60: 30 ～ 80: 5 ～ 30: 5 ～ 30, more preferably 10 ～ 40: 40 ～ 80: 5 ～ 20: More preferably, it is 5 to 20.
　上記（４）の態様において、赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤の質量比は、赤色着色剤：青色着色剤：黄色着色剤：紫色着色剤：緑色着色剤＝１０～８０：２０～８０：５～４０：５～４０：５～４０であることが好ましく、１０～６０：３０～８０：５～３０：５～３０：５～３０であることがより好ましく、１０～４０：４０～８０：５～２０：５～２０：５～２０であることが更に好ましい。 In the above embodiment (4), the mass ratio of the red colorant, the blue colorant, the yellow colorant, the purple colorant, and the green colorant is red colorant: blue colorant: yellow colorant: purple colorant: green colorant. Agent = 10 to 80:20 to 80: 5 to 40: 5 to 40: 5 to 40, preferably 10 to 60:30 to 80: 5 to 30: 5 to 30: 5 to 30 The ratio is more preferably 10 to 40:40 to 80: 5 to 20: 5 to 20: 5 to 20.
　上記（５）の態様において、赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤の質量比は、赤色着色剤：青色着色剤：黄色着色剤：緑色着色剤＝１０～８０：２０～８０：５～４０：５～４０であることが好ましく、１０～６０：３０～８０：５～３０：５～３０であることがより好ましく、１０～４０：４０～８０：５～２０：５～２０であることが更に好ましい。 In the above embodiment (5), the mass ratio of the red colorant, the blue colorant, the yellow colorant, and the green colorant is as follows: red colorant: blue colorant: yellow colorant: green colorant = 10 to 80:20 to 80: 5 to 40: 5 to 40, preferably 10 to 60:30 to 80: 5 to 30: 5 to 30, more preferably 10 to 40:40 to 80: 5 to 20: 5. More preferably, it is -20.
　上記（６）の態様において、赤色着色剤と青色着色剤と緑色着色剤の質量比は、赤色着色剤：青色着色剤：緑色着色剤＝１０～８０：２０～８０：１０～４０であることが好ましく、１０～６０：３０～８０：１０～３０であることがより好ましく、１０～４０：４０～８０：１０～２０であることが更に好ましい。 In the above aspect (6), the mass ratio of the red colorant, the blue colorant, and the green colorant is red colorant: blue colorant: green colorant = 10 to 80:20 to 80:10 to 40. Is preferably 10 to 60:30 to 80:10 to 30, more preferably 10 to 40:40 to 80:10 to 20.
　上記（７）の態様において、黄色着色剤と紫色着色剤の質量比は、黄色着色剤：紫色着色剤＝１０～５０：４０～８０であることが好ましく、２０～４０：５０～７０であることがより好ましく、３０～４０：６０～７０であることが更に好ましい。 In the above embodiment (7), the mass ratio of the yellow colorant to the purple colorant is preferably yellow colorant: purple colorant = 10 to 50:40 to 80, and is 20 to 40:50 to 70. More preferably, it is more preferably 30 to 40:60 to 70.
　黄色着色剤としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９，１５０，１８５が好ましく、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９，１５０がより好ましく、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９が更に好ましい。青色着色剤としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６が好ましい。紫色着色剤としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３が好ましい。赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２，１７７，２２４，２５４が好ましく、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２，１７７，２５４がより好ましく、Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４が更に好ましい。緑色着色剤としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７、３６、５８、５９が好ましい。 と し て As the yellow colorant, C.I. I. Pigment Yellow 139, 150, and 185, and C.I. I. Pigment \ Yellow \ 139,150 is more preferable, and C.I. I. Pigment \ Yellow \ 139 is more preferable. Examples of blue colorants include C.I. I. Pigment Blue 15: 6 is preferred. Examples of the purple colorant include C.I. I. Pigment Violet 23 is preferred. As the red colorant, Pigment Red 122, 177, 224, 254 is preferable, Pigment Red 122, 177, 254 is more preferable, and Pigment Red 254 is more preferable. Green colorants include C.I. I. Pigment Green 7, 36, 58, 59 are preferred.
＜＜＜有機系黒色着色剤＞＞＞
　本発明において、有機系黒色着色剤は、顔料であってもよく、染料であってもよく、好ましくは顔料である。有機系黒色着色剤は、例えば、ビスベンゾフラノン化合物（あるいはベンゾジフラノン化合物とも言われる。）、アゾメチン化合物、ペリレン化合物およびアゾ化合物などが挙げられる。有機系黒色着色剤は、ビスベンゾフラノン化合物、ペリレン化合物およびアゾ化合物の少なくとも１種を含むことが好ましい。ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、特表２０１２－５１５２３４号公報などに記載の化合物が挙げられ、例えば、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」として入手可能である。ペリレン化合物としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２、特開２０１７－２２６８２１号公報の段落００１６～００２０に記載の化合物などが挙げられる。アゾメチン化合物としては、特開平０１－１７０６０１号公報、特開平０２－０３４６６４号公報などに記載のものが挙げられ、例えば、大日精化社製の「クロモファインブラックＡ１１０３」として入手できる。 <<< Organic black colorant >>>
In the present invention, the organic black colorant may be a pigment or a dye, and is preferably a pigment. Examples of the organic black colorant include a bisbenzofuranone compound (also referred to as a benzodifuranone compound), an azomethine compound, a perylene compound, and an azo compound. The organic black colorant preferably contains at least one of a bisbenzofuranone compound, a perylene compound and an azo compound. Examples of the bisbenzofuranone compound include compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, and the like. For example, as “Irgaphor Black” manufactured by BASF Available. Examples of perylene compounds include C.I. I. Pigment Black 31, 32, and the compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821. Examples of the azomethine compound include those described in JP-A-01-170601 and JP-A-02-034664, and for example, it can be obtained as "Chromofine Black A1103" manufactured by Dainichi Seika.
　本発明において、ビスベンゾフラノン化合物は、下記式で表される化合物およびこれらの混合物であることが好ましい。 に お い て In the present invention, the bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式中、Ｒ1およびＲ2はそれぞれ独立して水素原子又は置換基を表し、Ｒ3およびＲ4はそれぞれ独立して置換基を表し、ａおよびｂはそれぞれ独立して０～４の整数を表し、ａが２以上の場合、複数のＲ3は、同一であってもよく、異なってもよく、複数のＲ3は結合して環を形成していてもよく、ｂが２以上の場合、複数のＲ4は、同一であってもよく、異なってもよく、複数のＲ4は結合して環を形成していてもよい。 In the formula, R 1 and R 2 each independently represent a hydrogen atom or a substituent, R 3 and R 4 each independently represent a substituent, and a and b each independently represent an integer of 0 to 4. And when a is 2 or more, a plurality of R 3 may be the same or different, and a plurality of R 3 may combine to form a ring, and when b is 2 or more, , A plurality of R 4 s may be the same or different, and a plurality of R 4 s may combine to form a ring.
　Ｒ1～Ｒ4が表す置換基は、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロアリール基、－ＯＲ301、－ＣＯＲ302、－ＣＯＯＲ303、－ＯＣＯＲ304、－ＮＲ305Ｒ306、－ＮＨＣＯＲ307、－ＣＯＮＲ308Ｒ309、－ＮＨＣＯＮＲ310Ｒ311、－ＮＨＣＯＯＲ312、－ＳＲ313、－ＳＯ2Ｒ314、－ＳＯ2ＯＲ315、－ＮＨＳＯ2Ｒ316または－ＳＯ2ＮＲ317Ｒ318を表し、Ｒ301～Ｒ318は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表す。 The substituents represented by R 1 to R 4 are a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR 301 , —COR 302 , and —COOR 303 , -OCOR 304 , -NR 305 R 306 , -NHCOR 307 , -CONR 308 R 309 , -NHCONR 310 R 311 , -NHCOOR 312 , -SR 313 , -SO 2 R 314 , -SO 2 OR 315 , -NHSO 2 R 316 or —SO 2 NR 317 represents R 318 , and R 301 to R 318 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
　ビスベンゾフラノン化合物の詳細については、特表２０１０－５３４７２６号公報の段落００１４～００３７の記載を参酌でき、この内容は本明細書に組み込まれる。 For details of the bisbenzofuranone compound, the description of paragraphs 0014 to 0037 of JP-T-2010-534726 can be referred to, and the contents thereof are incorporated herein.
　本発明において、色材として有機系黒色着色剤を用いる場合、有彩色着色剤と組み合わせて使用することが好ましい。有機系黒色着色剤と有彩色着色剤とを併用することで、優れた分光特性が得られやすい。有機系黒色着色剤と組み合わせて用いる有彩色着色剤としては、例えば、赤色着色剤、青色着色剤、紫色着色剤などが挙げられ、赤色着色剤および青色着色剤が好ましい。これらは単独で使用してもよく、２種以上を併用してもよい。 In the present invention, when an organic black colorant is used as a coloring material, it is preferable to use it in combination with a chromatic colorant. By using an organic black colorant and a chromatic colorant in combination, it is easy to obtain excellent spectral characteristics. Examples of the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more.
　また、有彩色着色剤と有機系黒色着色剤との混合割合は、有機系黒色着色剤１００質量部に対して、有彩色着色剤が１０～２００質量部が好ましく、１５～１５０質量部がより好ましい。 The mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, per 100 parts by mass of the organic black colorant. preferable.
　本発明において、色材における顔料の含有量は、色材の全量に対して９５質量％以上であることが好ましく、９７質量％以上であることがより好ましく、９９質量％以上であることが更に好ましい。 In the present invention, the content of the pigment in the coloring material is preferably 95% by mass or more, more preferably 97% by mass or more, and more preferably 99% by mass or more based on the total amount of the coloring material. preferable.
　本発明の硬化性組成物において、色材の含有量は、組成物の全固形分に対して３０質量％以上であり、３５質量％以上がより好ましく、４０質量％以上が更に好ましく、４５質量％以上がより一層好ましく、５０質量％以上が特に好ましい。また、色材の含有量は、組成物の全固形分に対して８０質量％以下であることが好ましく、７５質量％以下であることが好ましく、７０質量％以下であることがより好ましい。 In the curable composition of the present invention, the content of the coloring material is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and more preferably 45% by mass, based on the total solid content of the composition. % Or more is more preferable, and 50% by mass or more is particularly preferable. Further, the content of the coloring material is preferably not more than 80% by mass, more preferably not more than 75% by mass, more preferably not more than 70% by mass based on the total solid content of the composition.
＜＜＜近赤外線吸収剤＞＞＞
　本発明の硬化性組成物は、近赤外線吸収剤を含有することができる。近赤外線吸収剤は、組成物の分光特性において、近赤外域で透過する光をより長波長側に限定する役割を有している。 <<<< Near infrared absorber >>
The curable composition of the present invention can contain a near infrared absorbing agent. The near-infrared absorbing agent has a role of limiting the light transmitted in the near-infrared region to a longer wavelength side in the spectral characteristics of the composition.
　本発明において、近赤外線吸収剤としては、近赤外領域（好ましくは、波長７００ｎｍを超え１３００ｎｍ以下）の波長領域に極大吸収波長を有する化合物を好ましく用いることができる。近赤外線吸収剤は、顔料であってもよく、染料であってもよい。 に お い て In the present invention, as the near-infrared absorbing agent, a compound having a maximum absorption wavelength in a near-infrared region (preferably, a wavelength exceeding 700 nm and 1,300 nm or less) can be preferably used. The near-infrared absorbing agent may be a pigment or a dye.
　本発明において、近赤外線吸収剤としては、単環または縮合環の芳香族環を含むπ共役平面を有する近赤外線吸収化合物を好ましく用いることができる。近赤外線吸収化合物が有するπ共役平面を構成する水素以外の原子数は、１４個以上であることが好ましく、２０個以上であることがより好ましく、２５個以上であることが更に好ましく、３０個以上であることが特に好ましい。上限は、例えば、８０個以下であることが好ましく、５０個以下であることがより好ましい。 In the present invention, as the near-infrared absorbing agent, a near-infrared absorbing compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring can be preferably used. The number of atoms other than hydrogen constituting the π-conjugate plane of the near-infrared absorbing compound is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, and 30 or more. It is particularly preferable that the above is satisfied. The upper limit is, for example, preferably 80 or less, and more preferably 50 or less.
　近赤外線吸収化合物が有するπ共役平面は、単環または縮合環の芳香族環を２個以上含むことが好ましく、前述の芳香族環を３個以上含むことがより好ましく、前述の芳香族環を４個以上含むことが更に好ましく、前述の芳香族環を５個以上含むことが特に好ましい。上限は、１００個以下が好ましく、５０個以下がより好ましく、３０個以下が更に好ましい。前述の芳香族環としては、ベンゼン環、ナフタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、クアテリレン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ピリジン環、キノリン環、イソキノリン環、イミダゾール環、ベンゾイミダゾール環、ピラゾール環、チアゾール環、ベンゾチアゾール環、トリアゾール環、ベンゾトリアゾール環、オキサゾール環、ベンゾオキサゾール環、イミダゾリン環、ピラジン環、キノキサリン環、ピリミジン環、キナゾリン環、ピリダジン環、トリアジン環、ピロール環、インドール環、イソインドール環、カルバゾール環、および、これらの環を有する縮合環が挙げられる。 The π-conjugate plane of the near-infrared absorbing compound preferably contains two or more monocyclic or condensed aromatic rings, more preferably contains three or more aromatic rings described above, More preferably, it contains four or more, particularly preferably five or more of the above-mentioned aromatic rings. The upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. As the aforementioned aromatic ring, a benzene ring, a naphthalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, a quaterylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, Triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine Ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, isoindole ring, carbazole ring, and condensed rings having these rings.
　近赤外線吸収化合物は、波長７００～１０００ｎｍの範囲に極大吸収波長を有する化合物であることが好ましい。なお、本明細書において、「波長７００～１０００ｎｍの範囲に極大吸収波長を有する」とは、近赤外線吸収化合物の溶液での吸収スペクトルにおいて、波長７００～１０００ｎｍの範囲に最大の吸光度を示す波長を有することを意味する。近赤外線吸収化合物の溶液中での吸収スペクトルの測定に用いる測定溶媒は、クロロホルム、メタノール、ジメチルスルホキシド、酢酸エチル、テトラヒドロフランが挙げられる。クロロホルムで溶解する化合物の場合は、クロロホルムを測定溶媒として用いる。クロロホルムで溶解しない化合物の場合は、メタノールを用いる。また、クロロホルムおよびメタノールのいずれにも溶解しない場合はジメチルスルホキシドを用いる。 The near-infrared absorbing compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm. In the present specification, “having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm” means a wavelength showing a maximum absorbance in a wavelength range of 700 to 1000 nm in an absorption spectrum of a solution of a near-infrared absorbing compound. Means to have. The measurement solvent used for measuring the absorption spectrum of the near-infrared absorbing compound in a solution includes chloroform, methanol, dimethyl sulfoxide, ethyl acetate, and tetrahydrofuran. In the case of a compound soluble in chloroform, chloroform is used as a measuring solvent. If the compound does not dissolve in chloroform, use methanol. If it does not dissolve in either chloroform or methanol, use dimethyl sulfoxide.
　本発明において、近赤外線吸収化合物は、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、クアテリレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、ジイモニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物及びジベンゾフラノン化合物から選ばれる少なくとも１種が好ましく、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物およびジイモニウム化合物から選ばれる少なくとも１種がより好ましく、ピロロピロール化合物、シアニン化合物およびスクアリリウム化合物から選ばれる少なくとも１種が更に好ましく、ピロロピロール化合物が特に好ましい。 In the present invention, the near-infrared absorbing compound is a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterylene compound, a merocyanine compound, a croconium compound, an oxonol compound, a diimonium compound, a dithiol compound, a triarylmethane compound, At least one selected from a pyrromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a diimonium compound is more preferable. At least one selected from a pyrrolopyrrole compound, a cyanine compound and a squarylium compound But more preferably, pyrrolo-pyrrole compounds are particularly preferred.
　ピロロピロール化合物としては、例えば、特開２００９－２６３６１４号公報の段落００１６～００５８に記載の化合物、特開２０１１－０６８７３１号公報の段落００１１～００５２に記載の化合物、国際公開第２０１５／１６６８７３号の段落００１０～００３３に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraphs 0011 to 0052 of JP-A-2011-068731, and WO 2015/166873. Examples include the compounds described in paragraphs 0010 to 0033, the contents of which are incorporated herein.
　スクアリリウム化合物としては、例えば、特開２０１１－２０８１０１号公報の段落００４４～００４９に記載の化合物、特許第６０６５１６９号公報の段落００６０～００６１に記載の化合物、国際公開第２０１６／１８１９８７号の段落００４０に記載の化合物、国際公開第２０１３／１３３０９９号に記載の化合物、国際公開第２０１４／０８８０６３号に記載の化合物、特開２０１４－１２６６４２号公報に記載の化合物、特開２０１６－１４６６１９号公報に記載の化合物、特開２０１５－１７６０４６号公報に記載の化合物、特開２０１７－０２５３１１号公報に記載の化合物、国際公開第２０１６／１５４７８２号に記載の化合物、特許５８８４９５３号公報に記載の化合物、特許６０３６６８９号公報に記載の化合物、特許５８１０６０４号公報に記載の化合物、特開２０１７－０６８１２０号公報に記載の化合物、特開２０１７－１９７４３７号公報に記載の化合物、国際公開第２０１７／２１３０４７号の段落００９０～０１０７に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the squarylium compound include compounds described in paragraphs 0044 to 0049 of JP-A-2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, and paragraph 0040 of WO 2016/181987. The compounds described in WO 2013/133030, the compounds described in WO 2014/088063, the compounds described in JP-A-2014-126642, and the compounds described in JP-A-2016-146619 Compounds, compounds described in JP-A-2015-176046, compounds described in JP-A-2017-025311, compounds described in International Publication No. WO2016 / 154772, compounds described in Patent No. 5884953, and Patent 6036689 Compounds described in the gazette, No. 5,810,604, compounds described in JP-A-2017-068120, compounds described in JP-A-2017-197439, compounds described in paragraphs 0090 to 0107 of WO2017 / 213047, and the like. And their contents are incorporated herein.
　シアニン化合物としては、例えば、特開２００９－１０８２６７号公報の段落００４４～００４５に記載の化合物、特開２００２－１９４０４０号公報の段落００２６～００３０に記載の化合物、特開２０１５－１７２００４号公報に記載の化合物、特開２０１５－１７２１０２号公報に記載の化合物、特開２００８－０８８４２６号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026 to 0030 of JP-A-2002-194040, and JP-A-2015-172004. And the compounds described in JP-A-2015-172102, the compounds described in JP-A-2008-088426, and the like, the contents of which are incorporated herein.
　また、ジイモニウム化合物としては、例えば、特表２００８－５２８７０６号公報に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。フタロシアニン化合物としては、例えば、特開２０１２－０７７１５３号公報の段落００９３に記載の化合物、特開２００６－３４３６３１号公報に記載のオキシチタニウムフタロシアニン、特開２０１３－１９５４８０号公報の段落００１３～００２９に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。ナフタロシアニン化合物としては、例えば、特開２０１２－０７７１５３号公報の段落００９３に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。また、シアニン化合物、フタロシアニン化合物、ナフタロシアニン化合物、ジイモニウム化合物およびスクアリリウム化合物は、特開２０１０－１１１７５０号公報の段落００１０～００８１に記載の化合物を使用してもよく、この内容は本明細書に組み込まれる。また、シアニン化合物は、例えば、「機能性色素、大河原信／松岡賢／北尾悌次郎／平嶋恒亮・著、講談社サイエンティフィック」を参酌することができ、この内容は本明細書に組み込まれる。また、近赤外線吸収化合物としては、特開２０１６－１４６６１９号公報に記載された化合物を用いることもでき、この内容は本明細書に組み込まれる。 Also, examples of the diimonium compound include the compounds described in JP-T-2008-528706, the contents of which are incorporated herein. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraphs 0013 to 0029 of JP-A-2013-195480. And the contents of which are incorporated herein. Examples of the naphthalocyanine compound include the compounds described in paragraph 0093 of JP-A-2012-077153, the contents of which are incorporated herein. Further, as the cyanine compound, phthalocyanine compound, naphthalocyanine compound, diimonium compound and squarylium compound, the compounds described in paragraphs 0010 to 0081 of JP-A-2010-11117 may be used, the contents of which are incorporated herein. It is. In addition, as for the cyanine compound, for example, “Functional Dye, Shin Ogawara / Sen Matsuoka / Teijiro Kitao / Tsunaki Hirashima / Author, Kodansha Scientific” can be referred to, and the contents thereof are incorporated herein. . Further, as the near-infrared absorbing compound, the compounds described in JP-A-2016-146519 can also be used, and the contents thereof are incorporated herein.
　また、近赤外線吸収剤として、特開２０１７－１９７４３７号公報に記載のスクアリリウム化合物、国際公開第２０１７／２１３０４７号の段落００９０～０１０７に記載のスクアリリウム化合物、特開２０１８－０５４７６０号公報の段落００１９～００７５に記載のピロール環含有化合物、特開２０１８－０４０９５５号公報の段落００７８～００８２に記載のピロール環含有化合物、特開２０１８－００２７７３号公報の段落００４３～００６９に記載のピロール環含有化合物、特開２０１８－０４１０４７号公報の段落００２４～００８６に記載のアミドα位に芳香環を有するスクアリリウム化合物、特開２０１７－１７９１３１号公報に記載のアミド連結型スクアリリウム化合物、特開２０１７－１４１２１５号公報に記載のピロールビス型スクアリリウム骨格又はクロコニウム骨格を有する化合物、特開２０１７－０８２０２９号公報に記載されたジヒドロカルバゾールビス型のスクアリリウム化合物、特開２０１７－０６８１２０号公報の段落００２７～０１１４に記載の非対称型の化合物、特開２０１７－０６７９６３号公報に記載されたピロール環含有化合物（カルバゾール型）、特許第６２５１５３０号公報に記載されたフタロシアニン化合物などを用いることもできる。 Examples of the near-infrared absorbing agent include a squarylium compound described in JP-A-2017-197439, a squarylium compound described in paragraphs 0090 to 0107 of WO2017 / 213047, and a paragraph 0019 to JP-A-2018-054760. A pyrrole ring-containing compound described in paragraphs 0078 to 0082 of JP-A-2018-040955, a pyrrole ring-containing compound described in paragraphs 0043 to 0069 of JP-A-2018-002773, Squarylium compounds having an aromatic ring at the amide α-position described in paragraphs 0024 to 0087 of JP-A-2018-041047, amide-linked squarylium compounds described in JP-A-2017-179131, and JP-A-2017-141215 No A compound having a rubbis squarylium skeleton or a croconium skeleton, a dihydrocarbazole bis squarylium compound described in JP-A-2017-082029, an asymmetric compound described in paragraphs 0027 to 0114 of JP-A-2017-068120, A pyrrole ring-containing compound (carbazole type) described in JP-A-2017-067963, a phthalocyanine compound described in JP-A-6251530, and the like can also be used.
　本発明において、近赤外線吸収化合物としては、市販品を用いることもできる。例えば、ＳＤＯ－Ｃ３３（有本化学工業（株）製）、イーエクスカラーＩＲ－１４、イーエクスカラーＩＲ－１０Ａ、イーエクスカラーＴＸ－ＥＸ－８０１Ｂ、イーエクスカラーＴＸ－ＥＸ－８０５Ｋ（（株）日本触媒製）、ＳｈｉｇｅｎｏｘＮＩＡ－８０４１、ＳｈｉｇｅｎｏｘＮＩＡ－８０４２、ＳｈｉｇｅｎｏｘＮＩＡ－８１４、ＳｈｉｇｅｎｏｘＮＩＡ－８２０、ＳｈｉｇｅｎｏｘＮＩＡ－８３９（ハッコーケミカル社製）、ＥｐｏｌｉｔｅＶ－６３、Ｅｐｏｌｉｇｈｔ３８０１、Ｅｐｏｌｉｇｈｔ３０３６（ＥＰＯＬＩＮ社製）、ＰＲＯ－ＪＥＴ８２５ＬＤＩ（富士フイルム（株）製）、ＮＫ－３０２７、ＮＫ－５０６０（（株）林原製）、ＹＫＲ－３０７０（三井化学（株）製）などが挙げられる。 市 販 In the present invention, as the near-infrared absorbing compound, a commercial product may be used. For example, SDO-C33 (manufactured by Arimoto Chemical Industry Co., Ltd.), EEX Color IR-14, EEX Color IR-10A, EEX Color TX-EX-801B, EEX Color TX-EX-805K ((Co., Ltd.) ) Manufactured by Nippon Shokubai), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (manufactured by Hako Chemical Co., Ltd., Hako Chemical Co., Ltd.) Film Co., Ltd.), NK-3027, NK-5060 (manufactured by Hayashibara), YKR-3070 (manufactured by Mitsui Chemicals, Inc.) and the like.
　本発明の組成物において、近赤外線吸収剤として、無機粒子を用いることもできる。無機粒子の形状は特に制限されず、球状、非球状を問わず、シート状、ワイヤー状、チューブ状であってもよい。無機粒子としては、金属酸化物粒子または金属粒子が好ましい。金属酸化物粒子としては、例えば、酸化インジウムスズ（ＩＴＯ）粒子、酸化アンチモンスズ（ＡＴＯ）粒子、酸化亜鉛（ＺｎＯ）粒子、Ａｌドープ酸化亜鉛（ＡｌドープＺｎＯ）粒子、フッ素ドープ二酸化スズ（ＦドープＳｎＯ2）粒子、ニオブドープ二酸化チタン（ＮｂドープＴｉＯ2）粒子などが挙げられる。金属粒子としては、例えば、銀（Ａｇ）粒子、金（Ａｕ）粒子、銅（Ｃｕ）粒子、ニッケル（Ｎｉ）粒子などが挙げられる。また、無機粒子としては酸化タングステン系化合物を用いることもできる。酸化タングステン系化合物は、セシウム酸化タングステンであることが好ましい。酸化タングステン系化合物の詳細については、特開２０１６－００６４７６号公報の段落００８０を参酌でき、この内容は本明細書に組み込まれる。 In the composition of the present invention, inorganic particles may be used as the near-infrared absorbing agent. The shape of the inorganic particles is not particularly limited, and may be sheet-like, wire-like, or tube-like regardless of spherical or non-spherical shape. As the inorganic particles, metal oxide particles or metal particles are preferable. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped). SnO 2 ) particles, niobium-doped titanium dioxide (Nb-doped TiO 2 ) particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. In addition, a tungsten oxide-based compound can be used as the inorganic particles. The tungsten oxide-based compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, paragraph 0080 of JP-A-2016-006476 can be referred to, and the contents thereof are incorporated herein.
　本発明の組成物において、近赤外線吸収剤の含有量は、組成物の全固形分に対して１～３０質量％であることが好ましい。上限は、２０質量％以下が好ましく、１０質量％以下がより好ましい。下限は、３質量％以上が好ましく、５質量％以上がより好ましい。 に お い て In the composition of the present invention, the content of the near-infrared absorbing agent is preferably 1 to 30% by mass based on the total solid content of the composition. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.
　また、近赤外線吸収剤と色材との合計量は、組成物の全固形分の１０～７０質量％であることが好ましい。下限は、２０質量％以上が好ましく、２５質量％以上がより好ましい。 合計 The total amount of the near-infrared absorbing agent and the coloring material is preferably 10 to 70% by mass of the total solids of the composition. The lower limit is preferably at least 20% by mass, more preferably at least 25% by mass.
　また、近赤外線吸収剤と色材との合計量中における、近赤外線吸収剤の含有量は、５～４０質量％であることが好ましい。上限は、３０質量％以下が好ましく、２５質量％以下がより好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。 The content of the near-infrared absorbing agent in the total amount of the near-infrared absorbing agent and the coloring material is preferably 5 to 40% by mass. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The lower limit is preferably at least 10% by mass, more preferably at least 15% by mass.
　本発明の組成物においては、近赤外線吸収剤は１種単独で用いてもよく、２種以上併用してもよい。近赤外線吸収剤を２種以上併用する場合は、その合計が上記範囲であることが好ましい。 近 In the composition of the present invention, one kind of the near-infrared absorber may be used alone, or two or more kinds may be used in combination. When two or more near-infrared absorbers are used in combination, the total is preferably within the above range.
　本発明において、近赤外線吸収化合物としては、市販品を用いることもできる。例えば、ＳＤＯ－Ｃ３３（有本化学工業（株）製）、イーエクスカラーＩＲ－１４、イーエクスカラーＩＲ－１０Ａ、イーエクスカラーＴＸ－ＥＸ－８０１Ｂ、イーエクスカラーＴＸ－ＥＸ－８０５Ｋ（（株）日本触媒製）、ＳｈｉｇｅｎｏｘＮＩＡ－８０４１、ＳｈｉｇｅｎｏｘＮＩＡ－８０４２、ＳｈｉｇｅｎｏｘＮＩＡ－８１４、ＳｈｉｇｅｎｏｘＮＩＡ－８２０、ＳｈｉｇｅｎｏｘＮＩＡ－８３９（ハッコーケミカル社製）、ＥｐｏｌｉｔｅＶ－６３、Ｅｐｏｌｉｇｈｔ３８０１、Ｅｐｏｌｉｇｈｔ３０３６（ＥＰＯＬＩＮ社製）、ＰＲＯ－ＪＥＴ８２５ＬＤＩ（富士フイルム（株）製）、ＮＫ－３０２７、ＮＫ－５０６０（（株）林原製）、ＹＫＲ－３０７０（三井化学（株）製）などが挙げられる。 市 販 In the present invention, as the near-infrared absorbing compound, a commercial product may be used. For example, SDO-C33 (manufactured by Arimoto Chemical Industry Co., Ltd.), EEX Color IR-14, EEX Color IR-10A, EEX Color TX-EX-801B, EEX Color TX-EX-805K ((Co., Ltd.) ) manufactured by Nippon Shokubai), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, manufactured by ShigenoxNIA-839 (Hakko Chemical Co., Ltd.), EpoliteV-63, Epolight3801, made Epolight3036 (EPOLIN, Inc.), PRO-JET825LDI (Fuji Film Co., Ltd.), NK-3027, NK-5060 (manufactured by Hayashibara), YKR-3070 (manufactured by Mitsui Chemicals, Inc.) and the like.
　本発明の硬化性組成物が近赤外線吸収剤を含有する場合、近赤外線吸収剤の含有量は、硬化性組成物の全固形分に対して１～３０質量％であることが好ましい。上限は、２５質量％以下が好ましく、２０質量％以下がより好ましい。下限は、３質量％以上が好ましく、５質量％以上がより好ましい。また、近赤外線吸収剤と色材との合計量は、硬化性組成物の全固形分の３５～８０質量％であることが好ましい。下限は、４０質量％以上が好ましく、４５質量％以上がより好ましく、５０質量％以上が更に好ましく、５５質量％以上が特に好ましい。上限は、７５質量％以下が好ましく、７０質量％以下がより好ましい。また、近赤外線吸収剤と色材との合計量中における、近赤外線吸収剤の含有量は、５～４０質量％であることが好ましい。上限は、３０質量％以下が好ましく、２５質量％以下がより好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。 場合 When the curable composition of the present invention contains a near-infrared absorbing agent, the content of the near-infrared absorbing agent is preferably 1 to 30% by mass based on the total solid content of the curable composition. The upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. Further, the total amount of the near-infrared absorbing agent and the coloring material is preferably 35 to 80% by mass of the total solid of the curable composition. The lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less. Further, the content of the near-infrared absorbing agent in the total amount of the near-infrared absorbing agent and the coloring material is preferably 5 to 40% by mass. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The lower limit is preferably at least 10% by mass, more preferably at least 15% by mass.
　本発明の硬化性組成物においては、近赤外線吸収剤は１種単独で用いてもよく、２種以上併用してもよい。近赤外線吸収剤を２種以上併用する場合は、その合計が上記範囲であることが好ましい。 近 In the curable composition of the present invention, the near-infrared absorbing agent may be used alone or in combination of two or more. When two or more near-infrared absorbers are used in combination, the total is preferably within the above range.
＜＜重合性化合物＞＞
　本発明の硬化性組成物は、重合性化合物を含有する。重合性化合物としては、エチレン性不飽和基を有する化合物などが挙げられる。エチレン性不飽和基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。重合性化合物はラジカルにより重合可能な化合物（ラジカル重合性化合物）であることが好ましい。 << polymerizable compound >>
The curable composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include a compound having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound is preferably a compound polymerizable by a radical (radical polymerizable compound).
　重合性化合物の分子量は、１００～２０００が好ましい。上限は、１５００以下が好ましく、１０００以下がより好ましい。下限は、１５０以上がより好ましく、２５０以上が更に好ましい。 The molecular weight of the polymerizable compound is preferably from 100 to 2,000. The upper limit is preferably 1500 or less, more preferably 1000 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.
　重合性化合物のエチレン性不飽和基価（以下、Ｃ＝Ｃ価という）は、組成物の経時安定性の観点から２～１４ｍｍｏｌ／ｇであることが好ましい。下限は、３ｍｍｏｌ／ｇ以上であることが好ましく、４ｍｍｏｌ／ｇ以上であることがより好ましく、５ｍｍｏｌ／ｇ以上であることが更に好ましい。上限は１２ｍｍｏｌ／ｇ以下であることが好ましく、１０ｍｍｏｌ／ｇ以下であることがより好ましく、８ｍｍｏｌ／ｇ以下であることが更に好ましい。重合性化合物のＣ＝Ｃ価は、重合性化合物の１分子中に含まれるエチレン性不飽和基の数を重合性化合物の分子量で割ることで算出した。 エ チ レ ン The ethylenically unsaturated group value (hereinafter referred to as C = C value) of the polymerizable compound is preferably 2 to 14 mmol / g from the viewpoint of the stability over time of the composition. The lower limit is preferably at least 3 mmol / g, more preferably at least 4 mmol / g, even more preferably at least 5 mmol / g. The upper limit is preferably at most 12 mmol / g, more preferably at most 10 mmol / g, even more preferably at most 8 mmol / g. The C = C value of the polymerizable compound was calculated by dividing the number of ethylenically unsaturated groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.
　重合性化合物は、エチレン性不飽和基を３個以上含む化合物であることが好ましく、エチレン性不飽和基を４個以上含む化合物であることがより好ましい。この態様によれば、露光による硬化性組成物の硬化性が良好である。エチレン性不飽和基の数の上限は、組成物の経時安定性の観点から１５個以下であることが好ましく、１０個以下であることがより好ましく、６個以下であることが更に好ましい。また、重合性化合物は、３官能以上の（メタ）アクリレート化合物であることが好ましく、３～１５官能の（メタ）アクリレート化合物であることがより好ましく、３～１０官能の（メタ）アクリレート化合物であることが更に好ましく、３～６官能の（メタ）アクリレート化合物であることが特に好ましい。 The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated groups, and more preferably a compound containing four or more ethylenically unsaturated groups. According to this aspect, the curability of the curable composition upon exposure is good. The upper limit of the number of ethylenically unsaturated groups is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less from the viewpoint of the stability over time of the composition. Further, the polymerizable compound is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 10 functional (meth) acrylate compound. More preferably, it is particularly preferably a tri- to hexafunctional (meth) acrylate compound.
　重合性化合物は、エチレン性不飽和基とアルキレンオキシ基とを含む化合物であることも好ましい。このような重合性化合物は柔軟性が高く、エチレン性不飽和基が移動し易いため、露光時において重合性化合物同士が反応し易く、支持体などとの密着性に優れた硬化膜（画素）を形成できる。また、光重合開始剤としてヒドロキシアルキルフェノン化合物を用いた場合においては、重合性化合物と光重合開始剤とが近接して重合性化合物の近傍でラジカルを発生させて重合性化合物をより効果的に反応させることができると推測され、より優れた密着性や耐溶剤性を有する硬化膜（画素）を形成し易い。 The polymerizable compound is also preferably a compound containing an ethylenically unsaturated group and an alkyleneoxy group. Since such a polymerizable compound has high flexibility and the ethylenically unsaturated group is easily moved, the polymerizable compound easily reacts with each other at the time of exposure, and a cured film (pixel) having excellent adhesion to a support or the like. Can be formed. Further, when a hydroxyalkylphenone compound is used as the photopolymerization initiator, the polymerizable compound and the photopolymerization initiator approach each other to generate radicals in the vicinity of the polymerizable compound to more effectively convert the polymerizable compound. It is presumed that they can be reacted, and it is easy to form a cured film (pixel) having better adhesion and solvent resistance.
　重合性化合物の１分子中に含まれるアルキレンオキシ基の数は、２個以上であることが好ましく、３個以上であることがより好ましく、４個以上であることがさらに好ましい。上限は、組成物の経時安定性の観点から２０個以下が好ましい。 数 The number of alkyleneoxy groups contained in one molecule of the polymerizable compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit is preferably 20 or less from the viewpoint of the stability over time of the composition.
　また、エチレン性不飽和基とアルキレンオキシ基とを含む化合物のＳＰ値（Ｓｏｌｕｂｉｌｉｔｙ　Ｐａｒａｍｅｔｅｒ）は、組成物中の他の成分との相溶性の観点から９．０～１１．０が好ましい。上限は、１０．７５以下が好ましく、１０．５以下がより好ましい。下限は、９．２５以上が好ましく、９．５以上が更に好ましい。なお、本明細書において、ＳＰ値はＦｅｄｏｒｓ法に基づく計算値を使用した。 The SP value (Solubility @Parameter) of the compound containing an ethylenically unsaturated group and an alkyleneoxy group is preferably from 9.0 to 11.0 from the viewpoint of compatibility with other components in the composition. The upper limit is preferably 10.75 or less, more preferably 10.5 or less. The lower limit is preferably 9.25 or more, and more preferably 9.5 or more. In addition, in this specification, the SP value used the calculated value based on the Fedors method.
　エチレン性不飽和基とアルキレンオキシ基とを有する化合物としては、下記式（Ｍ－１）で表される化合物が挙げられる。 化合物 Examples of the compound having an ethylenically unsaturated group and an alkyleneoxy group include a compound represented by the following formula (M-1).
式（Ｍ－１）
Figure JPOXMLDOC01-appb-C000005
 Formula (M-1)
Figure JPOXMLDOC01-appb-C000005
　式中Ａ1は、エチレン性不飽和基を表し、Ｌ1は単結合または２価の連結基を表し、Ｒ1は、アルキレン基を表し、ｍは１～３０の整数を表し、ｎは３以上の整数を表し、Ｌ2はｎ価の連結基を表す。 In the formula, A 1 represents an ethylenically unsaturated group, L 1 represents a single bond or a divalent linking group, R 1 represents an alkylene group, m represents an integer of 1 to 30, and n represents 3 L 2 represents an n-valent linking group.
　Ａ1が表すエチレン性不飽和基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基が挙げられ、（メタ）アクリロイル基が好ましい。 Examples of the ethylenically unsaturated group represented by A 1 include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
　Ｌ1が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。 Examples of the divalent linking group represented by L 1 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, and a group combining two or more of these. . The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be linear, branched or cyclic. The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
　Ｒ1が表すアルキレン基の炭素数は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましく、２または３が特に好ましく、２が最も好ましい。Ｒ1が表すアルキレン基は、直鎖、分岐が好ましく、直鎖がより好ましい。Ｒ1が表すアルキレンの具体例は、エチレン基、直鎖または分岐のプロピレン基などが挙げられ、エチレン基が好ましい。 The carbon number of the alkylene group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2. The alkylene group represented by R 1 is preferably linear or branched, and more preferably linear. Specific examples of the alkylene represented by R 1 include an ethylene group, a linear or branched propylene group, and an ethylene group is preferable.
　ｍは、１～３０の整数を表し、１～２０の整数が好ましく、１～１０の整数がより好ましく、１～５が更に好ましい。
　ｎは３以上の整数を表し、４以上の整数が好ましい。ｎの上限は１５以下の整数が好ましく、１０以下の整数がより好ましく、６以下の整数が更に好ましい。 m represents an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and still more preferably 1 to 5.
n represents an integer of 3 or more, and preferably an integer of 4 or more. The upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and even more preferably an integer of 6 or less.
　Ｌ2が表すｎ価の連結基としては、脂肪族炭化水素基、芳香族炭化水素基、複素環基およびこれらの組み合わせからなる基、ならびに、脂肪族炭化水素基、芳香族炭化水素基および複素環基から選ばれる少なくとも１種と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－および－ＮＨ－から選ばれる少なくとも１種とを組み合わせてなる基が挙げられる。脂肪族炭化水素基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。芳香族炭化水素基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。複素環基は、非芳香族の複素環基であってもよく、芳香族複素環基であってもよい。複素環基は、５員環または６員環が好ましい。複素環基を構成するヘテロ原子の種類は窒素原子、酸素原子、硫黄原子などが挙げられる。複素環基を構成するヘテロ原子の数は１～３が好ましい。複素環基は、単環であってもよく、縮合環であってもよい。Ｌ2が表すｎ価の連結基は、多官能アルコールから誘導される基であることも好ましい。 Examples of the n-valent linking group represented by L 2 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group and a group formed by a combination thereof, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group. Examples include a group formed by combining at least one selected from a ring group and at least one selected from -O-, -CO-, -COO-, -OCO- and -NH-. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched. The carbon number of the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered ring. Examples of the types of hetero atoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The heterocyclic group may be a single ring or a condensed ring. The n-valent linking group represented by L 2 is also preferably a group derived from a polyfunctional alcohol.
　エチレン性不飽和基とアルキレンオキシ基とを有する化合物としては、下記式（Ｍ－２）で表される化合物がより好ましい。 As the compound having an ethylenically unsaturated group and an alkyleneoxy group, a compound represented by the following formula (M-2) is more preferable.
式（Ｍ－２）
Figure JPOXMLDOC01-appb-C000006
 Formula (M-2)
Figure JPOXMLDOC01-appb-C000006
　式中Ｒ2は水素原子またはメチル基を表し、Ｒ1は、アルキレン基を表し、ｍは１～３０の整数を表し、ｎは３以上の整数を表し、Ｌ2はｎ価の連結基を表す。式（Ｍ－２）のＲ1、Ｌ2、ｍ、ｎは、式（Ｍ－１）のＲ1、Ｌ2、ｍ、ｎと同義であり、好ましい範囲も同様である。 In the formula, R 2 represents a hydrogen atom or a methyl group, R 1 represents an alkylene group, m represents an integer of 1 to 30, n represents an integer of 3 or more, and L 2 represents an n-valent linking group. Represent. R 1, L 2, m, n of formula (M-2) is R 1, L 2, m, synonymous with n in formula (M-1), and preferred ranges are also the same.
　エチレン性不飽和基とアルキレンオキシ基とを有する重合性化合物の市販品としては、ＫＡＹＡＲＡＤ　Ｔ－１４２０（Ｔ）、ＲＰ－１０４０（日本化薬（株）製）などが挙げられる。 Commercially available polymerizable compounds having an ethylenically unsaturated group and an alkyleneoxy group include KAYARAD T-1420 (T), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
　重合性化合物として、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）などを用いることもできる。 As polymerizable compounds, dipentaerythritol triacrylate (KAYARAD @ D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD @ D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Nippon Kayaku), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD @ D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD @ DPHA; Nippon Kayaku ( NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. (For example, commercially available from Sartomer It is may SR454, SR499) be used.
　また、重合性化合物として、アロニックス　Ｍ－４０２（東亞合成（株）製、ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合物）を用いることも好ましい。 Also, as the polymerizable compound, it is preferable to use ARONIX M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.).
　また、重合性化合物として、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシ変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシ変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシ変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることもできる。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。 Further, as the polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropanepropyleneoxy-modified tri (meth) acrylate, trimethylolpropaneethyleneoxy-modified tri (meth) acrylate, isocyanuric acid ethyleneoxy-modified tri (meth) acrylate And a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester # A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD @ GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And the like.
　重合性化合物として、酸基を有する重合性化合物を用いることも好ましい。酸基を有する重合性化合物を用いることで、現像時に未露光部の硬化性組成物層が除去されやすく、現像残渣の発生を抑制できる。酸基としては、カルボキシル基、スルホ基、リン酸基等が挙げられ、カルボキシル基が好ましい。酸基を有する重合性化合物としては、コハク酸変性ジペンタエリスリトールペンタ（メタ）アクリレートなどが挙げられる。酸基を有する重合性化合物の市販品としては、アロニックスＭ－５１０、Ｍ－５２０、アロニックスＴＯ－２３４９（東亞合成（株）製）等が挙げられる。酸基を有する重合性化合物の好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像液に対する溶解性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造や取扱い上、有利である。 It is also preferable to use a polymerizable compound having an acid group as the polymerizable compound. By using a polymerizable compound having an acid group, the curable composition layer in an unexposed portion is easily removed at the time of development, and the generation of a development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable. Examples of the polymerizable compound having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate. Commercial products of the polymerizable compound having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like. The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developer is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.
　重合性化合物は、カプロラクトン構造を有する化合物であることも好ましい。カプロラクトン構造を有する重合性化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。 The polymerizable compound is also preferably a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD @ DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
　重合性化合物は、特開２０１７－０４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報に記載されている化合物、特開２０１７－１９４６６２号公報に記載されている化合物、８ＵＨ－１００６、８ＵＨ－１０１２（以上、大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることも好ましい。 Polymerizable compounds include compounds described in JP-A-2017-048367, JP-A-6057891, and JP-A-6031807, compounds described in JP-A-2017-194662, 8UH-1006, and 8UH. It is also preferable to use -1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like.
　重合性化合物の含有量は、硬化性組成物の全固形分中５．０～３５質量％であることが好ましい。上限は、３０質量％以下であることが好ましく、２５質量％以下であることがより好ましい。下限は、７．５質量％以上であることが好ましく、１０質量％以上であることがより好ましい。 The content of the polymerizable compound is preferably 5.0 to 35% by mass based on the total solid content of the curable composition. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
＜＜光重合開始剤＞＞
　本発明の硬化性組成物は光重合開始剤を含有する。光重合開始剤としては、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール化合物、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル化合物、アミノアルキルフェノン化合物、ヒドロキシアルキルフェノン化合物、フェニルグリオキシレート化合物などが挙げられる。光重合開始剤の具体例としては、例えば、特開２０１３－０２９７６０号公報の段落０２６５～０２６８、特許第６３０１４８９号公報の記載を参酌することができ、これらの内容は本明細書に組み込まれる。 << Photopolymerization initiator >>
The curable composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoalkylphenone compounds, hydroxyalkylphenone compounds, phenylglyoxylate compounds, and the like. As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-029760 and JP-A-6301489 can be referred to, and the contents thereof are incorporated herein.
　フェニルグリオキシレート化合物としては、フェニルグリオキシリックアシッドメチルエステルなどが挙げられる。市販品としては、ＤＡＲＯＣＵＲ－ＭＢＦ（ＢＡＳＦ社製）などが挙げられる。 Phenylglyoxylate compounds include phenylglyoxylic acid methyl ester and the like. Commercially available products include DAROCUR-MBF (manufactured by BASF).
　アミノアルキルフェノン化合物としては、例えば、特開平１０－２９１９６９号公報に記載のアミノアルキルフェノン化合物が挙げられる。また、アミノアルキルフェノン化合物としては、ＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、ＩＲＧＡＣＵＲＥ－３７９（いずれもＢＡＳＦ社製）を用いることもできる。 Examples of the aminoalkylphenone compound include, for example, an aminoalkylphenone compound described in JP-A-10-291969. Further, as the aminoalkylphenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can also be used.
　アシルホスフィン化合物としては、特許第４２２５８９８号公報に記載のアシルホスフィン化合物が挙げられる。具体例としては、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイドなどが挙げられる。アシルホスフィン化合物としては、ＩＲＧＡＣＵＲＥ－８１９、ＤＡＲＯＣＵＲ－ＴＰＯ（いずれもＢＡＳＦ社製）を用いることもできる。 Examples of the acylphosphine compound include the acylphosphine compounds described in Japanese Patent No. 422598. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.
　ヒドロキシアルキルフェノン化合物としては、下記式（Ｖ）で表される化合物が挙げられる。 Examples of the hydroxyalkylphenone compound include a compound represented by the following formula (V).
式（Ｖ）
Figure JPOXMLDOC01-appb-C000007
 Equation (V)
Figure JPOXMLDOC01-appb-C000007
　式中Ｒｖ1は、置換基を表し、Ｒｖ2およびＲｖ3は、それぞれ独立して水素原子または置換基を表し、Ｒｖ2とＲｖ3とが互いに結合して環を形成していてもよく、ｍは０～５の整数を表す。 In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may combine with each other to form a ring, m represents an integer of 0 to 5.
　Ｒｖ1が表す置換基としては、アルキル基（好ましくは、炭素数１～１０のアルキル基）、アルコキシ基（好ましくは、炭素数１～１０のアルコキシ基）が挙げられる。アルキル基およびアルコキシ基は、直鎖または分岐が好ましく、直鎖がより好ましい。Ｒｖ1が表すアルキル基およびアルコキシ基は、無置換であってもよく、置換基を有していてもよい。置換基としては、ヒドロキシル基や、ヒドロキシアルキルフェノン構造を有する基などが挙げられる。ヒドロキシアルキルフェノン構造を有する基としては、式（Ｖ）におけるＲｖ1が結合したベンゼン環またはＲｖ1から水素原子を１個除去した構造の基が挙げられる。 Examples of the substituent represented by Rv 1 include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). The alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear. The alkyl group and the alkoxy group represented by Rv 1 may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxyl group and a group having a hydroxyalkylphenone structure. Examples of the group having a hydroxyalkylphenone structure include a benzene ring to which Rv 1 is bonded in Formula (V) or a group having a structure in which one hydrogen atom is removed from Rv 1 .
　Ｒｖ2およびＲｖ3は、それぞれ独立して水素原子または置換基を表す。置換基としては、アルキル基（好ましくは炭素数１～１０のアルキル基）が好ましい。また、Ｒｖ2とＲｖ3は互いに結合して環（好ましくは炭素数４～８の環、より好ましくは、炭素数４～８の脂肪族環）を形成していてもよい。アルキル基は、直鎖または分岐が好ましく、直鎖がより好ましい。 Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferable. Rv 2 and Rv 3 may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably linear or branched, and more preferably linear.
　式（Ｖ）で表される化合物の具体例としては、下記化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000008
 Specific examples of the compound represented by the formula (V) include the following compounds.
Figure JPOXMLDOC01-appb-C000008
　ヒドロキシアルキルフェノン化合物としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（商品名：いずれもＢＡＳＦ社製）を用いることもできる。 As the hydroxyalkylphenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can also be used.
　オキシム化合物としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－０６６３８５号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１７－０１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開第２０１５／１５２１５３号に記載の化合物、国際公開第２０１７／０５１６８０号に記載の化合物、特開２０１７－１９８８６５号公報に記載の化合物、国際公開第２０１７／１６４１２７号の段落００２５～００３８に記載の化合物などが挙げられる。オキシム化合物の具体例としては、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。市販品としては、ＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３、ＩＲＧＡＣＵＲＥ－ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光重合開始剤２）が挙げられる。 Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, and J.I. C. S. Compounds described in Perkin II (1979, pp. 1653-1660); C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer, Science and and Technology (1995, pp. 202-232), a compound described in JP-A-2000-066385, Compounds described in JP-A-2000-080068, compounds described in JP-T-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-0197766, and Patent No. No. 6065596, compounds described in WO2015 / 152153, compounds described in WO2017 / 051680, compounds described in JP-A-2017-198865, WO2017 / 1 And compounds described in paragraphs 0025 to 0038 of JP 4127 and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one. Commercial products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and Adeka Optomer N-1919. (Photopolymerization initiator 2 manufactured by ADEKA Corporation and described in JP-A-2012-014052).
　またオキシム化合物としては、カルバゾール環のＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号明細書に記載の化合物、色素部位にニトロ基が導入された特開２０１０－０１５０２５号公報および米国特許出願公開第２００９／０２９２０３９号明細書に記載の化合物、国際公開第２００９／１３１１８９号に記載のケトオキシム化合物、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許第７５５６９１０号明細書に記載の化合物、４０５ｎｍに吸収極大を有し、ｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報に記載の化合物などを用いてもよい。好ましくは、例えば、特開２０１３－０２９７６０号公報の段落０２７４～０３０６を参酌することができ、この内容は本明細書に組み込まれる。 Examples of the oxime compound include compounds described in JP-A-2009-519904 in which an oxime is linked to the N-position of a carbazole ring, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds described in JP-A-2010-015025 and US Patent Application Publication No. 2009/0292039 in which a nitro group is introduced into a dye moiety, ketoxime compounds described in WO2009 / 131189, triazine skeletons and oximes A compound described in US Pat. No. 7,556,910 containing a skeleton in the same molecule, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and having good sensitivity to a g-line light source Or the like may be used. Preferably, for example, paragraphs 0274 to 0306 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated in the present specification.
　オキシム化合物は、フッ素原子を含むオキシム化合物であることが好ましい。フッ素原子を含むオキシム化合物は、フッ素原子を有するアルキル基（以下、含フッ素アルキル基ともいう）、および、フッ素原子を有するアルキル基を含む基（以下、含フッ素基ともいう）を有することが好ましい。含フッ素基としては、－ＯＲF1、－ＳＲF1、－ＣＯＲF1、－ＣＯＯＲF1、－ＯＣＯＲF1、－ＮＲF1ＲF2、－ＮＨＣＯＲF1、－ＣＯＮＲF1ＲF2、－ＮＨＣＯＮＲF1ＲF2、－ＮＨＣＯＯＲF1、－ＳＯ2ＲF1、－ＳＯ2ＯＲF1および－ＮＨＳＯ2ＲF1から選ばれる少なくとも１種の基が好ましい。ＲF1は、含フッ素アルキル基を表し、ＲF2は、水素原子、アルキル基、含フッ素アルキル基、アリール基またはヘテロ環基を表す。含フッ素基は、－ＯＲF1が好ましい。 The oxime compound is preferably an oxime compound containing a fluorine atom. The oxime compound containing a fluorine atom preferably has an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated alkyl group), and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated group). . Examples of the fluorinated group include -OR F1 , -SR F1 , -COR F1 , -COOR F1 , -OCOR F1 , -NR F1 R F2 , -NHCOR F1 , -CONR F1 R F2 , -NHCONR F1 R F2 , -NHCOOR At least one group selected from F1 , —SO 2 R F1 , —SO 2 OR F1, and —NHSO 2 R F1 is preferable. R F1 represents a fluorine-containing alkyl group, and R F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group or a heterocyclic group. The fluorine-containing group is preferably -OR F1 .
　アルキル基および含フッ素アルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましく、１～４が特に好ましい。アルキル基および含フッ素アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。含フッ素アルキル基において、フッ素原子の置換率は４０～１００％であることが好ましく、５０～１００％であることがより好ましく、６０～１００％であることがさらに好ましい。なお、フッ素原子の置換率とは、アルキル基が有する全水素原子の数に対してフッ素原子に置換されている数の比率（％）をいう。 The carbon number of the alkyl group and the fluorine-containing alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group and the fluorine-containing alkyl group may be linear, branched or cyclic, but are preferably linear or branched. In the fluorinated alkyl group, the substitution ratio of fluorine atoms is preferably from 40 to 100%, more preferably from 50 to 100%, even more preferably from 60 to 100%. In addition, the substitution rate of a fluorine atom means the ratio (%) of the number of substitution with a fluorine atom to the total number of hydrogen atoms of the alkyl group.
　アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。 The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
　ヘテロ環基は、５員環または６員環が好ましい。ヘテロ環基は、単環であってもよく、縮合環であってもよい。縮合数は、２～８が好ましく、２～６がより好ましく、３～５が更に好ましく、３～４が特に好ましい。ヘテロ環基を構成する炭素原子の数は３～４０が好ましく、３～３０がより好ましく、３～２０がより好ましい。ヘテロ環基を構成するヘテロ原子の数は１～３が好ましい。ヘテロ環基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましく、窒素原子がより好ましい。 The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and more preferably 3 to 20. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom.
　フッ素原子を含む基は、式（１）または（２）で表される末端構造を有することが好ましい。
－ＣＨＦ2　　　（１）
－ＣＦ3　　　（２）
　フッ素原子を含むオキシム化合物中の全フッ素原子数は３以上が好ましく、４～１０がより好ましい。 The group containing a fluorine atom preferably has a terminal structure represented by the formula (1) or (2).
-CHF 2 (1)
-CF 3 (2)
The total number of fluorine atoms in the fluorine-containing oxime compound is preferably 3 or more, more preferably 4 to 10.
　フッ素原子を含むオキシム化合物は、式（ＯＸ－１）で表される化合物が好ましい。
（ＯＸ－１）
Figure JPOXMLDOC01-appb-C000009
 The oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1).
(OX-1)
Figure JPOXMLDOC01-appb-C000009
　式（ＯＸ－１）において、Ａｒ1およびＡｒ2は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表し、Ｒ1は、フッ素原子を含む基を有するアリール基を表し、Ｒ2およびＲ3は、それぞれ独立に、アルキル基またはアリール基を表す。 In the formula (OX-1), Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent, and R 1 represents an aryl group having a group containing a fluorine atom. And R 2 and R 3 each independently represent an alkyl group or an aryl group.
　Ａｒ1およびＡｒ2は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表す。芳香族炭化水素環は、単環でもよく、縮合環であってもよい。芳香族炭化水素環の環を構成する炭素原子数は、６～２０が好ましく、６～１５がより好ましく、６～１０が特に好ましい。芳香族炭化水素環は、ベンゼン環およびナフタレン環が好ましい。なかでも、Ａｒ1およびＡｒ2の少なくとも一方がベンゼン環であることが好ましく、Ａｒ1がベンゼン環であることがより好ましい。Ａｒ2は、ベンゼン環またはナフタレン環が好ましく、ナフタレン環がより好ましい。 Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent. The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10. As the aromatic hydrocarbon ring, a benzene ring and a naphthalene ring are preferable. Among them, at least one of Ar 1 and Ar 2 is preferably a benzene ring, and more preferably Ar 1 is a benzene ring. Ar 2 is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.
　Ａｒ1およびＡｒ2が有してもよい置換基としては、アルキル基、アリール基、ヘテロ環基、ニトロ基、シアノ基、ハロゲン原子、－ＯＲX1、－ＳＲX1、－ＣＯＲX1、－ＣＯＯＲX1、－ＯＣＯＲX1、－ＮＲX1ＲX2、－ＮＨＣＯＲX1、－ＣＯＮＲX1ＲX2、－ＮＨＣＯＮＲX1ＲX2、－ＮＨＣＯＯＲX1、－ＳＯ2ＲX1、－ＳＯ2ＯＲX1、－ＮＨＳＯ2ＲX1などが挙げられる。ＲX1およびＲX2は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロ環基を表す。 Examples of the substituent which Ar 1 and Ar 2 may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR X1 , —SR X1 , —COR X1 , and —COOR X1. , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 No. R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
　ハロゲン原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられ、フッ素原子が好ましい。置換基としてのアルキル基、ならびに、ＲX1およびＲX2が表すアルキル基の炭素数は、１～３０が好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アルキル基は、水素原子の一部または全部がハロゲン原子（好ましくは、フッ素原子）で置換されていてもよい。また、アルキル基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。置換基としてのアリール基、ならびに、ＲX1およびＲX2が表すアリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。アリール基は、単環であってもよく、縮合環であってもよい。また、アリール基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。置換基としてのヘテロ環基、ならびに、ＲX1およびＲX2が表すヘテロ環基は、５員環または６員環が好ましい。ヘテロ環基は、単環であってもよく、縮合環であってもよい。ヘテロ環基を構成する炭素原子の数は３～３０が好ましく、３～１８がより好ましく、３～１２がより好ましい。ヘテロ環基を構成するヘテロ原子の数は１～３が好ましい。ヘテロ環基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。また、ヘテロ環基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. The alkyl group as a substituent and the alkyl group represented by R X1 and R X2 preferably have 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. In the alkyl group, some or all of the hydrogen atoms may be substituted with halogen atoms (preferably, fluorine atoms). In the alkyl group, part or all of the hydrogen atoms may be substituted with the above substituents. The carbon number of the aryl group as a substituent and the aryl group represented by R X1 and R X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a single ring or a condensed ring. Further, in the aryl group, part or all of the hydrogen atoms may be substituted with the above substituents. The heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably a 5- or 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above substituents.
　Ａｒ1が表す芳香族炭化水素環は、無置換が好ましい。Ａｒ2が表す芳香族炭化水素環は、無置換であってもよく、置換基を有していてもよい。置換基を有していることが好ましい。置換基としては、－ＣＯＲX1が好ましい。ＲX1は、アルキル基、アリール基またはヘテロ環基が好ましく、アリール基がより好ましい。アリール基は置換基を有していてもよく、無置換であってもよい。置換基としては、炭素数１～１０のアルキル基などが挙げられる。 The aromatic hydrocarbon ring represented by Ar 1 is preferably unsubstituted. The aromatic hydrocarbon ring represented by Ar 2 may be unsubstituted or may have a substituent. It preferably has a substituent. As the substituent, —COR X1 is preferable. R X1 is preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an aryl group. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.
　Ｒ1は、フッ素原子を含む基を有するアリール基を表す。アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。フッ素原子を含む基は、フッ素原子を有するアルキル基（含フッ素アルキル基）およびフッ素原子を有するアルキル基を含む基（含フッ素基）が好ましい。フッ素原子を含む基については、上述した範囲と同義であり、好ましい範囲も同様である。 R 1 represents an aryl group having a group containing a fluorine atom. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10. As the group containing a fluorine atom, an alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing a fluorine atom-containing alkyl group (fluorine-containing group) are preferable. The group containing a fluorine atom has the same meaning as the above-mentioned range, and the preferred range is also the same.
　Ｒ2は、アルキル基またはアリール基を表し、アルキル基が好ましい。アルキル基およびアリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述したＡｒ1およびＡｒ2が有してもよい置換基で説明した置換基が挙げられる。アルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましく、１～４が特に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。 R 2 represents an alkyl group or an aryl group, and is preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have. The carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
　Ｒ3は、アルキル基またはアリール基を表し、アルキル基が好ましい。アルキル基およびアリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述したＡｒ1およびＡｒ2が有してもよい置換基で説明した置換基が挙げられる。Ｒ3が表すアルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。Ｒ3が表すアリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。 R 3 represents an alkyl group or an aryl group, and is preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have. The number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The aryl group represented by R 3 preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and still more preferably has 6 to 10 carbon atoms.
　フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。 Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471. Compound (C-3).
　また、オキシム化合物は、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物が挙げられる。この内容は本明細書に組み込まれる。 オ キ シ Also, as the oxime compound, an oxime compound having a fluorene ring can be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
　また、オキシム化合物は、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第２０１５／０３６９１０号に記載の化合物ＯＥ－０１～ＯＥ－７５が挙げられる。 オ キ シ Alternatively, as the oxime compound, an oxime compound having a benzofuran skeleton can be used. Specific examples include compounds OE-01 to OE-75 described in WO 2015/036910.
　また、オキシム化合物は、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられる。 オ キ シ Alternatively, as the oxime compound, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can be used. Specific examples of such oxime compounds include the compounds described in WO2013 / 083505.
　また、オキシム化合物は、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落００３１～００４７、特開２０１４－１３７４６６号公報の段落０００８～００１２、００７０～００７９に記載の化合物、特許４２２３０７１号公報の段落０００７～００２５に記載の化合物などが挙げられる。 オ キ シ As the oxime compound, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 of JP-A-2014-137466, and 0070 to 0079, and JP-A-4223071. And the like.
　オキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of the oxime compound are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　そして、本発明では、上記のとおり、光重合開始剤として、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ１と、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ２とを併用する。この態様によれば、露光によって組成物を充分に硬化させやすく、低温プロセス（例えば全工程を通じて２００℃未満、または１５０℃以下、さらには１２０℃以下の温度下）にて、密着性に優れ、さらには、耐溶剤性、平坦性、および、パターンの矩形性にも優れる硬化膜を形成することができる。光重合開始剤Ａ１および光重合開始剤Ａ２としては、上述した化合物の中から上記の吸光係数を有する化合物を選択して用いることが好ましい。 Then, in the present invention, as described above, as a photopolymerization initiator, a photopolymerization initiator A1 having an absorption coefficient of 1.0 × 10 3 mL / gcm or more in methanol at a wavelength of 365 nm, and a wavelength of 365 nm in methanol. Is used in combination with a photopolymerization initiator A2 having an extinction coefficient of 1.0 × 10 2 mL / gcm or less and an extinction coefficient at a wavelength of 254 nm of 1.0 × 10 3 mL / gcm or more. According to this aspect, the composition is easily cured sufficiently by exposure, and has excellent adhesion in a low-temperature process (for example, at a temperature of less than 200 ° C., or 150 ° C. or less, and even 120 ° C. or less throughout the entire process), Furthermore, a cured film having excellent solvent resistance, flatness, and rectangularity of the pattern can be formed. As the photopolymerization initiator A1 and the photopolymerization initiator A2, a compound having the above-mentioned extinction coefficient is preferably selected from the above-mentioned compounds and used.
　なお、本発明において、光重合開始剤の上記波長における吸光係数は、以下のようにして測定した値である。すなわち、光重合開始剤をメタノールに溶解させて測定溶液を調製し、前述の測定溶液の吸光度を測定することで算出した。具体的には、前述の測定溶液を幅１ｃｍのガラスセルに入れ、Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製ＵＶ－Ｖｉｓ－ＮＩＲスペクトルメーター（Ｃａｒｙ５０００）を用いて吸光度を測定し、下記式に当てはめて、波長３６５ｎｍおよび波長２５４ｎｍにおける吸光係数（ｍＬ／ｇｃｍ）を算出した。 In the present invention, the extinction coefficient of the photopolymerization initiator at the above-mentioned wavelength is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Carry5000) manufactured by Agilent Technologies, and the wavelength was 365 nm and the wavelength was applied by applying the following formula. The extinction coefficient (mL / gcm) at 254 nm was calculated.
Figure JPOXMLDOC01-appb-M000012
Figure JPOXMLDOC01-appb-M000012
　上記式においてεは吸光係数（ｍＬ／ｇｃｍ）、Ａは吸光度、ｃは光重合開始剤の濃度（ｇ／ｍＬ）、ｌは光路長（ｃｍ）を表す。 に お い て In the above formula, ε represents the extinction coefficient (mL / gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g / mL), and l represents the optical path length (cm).
　光重合開始剤Ａ１のメタノール中での波長３６５ｎｍにおける吸光係数は、１．０×１０3ｍＬ／ｇｃｍ以上であり、１．０×１０4ｍＬ／ｇｃｍ以上であることが好ましく、１．１×１０4ｍＬ／ｇｃｍ以上であることがより好ましく、１．２×１０4～１．０×１０5ｍＬ／ｇｃｍであることが更に好ましく、１．３×１０4～５．０×１０4ｍＬ／ｇｃｍであることがより一層好ましく、１．５×１０4～３．０×１０4ｍＬ／ｇｃｍであることが特に好ましい。 The extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm is 1.0 × 10 3 mL / gcm or more, preferably 1.0 × 10 4 mL / gcm or more, and more preferably 1.1 × 10 4 mL / gcm. It is more preferably at least 10 4 mL / gcm, even more preferably 1.2 × 10 4 to 1.0 × 10 5 mL / gcm, and 1.3 × 10 4 to 5.0 × 10 4 mL. / Gcm, more preferably 1.5 × 10 4 to 3.0 × 10 4 mL / gcm.
　また、光重合開始剤Ａ１のメタノール中での波長２５４ｎｍの光の吸光係数は、１．０×１０4～１．０×１０5ｍＬ／ｇｃｍであることが好ましく、１．５×１０4～９．５×１０4ｍＬ／ｇｃｍであることがより好ましく、３．０×１０4～８．０×１０4ｍＬ／ｇｃｍであることが更に好ましい。 Further, the extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm in methanol is preferably 1.0 × 10 4 to 1.0 × 10 5 mL / gcm, and 1.5 × 10 4 to 1.5 × 10 4 mL / gcm. It is more preferably 9.5 × 10 4 mL / gcm, and still more preferably 3.0 × 10 4 to 8.0 × 10 4 mL / gcm.
　光重合開始剤Ａ１としては、オキシム化合物、アミノアルキルフェノン化合物、アシルホスフィン化合物が好ましく、オキシム化合物およびアシルホスフィン化合物がより好ましく、オキシム化合物が更に好ましく、組成物に含まれる他の成分との相溶性の観点からフッ素原子を含むオキシム化合物であることが特に好ましい。フッ素原子を含むオキシム化合物としては、上述した式（ＯＸ－１）で表される化合物が好ましい。光重合開始剤Ａ１の具体例としては、１，２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＢＡＳＦ社製）、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＢＡＳＦ社製）、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－８１９、ＢＡＳＦ社製）、上記のオキシム化合物の具体例で示した（Ｃ－１３）、（Ｃ－１４）などが挙げられる。 The photopolymerization initiator A1 is preferably an oxime compound, an aminoalkylphenone compound or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, further preferably an oxime compound, and has compatibility with other components contained in the composition. From the viewpoint of, an oxime compound containing a fluorine atom is particularly preferred. As the oxime compound containing a fluorine atom, a compound represented by the above formula (OX-1) is preferable. Specific examples of the photopolymerization initiator A1 include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (as commercial products, for example, IRGACURE-OXE01, BASF , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (commercially available, for example, IRGACURE- OXE02, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercially available, for example, IRGACURE-819, manufactured by BASF), and specific examples of the above oxime compounds ( C-13) and (C-14).
　光重合開始剤Ａ２のメタノール中での波長３６５ｎｍの光の吸光係数は、１．０×１０2ｍＬ／ｇｃｍ以下であり、１０～１．０×１０2ｍＬ／ｇｃｍであることが好ましく、２０～１．０×１０2ｍＬ／ｇｃｍであることがより好ましい。また、光重合開始剤Ａ１のメタノール中での波長３６５ｎｍの光の吸光係数と、光重合開始剤Ａ２のメタノール中での波長３６５ｎｍの光の吸光係数との差は、９．０×１０2ｍＬ／ｇｃｍ以上であり、１．０×１０3ｍＬ／ｇｃｍ以上であることが好ましく、５．０×１０3～３．０×１０4ｍＬ／ｇｃｍであることがより好ましく、１．０×１０4～２．０×１０4ｍＬ／ｇｃｍであることが更に好ましい。また、光重合開始剤Ａ２のメタノール中での波長２５４ｎｍの光の吸光係数は、１．０×１０3ｍＬ／ｇｃｍ以上であり、１．０×１０3～１．０×１０6ｍＬ／ｇｃｍであることが好ましく、５．０×１０3～１．０×１０5ｍＬ／ｇｃｍであることがより好ましい。 The extinction coefficient of the photopolymerization initiator A2 for light having a wavelength of 365 nm in methanol is 1.0 × 10 2 mL / gcm or less, preferably 10 to 1.0 × 10 2 mL / gcm. More preferably, it is about 1.0 × 10 2 mL / gcm. The difference between the extinction coefficient of photopolymerization initiator A1 at 365 nm in methanol and the extinction coefficient of photopolymerization initiator A2 at 365 nm in methanol is 9.0 × 10 2 mL. / Gcm or more, preferably 1.0 × 10 3 mL / gcm or more, more preferably 5.0 × 10 3 to 3.0 × 10 4 mL / gcm, and more preferably 1.0 × 10 3 mL / gcm. More preferably, it is 4 to 2.0 × 10 4 mL / gcm. Further, the extinction coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 254 nm in methanol is 1.0 × 10 3 mL / gcm or more, and 1.0 × 10 3 to 1.0 × 10 6 mL / gcm. And more preferably from 5.0 × 10 3 to 1.0 × 10 5 mL / gcm.
　光重合開始剤Ａ２としては、ヒドロキシアルキルフェノン化合物、フェニルグリオキシレート化合物、アミノアルキルフェノン化合物、アシルホスフィン化合物が好ましく、ヒドロキシアルキルフェノン化合物およびフェニルグリオキシレート化合物がより好ましく、ヒドロキシアルキルフェノン化合物が更に好ましい。また、ヒドロキシアルキルフェノン化合物としては、上述した式（Ｖ）で表される化合物が好ましい。光重合開始剤Ａ２の具体例としては、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－１８４、ＢＡＳＦ社製）、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－２９５９、ＢＡＳＦ社製）などが挙げられる。 The photopolymerization initiator A2 is preferably a hydroxyalkylphenone compound, a phenylglyoxylate compound, an aminoalkylphenone compound, an acylphosphine compound, more preferably a hydroxyalkylphenone compound and a phenylglyoxylate compound, and further preferably a hydroxyalkylphenone compound. preferable. Further, as the hydroxyalkylphenone compound, a compound represented by the above formula (V) is preferable. Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl 2-hydroxy-2-methyl-1-propan-1-one (commercially available, for example, IRGACURE-2959, manufactured by BASF).
　光重合開始剤Ａ１と光重合開始剤Ａ２との組み合わせとしては、光重合開始剤Ａ１がオキシム化合物であり、光重合開始剤Ａ２がヒドロキシアルキルフェノン化合物である組み合わせが好ましく、光重合開始剤Ａ１がオキシム化合物であり、光重合開始剤Ａ２が上述した式（Ｖ）で表される化合物である組み合わせがより好ましく、光重合開始剤Ａ１がフッ素原子を含むオキシム化合物であり、光重合開始剤Ａ２が上述した式（Ｖ）で表される化合物である組み合わせが特に好ましい。 As a combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound is preferable, and the photopolymerization initiator A1 is preferably More preferably, the combination is an oxime compound, wherein the photopolymerization initiator A2 is a compound represented by the above formula (V), wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator A2 is Combinations of the compounds of formula (V) described above are particularly preferred.
　光重合開始剤Ａ１の含有量は、本発明の硬化性組成物の全固形分中１．０～２０．０質量％であることが好ましい。現像後の硬化膜（パターン）の支持体への密着性の観点から光重合開始剤Ａ１の含有量の下限は、２．０質量％以上であることが好ましく、３．０質量％以上であることがより好ましく、４．０質量％以上であることが更に好ましい。現像後のパターンの微細化の観点から光重合開始剤Ａ１の含有量の上限は、１５．０質量％以下であることが好ましく、１２．５質量％以下であることがより好ましく、１０．０質量％以下であることが更に好ましい。 The content of the photopolymerization initiator A1 is preferably 1.0 to 20.0% by mass based on the total solid content of the curable composition of the present invention. From the viewpoint of the adhesion of the cured film (pattern) to the support after development, the lower limit of the content of the photopolymerization initiator A1 is preferably 2.0% by mass or more, and more preferably 3.0% by mass or more. More preferably, it is more preferably 4.0% by mass or more. In light of miniaturization of the pattern after development, the upper limit of the content of the photopolymerization initiator A1 is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, and 10.0% or less. It is more preferable that the content be not more than mass%.
　光重合開始剤Ａ２の含有量は、本発明の硬化性組成物の全固形分中０．５～１５．０質量％が好ましい。得られる硬化膜の耐溶剤性の観点から光重合開始剤Ａ２の含有量の下限は、１．０質量％以上であることが好ましく、１．５質量％以上であることがより好ましく、２．０質量％以上であることが更に好ましい。現像後のパターンの微細化の観点から光重合開始剤Ａ２の含有量の上限は、１２．５質量％以下であることが好ましく、１０．０質量％以下であることがより好ましく、７．５質量％以下であることが更に好ましい。 含有 The content of the photopolymerization initiator A2 is preferably 0.5 to 15.0% by mass based on the total solid content of the curable composition of the present invention. From the viewpoint of the solvent resistance of the obtained cured film, the lower limit of the content of the photopolymerization initiator A2 is preferably 1.0% by mass or more, more preferably 1.5% by mass or more. More preferably, it is 0% by mass or more. From the viewpoint of miniaturization of the pattern after development, the upper limit of the content of the photopolymerization initiator A2 is preferably 12.5% by mass or less, more preferably 10.0% by mass or less, and 7.5. It is more preferable that the content be not more than mass%.
　本発明の硬化性組成物は、光重合開始剤Ａ１の１００質量部に対して、光重合開始剤Ａ２を５０～２００質量部含有することが好ましい。現像後のパターンの微細化の観点から上限は、１７５質量部以下であることが好ましく、１５０質量部以下であることがより好ましい。また、得られる硬化膜の耐溶剤性の観点から下限は、６０質量部以上であることが好ましく、７０質量部以上であることが更に好ましい。 硬化 The curable composition of the present invention preferably contains 50 to 200 parts by mass of the photopolymerization initiator A2 based on 100 parts by mass of the photopolymerization initiator A1. The upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less, from the viewpoint of miniaturization of the pattern after development. The lower limit is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, from the viewpoint of the solvent resistance of the obtained cured film.
　本発明の硬化性組成物の全固形分中における光重合開始剤Ａ１と光重合開始剤Ａ２との合計の含有量は、５～１５質量％以上であることが好ましい。組成物の経時安定性の観点から下限は、６質量％以上であることが好ましく、７質量％以上であることがより好ましく、８質量％以上であることが更に好ましい。現像後のパターンの微細化の観点から上限は、１４．５質量％以下であることが好ましく、１４．０質量％以下であることがより好ましく、１３．０質量％以下であることが更に好ましい。 合計 The total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the curable composition of the present invention is preferably 5 to 15% by mass or more. From the viewpoint of the stability over time of the composition, the lower limit is preferably 6% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more. The upper limit is preferably 14.5% by mass or less, more preferably 14.0% by mass or less, and still more preferably 13.0% by mass or less, from the viewpoint of miniaturization of the pattern after development. .
　本発明の硬化性組成物は、光重合開始剤として光重合開始剤Ａ１および光重合開始剤Ａ２以外の光重合開始剤（以下、他の光重合開始剤ともいう）を含有することもできるが、他の光重合開始剤は実質的に含有しないことが好ましい。他の光重合開始剤を実質的に含有しない場合とは、他の光重合開始剤の含有量が、光重合開始剤Ａ１と光重合開始剤Ａ２との合計１００質量部に対して１質量部以下であることが好ましく、０．５質量部以下であることがより好ましく、０．１質量部以下であることが更に好ましく、他の光重合開始剤を含有しないことが一層好ましい。 The curable composition of the present invention can contain a photopolymerization initiator other than the photopolymerization initiator A1 and the photopolymerization initiator A2 (hereinafter, also referred to as another photopolymerization initiator) as a photopolymerization initiator. It is preferable that other photopolymerization initiators are not substantially contained. The case where the other photopolymerization initiator is not substantially contained means that the content of the other photopolymerization initiator is 1 part by mass with respect to 100 parts by mass in total of the photopolymerization initiator A1 and the photopolymerization initiator A2. It is preferably at most 0.5 part by mass, more preferably at most 0.5 part by mass, even more preferably at most 0.1 part by mass, and even more preferably not containing other photopolymerization initiator.
＜＜樹脂＞＞
　本発明の組成物は、樹脂を含有することができる。本発明において樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。 << Resin >>
The composition of the present invention can contain a resin. In the present invention, the resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition or for the purpose of a binder. Note that a resin mainly used for dispersing particles such as a pigment is also referred to as a dispersant. However, such a use of the resin is an example, and the resin may be used for a purpose other than the use.
　樹脂の重量平均分子量（Ｍｗ）は、２,０００～２,０００,０００が好ましい。上限は、１,０００,０００以下が好ましく、５００,０００以下がより好ましい。下限は、３,０００以上が好ましく、５,０００以上がより好ましい。 The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.
　樹脂としては、（メタ）アクリル樹脂、エポキシ樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂などが挙げられる。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。環状オレフィン樹脂としては、耐熱性向上の観点からノルボルネン樹脂が好ましく用いることができる。ノルボルネン樹脂の市販品としては、例えば、ＪＳＲ（株）製のＡＲＴＯＮシリーズ（例えば、ＡＲＴＯＮ　Ｆ４５２０）などが挙げられる。エポキシ樹脂としては、例えばフェノール化合物のグリシジルエーテル化物であるエポキシ樹脂、各種ノボラック樹脂のグリシジルエーテル化物であるエポキシ樹脂、脂環式エポキシ樹脂、脂肪族系エポキシ樹脂、複素環式エポキシ樹脂、グリシジルエステル系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、ハロゲン化フェノール類をグリシジル化したエポキシ樹脂、エポキシ基をもつケイ素化合物とそれ以外のケイ素化合物との縮合物、エポキシ基を持つ重合性不飽和化合物とそれ以外の他の重合性不飽和化合物との共重合体等が挙げられる。また、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（日油（株）製、エポキシ基含有ポリマー）などを用いることもできる。また、樹脂は、国際公開第２０１６／０８８６４５号の実施例に記載された樹脂、特開２０１７－０５７２６５号公報に記載された樹脂、特開２０１７－０３２６８５号公報に記載された樹脂、特開２０１７－０７５２４８号公報に記載された樹脂、特開２０１７－０６６２４０号公報に記載された樹脂を用いることもでき、これらの内容は本明細書に組み込まれる。また、フルオレン骨格を有する樹脂を好ましく用いることもできる。フルオレン骨格を有する樹脂としては、下記構造の樹脂が挙げられる。以下の構造式中、Ａは、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物およびジフェニルエーテルテトラカルボン酸二無水物から選択されるカルボン酸二無水物の残基であり、Ｍはフェニル基またはベンジル基である。フルオレン骨格を有する樹脂については、米国特許出願公開第２０１７／０１０２６１０号明細書の記載を参酌でき、この内容は本明細書に組み込まれる。 As the resin, (meth) acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Examples thereof include a polyamideimide resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, and a styrene resin. One of these resins may be used alone, or two or more thereof may be used in combination. As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improving heat resistance. Examples of commercially available norbornene resin include ARTON series (for example, ARTON @ F4520) manufactured by JSR Corporation. Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester resin. Epoxy resin, glycidylamine-based epoxy resin, epoxy resin obtained by glycidylation of halogenated phenols, condensate of silicon compound with epoxy group and other silicon compound, polymerizable unsaturated compound with epoxy group and other Copolymers with other polymerizable unsaturated compounds and the like can be mentioned. Also, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation) , An epoxy group-containing polymer) and the like. In addition, resins described in Examples of International Publication WO 2016/088865, resins described in JP-A-2017-057265, resins described in JP-A-2017-032685, A resin described in JP-A-0-75248 and a resin described in JP-A-2017-066240 can also be used, and the contents thereof are incorporated herein. Further, a resin having a fluorene skeleton can be preferably used. Examples of the resin having a fluorene skeleton include a resin having the following structure. In the following structural formula, A is a residue of a carboxylic acid dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride. And M is a phenyl or benzyl group. Regarding the resin having a fluorene skeleton, the description in U.S. Patent Application Publication No. 2017/0102610 can be referred to, and the contents thereof are incorporated herein.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　本発明で用いる樹脂は、酸基を有していてもよい。酸基としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシル基などが挙げられ、カルボキシル基が好ましい。これら酸基は、１種のみであってもよいし、２種以上であってもよい。酸基を有する樹脂はアルカリ可溶性樹脂として用いることもできる。 樹脂 The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group, and a carboxyl group is preferable. These acid groups may be used alone or in combination of two or more. The resin having an acid group can be used as an alkali-soluble resin.
　酸基を有する樹脂としては、側鎖にカルボキシル基を有するポリマーが好ましい。具体例としては、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、ノボラック樹脂などのアルカリ可溶性フェノール樹脂、側鎖にカルボキシル基を有する酸性セルロース誘導体、ヒドロキシル基を有するポリマーに酸無水物を付加させた樹脂が挙げられる。特に、（メタ）アクリル酸と、これと共重合可能な他のモノマーとの共重合体が、アルカリ可溶性樹脂として好適である。（メタ）アクリル酸と共重合可能な他のモノマーとしては、アルキル（メタ）アクリレート、アリール（メタ）アクリレート、ビニル化合物などが挙げられる。アルキル（メタ）アクリレートおよびアリール（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、ナフチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等、ビニル化合物としては、スチレン、α－メチルスチレン、ビニルトルエン、グリシジルメタクリレート、アクリロニトリル、ビニルアセテート、Ｎ－ビニルピロリドン、テトラヒドロフルフリルメタクリレート、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等が挙げられる。また他のモノマーは、特開平１０－３００９２２号公報に記載のＮ位置換マレイミドモノマー、例えば、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等を用いることもできる。なお、これらの（メタ）アクリル酸と共重合可能な他のモノマーは１種のみであってもよいし、２種以上であってもよい。 As the resin having a diacid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples include alkali-soluble polymers such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins. Examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, and cyclohexyl (meth) acrylate include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used. The other monomer copolymerizable with the (meth) acrylic acid may be only one kind or two or more kinds.
　酸基を有する樹脂は、更に重合性基を有していてもよい。重合性基としては、アリル基、メタリル基、（メタ）アクリロイル基等が挙げられる。市販品としては、ダイヤナールＮＲシリーズ（三菱レイヨン（株）製）、Ｐｈｏｔｏｍｅｒ６１７３（カルボキシル基含有ポリウレタンアクリレートオリゴマー、Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．，Ｌｔｄ．製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業株式会社製）、サイクロマーＰシリーズ（例えば、ＡＣＡ２３０ＡＡ）、プラクセル　ＣＦ２００シリーズ（いずれも（株）ダイセル製）、Ｅｂｅｃｒｙｌ３８００（ダイセルユーシービー（株）製）、アクリキュアーＲＤ－Ｆ８(（株）日本触媒製)などが挙げられる。 The resin having a diacid group may further have a polymerizable group. Examples of the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group. Commercial products include Dianar NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, and KS Resist 106 (all of Osaka Organic Chemicals, Inc.) Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel @ CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Accrecur RD-F8 (Co., Ltd.) Nippon Shokubai).
　酸基を有する樹脂は、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／２－ヒドロキシエチル（メタ）アクリレート共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好ましく用いることができる。また、２－ヒドロキシエチル（メタ）アクリレートを共重合したもの、特開平０７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体なども好ましく用いることができる。 Resins having an acid group include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multi-component copolymer composed of acrylate / (meth) acrylic acid / other monomer can be preferably used. Also, copolymers of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, described in JP-A-07-140654. -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.
　酸基を有する樹脂は、下記式（ＥＤ１）で示される化合物および／または下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）を含むモノマー成分に由来する繰り返し単位を含むポリマーであることも好ましい。 The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferable that the polymer contains a repeating unit derived from a component.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（ＥＤ１）中、Ｒ1およびＲ2は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。 In the formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の詳細については、特開２０１０－１６８５３９号公報の記載を参酌できる。 ＲIn the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), the description in JP-A-2010-168538 can be referred to.
　エーテルダイマーの具体例としては、例えば、特開２０１３－０２９７６０号公報の段落０３１７を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。 As a specific example of the ether dimer, for example, paragraph 0317 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated herein. The ether dimer may be only one kind or two or more kinds.
　酸基を有する樹脂は、下記式（Ｘ）で示される化合物に由来する繰り返し単位を含んでいてもよい。
Figure JPOXMLDOC01-appb-C000016
 The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000016
　式（Ｘ）において、Ｒ1は、水素原子またはメチル基を表し、Ｒ2は炭素数２～１０のアルキレン基を表し、Ｒ3は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 In the formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a carbon atom having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.
　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。例えば、アクリベースＦＦ－４２６（藤倉化成（株）製）などが挙げられる。 The resin having an acid group is described in paragraphs 0558 to 0571 of JP-A-2012-208494 (paragraphs 0885 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) and JP-A-2012-198408. Can be referred to, and the contents thereof are incorporated in the present specification. A commercially available resin can be used as the resin having an acid group. For example, Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.) and the like can be mentioned.
　酸基を有する樹脂の酸価は、３０～２００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上が好ましく、７０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、１５０ｍｇＫＯＨ／ｇ以下が好ましく、１２０ｍｇＫＯＨ／ｇ以下がより好ましい。 The acid value of the resin having an acid group is preferably from 30 to 200 mgKOH / g. The lower limit is preferably at least 50 mgKOH / g, more preferably at least 70 mgKOH / g. The upper limit is preferably equal to or less than 150 mgKOH / g, and more preferably equal to or less than 120 mgKOH / g.
　酸基を有する樹脂としては、例えば下記構造の樹脂などが挙げられる。以下の構造式中、Ｍｅはメチル基を表す。
Figure JPOXMLDOC01-appb-C000017
 Examples of the resin having an acid group include a resin having the following structure. In the following structural formulas, Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000017
　本発明の組成物は、分散剤としての樹脂を含むこともできる。分散剤は、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシル基が好ましい。酸性分散剤（酸性樹脂）の酸価は、４０～１０５ｍｇＫＯＨ／ｇが好ましく、５０～１０５ｍｇＫＯＨ／ｇがより好ましく、６０～１０５ｍｇＫＯＨ／ｇがさらに好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基であることが好ましい。 組成 The composition of the present invention can also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of an acid group is larger than the amount of a basic group. The acid dispersant (acidic resin) is preferably a resin in which the amount of the acid group accounts for 70 mol% or more when the total amount of the acid group and the basic group is 100 mol%. More preferred are resins consisting only of groups. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably from 40 to 105 mgKOH / g, more preferably from 50 to 105 mgKOH / g, even more preferably from 60 to 105 mgKOH / g. The basic dispersant (basic resin) refers to a resin in which the amount of the basic group is larger than the amount of the acid group. The basic dispersant (basic resin) is preferably a resin in which the amount of the basic group exceeds 50 mol% when the total amount of the acid group and the amount of the basic group is 100 mol%. The basic group of the basic dispersant is preferably an amino group.
　分散剤として用いる樹脂は、酸基を有する繰り返し単位を含むことが好ましい。分散剤として用いる樹脂が酸基を有する繰り返し単位を含むことにより、フォトリソグラフィ法によりパターン形成する際、画素の下地に発生する残渣をより低減することができる。 樹脂 The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, residues generated on the base of the pixel can be further reduced when a pattern is formed by a photolithography method.
　分散剤として用いる樹脂は、グラフト共重合体であることも好ましい。グラフト共重合体は、グラフト鎖によって溶剤との親和性を有するために、顔料の分散性、及び、経時後の分散安定性に優れる。グラフト共重合体の詳細は、特開２０１２－２５５１２８号公報の段落００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。また、グラフト共重合体の具体例は、下記の樹脂が挙げられる。以下の樹脂は酸基を有する樹脂（アルカリ可溶性樹脂）でもある。また、グラフト共重合体としては特開２０１２－２５５１２８号公報の段落００７２～００９４に記載の樹脂が挙げられ、この内容は本明細書に組み込まれる。 樹脂 The resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for a solvent due to the graft chain, the dispersibility of the pigment and the dispersion stability after aging are excellent. The details of the graft copolymer can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein. Further, specific examples of the graft copolymer include the following resins. The following resins are also resins having an acid group (alkali-soluble resins). Further, examples of the graft copolymer include resins described in paragraphs 0072 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　また、本発明において、樹脂（分散剤）は、主鎖及び側鎖の少なくとも一方に窒素原子を含むオリゴイミン系分散剤を用いることも好ましい。オリゴイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造Ｘを有する構造単位と、原子数４０～１０，０００の側鎖Ｙを含む側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子とは、塩基性を呈する窒素原子であれば特に制限はない。オリゴイミン系分散剤については、特開２０１２－２５５１２８号公報の段落０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。オリゴイミン系分散剤としては、下記構造の樹脂や、特開２０１２－２５５１２８号公報の段落０１６８～０１７４に記載の樹脂を用いることができる。 In the present invention, it is also preferable to use an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain as the resin (dispersant). The oligoimine-based dispersant includes a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain including a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain. Resins having a basic nitrogen atom on at least one side are preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the oligoimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein. As the oligoimine-based dispersant, a resin having the following structure or a resin described in paragraphs 0168 to 0174 of JP-A-2012-255128 can be used.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　分散剤は、市販品としても入手可能であり、そのような具体例としては、Ｄｉｓｐｅｒｂｙｋ－１１１（ＢＹＫＣｈｅｍｉｅ社製）、ソルスパース７６５００（日本ルーブリゾール（株）製）などが挙げられる。また、特開２０１４－１３０３３８号公報の段落００４１～０１３０に記載された顔料分散剤を用いることもでき、この内容は本明細書に組み込まれる。また、上述した酸基を有する樹脂などを分散剤として用いることもできる。 The dispersant is also available as a commercial product, and specific examples of such a dispersant include Disperbyk-111 (manufactured by BYK Chemie), Solsperse 76500 (manufactured by Nippon Lubrizol Co., Ltd.), and the like. Further, pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated herein. Further, the above-mentioned resin having an acid group can be used as a dispersant.
　その他、特開２０１７－２０６６８９号公報の段落００４１～００６０に記載の樹脂も好適に使用することができる。 In addition, resins described in paragraphs 0041 to 0060 of JP-A-2017-206689 can also be suitably used.
　樹脂の含有量は、本発明の組成物の全固形分に対し、１～５０質量％が好ましい。下限は、２質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上が更に好ましく、１０質量％以上が特に好ましい。上限は、４０質量％以下がより好ましく、３０質量％以下が更に好ましい。また、酸基を有する樹脂の含有量は、本発明の組成物の全固形分に対し、１～５０質量％が好ましい。下限は、２質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上が更に好ましく、１０質量％以上が特に好ましい。上限は、４０質量％以下がより好ましく、３０質量％以下が更に好ましい。本発明の組成物は、樹脂を、１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the resin is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less. Further, the content of the resin having an acid group is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less. The composition of the present invention may include only one type of resin, or may include two or more types of resins. When two or more kinds are contained, the total amount thereof is preferably within the above range.
＜＜フリル基含有化合物＞＞
　本発明の硬化性組成物は、フリル基を含む化合物（以下、フリル基含有化合物ともいう）を含有することが好ましい。この態様によれば、上記フリル基と、上記重合性化合物が有するエチレン性不飽和基とが、Ｄｉｅｌｓ－Ａｌｄｅｒ反応により、２００℃未満の低温でも結合を形成するため、低温硬化に優れる。 << Frill group-containing compound >>
The curable composition of the present invention preferably contains a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound). According to this aspect, the furyl group and the ethylenically unsaturated group of the polymerizable compound form a bond by the Diels-Alder reaction even at a low temperature of less than 200 ° C., and thus are excellent in low-temperature curing.
　フリル基含有化合物は、フリル基（フランから１つの水素原子を除いた基）を含んでいれば特にその構造が限定されるものではない。フリル基含有化合物については、特開２０１７－１９４６６２号公報の段落００４９～００８９に記載された化合物を用いることができる。また、特開２０００－２３３５８１号公報、特開１９９４－２７１５５８号公報、特開１９９４－２９３８３０号公報、特開１９９６－２３９４２１号公報、特開１９９８－５０８６５５号公報、特開２０００－００１５２９号公報、特開２００３－１８３３４８号公報、特開２００６－１９３６２８号公報、特開２００７－１８６６８４号公報、特開２０１０－２６５３７７号公報、特開２０１１－１７００６９号公報などに記載されている化合物を用いることもできる。 構造 The structure of the furyl group-containing compound is not particularly limited as long as it contains a furyl group (a group obtained by removing one hydrogen atom from furan). As the furyl group-containing compound, the compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used. Also, JP-A-2000-233581, JP-A-1994-271558, JP-A-1994-293830, JP-A-1996-239421, JP-A-1998-508655, JP-A-2000-001529, Compounds described in JP-A-2003-183348, JP-A-2006-193628, JP-A-2007-186684, JP-A-2010-265377, JP-A-2011-170069 and the like can also be used. it can.
　フリル基含有化合物は、モノマーであってもよく、オリゴマー、ポリマーであってもよい。得られる膜の耐久性を向上させやすいという理由からポリマーであることが好ましい。ポリマーの場合、重量平均分子量は、２０００～７００００が好ましい。上限は、６００００以下が好ましく、５００００以下がより好ましい。下限は、３０００以上が好ましく、４０００以上がより好ましく、５０００以上が更に好ましい。モノマーの場合、重量平均分子量は、２０００未満が好ましい。なお、ポリマータイプのフリル基含有化合物は、本発明の硬化性組成物における樹脂にも該当する成分であり、モノマータイプのフリル基含有化合物は、本発明の硬化性組成物における重合性化合物にも該当する成分である。 The difuryl group-containing compound may be a monomer, an oligomer, or a polymer. The polymer is preferably used because it is easy to improve the durability of the obtained film. In the case of a polymer, the weight average molecular weight is preferably from 2000 to 70000. The upper limit is preferably 60,000 or less, more preferably 50,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more. In the case of a monomer, the weight average molecular weight is preferably less than 2000. Incidentally, the polymer type furyl group-containing compound is a component corresponding to the resin in the curable composition of the present invention, and the monomer type furyl group-containing compound is also a polymerizable compound in the curable composition of the present invention. The corresponding component.
　モノマータイプのフリル基含有化合物（以下、フリル基含有モノマーともいう）としては、下記式（ｆｕｒ－１）で表される化合物が挙げられる。この化合物は、フリル基に加えて、重合性基も有する化合物である。 Examples of the monomer type furyl group-containing compound (hereinafter, also referred to as a furyl group-containing monomer) include compounds represented by the following formula (fur-1). This compound has a polymerizable group in addition to the furyl group.
式（ｆｕｒ－１）
Figure JPOXMLDOC01-appb-C000020
 Equation (fur-1)
Figure JPOXMLDOC01-appb-C000020
　式中、Ｒｆ1は水素原子またはメチル基を表し、Ｒｆ2は２価の連結基を表す。 In the formula, Rf 1 represents a hydrogen atom or a methyl group, and Rf 2 represents a divalent linking group.
　Ｒｆ2が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシル基などが挙げられる。 Examples of the divalent linking group represented by Rf 2 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups. The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be linear, branched or cyclic. The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group.
　フリル基含有モノマーは、下記式（ｆｕｒ－２）で表される化合物であることが好ましい。 The furyl group-containing monomer is preferably a compound represented by the following formula (fur-2).
式（ｆｕｒ－２）
Figure JPOXMLDOC01-appb-C000021
 Formula (fur-2)
Figure JPOXMLDOC01-appb-C000021
　式中、Ｒｆ1は水素原子またはメチル基を表し、Ｒｆ11は－Ｏ－または－ＮＨ－を表し、Ｒｆ12は単結合または２価の連結基を表す。Ｒｆ12が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシル基などが挙げられる。 In the formula, Rf 1 represents a hydrogen atom or a methyl group, Rf 11 represents —O— or —NH—, and Rf 12 represents a single bond or a divalent linking group. Examples of the divalent linking group represented by Rf 12 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups. The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be linear, branched or cyclic. The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxyl group.
　フリル基含有モノマーの具体例としては、下記構造の化合物が挙げられる。以下の構造式中、Ｒｆ1は水素原子またはメチル基を表す。 Specific examples of the furyl group-containing monomer include a compound having the following structure. In the following structural formula, Rf 1 represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　ポリマータイプのフリル基含有化合物（以下、フリル基含有ポリマーともいう）としては、フリル基を含む繰り返し単位を含む樹脂であることが好ましく、上記式（ｆｕｒ－１）で表される化合物由来の繰り返し単位を含む樹脂であることがより好ましい。フリル基含有ポリマー中のフリル基の濃度は、フリル基含有ポリマー１ｇあたり０．５～６．０ｍｍｏｌが好ましく、１．０～４．０ｍｍｏｌがさらに好ましい。フリル基の濃度が０．５ｍｍｏｌ以上、好ましくは１．０ｍｍｏｌ以上であると耐溶剤性などにより優れた画素を形成しやすい。フリル基の濃度が６．０ｍｍｏｌ以下、好ましくは４．０ｍｍｏｌ以下であれば、硬化性組成物の経時安定性がより良好である。 The polymer type furyl group-containing compound (hereinafter also referred to as a furyl group-containing polymer) is preferably a resin containing a repeating unit containing a furyl group, and is preferably a resin derived from the compound represented by the above formula (fur-1). More preferably, the resin contains units. The concentration of the furyl group in the furyl group-containing polymer is preferably 0.5 to 6.0 mmol, more preferably 1.0 to 4.0 mmol, per 1 g of the furyl group-containing polymer. When the concentration of the furyl group is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form a pixel having excellent solvent resistance and the like. If the concentration of the furyl group is 6.0 mmol or less, preferably 4.0 mmol or less, the curable composition has better stability over time.
　フリル基含有ポリマーは、フリル基を有する繰り返し単位の他に、酸基を有する繰り返し単位および／または重合性基を有する繰り返し単位を含んでいてもよい。酸基としては、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシル基などが挙げられる。重合性基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基等のエチレン性不飽和基が挙げられる。フリル基含有ポリマーが酸基を有する繰り返し単位を含む場合、その酸価は１０～２００ｍｇＫＯＨ／ｇが好ましく、４０～１３０ｍｇＫＯＨ／ｇがより好ましい。 The furyl group-containing polymer may contain a repeating unit having an acid group and / or a repeating unit having a polymerizable group in addition to the repeating unit having a furyl group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group. Examples of the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. When the furyl group-containing polymer contains a repeating unit having an acid group, its acid value is preferably from 10 to 200 mgKOH / g, more preferably from 40 to 130 mgKOH / g.
　フリル基含有ポリマーが重合性基を有する繰り返し単位を含む場合は、より耐溶剤性などに優れた画素を形成しやすい。 When the furyl group-containing polymer contains a repeating unit having a polymerizable group, it is easy to form a pixel having more excellent solvent resistance and the like.
　フリル基含有ポリマーは、特開２０１７－１９４６６２号公報の段落００５２～０１０１に記載された方法で製造することができる。 The furyl group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP-A-2017-194662.
　フリル基含有化合物の含有量は、硬化性組成物の全固形分中０．１～７０質量％であることが好ましい。下限は、２．５質量％以上であることが好ましく、５．０質量％以上であることがより好ましく、７．５質量％以上であることが更に好ましい。上限は、６５質量％以下であることが好ましく、６０質量％以下であることがより好ましく、５０質量％以下であることが更に好ましい。 The content of the furyl group-containing compound is preferably 0.1 to 70% by mass based on the total solid content of the curable composition. The lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and even more preferably 7.5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
　また、フリル基含有化合物としてフリル基含有ポリマーを用いた場合、硬化性組成物に含まれる樹脂中におけるフリル基含有ポリマーの含有量は、０．１～１００質量％であることが好ましい。下限は、１０質量％以上であることが好ましく、１５質量％以上であることがより好ましい。上限は、９０質量％以下であることが好ましく、８０質量％以下であることがより好ましい。 When a furyl group-containing polymer is used as the furyl group-containing compound, the content of the furyl group-containing polymer in the resin contained in the curable composition is preferably 0.1 to 100% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
＜＜環状エーテル基を有する化合物＞＞
　本発明の硬化性組成物は、更に、環状エーテル基を有する化合物を含有することができる。また、この場合、本発明の硬化性組成物は、この環状エーテル基を有する化合物の硬化促進剤を含有することが好ましい。環状エーテル基は、例えば、エポキシ基およびオキセタン基であり、エポキシ基が好ましい。 << compound having a cyclic ether group >>
The curable composition of the present invention can further contain a compound having a cyclic ether group. In this case, the curable composition of the present invention preferably contains a curing accelerator for the compound having a cyclic ether group. The cyclic ether group is, for example, an epoxy group and an oxetane group, and an epoxy group is preferable.
　エポキシ基を有する化合物としては、１分子内にエポキシ基を２つ以上有する化合物が好ましい。エポキシ基は、１分子内に２～１００個有することが好ましい。上限は、例えば、１０個以下とすることもでき、５個以下とすることもできる。エポキシ基を有する化合物のエポキシ当量（＝エポキシ基を有する化合物の分子量／エポキシ基の数）は、５００ｇ／ｅｑ以下であることが好ましく、１００～４００ｇ／ｅｑであることがより好ましく、１００～３００ｇ／ｅｑであることがさらに好ましい。エポキシ基を有する化合物は、低分子化合物（例えば、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）のいずれでもよい。エポキシ基を有する化合物の分子量（ポリマーの場合は、重量平均分子量）は、２００～１０００００が好ましく、５００～５００００がより好ましい。分子量（ポリマーの場合は、重量平均分子量）の上限は、３０００以下が好ましく、２０００以下がより好ましく、１５００以下が更に好ましい。なお、環状エーテル基を有する化合物がポリマータイプである場合には、この化合物は、本発明の硬化性組成物における樹脂にも該当する成分である。 化合物 As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. The epoxy group preferably has 2 to 100 epoxy groups in one molecule. The upper limit can be, for example, 10 or less, or 5 or less. The epoxy equivalent of the compound having an epoxy group (= the molecular weight of the compound having an epoxy group / the number of epoxy groups) is preferably 500 g / eq or less, more preferably 100 to 400 g / eq, and more preferably 100 to 300 g. / Eq is more preferable. The compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (a macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). . The molecular weight (weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000. The upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less. When the compound having a cyclic ether group is a polymer type, this compound is a component corresponding to the resin in the curable composition of the present invention.
　エポキシ基を有する化合物としては、特開２０１３－０１１８６９号公報の段落００３４～００３６、特開２０１４－０４３５５６号公報の段落０１４７～０１５６、特開２０１４－０８９４０８号公報の段落００８５～００９２に記載された化合物、特開２０１７－１７９１７２号公報に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。 Compounds having an epoxy group are described in paragraphs 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408. Compounds and compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.
　環状エーテル基を有する化合物の市販品としては、例えば、ＥＨＰＥ３１５０（（株）ダイセル製）、ＥＰＩＣＬＯＮ　Ｎ－６９５（ＤＩＣ（株）製）、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（以上、日油（株）製、エポキシ基含有ポリマー）等が挙げられる。 Commercially available compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON @ N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (both manufactured by NOF Corporation, epoxy group-containing polymer) and the like.
　本発明の組成物が、環状エーテル基を有する化合物を含有する場合、この化合物の含有量は、組成物の全固形分中０．１～２０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、１５質量％以下がより好ましく、１０質量％以下が更に好ましい。環状エーテル基を有する化合物は、１種単独であってもよいし、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲となることが好ましい。 場合 When the composition of the present invention contains a compound having a cyclic ether group, the content of the compound is preferably 0.1 to 20% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably equal to or less than 15% by mass, and still more preferably equal to or less than 10% by mass. The compound having a cyclic ether group may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
　また、環状エーテル基を有する化合物の硬化促進剤は、後述する硬化促進剤の中でも、特に、エポキシ化合物用の硬化促進剤として一般的に使用されている化合物を使用でき、例えば、酸無水物、アミン、カルボン酸およびアルコールなどが好ましい。 Further, as the curing accelerator of the compound having a cyclic ether group, among the curing accelerators described below, in particular, a compound generally used as a curing accelerator for an epoxy compound can be used, for example, acid anhydride, Amines, carboxylic acids and alcohols are preferred.
　硬化促進剤としての酸無水物は、例えば、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、２，４－ジエチル無水グルタル酸、ブタンテトラカルボン酸無水物、ビシクロ［２，２，１］ヘプタン－２，３－ジカルボン酸無水物、メチルビシクロ［２，２，１］ヘプタン－２，３－ジカルボン酸無水物、シクロヘキサン－１，３，４－トリカルボン酸－３，４－無水物等が、耐光性、透明性、作業性の観点から好ましい。 Acid anhydrides as curing accelerators include, for example, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, 2,4-diethyl glutaric anhydride, butane tetra Carboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3 4-Tricarboxylic acid-3,4-anhydride and the like are preferred from the viewpoints of light resistance, transparency and workability.
　硬化促進剤としてのカルボン酸は、２～６官能のカルボン酸が好ましい。このようなカルボン酸は、例えば、１，２，３，４－ブタンテトラカルボン酸、１，２，３－プロパントリカルボン酸、１，３，５－ペンタントリカルボン酸、クエン酸等のアルキルトリカルボン酸類；フタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、シクロヘキサントリカルボン酸、ナジック酸、メチルナジック酸等の脂肪族環状多価カルボン酸類；リノレン酸やオレイン酸などの不飽和脂肪酸の多量体およびそれらの還元物であるダイマー酸類；リンゴ酸等の直鎖アルキル二酸類等が好ましく、さらにはヘキサン二酸、ペンタン二酸、ヘプタン二酸、オクタン二酸、ノナン二酸、デカン二酸が好ましく、特にブタン二酸が、耐熱性、膜の透明性の観点からより好ましい。 カ ル ボ ン The carboxylic acid as a curing accelerator is preferably a di- to hexa-functional carboxylic acid. Such carboxylic acids include, for example, alkyltricarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid and citric acid; Aliphatic cyclic polycarboxylic acids such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid, nadic acid and methylnadic acid; linolenic acid and oleic acid Dimer acids which are multimers of unsaturated fatty acids and their reduced products; linear alkyl diacids such as malic acid and the like are preferable, and hexane diacid, pentanedioic acid, heptane diacid, octane diacid, nonanedioic acid and the like are preferable. And decandioic acid are preferred, and butanedioic acid is more preferred from the viewpoint of heat resistance and film transparency. There.
　硬化促進剤としてのアミンは、多価アミンが好ましく、ジアミンがより好ましい。このようなアミンは、例えば、ヘキサメチレンジアミン、トリエチレンテトラミン、ポリエチレンイミンなどである。 ア ミ ン The amine as the curing accelerator is preferably a polyvalent amine, and more preferably a diamine. Such amines are, for example, hexamethylenediamine, triethylenetetramine, polyethyleneimine and the like.
　硬化促進剤としてのアルコールは、多価アルコールが好ましく、ジオールがより好ましい。このようなアルコールは、例えば、ポリエーテルジオール化合物、ポリエステルジオール化合物、ポリカーボネートジオール化合物等である。 ア ル コ ー ル Alcohols as curing accelerators are preferably polyhydric alcohols, more preferably diols. Such alcohols are, for example, polyether diol compounds, polyester diol compounds, polycarbonate diol compounds and the like.
　そのほか、上記のような硬化促進剤として、特許第５７６５０５９号公報の段落００８５～００９２に記載の反応促進剤を使用してもよい。 In addition, as the above-mentioned curing accelerator, a reaction accelerator described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059 may be used.
　本発明の組成物が、上記硬化促進剤を含有する場合、この硬化促進剤の含有量は、環状エーテル基を有する化合物１００質量部に対して、１～３０質量部が好ましく、５～２５質量部がより好ましく、１０～２０質量部がさらに好ましい。上記硬化促進剤は、１種単独であってもよいし、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲となることが好ましい。 When the composition of the present invention contains the above curing accelerator, the content of the curing accelerator is preferably 1 to 30 parts by mass, and more preferably 5 to 25 parts by mass based on 100 parts by mass of the compound having a cyclic ether group. Part by mass, more preferably 10 to 20 parts by mass. The curing accelerators may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
＜＜溶剤＞＞
　本発明の硬化性組成物は、溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤は、各成分の溶解性や硬化性組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第２０１５／１６６７７９号の段落０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドなどが挙げられる。ただし溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 << Solvent >>
The curable composition of the present invention preferably contains a solvent. Examples of the solvent include an organic solvent. The solvent is basically not particularly limited as long as the solubility of each component and the coatability of the curable composition are satisfied. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For details thereof, paragraph 0223 of WO 2015/166779 can be referred to, and the contents thereof are incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for environmental reasons or the like (for example, 50 ppm by mass (parts per part with respect to the total amount of the organic solvent). (million) or less, 10 mass ppm or less, or 1 mass ppm or less).
　本発明においては、金属含有量の少ない溶剤を用いることが好ましく、溶剤の金属含有量は、例えば１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの溶剤を用いてもよく、そのような高純度溶剤は例えば東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。 に お い て In the present invention, it is preferable to use a solvent having a low metal content, and it is preferable that the metal content of the solvent be, for example, 10 mass ppb (parts per per billion) or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
　溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 方法 Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one isomer may be contained, or a plurality of isomers may be contained.
　本発明において、有機溶剤中の過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 に お い て In the present invention, the content of the peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide.
　硬化性組成物中における溶剤の含有量は、６０～９５質量％であることが好ましい。上限は９０質量％以下であることが好ましく、８７．５質量％以下であることがより好ましく、８５質量％以下であることが更に好ましい。下限は、６５質量％以上であることが好ましく、７０質量％以上であることがより好ましく、７５質量％以上であることが更に好ましい。 溶 剤 The content of the solvent in the curable composition is preferably from 60 to 95% by mass. The upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and even more preferably 85% by mass or less. The lower limit is preferably at least 65% by mass, more preferably at least 70% by mass, even more preferably at least 75% by mass.
　また、本発明の硬化性組成物は、環境規制の観点から環境規制物質を実質的に含有しないことが好ましい。なお、本発明において、環境規制物質を実質的に含有しないとは、硬化性組成物中における環境規制物質の含有量が５０質量ｐｐｍ以下であることを意味し、３０質量ｐｐｍ以下であることが好ましく、１０質量ｐｐｍ以下であることが更に好ましく、１質量ｐｐｍ以下であることが特に好ましい。環境規制物質は、例えばベンゼン；トルエン、キシレン等のアルキルベンゼン類；クロロベンゼン等のハロゲン化ベンゼン類等が挙げられる。これらは、ＲＥＡＣＨ（Ｒｅｇｉｓｔｒａｔｉｏｎ　Ｅｖａｌｕａｔｉｏｎ　Ａｕｔｈｏｒｉｚａｔｉｏｎ　ａｎｄ　Ｒｅｓｔｒｉｃｔｉｏｎ　ｏｆ　ＣＨｅｍｉｃａｌｓ）規則、ＰＲＴＲ（Ｐｏｌｌｕｔａｎｔ　Ｒｅｌｅａｓｅ　ａｎｄ　Ｔｒａｎｓｆｅｒ　Ｒｅｇｉｓｔｅｒ）法、ＶＯＣ（Ｖｏｌａｔｉｌｅ　Ｏｒｇａｎｉｃ　Ｃｏｍｐｏｕｎｄｓ）規制等のもとに環境規制物質として登録されており、使用量や取り扱い方法が厳しく規制されている。これらの化合物は、本発明の硬化性組成物に用いられる各成分などを製造する際に溶媒として用いられることがあり、残留溶媒として硬化性組成物中に混入することがある。人への安全性、環境への配慮の観点よりこれらの物質は可能な限り低減することが好ましい。環境規制物質を低減する方法としては、系中を加熱や減圧して環境規制物質の沸点以上にして系中から環境規制物質を留去して低減する方法が挙げられる。また、少量の環境規制物質を留去する場合においては、効率を上げる為に該当溶媒と同等の沸点を有する溶媒と共沸させることも有用である。また、ラジカル重合性を有する化合物を含有する場合、減圧留去中にラジカル重合反応が進行して分子間で架橋してしまうことを抑制するために重合禁止剤等を添加して減圧留去してもよい。これらの留去方法は、原料の段階、原料を反応させた生成物（例えば重合した後の樹脂溶液や多官能モノマー溶液）の段階、またはこれらの化合物を混ぜて作製した硬化性組成物の段階いずれの段階でも可能である。 硬化 In addition, it is preferable that the curable composition of the present invention does not substantially contain an environmental regulation substance from the viewpoint of environmental regulation. In the present invention, the term "substantially not containing an environmental control substance" means that the content of the environmental control substance in the curable composition is 50 mass ppm or less, and 30 mass ppm or less. It is more preferably at most 10 ppm by mass, particularly preferably at most 1 ppm by mass. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are regulated by REACH (Registration, Evaluation, Authorization, Restriction, of Chemicals) rules, PRTR (Pollutant Release, Transfer and Register), VOC (Volatile, Regulated, etc.) The method is strictly regulated. These compounds may be used as a solvent when producing each component used in the curable composition of the present invention, and may be mixed into the curable composition as a residual solvent. It is preferable to reduce these substances as much as possible from the viewpoint of human safety and environmental considerations. As a method of reducing the amount of environmentally controlled substances, there is a method of heating or reducing the pressure in the system to make the temperature equal to or higher than the boiling point of the environmentally controlled substances and distilling and reducing the environmentally controlled substances from the system. When a small amount of environmentally regulated substances are distilled off, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency. When a compound having a radical polymerizability is contained, a polymerization inhibitor or the like is added in order to suppress the radical polymerization reaction from proceeding and crosslinking between molecules during the distillation under reduced pressure, followed by distillation under reduced pressure. You may. These distillation methods include a raw material stage, a product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or a curable composition prepared by mixing these compounds. Either stage is possible.
＜＜顔料誘導体＞＞
　本発明の硬化性組成物は、顔料誘導体を含有することができる。顔料誘導体としては、発色団の一部分を、酸基、塩基性基またはフタルイミドメチル基で置換した構造を有する化合物が挙げられる。顔料誘導体を構成する発色団としては、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、フタロシアニン系骨格、アンスラキノン系骨格、キナクリドン系骨格、ジオキサジン系骨格、ペリノン系骨格、ペリレン系骨格、チオインジゴ系骨格、イソインドリン系骨格、イソインドリノン系骨格、キノフタロン系骨格、スレン系骨格、金属錯体系骨格等が挙げられ、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、キノフタロン系骨格、イソインドリン系骨格およびフタロシアニン系骨格が好ましく、アゾ系骨格およびベンゾイミダゾロン系骨格がより好ましい。顔料誘導体が有する酸基としては、スルホ基、カルボキシル基が好ましく、スルホ基がより好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、三級アミノ基がより好ましい。顔料誘導体の具体例としては、例えば、特開２０１１－２５２０６５号公報の段落０１６２～０１８３の記載を参酌でき、この内容は本明細書に組み込まれる。 << Pigment derivative >>
The curable composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include a compound having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. Examples of the chromophore constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, and a perinone skeleton. Skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, sullen skeleton, metal complex skeleton, etc., quinoline skeleton, benzimidazolone skeleton, diketo A pyrrolopyrrole-based skeleton, an azo-based skeleton, a quinophthalone-based skeleton, an isoindoline-based skeleton, and a phthalocyanine-based skeleton are preferred, and an azo-based skeleton and a benzimidazolone-based skeleton are more preferred. As the acid group of the pigment derivative, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable. As specific examples of the pigment derivative, for example, the description in paragraphs 0162 to 0183 of JP-A-2011-252665 can be referred to, and the contents thereof are incorporated herein.
　顔料誘導体の含有量は、顔料１００質量部に対し、１～３０質量部が好ましく、３～２０質量部がさらに好ましい。顔料誘導体は、１種のみを用いてもよいし、２種以上を併用してもよい。 含有 The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the pigment. One kind of the pigment derivative may be used alone, or two or more kinds thereof may be used in combination.
＜＜硬化促進剤＞＞
　本発明の硬化性組成物は、重合性化合物の反応を促進させたり、硬化温度を下げる目的で、硬化促進剤を添加してもよい。硬化促進剤としては、分子内に２個以上のメルカプト基を有する多官能チオール化合物などが挙げられる。多官能チオール化合物は安定性、臭気、解像性、現像性、密着性等の改良を目的として添加してもよい。多官能チオール化合物は、２級のアルカンチオール類であることが好ましく、式（Ｔ１）で表される化合物であることがより好ましい。 << Curing accelerator >>
The curable composition of the present invention may contain a curing accelerator for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. Examples of the curing accelerator include a polyfunctional thiol compound having two or more mercapto groups in a molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound represented by the formula (T1).
　式（Ｔ１）
Figure JPOXMLDOC01-appb-C000023
 Equation (T1)
Figure JPOXMLDOC01-appb-C000023
　式（Ｔ１）中、ｎは２～４の整数を表し、Ｌは２～４価の連結基を表す。式（Ｔ１）において、連結基Ｌは炭素数２～１２の脂肪族基であることが好ましく、ｎが２であり、Ｌが炭素数２～１２のアルキレン基であることが特に好ましい。 中 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group. In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
　また、硬化促進剤は、メチロール系化合物（例えば特開２０１５－０３４９６３号公報の段落０２４６において、架橋剤として例示されている化合物）、アミン類、ホスホニウム塩、アミジン塩、アミド化合物（以上、例えば特開２０１３－０４１１６５号公報の段落０１８６に記載の硬化剤）、塩基発生剤（例えば、特開２０１４－０５５１１４号公報に記載のイオン性化合物）、シアネート化合物（例えば、特開２０１２－１５０１８０号公報の段落００７１に記載の化合物）、アルコキシシラン化合物（例えば、特開２０１１－２５３０５４号公報に記載のエポキシ基を有するアルコキシシラン化合物）、オニウム塩化合物（例えば、特開２０１５－０３４９６３号公報の段落０２１６に酸発生剤として例示されている化合物、特開２００９－１８０９４９号公報に記載の化合物）などを用いることもできる。 Examples of the curing accelerator include a methylol-based compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of JP-A-2005-034963), amines, phosphonium salts, amidine salts, and amide compounds (for example, JP-A-2013-041165, a curing agent described in paragraph 0186), a base generator (for example, an ionic compound described in JP-A-2014-055114), and a cyanate compound (for example, JP-A-2012-150180) The compound described in paragraph 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253054), and an onium salt compound (for example, described in paragraph 0216 of JP-A-2015-034963) Compounds exemplified as acid generators, JP Compounds described in JP-009-180949) or the like can be used.
　本発明の硬化性組成物が硬化促進剤を含有する場合、硬化促進剤の含有量は、硬化性組成物の全固形分中０．３～８．９質量％が好ましく、０．８～６．４質量％がより好ましい。 When the curable composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass based on the total solid content of the curable composition, and 0.8 to 6% by mass. 0.4 mass% is more preferred.
＜＜シランカップリング剤＞＞
　本発明の硬化性組成物は、シランカップリング剤を含有することできる。シランカップリング剤としては、一分子中に少なくとも２種の反応性の異なる官能基を有するシラン化合物が好ましい。シランカップリング剤は、ビニル基、エポキシ基、スチレン基、メタクリル基、アミノ基、イソシアヌレート基、ウレイド基、メルカプト基、スルフィド基、および、イソシアネート基から選ばれる少なくとも１種の基と、アルコキシ基とを有するシラン化合物が好ましい。シランカップリング剤の具体例としては、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン（信越化学工業（株）製、ＫＢＭ－６０２）、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－６０３）、３－アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－９０３）、３－アミノプロピルトリエトキシシラン（信越化学工業（株）製、ＫＢＥ－９０３）、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－５０３）、３－グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－４０３）等が挙げられる。シランカップリング剤の詳細については、特開２０１３－２５４０４７号公報の段落０１５５～０１５８の記載を参酌でき、この内容は本明細書に組み込まれる。本発明の硬化性組成物がシランカップリング剤を含有する場合、シランカップリング剤の含有量は、硬化性組成物の全固形分中０．００１～２０質量％が好ましく、０．０１～１０質量％がより好ましく、０．１質量％～５質量％が特に好ましい。本発明の硬化性組成物は、シランカップリング剤を、１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 << silane coupling agent >>
The curable composition of the present invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two types of functional groups having different reactivities in one molecule is preferable. The silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureide group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. Is preferred. Specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), 3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu) Chemical Industry Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) And KBM-403). For details of the silane coupling agent, the description in paragraphs 0155 to 0158 of JP-A-2013-254407 can be referred to, and the contents thereof are incorporated herein. When the curable composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass based on the total solid content of the curable composition, and 0.01 to 10% by mass. % By mass is more preferable, and 0.1 to 5% by mass is particularly preferable. The curable composition of the present invention may include only one type of silane coupling agent, or may include two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
＜＜重合禁止剤＞＞
　本発明の硬化性組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、４，４'－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２'－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシルアミン塩（アンモニウム塩、第一セリウム塩等）等が挙げられる。本発明の硬化性組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、硬化性組成物の全固形分中０．０００１～５質量％が好ましい。本発明の硬化性組成物は、重合禁止剤を、１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 << polymerization inhibitor >>
The curable composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine salts (ammonium salts, cerous salts) and the like. When the curable composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the curable composition. The curable composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
＜＜紫外線吸収剤＞＞
　本発明の硬化性組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。これらの詳細については、特開２０１２－２０８３７４号公報の段落００５２～００７２、特開２０１３－０６８８１４号公報の段落０３１７～０３３４、特開２０１６－１６２９４６号公報の段落００６１～００８０の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、ＵＶ－５０３（大東化学（株）製）などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）が挙げられる。また、紫外線吸収剤として特許第６２６８９６７号公報の段落００４９～００５９に記載の化合物も使用できる。本発明の硬化性組成物が紫外線吸収剤を含有する場合、紫外線吸収剤の含有量は、硬化性組成物の全固形分中０．１～１０質量％が好ましく、０．１～５質量％がより好ましく、０．１～３質量％が特に好ましい。また、紫外線吸収剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 <<<< UV absorber >>
The curable composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used. For details of these, paragraphs 0052 to 0072 of JP-A-2012-208374, paragraphs 0317 to 0334 of JP-A-2013-068814, and paragraphs 0061 to 0080 of JP-A-2016-162946 can be referred to. These contents are incorporated herein. Commercially available UV absorbers include, for example, UV-503 (manufactured by Daito Chemical Co., Ltd.). Examples of the benzotriazole compound include MYUA series (manufactured by Miyoshi Oil & Fats, Chemical Daily, February 1, 2016). Further, compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as an ultraviolet absorber. When the curable composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the curable composition. Is more preferable, and 0.1 to 3% by mass is particularly preferable. In addition, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.
＜＜界面活性剤＞＞
　本発明の硬化性組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤については、国際公開第２０１５／１６６７７９号の段落０２３８～０２４５を参酌でき、この内容は本明細書に組み込まれる。 << Surfactant >>
The curable composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Regarding surfactants, paragraphs 0238 to 0245 of WO 2015/166779 can be referred to, and the contents thereof are incorporated herein.
　本発明において、界面活性剤はフッ素系界面活性剤であることが好ましい。硬化性組成物にフッ素系界面活性剤を含有させることで液特性（特に、流動性）がより向上し、省液性をより改善することができる。また、厚さムラの小さい膜を形成することもできる。 に お い て In the present invention, the surfactant is preferably a fluorinated surfactant. By including a fluorine-based surfactant in the curable composition, liquid properties (particularly, fluidity) are further improved, and liquid saving properties can be further improved. In addition, a film with small thickness unevenness can be formed.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、硬化性組成物中における溶解性も良好である。 フ ッ 素 The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of a coating film and liquid saving properties, and has good solubility in a curable composition.
　フッ素系界面活性剤としては、特開２０１４－０４１３１８号公報の段落００６０～００６４（対応する国際公開第２０１４／０１７６６９号の段落００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落０１１７～０１３２に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ１７１、Ｆ１７２、Ｆ１７３、Ｆ１７６、Ｆ１７７、Ｆ１４１、Ｆ１４２、Ｆ１４３、Ｆ１４４、Ｒ３０、Ｆ４３７、Ｆ４７５、Ｆ４７９、Ｆ４８２、Ｆ５５４、Ｆ７８０、ＥＸＰ、ＭＦＳ－３３０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）等が挙げられる。 Examples of the fluorinated surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraphs 0060 to 0064 of WO 2014/017669), and JP-A-2011-132503. The surfactants described in paragraphs 0117 to 0132 of the gazette are exemplified, and the contents thereof are incorporated herein. Commercially available fluorine surfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PolyFox @ PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like. .
　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報、２０１６年２月２２日）（日経産業新聞、２０１６年２月２３日）、例えばメガファックＤＳ－２１が挙げられる。 In addition, fluorine-based surfactants have a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off when heat is applied and the fluorine atom is volatilized. It can be suitably used. Examples of such a fluorinated surfactant include Megafac DS series (manufactured by DIC Corporation, Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21.
　また、フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開２０１６－２１６６０２号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 Also, it is preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant. The description of JP-A-2016-216602 can be referred to for such a fluorine-based surfactant, and the contents thereof are incorporated herein.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－０８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。 ブ ロ ッ ク A block polymer can also be used as the fluorine-based surfactant. For example, compounds described in JP-A-2011-089090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom, and has 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorinated surfactant used in the present invention.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 重量 The above compound has a weight average molecular weight of preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of the repeating unit is mol%.
　また、フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落００５０～００９０および段落０２８９～０２９５に記載された化合物、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落００１５～０１５８に記載の化合物を用いることもできる。 Alternatively, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, Megafac RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation. -72-K and the like. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（富士フイルム和光純薬（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Co., Ltd.), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS ), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, and Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.).
　シリコン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ－３４１、ＫＦ－６００１、ＫＦ－６００２（以上、信越化学工業（株）製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー社製）等が挙げられる。 Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Inc.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all made by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (all, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (all manufactured by Big Chemie).
　硬化性組成物の全固形分中における界面活性剤の含有量は、０．００１～５．０質量％が好ましく、０．００５～３．０質量％がより好ましい。界面活性剤は１種のみでもよく、２種以上でもよい。２種以上の場合は、それらの合計量が上記範囲となることが好ましい。 は The content of the surfactant in the total solid content of the curable composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is within the above range.
＜＜その他添加剤＞＞
　本発明の硬化性組成物には、必要に応じて、各種添加剤、例えば、充填剤、密着促進剤、酸化防止剤、凝集防止剤等を配合することができる。これらの添加剤としては、特開２００４－２９５１１６号公報の段落０１５５～０１５６に記載の添加剤を挙げることができ、この内容は本明細書に組み込まれる。また、酸化防止剤としては、例えばフェノール化合物、リン系化合物（例えば特開２０１１－０９０１４７号公報の段落００４２に記載の化合物）、チオエーテル化合物などを用いることができる。市販品としては、例えば（株）ＡＤＥＫＡ製のアデカスタブシリーズ（ＡＯ－２０、ＡＯ－３０、ＡＯ－４０、ＡＯ－５０、ＡＯ－５０Ｆ、ＡＯ－６０、ＡＯ－６０Ｇ、ＡＯ－８０、ＡＯ－３３０など）が挙げられる。また、酸化防止剤として、国際公開第２０１７／００６６００号に記載された多官能ヒンダードアミン酸化防止剤、国際公開第２０１７／１６４０２４号に記載された酸化防止剤、特許第６２６８９６７号公報の段落００２３～００４８に記載された酸化防止剤を用いることもできる。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。また、本発明の硬化性組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤の具体例としては、国際公開第２０１４／０２１０２３号、国際公開第２０１７／０３０００５号、特開２０１７－００８２１９号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。また、本発明の硬化性組成物は、特開２００４－２９５１１６号公報の段落００７８に記載の増感剤や光安定剤、同公報の段落００８１に記載の熱重合防止剤、特開２０１８－０９１９４０号公報の段落０２４２に記載の貯蔵安定化剤を含有することができる。 << Other additives >>
The curable composition of the present invention may optionally contain various additives, for example, a filler, an adhesion promoter, an antioxidant, and an anti-agglomeration agent. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein. Further, as the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0042 of JP-A-2011-090147), a thioether compound, or the like can be used. Commercially available products include, for example, ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330 etc.). Examples of the antioxidant include a polyfunctional hindered amine antioxidant described in International Publication No. 2017/0066600, an antioxidant described in International Publication No. 2017/164024, and paragraphs 0023 to 0048 of Japanese Patent No. 6268967. The antioxidants described in (1) can also be used. One type of antioxidant may be used, or two or more types may be used. Further, the curable composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which a protecting group is eliminated to function as an antioxidant can be mentioned. Specific examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP-A-2017-008219. Commercially available products include Adeka Aquel's GPA-5001 (manufactured by ADEKA Corporation). Further, the curable composition of the present invention may be a sensitizer or a light stabilizer described in paragraph 0078 of JP-A-2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of the same, or JP-A-2018-091940. The storage stabilizer described in paragraph No. 0242 of JP-A No. 2-1980 can be contained.
　本発明の硬化性組成物は、顔料などと結合または配位していない遊離の金属の含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、１０ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。この態様によれば、顔料分散性の安定化（凝集抑止）、分散性向上に伴う分光特性の向上、硬化性成分の安定化や、金属原子・金属イオンの溶出に伴う導電性変動の抑止、表示特性の向上などの効果が期待できる。上記の遊離の金属の種類としては、Ｎａ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｍｎ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｒ、Ｆｅ、Ｃｏ、Ｍｇ、Ａｌ、Ｔｉ、Ｓｎ、Ｚｎ、Ｚｒ、Ｇａ、Ｇｅ、Ａｇ、Ａｕ、Ｐｔ、Ｃｓ、Ｂｉ等が挙げられる。また、本発明の硬化性組成物は、顔料などと結合または配位していない遊離のハロゲンの含有量が１００質量ｐｐｍ以下であることが好ましく、５０質量ｐｐｍ以下であることがより好ましく、１０質量ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。硬化性組成物中の遊離の金属やハロゲンの低減方法としては、イオン交換水による洗浄、ろ過、限外ろ過、イオン交換樹脂による精製等の方法が挙げられる。 The curable composition of the present invention preferably has a content of free metal not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, further preferably 10 ppm or less. Preferably, it is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of a curable component, suppression of conductivity fluctuation due to elution of metal atoms and metal ions, Effects such as improvement of display characteristics can be expected. The types of the above free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Fe, Co, Mg, Al, Ti, Sn, Zn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Bi, and the like. Further, the curable composition of the present invention preferably has a content of free halogen not bound or coordinated with a pigment or the like of 100 mass ppm or less, more preferably 50 mass ppm or less, and 10 mass ppm or less. The content is more preferably not more than ppm by mass, and particularly preferably substantially not contained. Examples of a method for reducing free metals and halogens in the curable composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
　本発明の硬化性組成物は、テレフタル酸エステルを実質的に含まないことも好ましい。ここで、「実質的に含まない」とは、テレフタル酸エステルの含有量が、組成物の固形分中、１０００質量ｐｐｂ以下であることを意味し、５００質量ｐｐｂ以下であることがより好ましく、ゼロであることが特に好ましい。 硬化 It is also preferable that the curable composition of the present invention contains substantially no terephthalate. Here, “substantially free” means that the content of the terephthalic acid ester in the solid content of the composition is 1000 mass ppb or less, more preferably 500 mass ppb or less, Particularly preferred is zero.
＜収容容器＞
　本発明の硬化性組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や硬化性組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。また、容器内壁からの金属溶出を防ぎ、組成物の保存安定性を高め、成分変質を抑制する観点から、収容容器の内壁はガラス製やステンレス製であることが好ましい。 <Container>
The container for storing the curable composition of the present invention is not particularly limited, and a known container can be used. Further, as a container, for the purpose of suppressing the contamination of impurities into the raw material and the curable composition, a multilayer bottle in which the inner wall of the container is composed of six types of six layers of resin and a six types of resin having a seven layer structure. It is also preferred to use bottles. Examples of such a container include a container described in JP-A-2015-123351. The inner wall of the container is preferably made of glass or stainless steel from the viewpoint of preventing metal elution from the inner wall of the container, increasing storage stability of the composition, and suppressing deterioration of components.
＜硬化性組成物の製造方法＞
　本発明の硬化性組成物は、前述の成分を混合することにより製造できる。硬化性組成物の製造に際しては、全成分を同時に溶剤に溶解および／または分散して硬化性組成物を製造してもよいし、必要に応じて、各成分を適宜２つ以上の溶液または分散液としておいて、使用時（塗布時）にこれらを混合して組成物を製造してもよい。 <Method for producing curable composition>
The curable composition of the present invention can be produced by mixing the above components. In the production of the curable composition, the curable composition may be produced by dissolving and / or dispersing all the components in a solvent at the same time. The composition may be manufactured by mixing these at the time of use (at the time of application) as a liquid.
　また、硬化性組成物の製造に際して、顔料などの粒子を分散させるプロセスを含んでいてもよい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落００２２に記載のプロセス及び分散機を好適に使用出来る。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。 In addition, the production of the curable composition may include a process of dispersing particles such as pigments. In the process of dispersing the pigment, examples of mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. In the pulverization of the pigment in a sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the filling rate of the beads, etc., so as to increase the pulverization efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. The process and the disperser for dispersing pigments are described in "Dispersion Technology Taizen, published by Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology and industrial application centering on suspension (solid / liquid dispersion system)". The process and the disperser described in paragraph 0022 of JP-A-2015-157893 can be suitably used. Further, in the process of dispersing the pigment, fine processing of particles may be performed in a salt milling step. The materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.
　硬化性組成物の製造にあたり、異物の除去や欠陥の低減などの目的で、硬化性組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。 あ た り In the production of the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.
　フィルタの孔径は、０．０１～７．０μｍが好ましく、０．０１～３．０μｍがより好ましく、０．０５～０．５μｍが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社（ＤＦＡ４２０１ＮＩＥＹなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 孔 The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. When the pore size of the filter is in the above range, fine foreign matter can be more reliably removed. As for the pore diameter value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。 It is also preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include a polypropylene fiber, a nylon fiber, and a glass fiber. Commercially available products include SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。 When using a filter, different filters (for example, a first filter and a second filter) may be combined. At that time, the filtration by each filter may be performed only once or may be performed twice or more. Further, filters having different hole diameters may be combined within the above-described range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after the other components are mixed, the filtration with the second filter may be performed.
＜硬化膜および光学フィルタ＞
　本発明の硬化膜は、上述した本発明の硬化性組成物の膜を形成し、この膜を乾燥し、硬化させることにより製造できる。本発明の硬化膜は、近赤外線透過フィルタとして好ましく用いることができる。この硬化膜の厚さは、目的に応じて適宜調整でき、１００μｍ以下が好ましく、１５μｍ以下がより好ましく、５μｍ以下がさらに好ましく、３μｍ以下が特に好ましい。厚さの下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 <Curing film and optical filter>
The cured film of the present invention can be produced by forming a film of the above-described curable composition of the present invention, drying and curing the film. The cured film of the present invention can be preferably used as a near infrared transmitting filter. The thickness of the cured film can be appropriately adjusted depending on the purpose, and is preferably 100 μm or less, more preferably 15 μm or less, further preferably 5 μm or less, and particularly preferably 3 μm or less. The lower limit of the thickness is preferably at least 0.1 μm, more preferably at least 0.2 μm, even more preferably at least 0.3 μm.
　厚さが１μｍ、２μｍ、３μｍ、４μｍまたは５μｍの上記硬化膜を形成した際に、膜の厚さ方向における光の透過率について、波長４００～６００ｎｍの範囲における最大値が２０％以下であり、波長１０００～１３００ｎｍの範囲における最小値が７０％以上である分光特性を満たしていることが好ましい。波長４００～６００ｎｍの範囲における最大値は、１５％以下が好ましく、１０％以下がより好ましい。波長１０００～１３００ｎｍの範囲における最小値は、７５％以上が好ましく、８０％以上がより好ましい。 When the cured film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm is formed, the maximum value of light transmittance in the thickness direction of the film in a wavelength range of 400 to 600 nm is 20% or less; It is preferable to satisfy the spectral characteristic that the minimum value in the wavelength range of 1000 to 1300 nm is 70% or more. The maximum value in the wavelength range of 400 to 600 nm is preferably 15% or less, more preferably 10% or less. The minimum value in the wavelength range of 1000 to 1300 nm is preferably at least 75%, more preferably at least 80%.
　本発明の硬化膜は、以下の（１１）～（１４）のいずれかの分光特性を満たしていることがより好ましい。 硬化 The cured film of the present invention more preferably satisfies any of the following spectral characteristics (11) to (14).
　（１１）：厚さ１μｍ、２μｍ、３μｍ、４μｍまたは５μｍの上記硬化膜を形成した際に、膜の厚さ方向における光の透過率について、波長４００～６４０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長８００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である。 (11): When the cured film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 640 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
　（１２）：厚さ１μｍ、２μｍ、３μｍ、４μｍまたは５μｍの上記硬化膜を形成した際に、膜の厚さ方向における光の透過率について、波長４００～７５０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長９００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である。 (12): When the cured film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm or 5 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
　（１３）：厚さ１μｍ、２μｍ、３μｍ、４μｍまたは５μｍの上記硬化膜を形成した際に、膜の厚さ方向における光の透過率について、波長４００～８３０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１０００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である。 (13): When the cured film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
　（１４）：厚さ１μｍ、２μｍ、３μｍ、４μｍまたは５μｍの上記硬化膜を形成した際に、膜の厚さ方向における光の透過率について、波長４００～９５０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である。 (14): When the cured film having a thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20% or less. (Preferably 15% or less, more preferably 10% or less), and the minimum value in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
　本発明の光学フィルタは、例えば、近赤外線透過フィルタであり、本発明の上記硬化膜を含む。本発明の光学フィルタは、硬化膜の表面に特開２０１７－１５１１７６号公報の段落００７３～００９２に記載の保護層が設けられていてもよい。また、本発明の光学フィルタは、有彩色着色剤を含むＲＧＢ用カラーフィルタを備えていてもよい。このようなカラーフィルタは、上記色材の説明で述べた有彩色着色剤と同様の有彩色着色剤を含む硬化性組成物を用いて製造される。 光学 The optical filter of the present invention is, for example, a near-infrared transmitting filter and includes the cured film of the present invention. The optical filter of the present invention may be provided with a protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 on the surface of the cured film. Further, the optical filter of the present invention may include an RGB color filter containing a chromatic colorant. Such a color filter is manufactured using a curable composition containing the same chromatic colorant as the chromatic colorant described in the description of the color material.
＜パターンの形成方法＞
　本発明のパターンの形成方法は、本発明の硬化性組成物を用いて支持体上に硬化性組成物層を形成する工程と、この硬化性組成物層に対して、３５０ｎｍを超え３８０ｎｍ以下の波長を有する光を照射し、パターン状に露光する第１の露光工程と、硬化性組成物層を現像する現像工程と、現像工程後に、硬化性組成物層に対して、２５４～３５０ｎｍの波長を有する光を照射する第２の露光工程とを含む。そして、本発明のパターンの形成方法では、全工程を通じて２００℃未満の温度下で処理を行うことができ、好ましくは１５０℃以下の温度下で行うこともできる。なお、本発明において、「全工程を通じて２００℃未満の温度で処理を行う」とは、硬化性組成物を用いてパターン状の硬化膜を形成する工程の全てを、２００℃未満の温度で行うことを意味する。本発明のパターンの形成方法において、第２の露光工程後に、さらに加熱する工程を設けることもできる。ただし、この場合には、加熱温度は２００℃未満とする。以下、各工程について詳細を述べる。 <Pattern forming method>
The pattern forming method of the present invention includes a step of forming a curable composition layer on a support using the curable composition of the present invention, and a step of forming a curable composition layer having a thickness of more than 350 nm to 380 nm or less. A first exposure step of irradiating light having a wavelength to expose in a pattern, a development step of developing the curable composition layer, and a wavelength of 254 to 350 nm for the curable composition layer after the development step. A second exposure step of irradiating light having the following. And, in the pattern forming method of the present invention, the treatment can be performed at a temperature of less than 200 ° C., preferably at a temperature of 150 ° C. or less throughout all the steps. In the present invention, “the treatment is performed at a temperature of less than 200 ° C. throughout the entire process” means that all of the steps of forming a patterned cured film using the curable composition are performed at a temperature of less than 200 ° C. Means that. In the pattern forming method of the present invention, a heating step may be further provided after the second exposure step. However, in this case, the heating temperature is lower than 200 ° C. Hereinafter, each step will be described in detail.
＜＜硬化性組成物層の形成工程＞＞
　硬化性組成物層を形成する工程では、支持体上に本発明の硬化性組成物を塗布して硬化性組成物層を形成する。支持体は、例えば、ガラス基板や樹脂基板である。樹脂基板としては、ポリカーボネート基板、ポリエステル基板、芳香族ポリアミド基板、ポリアミドイミド基板、ポリイミド基板等が挙げられる。これらの基板上には有機発光層や光電変換層が形成されていてもよい。また、基板には、上部の層との密着性改良、物質の拡散防止或いは表面の平坦化のために下塗り層が設けられていてもよい。下塗り層は、例えば、本発明の硬化性組成物から色材を抜いたような硬化性組成物を塗布することで形成してもよい。 <<< Step of Forming Curable Composition Layer >>>
In the step of forming the curable composition layer, the curable composition of the present invention is applied on a support to form a curable composition layer. The support is, for example, a glass substrate or a resin substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light emitting layer or a photoelectric conversion layer may be formed on these substrates. In addition, the substrate may be provided with an undercoat layer for improving adhesion to an upper layer, preventing diffusion of a substance, or planarizing the surface. The undercoat layer may be formed, for example, by applying a curable composition obtained by removing a coloring material from the curable composition of the present invention.
　組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、組成物の塗布方法については、国際公開第２０１７／０３０１７４号、国際公開第２０１７／０１８４１９号の記載を参酌でき、これらの内容は本明細書に組み込まれる。 公 知 A known method can be used as a method for applying the composition. For example, a dropping method (drop casting); a slit coating method; a spraying method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, JP-A-2009-145395). Publications); inkjet (eg, on-demand method, piezo method, thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; a transfer method using a mold or the like; a nanoimprint method, and the like. The application method in the ink jet is not particularly limited, and for example, a method shown in “Spread and usable ink jets—infinite possibilities seen in patents”, published in February 2005, Sumibe Techno Research (especially from page 115). 133 page), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261828, JP-A-2012-126830, JP-A-2006-169325, and the like. No. In addition, as to the method for applying the composition, the descriptions in WO2017 / 030174 and WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.
　支持体上に形成した硬化組成物層は、乾燥（プリベーク）してもよい。プリベークを行う場合、プリベーク温度は、８０℃以下が好ましく、７０℃以下がより好ましく、６０℃以下が更に好ましく、５０℃以下が特に好ましい。下限は、例えば、４０℃以上とすることができる。プリベーク時間は、１０～３６００秒が好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。 硬化 The cured composition layer formed on the support may be dried (prebaked). When performing prebaking, the prebaking temperature is preferably 80 ° C or lower, more preferably 70 ° C or lower, still more preferably 60 ° C or lower, and particularly preferably 50 ° C or lower. The lower limit can be, for example, 40 ° C. or higher. The prebake time is preferably from 10 to 3600 seconds. Prebaking can be performed on a hot plate, an oven, or the like.
＜＜第１の露光工程＞＞
　第１の露光工程では、硬化性組成物層に対して、３５０ｎｍを超え３８０ｎｍ以下の波長の光を照射してパターン状に露光する。例えば、硬化性組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン状に露光することができる。これにより、硬化性組成物層の露光部分を硬化させることができる。露光に際して用いることができる光としては、３５０ｎｍを超え３８０ｎｍ以下の波長の光であり、波長３５５～３７０ｎｍの光が好ましく、ｉ線（３６５ｎｍ）がより好ましい。また、この露光処理は、ＫＲ１０２０１７０１２２１３０Ａに記載されているように、ｉ線よりも短い波長の光をカットしながら行ってもよい。 << First exposure step >>
In the first exposure step, light is applied to the curable composition layer in a pattern by irradiating light having a wavelength of more than 350 nm and not more than 380 nm. For example, the curable composition layer can be exposed in a pattern by using an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, the exposed portion of the curable composition layer can be cured. Light that can be used for exposure is light having a wavelength of more than 350 nm and not more than 380 nm, preferably light having a wavelength of 355 to 370 nm, and more preferably i-line (365 nm). This exposure processing may be performed while cutting light having a wavelength shorter than the i-line, as described in KR10201702122130A.
　照射量（露光量）としては、例えば、３０～１５００ｍＪ／ｃｍ2が好ましく、５０～１０００ｍＪ／ｃｍ2がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ2～１０００００Ｗ／ｍ2（例えば、５０００Ｗ／ｍ2、１５０００Ｗ／ｍ2、３５０００Ｗ／ｍ2）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ2、酸素濃度３５体積％で照度２００００Ｗ／ｍ2などとすることができる。 The irradiation dose (exposure dose), for example, preferably 30 ~ 1500mJ / cm 2, more preferably 50 ~ 1000mJ / cm 2. The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing the exposure under the air, for example, under a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free) ), Or under a high oxygen atmosphere having an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). The exposure illuminance can be appropriately set and can be selected from a range of usually 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ). . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
　第１の露光工程において、露光後の硬化性組成物層中の重合性化合物の反応率は、３０％を超え８０％未満であることが好ましい。このような反応率にすることにより重合性化合物を適度に硬化させた状態にすることができる。色材の濃度が高く、光が透過しにくい傾向にある近赤外線透過フィルタ用の組成物においては、現像に耐えうる程度に深層部を硬化させるため、カラーフィルタ用の組成物の場合に比べ、上記反応率は、高めに設定することが好ましい。さらに、本発明において、上記反応率は、４０～７５％であることがより好ましく、５０～７０％であることがさらに好ましい。ここで、重合性化合物の反応率とは、第１の露光工程前において重合性化合物が有していた重合性基のうち、反応した重合性基の割合をいう。重合性化合物の反応率は、赤外吸収スペクトル法により８１０ｃｍ-1付近のピーク面積を解析することにより、膜の厚さ方向の平均値として求めることができる。 In the first exposure step, the reaction rate of the polymerizable compound in the curable composition layer after exposure is preferably more than 30% and less than 80%. With such a reaction rate, the polymerizable compound can be in a state of being appropriately cured. In the composition for a near-infrared transmission filter in which the concentration of the coloring material is high and light tends to be hard to transmit, in order to cure the deep layer to the extent that it can withstand development, compared to the case of the composition for a color filter, The reaction rate is preferably set to be higher. Further, in the present invention, the reaction rate is more preferably from 40 to 75%, further preferably from 50 to 70%. Here, the reaction rate of the polymerizable compound refers to a ratio of the reacted polymerizable group among the polymerizable groups included in the polymerizable compound before the first exposure step. The reaction rate of the polymerizable compound can be determined as an average value in the thickness direction of the film by analyzing a peak area near 810 cm -1 by an infrared absorption spectrum method.
＜＜現像工程＞＞
　現像工程では、硬化性組成物層の未露光部を現像除去してパターン（画素）を形成する。硬化性組成物層の未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の硬化性組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液としては、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液であることが好ましい。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 <<< Development Step >>>
In the development step, a pattern (pixel) is formed by developing and removing an unexposed portion of the curable composition layer. The development removal of the unexposed portion of the curable composition layer can be performed using a developer. As a result, the curable composition layer in the unexposed portion in the exposure step elutes into the developer, leaving only the photocured portion. Examples of the developer include an organic solvent and an alkali developer, and an alkali developer is preferable. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
　アルカリ現像液は、アルカリ剤を純水で希釈したアルカリ性水溶液であることが好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。界面活性剤としては、上述した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。 The alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Alkaline compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate. As the alkali agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. Further, the developer may further contain a surfactant. Examples of the surfactant include the surfactants described above, and a nonionic surfactant is preferable. The developer may be once produced as a concentrated solution and diluted to a necessary concentration at the time of use, from the viewpoint of convenience of transportation and storage. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
　また、現像後純水で洗浄（リンス）することも好ましい。また、リンスは、現像後の硬化性組成物層が形成された支持体を回転させつつ、現像後の硬化性組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルを支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 It is also preferable to wash (rinse) with pure water after development. The rinsing is preferably performed by supplying a rinsing liquid to the curable composition layer after development while rotating the support on which the curable composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the peripheral edge of the support. At this time, when the nozzle is moved from the central portion to the peripheral portion of the support, the nozzle may be moved while gradually lowering the moving speed. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually lowering the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.
＜＜第２の露光工程＞＞
　第２の露光工程では、波長２５４～３５０ｎｍの光を照射して硬化性組成物層を露光する。照射する光は、波長３００ｎｍ以下の光を含むことが好ましく、波長２５４ｎｍの光を含むことがより好ましい。第２の露光工程は、例えば紫外線フォトレジスト硬化装置を用いて行うことができる。紫外線フォトレジスト硬化装置からは、例えば波長２５４～３５０ｎｍの光とともに、これ以外の光（例えばｉ線）が照射されてもよい。上述した現像前の露光で用いられる光の波長と、現像後の露光（後露光）で用いられる光の波長の差は、２００ｎｍ以下であることが好ましく、１００～１５０ｎｍであることがより好ましい。 << Second exposure step >>
In the second exposure step, the curable composition layer is exposed to light having a wavelength of 254 to 350 nm. The light to be irradiated preferably contains light having a wavelength of 300 nm or less, and more preferably contains light having a wavelength of 254 nm. The second exposure step can be performed using, for example, an ultraviolet photoresist curing device. From the ultraviolet photoresist curing device, for example, light having a wavelength of 254 to 350 nm and other light (for example, i-line) may be irradiated. The difference between the wavelength of light used in the above-described exposure before development and the wavelength of light used in the exposure after development (post-exposure) is preferably 200 nm or less, and more preferably 100 to 150 nm.
　照射量（露光量）は、３０～４０００ｍＪ／ｃｍ2が好ましく、５０～３５００ｍＪ／ｃｍ2がより好ましい。露光時における酸素濃度については、第１の露光工程時の条件と同様に、適宜選択することができる。 Irradiation dose (exposure dose) is preferably 30 ~ 4000mJ / cm 2, more preferably 50 ~ 3500mJ / cm 2. The oxygen concentration at the time of exposure can be appropriately selected, similarly to the conditions at the time of the first exposure step.
　第２の露光工程において、露光後の硬化性組成物層中の重合性化合物の反応率は、６０％以上であることが好ましい。上限は、１００％以下とすることもでき、９０％以下とすることもできる。このような反応率にすることにより、露光後の硬化性組成物層の硬化状態をより強固にすることができる。 に お い て In the second exposure step, the reaction rate of the polymerizable compound in the curable composition layer after exposure is preferably 60% or more. The upper limit may be set to 100% or less, or may be set to 90% or less. By setting such a reaction rate, the cured state of the curable composition layer after exposure can be further strengthened.
　本発明では、現像前および現像後の２段階で硬化性組成物層を露光することにより、第１の露光（現像前の露光）で硬化性組成物層を適度に硬化させることができ、第２の露光（現像後の露光）で硬化性組成物層全体をほぼ完全に硬化させることができる。結果として、２００℃未満の低温条件でも、硬化性組成物を充分に硬化させて、密着性に優れ、さらには、耐溶剤性、平坦性および矩形性にも優れるパターン状の硬化膜を形成することができる。 In the present invention, by exposing the curable composition layer at two stages before and after development, the curable composition layer can be appropriately cured by the first exposure (exposure before development). Exposure 2 (exposure after development) makes it possible to almost completely cure the entire curable composition layer. As a result, even under a low temperature condition of less than 200 ° C., the curable composition is sufficiently cured to form a pattern-like cured film having excellent adhesiveness and excellent solvent resistance, flatness and rectangularity. be able to.
＜＜ポストベーク＞＞
　本発明のパターン形成においては、さらに、現像工程と第２の露光工程の間、および、第２の露光工程の後の少なくともいずれかの期間に、所定の温度で硬化性組成物層を加熱する工程（ポストベーク）を行ってもよい。ポストベークの加熱温度は、２００℃未満であることが好ましく、１５０℃以下であることがより好ましく、１２０℃以下であることがさらに好ましい。また、ポストベークの加熱温度は、４５℃以上であることが好ましく、５０℃以上であることがより好ましく、８０℃以上であることがさらに好ましい。特に、樹脂基板を使用する場合や、光電変換層を有機材料などで構成した場合においては、加熱温度は、５０～１２０℃であることが好ましく、８０～１００℃がより好ましく、８０～９０℃がさらに好ましい。加熱時間は、適宜選択でき、例えば１～１０分であり、２～８分であることが好ましく、３～６分であることがより好ましい。 << post bake >>
In the pattern formation of the present invention, the curable composition layer is heated at a predetermined temperature between the developing step and the second exposure step, and at least one of the periods after the second exposure step. A step (post bake) may be performed. The heating temperature of post-baking is preferably lower than 200 ° C., more preferably 150 ° C. or lower, further preferably 120 ° C. or lower. Further, the heating temperature of the post-baking is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 80 ° C. or higher. In particular, when a resin substrate is used or when the photoelectric conversion layer is made of an organic material, the heating temperature is preferably 50 to 120 ° C, more preferably 80 to 100 ° C, and 80 to 90 ° C. Is more preferred. The heating time can be appropriately selected and is, for example, 1 to 10 minutes, preferably 2 to 8 minutes, and more preferably 3 to 6 minutes.
　ポストベークは、大気下で行ってもよく、低酸素雰囲気下で行ってもよい。ポストベークは、組成物の酸化による劣化を抑制する等の観点から、例えば酸素濃度が１９体積％以下の低酸素雰囲気下で行うことが好ましく、酸素濃度は、１５体積％以下であることがより好ましく、５体積％以下であることがさらに好ましく、１体積％以下（実質的に無酸素）であることが特に好ましい。 The post bake may be performed in the air or in a low oxygen atmosphere. For example, from the viewpoint of suppressing deterioration of the composition due to oxidation, the post-baking is preferably performed in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less, and the oxygen concentration is preferably 15% by volume or less. It is more preferably at most 5% by volume, particularly preferably at most 1% by volume (substantially oxygen-free).
　ポストベークは、ホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。一方、露光後の構造体を加熱することに支障がある場合や、硬化性組成物層が充分に硬化している場合には、ポストベークは行わなくてもよい。 The post-bake can be performed continuously or batch-wise using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), a high frequency heater or the like. On the other hand, when there is a problem in heating the structure after exposure, or when the curable composition layer is sufficiently cured, post-baking may not be performed.
　第２の露光工程後（第２の露光工程後にポストベークを行った場合はポストベーク後）のパターン状の硬化膜の厚さは、０．１～５．０μｍであることが好ましい。下限は、０．２μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましい。上限は、４．０μｍ以下であることが好ましく、２．５μｍ以下であることがより好ましい。硬化膜のパターンの幅は、０．５～２０．０μｍであることが好ましい。下限は、１．０μｍ以上であることが好ましく、２．０μｍ以上であることがより好ましい。上限は、１５．０μｍ以下であることが好ましく、１０．０μｍ以下であることがより好ましい。パターン状の硬化膜のヤング率は、０．５～２０ＧＰａが好ましく、２．５～１５ＧＰａがより好ましい。ヤング率は、例えば、ナノインデンテーション法を用いて測定できる。 パ タ ー ン The thickness of the patterned cured film after the second exposure step (after post-baking when post-baking is performed after the second exposure step) is preferably 0.1 to 5.0 μm. The lower limit is preferably at least 0.2 μm, more preferably at least 0.5 μm. The upper limit is preferably 4.0 μm or less, more preferably 2.5 μm or less. The width of the pattern of the cured film is preferably 0.5 to 20.0 μm. The lower limit is preferably at least 1.0 μm, more preferably at least 2.0 μm. The upper limit is preferably 15.0 μm or less, more preferably 10.0 μm or less. The patterned cured film preferably has a Young's modulus of 0.5 to 20 GPa, more preferably 2.5 to 15 GPa. The Young's modulus can be measured using, for example, a nanoindentation method.
＜光センサ＞
　本発明の光センサは、例えば、受光素子を構成する固体撮像素子と、この固体撮像素子の受光側に設置された本発明の近赤外線透過フィルタを有する。このような構成により、所望の波長範囲の近赤外線を受光素子で受光することができる。本発明の近赤外線透過フィルタが組み込まれた光センサは、ＣＣＤ（電荷結合素子）イメージセンサおよびＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサなどに応用することができ、生体認証用途、監視用途、モバイル用途、自動車用途、農業用途、医療用途、距離計測用途、ジェスチャー認識用途などの用途に好ましく用いることができる。 <Optical sensor>
The optical sensor of the present invention includes, for example, a solid-state imaging device constituting a light-receiving element, and a near-infrared transmission filter of the present invention installed on the light-receiving side of the solid-state imaging device. With such a configuration, near infrared rays in a desired wavelength range can be received by the light receiving element. The optical sensor incorporating the near-infrared transmission filter of the present invention can be applied to a CCD (charge coupled device) image sensor, a CMOS (complementary metal oxide semiconductor) image sensor, and the like. It can be preferably used for mobile applications, automobile applications, agricultural applications, medical applications, distance measurement applications, gesture recognition applications, and the like.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。「部」、「％」は特に述べない限り、質量基準である。 The present invention will be described more specifically with reference to the following examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. “Parts” and “%” are based on mass unless otherwise specified.
＜分散液の調製＞
　下記の表に記載の原料を混合したのち、混合原料１００質量部に対して、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて５時間分散処理を行い、ビーズをろ過で分離して分散液を製造した。下記の表に記載の数値は質量部である。 <Preparation of dispersion>
After mixing the raw materials described in the table below, 230 parts by mass of zirconia beads having a diameter of 0.3 mm are added to 100 parts by mass of the mixed raw materials, and the mixture is dispersed for 5 hours using a paint shaker, and the beads are filtered. To produce a dispersion. The numerical values in the following table are parts by mass.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
＜組成物の調製＞
　下記の表に記載の原料を混合して、組成物（硬化性組成物）を調製した。下記の表に記載の数値は質量部である。 <Preparation of composition>
The composition (curable composition) was prepared by mixing the raw materials described in the following table. The numerical values in the following table are parts by mass.
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
　上記表に記載の原料は以下の通りである。 原料 The raw materials described in the above table are as follows.
＜＜着色剤＞＞
ＩＢ　：Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ　Ｓ　０１００　ＣＦ（ＢＡＳＦ社製、下記構造の化合物、ラクタム系顔料）
Figure JPOXMLDOC01-appb-C000027
 ＰＢｋ３２　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３２（下記構造の化合物、ペリレン系顔料）
Figure JPOXMLDOC01-appb-C000028
 ＰＲ２５４　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４
ＰＹ１３９　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９
ＰＢ１５：６　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６
ＰＢ１６　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１６
ＰＶ２３　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３ << Colorant >>
IB: Irgaphor Black S 0100 CF (manufactured by BASF, compound having the following structure, lactam pigment)
Figure JPOXMLDOC01-appb-C000027
 PBk32: C.I. I. Pigment Black 32 (compound having the following structure, perylene pigment)
Figure JPOXMLDOC01-appb-C000028
 PR254: C.I. I. Pigment Red 254
PY139: C.I. I. Pigment Yellow 139
PB15: 6: C.I. I. Pigment Blue 15: 6
PB16: C.I. I. Pigment Blue 16
PV23: C.I. I. Pigment Violet 23
＜＜顔料誘導体＞＞
Ｂ１：下記構造の化合物。
Figure JPOXMLDOC01-appb-C000029
 << Pigment derivative >>
B1: Compound having the following structure.
Figure JPOXMLDOC01-appb-C000029
＜＜分散剤＞＞
Ｃ１：下記構造の樹脂。主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２０，０００。
Ｃ２：下記構造の樹脂。主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２４，０００。
Figure JPOXMLDOC01-appb-C000030
 << dispersant >>
C1: Resin having the following structure. The numerical value added to the main chain is a molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 20,000.
C2: Resin having the following structure. The numerical value added to the main chain is a molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 24,000.
Figure JPOXMLDOC01-appb-C000030
＜＜樹脂＞＞
Ｐ１：下記構造の樹脂（Ｍｗ＝１１，０００、主鎖に付記した数値はモル比である。）
Figure JPOXMLDOC01-appb-C000031
 Ｐ２：下記構造の樹脂
Figure JPOXMLDOC01-appb-C000032
 << Resin >>
P1: Resin having the following structure (Mw = 11,000, the numerical value added to the main chain is a molar ratio)
Figure JPOXMLDOC01-appb-C000031
 P2: Resin with the following structure
Figure JPOXMLDOC01-appb-C000032
＜＜重合性化合物＞＞
Ｄ１：ＴＭＰＥＯＴＡ（ダイセル・オルネクス社製）
Ｄ２：下記構造のモノマー。
Figure JPOXMLDOC01-appb-C000033
 Ｄ３：下記構造のモノマー。
Figure JPOXMLDOC01-appb-C000034
 Ｄ４：下記構造の化合物の混合物（左側化合物（６官能の（メタ）アクリレート化合物）と右側化合物（５官能の（メタ）アクリレート化合物）とのモル比が７：３の混合物）
Figure JPOXMLDOC01-appb-C000035
 Ｄ５：下記構造の化合物（アルキレンオキシ基を有する４官能の（メタ）アクリレート化合物）
Figure JPOXMLDOC01-appb-C000036
 << polymerizable compound >>
D1: TMPEOTA (manufactured by Daicel Ornex)
D2: Monomer having the following structure.
Figure JPOXMLDOC01-appb-C000033
 D3: Monomer having the following structure.
Figure JPOXMLDOC01-appb-C000034
 D4: a mixture of compounds having the following structure (a mixture in which the molar ratio of the left compound (6-functional (meth) acrylate compound) to the right compound (pentafunctional (meth) acrylate compound) is 7: 3)
Figure JPOXMLDOC01-appb-C000035
 D5: Compound having the following structure (tetrafunctional (meth) acrylate compound having an alkyleneoxy group)
Figure JPOXMLDOC01-appb-C000036
＜＜光重合開始剤＞＞
Ｉ－Ａ１：ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ社製）
Ｉ－Ａ２：ＩＲＧＡＣＵＲＥ－ＯＸＥ０３（ＢＡＳＦ社製）
Ｉ－Ａ３：ＩＲＧＡＣＵＲＥ３７９（ＢＡＳＦ社製）
Ｉ－Ｂ１：ＩＲＧＡＣＵＲＥ２９５９（ＢＡＳＦ社製）
Ｉ－Ｂ２：ＩＲＧＡＣＵＲＥ１１７３（ＢＡＳＦ社製） << Photopolymerization initiator >>
I-A1: IRGACURE-OXE02 (manufactured by BASF)
I-A2: IRGACURE-OXE03 (manufactured by BASF)
I-A3: IRGACURE379 (manufactured by BASF)
I-B1: IRGACURE2959 (manufactured by BASF)
I-B2: IRGACURE 1173 (manufactured by BASF)
＜＜界面活性剤＞＞
Ｆ１：下記構造の化合物（Ｍｗ＝１４０００、繰り返し単位の割合を示す％の数値はモル％である、フッ素系界面活性剤）
Figure JPOXMLDOC01-appb-C000037
 << Surfactant >>
F1: Compound having the following structure (Mw = 14000, the value of% indicating the ratio of repeating units is mol%, fluorine-based surfactant)
Figure JPOXMLDOC01-appb-C000037
＜＜重合禁止剤＞＞
Ｇ１：ｐ－メトキシフェノール << polymerization inhibitor >>
G1: p-methoxyphenol
＜＜溶剤＞＞
　Ｊ１：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ） << Solvent >>
J1: Propylene glycol monomethyl ether acetate (PGMEA)
＜＜シランカップリング剤＞＞
　Ｈ１：下記構造
Figure JPOXMLDOC01-appb-C000038
 << silane coupling agent >>
H1: The following structure
Figure JPOXMLDOC01-appb-C000038
＜＜エポキシ樹脂＞＞
Ｑ１：ＥＰＩＣＬＯＮ　Ｎ－６９５（ＤＩＣ（株）製）
Ｑ２：ＥＨＰＥ３１５０（（株）ダイセル製） << Epoxy resin >>
Q1: EPICLON N-695 (manufactured by DIC Corporation)
Q2: EHPE3150 (manufactured by Daicel Corporation)
＜＜硬化剤＞＞
Ｒ１：ピロメリット酸無水物 << curing agent >>
R1: pyromellitic anhydride
＜吸光度および分光特性＞
　ポストベーク後の膜厚が下記表に記載の膜厚となるように、各組成物をガラス基板上にスピンコート法により塗布し、ホットプレートを用いて、１００℃で１２０秒間加熱乾燥した後、さらに、２００℃で３００秒間加熱処理（ポストベーク）を行い、膜を形成した。膜が形成されたガラス基板を、紫外可視近赤外分光光度計Ｕ－４１００（日立ハイテク製）を用いて、波長４００～６００ｎｍの範囲における吸光度の最小値Ａ、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂを測定した。 <Absorbance and spectral characteristics>
Each composition was applied on a glass substrate by spin coating so that the film thickness after the post-baking had the film thickness described in the following table, and after heating and drying at 100 ° C. for 120 seconds using a hot plate, Further, a heat treatment (post-bake) was performed at 200 ° C. for 300 seconds to form a film. The glass substrate on which the film was formed was measured using a UV-visible-near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech) to measure the minimum absorbance A in the wavelength range of 400 to 600 nm and the absorbance in the wavelength range of 1000 to 1300 nm. The maximum value B was measured.
＜密着性の評価＞
　８インチ（１インチは約２．５４ｃｍ）のシリコンウエハ上に、ＣＴ－４０００Ｌ（富士フイルムエレクトロニクスマテリアルズ（株）製）をスピンコートで均一に塗布して塗布膜を形成し、形成された塗布膜を２２０℃のオーブンで１時間処理し、塗布膜を硬化させ、下塗り層を形成した。なお、スピンコートの塗布回転数は、加熱処理後の下塗り層の膜厚が約０．１μｍとなるように調整した。 <Evaluation of adhesion>
CT-4000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on an 8-inch (1 inch is approximately 2.54 cm) silicon wafer by spin coating to form a coating film. The film was treated in an oven at 220 ° C. for 1 hour to cure the applied film and form an undercoat layer. The spinning speed of spin coating was adjusted so that the thickness of the undercoat layer after the heat treatment was about 0.1 μm.
　次に、上記で得た各組成物を、上記シリコンウエハの下塗り層上に、乾燥後膜厚が下記表に記載の膜厚となるようにスピンコーターを用いて塗布し、ホットプレートを用いて１００℃で１２０秒間乾燥した。 Next, each composition obtained above is applied on an undercoat layer of the silicon wafer using a spin coater so that the film thickness after drying becomes a film thickness described in the following table, and using a hot plate. Dry at 100 ° C. for 120 seconds.
　次に、ｉ線ステッパー露光装置ＦＰＡ－ｉ５＋（キヤノン（株）製）を使用して、塗布膜に３６５ｎｍの波長の光を、２．０μｍ四方のアイランドパターンを有するマスクを通し、５０～１７００ｍＪ／ｃｍ2の露光量で照射し、第１の露光を実施した。露光後、アルカリ現像液（ＣＤ－２０００、富士フイルムエレクトロニクスマテリアルズ（株）製）を使用して、２５℃４０秒間の条件で現像した。その後、流水で３０秒間リンスした後、スプレー乾燥した。その後、ガラスウェハ全体に、紫外線フォトレジスト硬化装置（ＭＭＡ－８０２－ＨＣ－５５２、ウシオ電気（株）製）を用いて、１００００ｍＪ／ｃｍ2の露光量で照射し、第２の露光を実施して、パターン状の硬化膜を得た。 Next, using an i-line stepper exposure apparatus FPA-i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm was passed through the coating film through a mask having an island pattern of 2.0 μm square to obtain 50 to 1700 mJ /. Irradiation was performed at an exposure amount of cm 2 to perform a first exposure. After the exposure, development was performed at 25 ° C. for 40 seconds using an alkaline developer (CD-2000, manufactured by Fuji Film Electronics Materials Co., Ltd.). Then, after rinsing with running water for 30 seconds, it was spray-dried. Thereafter, the entire glass wafer was irradiated with an exposure amount of 10,000 mJ / cm 2 by using an ultraviolet photoresist curing device (MMA-802-HC-552, manufactured by Ushio Electric Co., Ltd.) to perform a second exposure. Thus, a patterned cured film was obtained.
　得られたパターンについて、セロハンテープを剥離試験用圧着ローラー（２ｋｇ）を用いて圧着させ、テープの端を４５°の角度に傾けながら秒速７５ｍｍの速さで引き剥がし、膜が残っているパターンの数を以下のように評価した。また光学顕微鏡を用いて以下の基準で密着性の評価を行った。 About the obtained pattern, a cellophane tape is pressed using a pressure roller (2 kg) for a peeling test, and the tape is peeled off at a speed of 75 mm / sec while tilting the end of the tape at an angle of 45 °. The numbers were evaluated as follows. The adhesion was evaluated using an optical microscope according to the following criteria.
５点：はがれが全く生じていない。
４点：はがれが生じている。はがれが生じた碁盤目の数が全体の５％未満。
３点：はがれが生じている。はがれが生じた碁盤目の数が全体の５％以上２５％未満。
２点：はがれが生じている。はがれが生じた碁盤目の数が全体の２５％以上６０％未満。
１点：はがれが生じている。はがれが生じた碁盤目の数が全体の６０％以上。 5 points: No peeling occurred.
4 points: Peeling has occurred. Less than 5% of the grids where peeling occurred.
3 points: Peeling has occurred. The number of grids where peeling occurred is 5% or more and less than 25%.
2 points: Peeling has occurred. The number of grids where peeling has occurred is 25% or more and less than 60% of the whole.
1 point: Peeling has occurred. The number of grids where peeling has occurred is 60% or more of the total.
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
　上記表に示すように、実施例の組成物は密着性に優れたパターンを形成することができた。 よ う As shown in the above table, the compositions of Examples were able to form patterns having excellent adhesion.

Claims (20)

  1. 　色材、重合性化合物、光重合開始剤を含有する硬化性組成物であって、
    　前記色材の含有量が、前記組成物の全固形分に対して３０質量％以上であり、
    　前記光重合開始剤は、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上である光重合開始剤Ａ１と、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上である光重合開始剤Ａ２とを含み、
    　前記組成物の波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上である、硬化性組成物。     A coloring material, a polymerizable compound, a curable composition containing a photopolymerization initiator,
    The content of the coloring material is 30% by mass or more based on the total solid content of the composition,
    The photopolymerization initiator includes a photopolymerization initiator A1 having an absorption coefficient at a wavelength of 365 nm in methanol of 1.0 × 10 3 mL / gcm or more, and an absorption coefficient of 1.0 × at a wavelength of 365 nm in methanol. A photopolymerization initiator A2 having an absorption coefficient of not more than 10 2 mL / gcm and a wavelength of 254 nm of not less than 1.0 × 10 3 mL / gcm,
    A curable composition, wherein the ratio A / B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more. .
  2. 　前記光重合開始剤Ａ１がオキシム化合物である、
    　請求項１に記載の硬化性組成物。     The photopolymerization initiator A1 is an oxime compound,
    The curable composition according to claim 1.
  3. 　前記オキシム化合物が、フッ素原子を含む化合物である、
    　請求項２に記載の硬化性組成物。     The oxime compound is a compound containing a fluorine atom,
    The curable composition according to claim 2.
  4. 　前記光重合開始剤Ａ２がヒドロキシアルキルフェノン化合物である、
    　請求項１～３のいずれか１項に記載の硬化性組成物。     The photopolymerization initiator A2 is a hydroxyalkylphenone compound,
    The curable composition according to any one of claims 1 to 3.
  5. 　前記光重合開始剤Ａ２が下記式（Ａ２－１）で表される化合物である、
    　請求項１～３のいずれか１項に記載の硬化性組成物；
    式（Ａ２－１）：
    Figure JPOXMLDOC01-appb-C000001
     　式中Ｒｖ1は、置換基を表し、Ｒｖ2およびＲｖ3は、それぞれ独立して、水素原子または置換基を表し、Ｒｖ2とＲｖ3とが互いに結合して環を形成していてもよく、ｍは０～５の整数を表す。     The photopolymerization initiator A2 is a compound represented by the following formula (A2-1):
    Curable composition according to any one of claims 1 to 3;
    Formula (A2-1):
    Figure JPOXMLDOC01-appb-C000001
     In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may combine with each other to form a ring. , M represents an integer of 0 to 5.
  6. 　前記光重合開始剤Ａ１の１００質量部に対して、前記光重合開始剤Ａ２を５０～２００質量部含有する、
    　請求項１～５のいずれか１項に記載の硬化性組成物。     The photopolymerization initiator A2 contains 50 to 200 parts by mass with respect to 100 parts by mass of the photopolymerization initiator A1.
    The curable composition according to any one of claims 1 to 5.
  7. 　前記硬化性組成物の全固形分中における前記光重合開始剤Ａ１と前記光重合開始剤Ａ２の合計の含有量が５～１５質量％である、
    　請求項１～６のいずれか１項に記載の硬化性組成物。     The total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the curable composition is 5 to 15% by mass.
    The curable composition according to any one of claims 1 to 6.
  8. 　前記重合性化合物がエチレン性不飽和基を３個以上含む化合物である、
    　請求項１～７のいずれか１項に記載の硬化性組成物。     The polymerizable compound is a compound containing three or more ethylenically unsaturated groups,
    The curable composition according to any one of claims 1 to 7.
  9. 　前記重合性化合物がエチレン性不飽和基とアルキレンオキシ基とを含む化合物である、
    　請求項１～８のいずれか１項に記載の硬化性組成物。     The polymerizable compound is a compound containing an ethylenically unsaturated group and an alkyleneoxy group,
    The curable composition according to any one of claims 1 to 8.
  10. 　前記光重合開始剤Ａ１と前記光重合開始剤Ａ２の合計１００質量部に対して、前記重合性化合物を１７０～３４５質量部含有する、
    　請求項１～９のいずれか１項に記載の硬化性組成物。     The polymerizable compound is contained in an amount of 170 to 345 parts by mass with respect to a total of 100 parts by mass of the photopolymerization initiator A1 and the photopolymerization initiator A2.
    The curable composition according to any one of claims 1 to 9.
  11. 　前記硬化性組成物の全固形分中における前記重合性化合物の含有量が１７．５～２７．５質量％である、
    　請求項１～１０のいずれか１項に記載の硬化性組成物。     The content of the polymerizable compound in the total solid content of the curable composition is 17.5 to 27.5% by mass;
    The curable composition according to any one of claims 1 to 10.
  12. 　前記色材が、ビスベンゾフラノン化合物、ペリレン化合物およびアゾ化合物の少なくとも１種を含む黒色色材である、
    　請求項１～１１のいずれか１項に記載の硬化性組成物。     The color material is a black color material containing at least one of a bisbenzofuranone compound, a perylene compound, and an azo compound.
    The curable composition according to any one of claims 1 to 11.
  13. 　前記色材が少なくとも３種の化合物を含む、
    　請求項１～１２のいずれか１項に記載の硬化性組成物。     The colorant includes at least three compounds,
    The curable composition according to any one of claims 1 to 12.
  14. 　さらに、環状エーテル構造を有する化合物と、前記環状エーテル構造を有する化合物の硬化促進剤とを含む、
    　請求項１～１３のいずれか１項に記載の硬化性組成物。     Further, comprising a compound having a cyclic ether structure and a curing accelerator for the compound having a cyclic ether structure,
    The curable composition according to any one of claims 1 to 13.
  15. 　さらに樹脂を含む、
    　請求項１～１４のいずれか１項に記載の硬化性組成物。     Further containing resin,
    The curable composition according to any one of claims 1 to 14.
  16. 　請求項１～１５のいずれか１項に記載の硬化性組成物を硬化して得られる硬化膜。 A cured film obtained by curing the curable composition according to any one of claims 1 to 15.
  17. 　請求項１～１５のいずれか１項に記載の硬化性組成物を用いて支持体上に硬化性組成物層を形成する工程と、
    　前記硬化性組成物層に対して、３５０ｎｍを超え３８０ｎｍ以下の波長を有する光を照射し、パターン状に露光する第１の露光工程と、
    　前記硬化性組成物層を現像する現像工程と、
    　前記現像工程後に、前記硬化性組成物層に対して、２５４～３５０ｎｍの波長を有する光を照射する第２の露光工程と、を有するパターンの形成方法。     A step of forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 15,
    A first exposure step of irradiating the curable composition layer with light having a wavelength of more than 350 nm and not more than 380 nm, and exposing in a pattern;
    A developing step of developing the curable composition layer,
    A second exposure step of irradiating the curable composition layer with light having a wavelength of 254 to 350 nm after the development step.
  18. 　前記現像工程と前記第２の露光工程の間、および、前記第２の露光工程の後の少なくともいずれかの期間に、低酸素雰囲気下、２００℃未満の温度で前記硬化性組成物層を加熱する工程を有する、
    　請求項１７に記載の方法。     Heating the curable composition layer at a temperature of less than 200 ° C. in a low oxygen atmosphere between the developing step and the second exposing step and / or at least any period after the second exposing step. Having a step of
    The method according to claim 17.
  19. 　請求項１６に記載の硬化膜を有する光学フィルタ。 An optical filter having the cured film according to claim 16.
  20. 　請求項１６に記載の硬化膜を有する光センサ。 An optical sensor having the cured film according to claim 16.
PCT/JP2019/036905 2018-09-26 2019-09-20 Curable composition, cured film, method for forming pattern, optical filter and photosensor WO2020066871A1 (en)

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