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WO2023068201A1 - Pigment dispersion, photosensitive resin composition, cured product, black matrix, and image display device - Google Patents

Pigment dispersion, photosensitive resin composition, cured product, black matrix, and image display device Download PDF

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Publication number
WO2023068201A1
WO2023068201A1 PCT/JP2022/038423 JP2022038423W WO2023068201A1 WO 2023068201 A1 WO2023068201 A1 WO 2023068201A1 JP 2022038423 W JP2022038423 W JP 2022038423W WO 2023068201 A1 WO2023068201 A1 WO 2023068201A1
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WO
WIPO (PCT)
Prior art keywords
group
sulfonic acid
mass
pigment
resin composition
Prior art date
Application number
PCT/JP2022/038423
Other languages
French (fr)
Japanese (ja)
Inventor
宏明 石井
謙一 入木
翔 藤本
Original Assignee
三菱ケミカル株式会社
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 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to KR1020247012626A priority Critical patent/KR20240090190A/en
Priority to JP2023554654A priority patent/JPWO2023068201A1/ja
Priority to CN202280069849.7A priority patent/CN118103464A/en
Publication of WO2023068201A1 publication Critical patent/WO2023068201A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C09C1/58—Agglomerating, pelleting, or the like by wet methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • 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
    • 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
    • G03F7/09—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
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

  • the present invention relates to a pigment dispersion, a photosensitive resin composition, a cured product, a black matrix (hereinafter sometimes abbreviated as "BM"), and an image display device.
  • BM black matrix
  • a color filter is usually formed by forming a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially forming pixels of three or more different colors such as red, green, and blue in a lattice or stripe pattern. It is formed in a pattern such as a shape or a mosaic shape.
  • the pattern size varies depending on the application of the color filter and each color, but is usually about 5 to 700 ⁇ m.
  • the pigment dispersion method is known as a representative manufacturing method for color filters.
  • a photosensitive resin composition containing a black pigment such as carbon black is applied on a transparent substrate, dried under reduced pressure in a vacuum drying apparatus, and then heated and dried on a hot plate.
  • the BM is formed by curing by high temperature treatment at 200° C. or higher, and this is repeated for each color such as red, green, and blue to form pixels.
  • a color filter with BM and pixels is formed.
  • the drying by heating on the hot plate progresses unevenly, the film thickness uniformity deteriorates, and uneven development may occur on the BM and pixels. There was a problem that was greatly exacerbated.
  • BM is generally arranged between red, green, and blue pixels in a grid, stripe, or mosaic pattern, and has the role of improving contrast by suppressing color mixing between pixels and preventing light leakage. . Therefore, BM is required to have a high light shielding property.
  • BM is required to have a high light shielding property.
  • a step is formed at the overlapping portion due to the influence of the film thickness of the BM. In this overlapping portion, the flatness of the pixels is impaired, and the liquid crystal cell gap becomes nonuniform or the orientation of the liquid crystal is disturbed, resulting in deterioration of the display performance. Therefore, in recent years, there has been a particular demand for thinning and thinning the film thickness of the BM. If unevenness occurs, deterioration in adhesion of the BM becomes particularly noticeable.
  • the pattern line width is 10 ⁇ m or more, even if one side of the BM thin line is inserted by about 1 to 2 ⁇ m (the total of both sides of the thin line is about 2 to 4 ⁇ m), the thin line adhesion to the substrate can be maintained, but the line width is 10 ⁇ m. Since the adhesion area at the BM/substrate interface becomes small in a fine line pattern having a thickness of less than 1 ⁇ m, the degree of reduction in pattern adhesion increases remarkably every time the line width is narrowed by 1 ⁇ m.
  • a photosensitive resin composition that is excellent in fine line adhesion and development solubility, and efforts are being made to improve pigment dispersions that affect fine line properties and development solubility.
  • a dispersing aid in a pigment dispersion, and examples of the dispersing aid include compounds containing a carboxy group, a sulfonic acid group, or a phosphoric acid group. From the viewpoint of industrial applicability, a sulfonic acid group-containing compound may be used.
  • Patent Document 1 development adhesion and residue are improved by blending a dispersion pigment using a dispersing aid (sulfonic acid group-containing compound) having an acid value of 0 to 30 in a specific alkali-soluble resin.
  • a dispersing aid sulfonic acid group-containing compound having an acid value of 0 to 30 in a specific alkali-soluble resin.
  • an object of the present invention is to provide a pigment dispersion from which a photosensitive resin composition having excellent solubility and fine line adhesion can be obtained, and a photosensitive resin composition using the same.
  • the gist of the present invention resides in the following.
  • the (C) sulfonic acid group-containing compound is a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfone.
  • [3] The pigment dispersion according to [1], wherein the (C) sulfonic acid group-containing compound contains a copper phthalocyanine sulfonic acid derivative.
  • the content ratio of the (A) pigment and the (C) sulfonic acid group-containing compound on a mass basis ((A) pigment/(C) sulfonic acid group-containing compound) is 10 or more
  • Any of [1] to [4], wherein the content ratio ((A) pigment/(B) dispersant) on a mass basis of the (A) pigment and the (B) dispersant is 4 or more The pigment dispersion according to 1.
  • Photosensitive containing (A) pigment, (B) dispersant, (C) sulfonic acid group-containing compound, (D) alkali-soluble resin, (E) photopolymerizable compound and (F) photopolymerization initiator
  • the (C) sulfonic acid group-containing compound has an electrical conductivity of 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less
  • the (C) sulfonic acid group-containing compound has an acid value of 40 mgKOH/g or more.
  • a photosensitive resin composition A photosensitive resin composition.
  • the (C) sulfonic acid group-containing compound is a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfone.
  • the photosensitive resin composition according to [7], wherein the (C) sulfonic acid group-containing compound comprises a copper phthalocyanine sulfonic acid derivative.
  • the present invention it is possible to provide a pigment dispersion from which a photosensitive resin composition having excellent solubility and fine line adhesion can be obtained, and a photosensitive resin composition using the same.
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device having a color filter of the present invention.
  • (meth)acryl means "acryl and/or methacryl", and the same applies to "(meth)acrylate” and "(meth)acryloyl”.
  • total solid content means all components other than the solvent contained in the photosensitive resin composition or the pigment dispersion, even if the components other than the solvent are liquid at room temperature, the solid content include in
  • the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
  • the "amine value” represents the amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. .
  • the measuring method will be described later.
  • the acid value represents an acid value in terms of effective solid content, and is calculated by neutralization titration.
  • the pigment dispersion of the present invention is a pigment dispersion containing (A) a pigment, (B) a dispersant and (C) a sulfonic acid group-containing compound, wherein the electrical conductivity of the (C) sulfonic acid group-containing compound is 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less, and the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
  • a photosensitive resin composition is prepared using the pigment dispersion of the present invention, the solubility and fine line adhesion are excellent.
  • a photosensitive resin composition can be obtained.
  • the pigment dispersion of the present invention may further contain other components as necessary, such as solvents, alkali-soluble resins, and dyes.
  • solvents such as solvents, alkali-soluble resins, and dyes.
  • the solvent and alkali-soluble resin used in the photosensitive resin composition of the present invention, which will be described later, can be preferably used.
  • the pigment dispersion of the present invention contains (A) a pigment.
  • (A) Pigment refers to a pigment that colors the pigment dispersion and the photosensitive resin composition of the present invention.
  • pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments can be used.
  • organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments
  • various inorganic pigments can also be used. is.
  • pigments that can be used in the present invention are shown below by pigment numbers.
  • terms such as "C.I. Pigment Red 2" mentioned below mean a color index (C.I.).
  • red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168,
  • C.I. I. Pigment Blue 1 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned.
  • C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60 more preferably C.I. I. Pigment Blue 15:6,60 may be mentioned.
  • C.I. I. Pigment Green 1 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 .
  • C.I. I. Pigment Green 7, 36, 58, 59 can be mentioned.
  • C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180, 185 can be mentioned.
  • C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.
  • C.I. I. Pigment Orange 38, 64, 71 may be mentioned.
  • C.I. I. Pigment Violet 1 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.
  • C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23, 29 may be mentioned.
  • a black pigment can be used as the pigment (A).
  • the black pigment may be a black pigment alone or a mixture of red, green, blue, and the like.
  • these pigments can be appropriately selected from inorganic or organic pigments.
  • Pigments that can be mixed to prepare black pigments include, for example, Victoria Pure Blue (42595), Auramine O (41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). , Safranin OK 70:100 (50240), Erioglaucine X (42080), No.
  • 120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), First Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36) (Note that the numbers in ( ) above mean the color index (C.I.).).
  • C.I. I. When indicated by number, for example, C.I. I. yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. orange pigments 36, 43, 51, 55, 59, 61, 64, C.I. I. red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, C.I. I. violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. blue pigment 15, 15:1, 15:4, 22, 60, 64, C.I. I. green pigment 7, C.I. I. Brown pigments 23, 25, 26 may be mentioned.
  • black pigments examples include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
  • black pigments when a black pigment is used, the above-described black pigment that can be used alone is preferable from the viewpoint of light shielding rate and image characteristics, and carbon black is particularly preferable.
  • carbon black examples include the following carbon blacks.
  • pigments for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide can be used. These various pigments can also be used in combination of multiple types. For example, a green pigment and a yellow pigment can be used together, or a blue pigment and a violet pigment can be used together for chromaticity adjustment.
  • the average particle size of the pigment (A) used in the present invention is not particularly limited as long as it can develop a desired color when used as a black matrix for a color filter, for example, and is also dependent on the type of pigment used. Although different, it is preferably 10 to 100 nm, more preferably 10 to 70 nm. When the average particle diameter of the pigment is within the above range, the color characteristics of the liquid crystal display device manufactured using the pigment dispersion of the present invention tend to be of high quality.
  • the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more. For example, 20 to 60 nm is preferable, and 20 to 50 nm is more preferable.
  • the average particle size of the pigment can be obtained by directly measuring the size of primary particles from an electron micrograph. Specifically, the short axis diameter and long axis diameter of each primary particle are measured, and the average thereof is taken as the particle size of the particle.
  • the volume (mass) of each particle is obtained by approximating the rectangular parallelepiped of the obtained particle diameter, and the volume average particle diameter is obtained and taken as the average particle diameter.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the pigment dispersion of the present invention may also contain a dye as long as the effect of the present invention is not affected.
  • Dyes that can be used in combination include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dyes examples include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. Mordant Black 7 is mentioned.
  • anthraquinone dyes examples include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 may be mentioned.
  • C.I. I. Vat Blue 5 can be used as a quinoneimine dye, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 can be used as a quinoline dye, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 can be used as a nitro dye, for example C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 is mentioned.
  • the photosensitive resin composition using the pigment dispersion of the present invention can be used for various applications described later, but the excellent image formability is particularly high when it is used to form a black matrix for color filters. Effective.
  • a black pigment such as the carbon black or titanium black described above may be used, or a plurality of types of pigments other than black may be mixed and adjusted to black. .
  • the photosensitive resin composition of the present invention which will be described later, has a large effect on fine line adhesion in a region where the pigment concentration is high. Especially in recent years, it is necessary to increase the pigment concentration in order to increase the degree of light blocking.
  • the content of the pigment (A) in such a region where the effect is increased is 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, relative to the total solid content of the photosensitive resin composition. , 52% by mass or more is particularly preferred. From the viewpoint of image forming performance, it is preferably 70% by mass or less, more preferably 65% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 30 to 70% by mass is preferable, 40 to 70% by mass is more preferable, 50 to 65% by mass is even more preferable, and 52 to 65% by mass is particularly preferable.
  • a photosensitive resin composition with high light-shielding properties can be obtained by setting the pigment content within the above range. Specifically, by setting the content of the pigment (A) to 50% by mass or more relative to the total solid content of the photosensitive resin composition, a black matrix having a thickness of 1 ⁇ m is formed using the photosensitive resin composition of the present invention.
  • the optical density when formed can be set to a value of 4.0 or more. The optical density is more preferably 4.1 or higher, still more preferably 4.2 or higher. In areas with high light-shielding properties, peeling of the patterning due to development is likely to be observed. The thin wire adhesion effect of the present invention can be well confirmed.
  • the content of (A) pigment is not particularly limited, but (D) per 100 parts by mass of alkali-soluble resin, preferably 20 parts by mass or more, more preferably 50 parts by mass or more, More preferably 100 parts by mass or more, still more preferably 120 parts by mass or more, even more preferably 150 parts by mass or more, particularly preferably 180 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass parts or less, more preferably 250 parts by mass or less.
  • (A) When the content of the pigment is equal to or higher than the lower limit, it tends to suppress the deterioration of the solubility of the unexposed area in the developing solution. tend to improve.
  • the above upper and lower limits can be combined arbitrarily. For example, preferably 20 to 500 parts by mass, more preferably 50 to 500 parts by mass, still more preferably 100 to 300 parts by mass, even more preferably 120 to 300 parts by mass, even more preferably 150 to 250 parts by mass, particularly preferably is 180 to 250 parts by mass.
  • the pigment dispersion liquid of the present invention contains (B) a dispersant because it is important to finely disperse (A) the pigment and stabilize the dispersion state in order to ensure the stability of the quality.
  • a dispersant a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxy group; Polymeric dispersants having functional groups such as primary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred.
  • polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are particularly preferred.
  • basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are particularly preferred.
  • polymer dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers.
  • examples include system dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • dispersants include trade names of EFKA (registered trademark, manufactured by EFKA Chemicals B.V. (EFKA)), Disperbyk (registered trademark, manufactured by BYK-Chemie), and Disparon (registered trademark).
  • EFKA registered trademark, manufactured by EFKA Chemicals B.V.
  • Disperbyk registered trademark, manufactured by BYK-Chemie
  • Disparon registered trademark
  • Kusumoto Kasei Co., Ltd. SOLSPERSE (registered trademark, manufactured by Lubrizol)
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow or Floren registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.
  • Ajisper registered trademark, Ajinomoto Fine manufactured by Techno Co., Ltd.
  • One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.
  • urethane polymer dispersant and/or an acrylic polymer dispersant having a basic functional group as the (B) dispersant in terms of fine line adhesion and linearity.
  • urethane-based polymer dispersants are preferred from the standpoint of fine wire adhesion.
  • Polymeric dispersants having basic functional groups and polyester and/or polyether bonds are preferred from the standpoint of dispersibility and storage stability.
  • the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less.
  • Mw weight average molecular weight
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably from 700 to 100,000, more preferably from 700 to 50,000, even more preferably from 1,000 to 30,000.
  • urethane-based and acrylic polymer dispersants include Disperbyk 160-167, 182 series (all of which are urethane-based), Disperbyk 2000, 2001, etc.
  • Disperbyk 167 and 182 are particularly preferred urethane polymer dispersants having a polyester and/or polyether bond and having a weight average molecular weight of 30,000 or less.
  • Urethane polymer dispersants include, for example, polyisocyanate compounds, compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, and compounds having active hydrogen and a tertiary amino group in the same molecule. and a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting with.
  • polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
  • Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.
  • trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part
  • trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
  • Examples of compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has 1 to 1 carbon atoms. Those alkoxylated with 25 alkyl groups and mixtures of two or more thereof are included.
  • Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof.
  • polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of
  • Polyether ester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly( polyoxytetramethylene)adipate.
  • the most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentane
  • polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate
  • polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. is mentioned. These may be used individually by 1 type, and may use 2 or more types together.
  • the compound having one or two hydroxyl groups in the same molecule preferably has a number average molecular weight of 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom
  • active hydrogen includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group.
  • a hydrogen atom of the amino group of is preferred.
  • the tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
  • Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N- dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1, 4-butanediamine may be mentioned.
  • the nitrogen-containing heterocyclic ring includes, for example, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, and benzimidazole ring.
  • N-containing hetero five-membered rings such as benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, nitrogen-containing hetero ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring
  • nitrogen-containing heterocycles are imidazole rings and triazole rings.
  • Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole and 1-(2-aminoethyl)imidazole.
  • Examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4 -triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl -1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole.
  • N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable. These may be used individually by 1 type, and may use 2 or more types together.
  • the compounding ratio of raw materials when producing a urethane polymer dispersant is 100 parts by mass of a polyisocyanate compound, and a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule, preferably 10. ⁇ 200 parts by mass, more preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, a compound having active hydrogen and a tertiary amino group in the same molecule, preferably 0.2 to 25 parts by mass, more It is preferably 0.3 to 24 parts by mass.
  • Urethane-based polymer dispersants are produced according to known methods for producing polyurethane resins.
  • Solvents for production include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane.
  • Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.
  • a urethanization reaction catalyst may be used in the above production.
  • this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; triethylamine and triethylenediamine; and a tertiary amine-based catalyst. These may be used individually by 1 type, and may use 2 or more types together.
  • the amine value of the dispersant is expressed by the mass of KOH equivalent to the amount of base per 1 g of the solid content excluding the solvent in the dispersant sample, and can be measured by the following method. Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO 4 (perchloric acid) acetic acid solution.
  • the inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.
  • Amine value [mgKOH/g] (561 x V)/(W x S) [However, W: Amount of weighed dispersant sample [g], V: Amount of titration [mL] at the end point of titration, S: Solid content concentration [% by mass] of dispersant sample. ]
  • the introduction amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled to 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably 5 to 95 mgKOH/g.
  • the amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. When the amine value is above the lower limit, the dispersibility tends to be good, and when the amine value is below the upper limit, the developability tends to be good.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 50,000.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 30,000 or less. For example, 1,000 to 30,000 is preferred, 2,000 to 30,000 is more preferred, and 3,000 to 30,000 is even more preferred.
  • the dispersibility and dispersion stability tend to be improved by setting the amount to the lower limit or more, and the solubility tends to be improved by setting the amount to the upper limit or less.
  • the molecular weight is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is particularly high.
  • Such particularly preferred commercially available urethane dispersants include, for example, Disperbyk 167 and 182 (manufactured by BYK-Chemie).
  • the content ratio ((A) pigment/(B) dispersant) based on mass of (A) pigment and (B) dispersant is preferably 1 or more, more preferably 3 or more, and 4 More preferably, 5 or more is particularly preferable. Moreover, it is preferably 50 or less, more preferably 30 or less, and particularly preferably 15 or less.
  • the content is at least the above lower limit, the development solubility tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 50 are preferred, 3 to 50 are more preferred, 4 to 30 are even more preferred, and 5 to 15 are particularly preferred.
  • the content of the dispersant (B) described later in the photosensitive resin composition of the present invention is not particularly limited, but the total solid content of the photosensitive resin composition is preferably 50% by mass or less, more preferably 30% by mass. % or less, more preferably 20% by mass or less, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass % or more.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, still more preferably 5 to 30% by mass, still more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass.
  • the content ratio of the dispersant (B) described later in the photosensitive resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the (A) pigment. More preferably 15 parts by mass or more, preferably 200 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 50 parts by mass or less.
  • the lower limit By making it equal to or higher than the lower limit, there is a tendency to easily ensure sufficient dispersibility.
  • the content to the above upper limit or less, there is a tendency to easily achieve sufficient color density, sensitivity, film formability, etc., without reducing the ratio of other components.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 200 parts by mass, more preferably 10 to 80 parts by mass, still more preferably 15 to 50 parts by mass.
  • the pigment dispersion liquid of the present invention contains (C) a sulfonic acid group-containing compound in order to improve dispersibility and storage stability.
  • the (C) sulfonic acid group-containing compound include azo compounds, phthalocyanine compounds, quinacridone compounds, benzimidazolone compounds, quinophthalone compounds, isoindolinone compounds, dioxazine compounds, anthraquinone compounds, indanthrene compounds, perylene compounds, and perinone compounds. derivatives of diketopyrrolopyrrole-based and dioxazine-based compounds. Among them, derivatives of phthalocyanine-based and quinophthalone-based compounds are preferred.
  • the sulfonic acid group-containing compound has a sulfonic acid group, and other substituents include, for example, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. Examples thereof include compounds that may be bonded directly to the skeleton of the compound or via, for example, an alkyl group, an aryl group, or a heterocyclic group.
  • the sulfonic acid group-containing compound has, in addition to the sulfonic acid group, other substituents such as a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. directly or via, for example, an alkyl group, an aryl group, or a heterocyclic group. These other substituents may be plurally substituted on the skeleton of one compound.
  • substituents such as a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. directly or via, for example, an alkyl group, an aryl group, or a heterocyclic group.
  • Sulfonic acid group-containing compounds include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. More preferably a phthalocyanine sulfonic acid derivative, and even more preferably a copper phthalocyanine sulfonic acid derivative.
  • the (C) sulfonic acid group-containing compound includes a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, or a dioxazine sulfonic acid derivative.
  • Acid derivatives are preferred, phthalocyanine sulfonic acid derivatives are more preferred, and copper phthalocyanine sulfonic acid derivatives are even more preferred. These may be used individually by 1 type, and may use 2 or more types together.
  • the content of (C) the sulfonic acid group-containing compound contained in the pigment dispersion of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the pigment dispersion. It is more preferably 1.0% by mass or more, more preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5.0% by mass or less.
  • the content is equal to or higher than the lower limit, there is a tendency that the dispersion stability is improved. Further, when the content is equal to or less than the above upper limit, there is a tendency that the pigment aggregation is suppressed and the coated film surface becomes uniform.
  • the content ratio ((A) pigment/(C) sulfonic acid group-containing compound) of (A) pigment and (C) sulfonic acid group-containing compound on a mass basis is preferably 10 or more. 20 or more is more preferable, and 25 or more is particularly preferable. Also, it is preferably 200 or less, more preferably 150 or less, still more preferably 100 or less, and particularly preferably 50 or less.
  • the content is equal to or higher than the lower limit, there is a tendency that the adhesion to the substrate is improved.
  • dispersion stability to improve by making it below the said upper limit.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 200 are preferred, 10 to 150 are more preferred, 20 to 100 are even more preferred, and 25 to 50 are particularly preferred.
  • the content ratio of (C) the sulfonic acid group-containing compound contained in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more relative to the total solid content of the photosensitive resin composition. , 0.5% by mass or more is more preferable, 1.0% by mass or more is more preferable, and 10% by mass or less is preferable, and 5% by mass or less is more preferable.
  • the content is at least the above lower limit, there is a tendency that the development solubility is improved. Further, when the content is set to the upper limit value or less, the developability tends to be stable and the patterning adhesion tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferable, 0.5 to 10% by mass is more preferable, and 1.0 to 5% by mass is even more preferable.
  • the electrical conductivity of the sulfonic acid group-containing compound is 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less.
  • the electrical conductivity of the (C) sulfonic acid group-containing compound is expressed by the electrical conductivity when the (C) sulfonic acid group-containing compound is stirred in ultrapure water so as to form a 5% solution, and is measured with an electrical conductivity meter. be able to.
  • the unit can be described in ⁇ S/cm.
  • the electrical conductivity of the sulfonic acid group-containing compound is 2000 ⁇ S/cm or more, preferably 2500 ⁇ S/cm or more, more preferably 3000 ⁇ S/cm or more, and 9000 ⁇ S/cm or less, preferably 8000 ⁇ S/cm or less. , 7000 ⁇ S/cm or less.
  • the content is equal to or higher than the lower limit, there is a tendency that the dispersion stability is improved.
  • the content is equal to or less than the above upper limit, there is a tendency that undercut is suppressed and development adhesion is improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is 2000 to 9000 ⁇ S/cm, preferably 2500 to 8000 ⁇ S/cm, more preferably 3000 to 7000 ⁇ S/cm.
  • the acid value of the sulfonic acid group-containing compound is 40 mgKOH/g or more, preferably 60 mgKOH/g or more, more preferably 80 mgKOH/g or more, still more preferably 90 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more; Also, it is preferably 500 mgKOH/g or less, more preferably 300 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.
  • the solubility tends to be improved by adjusting the content to be equal to or higher than the above lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that undercutting is suppressed and fine line adhesion is improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 40 to 500 mgKOH/g is preferred, 60 to 500 mgKOH/g is more preferred, 80 to 300 mgKOH/g is still more preferred, 90 to 200 mgKOH/g is even more preferred, and 100 to 150 mgKOH/g is particularly preferred.
  • the pigment dispersion of the present invention for example, (A) a pigment, (B) a dispersant and (C) a sulfonic acid group-containing compound, and optionally various materials used are dissolved or dispersed in a solvent.
  • a solvent water or an organic solvent used in the photosensitive resin composition of the present invention, which will be described later, can be suitably used.
  • the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the pigment dispersion is preferably 5% by mass or more. , More preferably 10% by mass or more, still more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, particularly preferably 35% by mass or less be.
  • the content is at least the lower limit, the coloring power is improved, and the optical density (OD value) tends to be easily increased.
  • the amount is equal to or less than the above upper limit, there is a tendency that the dispersion stability becomes good.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 50% by mass, more preferably 5 to 45% by mass, even more preferably 10 to 40% by mass, particularly preferably 20 to 35% by mass.
  • the photosensitive resin composition of the present invention includes (A) a pigment, (B) a dispersant, (C) a sulfonic acid group-containing compound, (D) an alkali-soluble resin, (E) a photopolymerizable compound and (F) a photopolymerization initiator.
  • the (C) sulfonic acid group-containing compound has an electrical conductivity of 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less, and the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
  • the (A) pigment, (B) dispersant, and (C) sulfonic acid group-containing compound contained in the photosensitive resin composition of the present invention can be preferably used.
  • Alkali-soluble resin especially if the solubility of the exposed area and the non-exposed area in alkali development changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed.
  • the alkali-soluble resin is preferably an alkali-soluble resin having a carboxy group.
  • those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxyl group are more preferable. An example is shown below.
  • the (D) alkali-soluble resin in the present invention preferably contains an alkali-soluble resin (d1) having a partial structure represented by the following general formula (d1-1). Including the alkali-soluble resin (d1) tends to improve adhesion.
  • the benzene ring in formula (d1-1) may be further substituted with any substituent.
  • Each R7 independently represents a hydrogen atom or a methyl group.
  • Each X independently represents O, S, CO, or a direct bond.
  • Each * represents a bond.
  • n represents an integer of 0 to 4;
  • n is preferably 3 or less, more preferably 2 or less, and even more preferably 0 from the viewpoint of sensitivity.
  • R7 is preferably a hydrogen atom.
  • X is preferably a direct bond from the viewpoint of sensitivity.
  • Alkali-soluble resin (d1) having a partial structure represented by formula (d1-1) is obtained, for example, by adding (meth)acrylic acid to an epoxy resin having a cardo skeleton represented by formula (d7-1) below. Furthermore, it is preferably an alkali-soluble resin obtained by reacting a polybasic acid and/or its anhydride.
  • the benzene ring in formula (d7-1) may be further substituted with any substituent.
  • Each X independently represents O, S, CO, or a direct bond.
  • n represents an integer of 0 to 4;
  • n represents an integer of 0 to 4, preferably 3 or less, more preferably 2 or less, and even more preferably 0.
  • a known technique can be used as a method for adding (meth)acrylic acid to the epoxy resin.
  • the reaction can be carried out at a temperature of 50-150° C. in the presence of an esterification catalyst.
  • the catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. , dodecyltrimethylammonium chloride and the like can be used.
  • the amount of (meth)acrylic acid used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the epoxy resin.
  • polybasic acids and/or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexacarboxylic acid, One or more selected from hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof can be mentioned.
  • polybasic acid and/or its anhydride For the addition reaction of polybasic acid and/or its anhydride, a known method can be used, and the desired product can be obtained by continuous reaction under the same conditions as the addition reaction of (meth)acrylic acid. .
  • Polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol are added during the addition reaction synthesis of the alkali-soluble resin (d1) polybasic acid and/or its anhydride to introduce a multibranched structure. good.
  • Alkali-soluble resin (d1) for example, after mixing a reaction product of epoxy resin and (meth)acrylic acid with polybasic acid and / or its anhydride, or after mixing epoxy resin and (meth)acrylic acid It is obtained by heating after mixing a polybasic acid and/or its anhydride and a polyhydric alcohol with a reactant.
  • the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. By heating, the polybasic acid and/or its anhydride undergo an addition reaction with any hydroxyl group present in the mixture of the reaction product with (meth)acrylic acid and the polyhydric alcohol.
  • the amount of the polyhydric alcohol used is the amount of the reaction product of the epoxy resin and (meth)acrylic acid and the polybasic acid and / or its anhydride from the viewpoint of exhibiting the effect while suppressing thickening and gelation. It is usually about 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight, the reactant.
  • the alkali-soluble resin (d1) may be used alone, or two or more resins may be mixed and used.
  • the acid value of the alkali-soluble resin (d1) is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, and 200 mgKOH/g or less. is preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. Residue tends to be reduced by making it equal to or higher than the lower limit. Moreover, there is a tendency that fine wire adhesion can be improved by adjusting the content to be equal to or less than the above upper limit. The above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH/g is preferred, 50 to 200 mgKOH/g is more preferred, 80 to 150 mgKOH/g is even more preferred, and 80 to 120 mgKOH/g is particularly preferred.
  • the polystyrene equivalent weight average molecular weight (Mw) of the alkali-soluble resin (d1) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 2000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. . Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 7,000 or less. By making it more than the said lower limit, there exists a tendency for thin line
  • the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,000 to 15,000 is more preferred, 2,000 to 10,000 is even more preferred, 4,000 to 8,000 is even more preferred, and 5,000 to 7,000 is particularly preferred.
  • the photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the alkali-soluble resin (d1) as the (D) alkali-soluble resin.
  • the alkali-soluble resin other than the alkali-soluble resin (d1) after the coating film obtained by applying and drying the photosensitive resin composition is exposed, the solubility of the exposed area and the non-exposed area in alkali development changes.
  • it is not particularly limited as long as it is a substance, it is preferably an alkali-soluble resin having a carboxy group.
  • those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxy group are more preferable.
  • Specific examples include an epoxy (meth)acrylate resin (d2) having a carboxy group other than the alkali-soluble resin (d1), an acrylic copolymer resin (d3), and other resins (d4).
  • Epoxy (meth)acrylate resin (d2) having a carboxy group other than alkali-soluble resin (d1) for example, the following epoxy (meth)acrylate resin (d2-1), epoxy (meth)acrylate resin (d2-2 ).
  • ⁇ Epoxy (meth)acrylate resin (d2-2)> An ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and/or its anhydride. Alkali-soluble resin obtained by
  • epoxy resins used as raw materials include bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corp.'s "jER (registered trademark; the same shall apply hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.), bisphenol Epoxy obtained by reaction of alcoholic hydroxyl group of A-type epoxy resin and epichlorohydrin (for example, "NER-1302” manufactured by Nippon Kayaku Co., Ltd.
  • bisphenol A type epoxy resins e.g., Mitsubishi Chemical Corp.'s "jER (registered trademark; the same shall apply hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.
  • bisphenol Epoxy obtained by reaction of alcoholic hydroxyl group of A-type epoxy resin and epichlorohydrin for example, "NER-1302” manufactured by Nippon Kayaku Co., Ltd.
  • TEPIC trisphenolmethane type epoxy resin
  • EPPN registered trademark
  • EPPN-502 manufactured by Nippon Kayaku Co., Ltd.
  • EPPN-503 trisphenolmethane type epoxy resin
  • alicyclic epoxy resins (“Celoxide (registered trademark) 2021P” and “Celoxide EHPE” manufactured by Daicel)
  • glycidylated phenolic resins by the reaction of dicyclopentadiene and phenol.
  • Epoxy resins e.g., "EXA-7200” manufactured by DIC Corporation, "NC-7300” manufactured by Nippon Kayaku Co., Ltd.
  • epoxy resins represented by the following general formulas (d2-a) to (d2-e) are preferred.
  • b11 indicates an average value and indicates a number from 0 to 10.
  • R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group.
  • a plurality of R 11 present in one molecule may be the same or different.
  • b12 represents an average value and represents a number from 0 to 10.
  • R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 21 in one molecule may be the same or different.
  • X represents a linking group represented by general formula (d2-c-1) or (d2-c-2) below. However, it contains one or more adamantane structures in its molecular structure.
  • b13 represents an integer of 2 or 3;
  • R 31 to R 34 and R 35 to R 37 each independently represent an optionally substituted adamantyl group, a hydrogen atom, It represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group.
  • the * mark in the formula represents the binding site in (d2-c).
  • each of R 51 to R 54 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • each R 55 is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; It is an alkylene group.
  • k is an integer of 1 to 5
  • l is an integer of 0 to 13
  • m is each independently an integer of 0 to 5.
  • n and o are each independently an integer of 1-9.
  • R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group.
  • a plurality of R 23 present in one molecule may be the same or different.
  • Examples of ⁇ , ⁇ -unsaturated monocarboxylic acids or ⁇ , ⁇ -unsaturated monocarboxylic acid esters having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, Monocarboxylic acids such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 - (meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2 - (meth) acryloyloxy
  • a monomer or Alternatively, a monomer having one hydroxyl group at the terminal such as hydroxyalkyl (meth)acrylate, or a compound having one hydroxyl group at the terminal such as pentaerythritol tri(meth)acrylate, (anhydrous) succinic acid examples include (meth)acrylic esters to which an acid (anhydride) such as (anhydride) phthalic acid and (anhydride) maleic acid is added and which has one or more ethylenically unsaturated groups and one carboxyl group at the end. (Meth)acrylic acid dimers are also included.
  • (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.
  • a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin a known technique can be used.
  • an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. can.
  • the catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. , dodecyltrimethylammonium chloride and the like can be used.
  • tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine
  • tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and
  • the epoxy resin, the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may be used singly, or two kinds may be used. You may use the above together.
  • the amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. , 0.7 to 1.1 equivalents is more preferred.
  • the amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group By setting the amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the amount of the unsaturated group introduced becomes sufficient, and the subsequent polybasic acid And/or the reaction with its anhydride becomes sufficient, and there is a tendency that a large amount of epoxy groups can be suppressed from remaining.
  • the amount to be equal to or less than the upper limit it is possible to suppress the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group from remaining as an unreacted product.
  • the same compound as the alkali-soluble resin (d1) can be used as the polybasic acid and/or its anhydride and polyhydric alcohol. Also, the same synthetic method as that for the alkali-soluble resin (d1) can be used.
  • the acid value of the epoxy (meth)acrylate resins (d2-1, d2-2) thus obtained is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 80 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH/g is preferred, 50 to 200 mgKOH/g is more preferred, and 80 to 150 mgKOH/g is even more preferred.
  • the polystyrene equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resins (d2-1, d2-2) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, and 2000 or more. is more preferable, and 2300 or more is particularly preferable. Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less. When the content is at least the above lower limit, sensitivity, coating film strength and alkali resistance tend to be improved.
  • the developability and the re-solubility can be improved by adjusting the content to the above upper limit or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,000 to 15,000 is more preferred, 1,500 to 10,000 is even more preferred, 2,000 to 8,000 is even more preferred, and 2,300 to 6,000 is particularly preferred.
  • acrylic copolymer resin (d3) examples include Japanese Patent Laid-Open Nos. 7-207211, 8-259876, 10-300922, and 11-140144. Publications, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2003-233179, Japanese Patent Application Publication No. 2007-270147, etc. Any polymeric compound can be used. Preferred are the following acrylic copolymer resins (d3-1) to (d3-4). Among them, the acrylic copolymer resin (d3-1) is particularly preferred.
  • Acrylic copolymer resin (d3-1) for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, at least some of the epoxy groups of the copolymer are unsaturated A resin obtained by adding a monobasic acid, or a resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction.
  • Acrylic copolymer resin (d3-2) Linear alkali-soluble resin containing a carboxy group in the main chain.
  • alkali-soluble resins (d4) are alkali-soluble resins (d1), epoxy (meth)acrylate resins (d2) having carboxy groups other than alkali-soluble resins (d1), and alkali-soluble resins (d3) other than acrylic copolymer resins (d3).
  • alkali-soluble resins (d1) alkali-soluble resins (d1), epoxy (meth)acrylate resins (d2) having carboxy groups other than alkali-soluble resins (d1), and alkali-soluble resins (d3) other than acrylic copolymer resins (d3).
  • the content of the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably, based on the total solid content of the photosensitive resin composition of the present invention. 15% by mass or more, particularly preferably 20% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, especially Preferably, it is 25% by mass or less.
  • the amount is at least the above lower limit, the solubility of the unexposed portion in the developer tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, still more preferably 10 to 50% by mass, even more preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass.
  • the content of (D) alkali-soluble resin relative to 100 parts by mass of (E) photopolymerizable compound is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and 200 parts by mass.
  • the above is more preferable.
  • it is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, still more preferably 600 parts by mass or less, and particularly preferably 400 parts by mass or less.
  • it is at least the above lower limit, there is a tendency that the unexposed portion has good solubility in a developer.
  • the above upper limit when it is not more than the above upper limit, it is possible to suppress excessive permeation of the developer into the exposed area, and there is a tendency that the sharpness of the image and the fine line adhesion are improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 1000 parts by mass, more preferably 100 to 800 parts by mass, even more preferably 150 to 600 parts by mass, and particularly preferably 200 to 400 parts by mass.
  • the photosensitive resin composition of the present invention contains (E) a photopolymerizable compound in terms of sensitivity and the like.
  • (E) As the photopolymerizable compound it is preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. is.
  • the sensitivity of the photosensitive resin composition tends to be high when it is equal to or higher than the lower limit, and shrinkage on curing during polymerization tends to be small when it is equal to or lower than the upper limit.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 2 to 10, more preferably 3 to 10, still more preferably 4 to 8.
  • polyfunctional ethylenic monomers examples include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Polyvalent hydroxy compounds such as polyhydroxy compounds, esters obtained by esterification reaction with unsaturated carboxylic acids and polybasic carboxylic acids, etc., and esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. .
  • ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • Acrylic acid esters of aliphatic polyhydroxy compounds such as acrylates, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylics obtained by replacing the acrylates of these exemplary compounds with methacrylates
  • Acid esters similarly, itaconic acid esters instead of itaconates, crotonic acid esters instead of clonates, and maleic acid esters instead of maleates are mentioned, and acrylic acid esters of aliphatic polyhydroxy compounds and meta-esters of aliphatic polyhydroxy compounds. Acrylic acid esters are preferred.
  • Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. and acid esters.
  • a polybasic carboxylic acid and an unsaturated carboxylic acid and an ester obtained by an esterification reaction of a polyhydric hydroxy compound are not necessarily single substances, but typical examples include acrylic acid, phthalic acid, and Condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol.
  • polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester.
  • urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful. These may be used individually by 1 type, and may use 2 or more types together.
  • the content of the photopolymerizable compound is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass, based on the total solid content of the photosensitive resin composition. %, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the content of the photopolymerizable compound is equal to or less than the above upper limit, there is a tendency that the penetration of the developer into the exposed area becomes moderate and good images can be obtained.
  • the lower limit of the content of (E) the photopolymerizable compound is not particularly limited, it is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 90% by mass, more preferably 1 to 70% by mass, still more preferably 1 to 50% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, particularly preferably is 5 to 10% by mass.
  • the photosensitive resin composition of the present invention contains (F) a photopolymerization initiator.
  • the photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. If necessary, an additive such as a sensitizing dye may be added for use.
  • Photopolymerization initiators include, for example, Japanese Patent Laid-Open Nos. 59-152396 and 61-151197, metallocene compounds containing titanocene compounds; Hexaarylbiimidazole derivatives described in JP-A-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl- ⁇ -amino acids such as N-phenylglycine described in JP-A-10-39503 Radical activators such as N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Examples thereof include oxime ester derivatives described in JP-A-2003-201215 and the like.
  • Titanocene derivatives include, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl-1-yl), Dicyclopentadienyl titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl
  • Biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl ) imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′ -methoxyphenyl)-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2 '-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6′′-benzofuryl)vinyl)]-1,3,4-oxadiazole , 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloro methyl)-s-triazine.
  • ⁇ -aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1 ,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone.
  • oxime ester derivatives are particularly effective in terms of sensitivity.
  • oxime ester derivatives oxime ester compounds and keto oxime ester compounds
  • having excellent sensitivity are useful.
  • oxime ester derivatives are preferred from the viewpoint of adhesion to substrates.
  • the photopolymerization initiator of the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so it is highly sensitive even in a small amount and can react with heat. It is stable against , and it is possible to design a highly sensitive photosensitive resin composition in a small amount.
  • an oxime ester compound containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring)
  • This structural characteristic is well expressed, which is more preferable.
  • a thin BM black matrix
  • the pigment concentration is also increasing more and more. It is particularly effective in such circumstances.
  • oxime ester-based compound examples include compounds containing a structural moiety represented by the following general formula (22), preferably oxime ester-based compounds represented by the following general formula (23).
  • R 22 is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, or 3 carbon atoms.
  • ⁇ 8 cycloalkanoyl group C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxycarbonylalkanoyl group, C2-C10 amino It represents an alkylcarbonyl group, an aroyl group having 7 to 20 carbon atoms, a heteroaroyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.
  • R 21a is hydrogen, or an optionally substituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 25 carbon atoms, heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, aminoalkyl group having 1 to 20 carbon atoms , a C2-12 alkanoyl group, a C3-25 alkenoyl group, a C3-8 cycloalkanoyl group, a C7-20 aroyl group, a C1-20 heteroaroyl group, a C2 1 to 10 alkoxycarbonyl groups, aryloxycarbonyl groups having 7 to 20 carbon atoms, or cycloalkylalkyl groups having 1 to 10 carbon atoms
  • R 22a represents the same group as R 22 in formula (22).
  • R 22 in formula (22) and R 22a in formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a cycloalkanoyl group having 3 to 8 carbon atoms. are mentioned.
  • R 21a in formula (23) is preferably an unsubstituted straight-chain alkyl group such as methyl, ethyl or propyl, or a cycloalkylalkyl group, or propyl substituted with an N-acetyl-N-acetoxyamino group. groups.
  • R 21b in formula (23) preferably includes an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenylsulfide group.
  • R 21b in formula (23) is an optionally substituted carbazolyl group
  • R 21b in formula (23) is an optionally substituted carbazolyl group
  • optionally substituted aryl groups having 6 to 25 carbon atoms optionally substituted arylcarbonyl groups having 7 to 25 carbon atoms
  • optionally substituted heteroaryl groups having 5 to 25 carbon atoms substituted A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms which may be substituted and a nitro group is preferred.
  • a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group and a nitro group is particularly preferred. Moreover, it is desirable that these groups are bonded to the 3-position of the carbazolyl group.
  • photopolymerization initiators for such oxime ester compounds include OXE-02 manufactured by BASF and TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics.
  • photopolymerization initiator of the oxime ester compound suitable for the present invention include the compounds exemplified below, but are not limited to these compounds.
  • the ketoxime ester-based compound includes a compound containing a structural moiety represented by the following general formula (24), preferably a ketoxime ester-based compound represented by the following general formula (25).
  • R 24 has the same definition as R 22 in formula (22).
  • R 23a is an optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms , an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aroyl group having 7 to 20 carbon atoms, a carbon number It represents a heteroaroyl group having 1 to 20 carbon atoms,
  • R 23b represents any substituent containing an aromatic or heteroaromatic ring.
  • R 24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a carbon heteroaroyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylaminocarbonyl group having 2 to 20 carbon atoms represents R 24 in formula (24) and R 24a in general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a cyclo An alkanoyl group and an aroyl group having 7 to 20 carbon atoms can be mentioned.
  • R 23a in formula (25) preferably includes an unsubstituted ethyl group, propyl group, butyl group, and an ethyl group or propyl group substituted with a methoxycarbonyl group.
  • R 23b in formula (25) preferably includes an optionally substituted carbazolyl group and an optionally substituted phenylsulfide group.
  • Specific examples of the ketoxime ester compounds suitable for the present invention include compounds as exemplified below, but are not limited to these compounds.
  • photopolymerization initiators for such ketoxime ester compounds include OXE-01 manufactured by BASF Corporation and TR-PBG-305 manufactured by Changzhou Power Electronics Co., Ltd.
  • oxime ester compounds and keto oxime ester compounds are themselves known compounds.
  • is a kind of compound of One type of the photopolymerization initiator may be used alone, or two or more types may be used in combination.
  • benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone anthraquinone derivatives; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2 -phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, ⁇ -hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropy
  • the photopolymerization initiator (F) can be combined with a sensitizing dye corresponding to the wavelength of the image exposure light source for the purpose of increasing the sensitivity.
  • these sensitizing dyes include, for example, JP-A-4-221958, xanthene dyes described in JP-A-4-219756, JP-A-3-239703, JP-A-5- A coumarin dye having a heterocycle described in JP-A-289335, a 3-ketocoumarin compound described in JP-A-3-239703, a 3-ketocoumarin compound described in JP-A-5-289335, and a JP-A-6-19240
  • JP-A-6-19240 The pyrromethene dyes described above, Japanese Patent Laid-Open Nos.
  • amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred.
  • Benzophenone compounds such as diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl) benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzo
  • the content of the photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 2% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. is 3% by mass or more, particularly preferably 4% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less, Particularly preferably, it is 8% by mass or less. Sensitivity tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that the adhesion stress with the substrate is improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass, still more preferably 3 to 10% by mass, and particularly preferably 4 to 8% by mass.
  • the content of the oxime ester compound is not particularly limited. It is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more, relative to the solid content. Also, it is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. When the content is equal to or higher than the lower limit, the sensitivity tends to be improved, and fine line adhesion is improved.
  • the amount is not more than the above upper limit, there is a tendency that the solubility of the unexposed portion in the developing solution is improved.
  • the above upper and lower limits can be combined arbitrarily. It is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass, even more preferably 3 to 10% by mass, and particularly preferably 4 to 8% by mass.
  • the content of the sensitizing dye is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, more preferably 0 to 15% by mass, in the total solid content of the photosensitive resin composition. 10% by mass.
  • the photosensitive resin composition of the present invention may contain a surfactant for the purpose of adjusting coatability.
  • surfactants include BYK-330 (manufactured by BYK-Chemie, surface tension 24.4 mN/m), F-475 (manufactured by DIC, surface tension 25.4 mN/m), F-554 (manufactured by DIC, surface tension of 23.3 mN/m).
  • 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and ratios.
  • the content of the surfactant is not particularly limited. 05% by mass or more is more preferable, 0.1% by mass or more is even more preferable, and 0.15% by mass or more is particularly preferable. Also, it is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.
  • the content is at least the above lower limit, the coating film uniformity tends to be improved and the fine line adhesion tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1.0% by mass is preferable, 0.05 to 0.7% by mass is more preferable, 0.1 to 0.5% by mass is more preferable, and 0.15 to 0.3% by mass is particularly preferable.
  • ⁇ Solvent> In the photosensitive resin composition of the present invention, for example, (D) an alkali-soluble resin, (E) a photopolymerizable compound and (F) a photopolymerization initiator and various materials used as necessary are dissolved in an organic solvent. Or used in a distributed state.
  • the organic solvent it is preferable to select an organic solvent having a boiling point (under a pressure of 1013.25 [hPa]; hereinafter, the same applies to all boiling points) in the range of 100 to 300°C.
  • Organic solvents are more preferred.
  • organic solvents examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, and propylene glycol-t.
  • -butyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl glycol monoalkyl ethers such as ethers, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
  • glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-
  • Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone
  • aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropi
  • Halogenated hydrocarbons such as butyl chloride, amyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile;
  • solvents include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve ("Cellosolve” is a registered trademark. The same shall apply hereinafter.), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (any are also trade names).
  • organic solvents may be used alone or in combination of two or more.
  • an organic solvent having a boiling point of 100 to 250°C more preferably an organic solvent having a boiling point of 120 to 230°C.
  • Glycol alkyl ether acetates are preferable as the organic solvent because they have a good balance of coatability, surface tension, etc., and the solubility of each component of the photosensitive resin composition is relatively high.
  • glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • organic solvents that may be used in combination, glycol monoalkyl ethers are preferred, and propylene glycol monomethyl ether is preferred in view of the solubility of the components in the composition.
  • the proportion of the glycol monoalkyl ether in the organic solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.
  • an organic solvent having a boiling point of 200°C or higher (hereinafter sometimes referred to as a "high boiling point solvent”) may be used together.
  • a high boiling point solvent makes the photosensitive resin composition difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to the deposition and solidification of the coloring material at the tip of the slit nozzle.
  • dipropylene glycol methyl ether acetate diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene Glycol diacetate, triacetin, 1,6-hexanediol diacetate are preferred.
  • the content of the high-boiling solvent in the organic solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass. .
  • the value is equal to or higher than the lower limit, it tends to be possible to suppress, for example, the deposition and solidification of the coloring material at the tip of the slit nozzle and the occurrence of foreign matter defects.
  • the drying temperature is set to the above upper limit or less, the drying temperature of the composition tends to be slowed, which tends to suppress the occurrence of problems such as tact failure in the reduced pressure drying process and pin marks during prebaking in the color filter manufacturing process.
  • the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, particularly preferably 20% by mass It is added so that it becomes the mass % or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the total solid content in the photosensitive resin composition is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 8 to 25% by mass, and particularly preferably 10 to 20% by mass. may be added as follows.
  • ⁇ Other compounding components of the photosensitive resin composition in addition to the components described above, for example, thiols, additives, development modifiers, ultraviolet absorbers, and antioxidants can be appropriately blended.
  • the photosensitive resin composition of the present invention may contain thiols in order to increase sensitivity and improve adhesion to substrates.
  • Thiols include, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate.
  • butanediol bisthiopropionate trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane (trade name; Karenz MT BD1, manufactured by Showa Denko KK), butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT
  • Polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are preferred, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are more preferred, and Karenz MT PE1 is even more preferred.
  • the content of the thiols is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, more preferably It is 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less.
  • the content is equal to or less than the above upper limit, there is a tendency that the storage stability tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 10% by mass, more preferably 0.3 to 10% by mass, still more preferably 0.5 to 5% by mass.
  • Additives may be added to improve adhesion to the substrate.
  • examples include silane coupling agents and titanium coupling agents.
  • a silane coupling agent is particularly preferred.
  • Silane coupling agents include, for example, KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040. , Z-6043 and Z-6062 (manufactured by Dow Corning Toray).
  • One type of silane coupling agent may be used, or two or more types may be used in combination.
  • additives other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, examples of which include phosphoric acid-based additives and other additives.
  • (meth)acryloyloxy group-containing phosphates are preferred. Among them, those represented by the following general formulas (g1), (g2) and (g3) are preferable.
  • R 51 each independently represents a hydrogen atom or a methyl group
  • l and l′ each independently represent an integer of 1 to 10
  • m each independently represents 1, 2 or 3.
  • Other additives include, for example, TEGO * Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesion agents may be used alone or in combination of two or more.
  • the content of the additive is not particularly limited, but the total solid content of the photosensitive resin composition is preferably 0.01% by mass or more, and 0.10% by mass. % or more, more preferably 0.50% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 2.0% by mass or less, and 1.5% by mass or less. % by mass or less is particularly preferred. Adhesion tends to be improved by making it more than the said lower limit. Further, when the content is set to the upper limit value or less, the developability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5.0% by mass is preferable, 0.01 to 3.0% by mass is more preferable, 0.10 to 2.0% by mass is more preferable, and 0.50 to 1.5% by mass is Especially preferred.
  • the photosensitive resin composition of the present invention can be suitably used for black matrix formation. From this point of view, it is preferable that the color is black. Moreover, it is preferable that the optical density (OD value) per 1.0 ⁇ m of film thickness of the cured coating film is 4.0 or more. It is more preferably 4.1 or more, further preferably 4.2 or more, and preferably 6.0 or less. By making it equal to or higher than the lower limit, there is a tendency that sufficient light shielding properties can be ensured. For example, 4.0 to 6.0 is preferred, 4.1 to 6.0 is more preferred, and 4.2 to 6.0 is even more preferred.
  • the optical density is the transmission optical density in which the spectral sensitivity characteristic of the light receiving portion is indicated by ISO visual density in the ISO 5-3 standard.
  • the A light source defined by CIE International Commission on Illumination
  • An example of a measuring instrument that can be used to measure transmission optical density is X-Rite 361T(V) manufactured by Sakata Inx Engineering.
  • the pigment dispersion of the present invention is produced by a conventional method.
  • the pigment is preferably dispersed in advance using, for example, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, or homogenizer. Since the pigment (A) is finely divided by the dispersion treatment, the application properties of the photosensitive resin composition are improved.
  • A When a black pigment is used as the pigment, it contributes to the improvement of the light shielding ability.
  • Dispersion treatment is usually carried out in a system in which (A) a pigment, (B) a dispersant, (C) a sulfonic acid group-containing compound, a solvent, and optionally (D) some or all of an alkali-soluble resin are used in combination.
  • A a pigment
  • B a dispersant
  • C a sulfonic acid group-containing compound
  • solvent a solvent
  • D some or all of an alkali-soluble resin
  • the temperature condition of the dispersion treatment is preferably 0°C to 100°C, more preferably room temperature (25°C) to 80°C.
  • the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate.
  • the aim of dispersion is to control the glossiness of the ink so that the 20° specular glossiness (JIS Z8741) of the photosensitive resin composition is in the range of 100-200.
  • the dispersion treatment is sufficient, residual coarse pigment (coloring material) particles are suppressed, and sufficient developability, adhesion, and resolution are obtained. easy to get Further, when the 20-degree specular gloss value is 200 or less, the pigment is not excessively crushed, the production of a large number of ultrafine particles is suppressed, and the dispersion stability is less likely to be impaired.
  • the photosensitive resin composition of the present invention is produced by a conventional method.
  • the ink obtained by the dispersion treatment described above and other components contained in the photosensitive resin composition can be mixed to form a uniform solution.
  • fine dust is often mixed in the liquid, so it is desirable to filter the obtained photosensitive resin composition with a filter or the like.
  • the cured product of the invention can be obtained by curing the photosensitive resin composition of the invention.
  • a cured product obtained by curing the photosensitive resin composition of the present invention can be suitably used as a member constituting a color filter such as a pixel, a black matrix or a colored spacer.
  • the black matrix of the invention consists of the cured product of the invention.
  • the material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength.
  • a transparent substrate is used.
  • Materials for the transparent substrate include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, epoxy resins, unsaturated polyester resins, Examples include thermosetting resin sheets such as poly(meth)acrylic resins and various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resin are preferable.
  • a transparent electrode such as ITO or IZO may be deposited on the surface of the substrate. Other than the transparent substrate, a transparent electrode may be formed on the TFT array.
  • the support may be subjected, if necessary, to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, and thin film formation treatment using various resins such as silane coupling agents and urethane resins. may be performed.
  • the thickness of the support is preferably 0.05-10 mm, more preferably 0.1-7 mm.
  • the film thickness is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m.
  • the photosensitive resin composition is applied onto a transparent substrate, dried, and then the photosensitive resin composition is applied and dried.
  • a black matrix can be formed by imagewise exposure through a photomask placed on a transparent substrate, development, and thermal curing or photocuring as necessary.
  • the coating of the photosensitive resin composition for the black matrix onto the transparent substrate can be performed by, for example, spinner method, wire bar method, flow coating method, It can be carried out by a die coating method, a roll coating method, or a spray coating method.
  • the die-coating method is preferable from the viewpoints that the amount of the coating liquid used is significantly reduced, and the mist that adheres when the spin-coating method is used does not have an effect, and the generation of foreign matter is suppressed.
  • the thickness of the coating film after drying is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 6 ⁇ m, even more preferably 1 to 4 ⁇ m.
  • the conditions for heat drying can be appropriately selected according to the type of organic solvent, the performance of the dryer to be used, and the like.
  • the temperature is 40 to 200° C. for 15 seconds to 5 minutes, more preferably 50 to 130° C. for 30 seconds to 3 minutes.
  • Imagewise exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating light of wavelengths from the ultraviolet region to the visible region through this mask pattern. can be done.
  • the exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film.
  • the light source used for the above image exposure is not particularly limited.
  • Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arcs.
  • An optical filter can also be used when using it by irradiating the light of a specific wavelength.
  • the black matrix of the present invention is prepared by subjecting a coating film made of a photosensitive resin composition to imagewise exposure with the light source described above, followed by an organic solvent or an aqueous solution containing a surfactant and an alkaline compound.
  • the development used can be used to form an image on the substrate.
  • This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes and pigments.
  • Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine , mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. compound. These alkaline compounds may be used singly or in combination of two or more.
  • TMAH tetramethylammonium hydroxide
  • surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters
  • Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate
  • organic solvents examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol.
  • the organic solvent may be used alone or in combination with an aqueous solution.
  • the developing temperature is preferably 10 to 50°C, more preferably 15 to 45°C, even more preferably 20 to 40°C.
  • the development method may be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
  • the substrate after development is subjected to heat curing treatment or photocuring treatment, preferably heat curing treatment.
  • the temperature is preferably 100-280°C, more preferably 150-250°C.
  • the time is preferably 5 to 60 minutes.
  • the height of the black matrix formed as described above is preferably 0.5 to 5 ⁇ m, more preferably 0.8 to 4 ⁇ m.
  • a photosensitive resin composition containing a coloring material of one of red, green, and blue is applied in the same process as (3-1) to (3-5) above, and dried. After that, a photomask is overlaid on the coating film, imagewise exposure through the photomask, development, and if necessary, thermal curing or photocuring are performed to form a pixel image, thereby forming a colored layer.
  • a color filter can be formed by performing this operation for each of the three photosensitive resin compositions of red, green, and blue (the order may be arbitrary).
  • the photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for colored spacers in addition to the black matrix.
  • the TFTs may malfunction as switching elements due to light incident on the TFTs.
  • Colored spacers are used to prevent this.
  • JP-A-2004-110003 describes that the spacer is light-shielding.
  • the colored spacers can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.
  • the color filter is used as a part of a color display, a liquid crystal display device, or the like by forming a transparent electrode such as ITO on an image as it is.
  • a transparent electrode such as ITO
  • a top coat layer such as polyamide or polyimide may be provided on the image, if necessary.
  • IPS mode planar orientation driving system
  • the image display device of the present invention has the cured product of the present invention.
  • the image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display.
  • the liquid crystal display device of the present invention has the cured product of the present invention, particularly the black matrix, and the order and positions of forming the color pixels and the black matrix are not particularly limited.
  • an alignment film is formed on a color filter, spacers are sprinkled on the alignment film, and then a counter substrate is attached to form a liquid crystal cell.
  • a resin film such as polyimide is suitable.
  • a gravure printing method and/or a flexographic printing method can be employed for forming the alignment film, and the thickness of the alignment film may be several tens of nm.
  • the surface After hardening the alignment film by heat baking, the surface may be processed by irradiating with ultraviolet rays or by treatment with a rubbing cloth so as to obtain a surface state capable of adjusting the tilt of the liquid crystal.
  • a spacer having a size corresponding to the gap (clearance) with the counter substrate is used, and a spacer of 2 to 8 ⁇ m is suitable.
  • a photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer.
  • An array substrate can be used as the opposing substrate, and a TFT (thin film transistor) substrate is particularly suitable.
  • the gap between the substrate and the opposing substrate may be 2 to 8 ⁇ m, depending on the application of the liquid crystal display device.
  • the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin.
  • the sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.
  • the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell.
  • the degree of pressure reduction in the liquid crystal cell is preferably 1 ⁇ 10 -2 to 1 ⁇ 10 -7 Pa, more preferably 1 ⁇ 10 -3 to 1 ⁇ 10 -6 Pa.
  • the heating temperature is preferably 30 to 100°C, more preferably 50 to 90°C. Heating and holding at reduced pressure may be for 10 to 60 minutes, and then immersed in liquid crystal.
  • a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curing resin.
  • the type of liquid crystal is not particularly limited.
  • it may be a conventionally known liquid crystal such as an aromatic system, an aliphatic system, or a polycyclic compound, such as a lyotropic liquid crystal or a thermotropic liquid crystal.
  • Thermotropic liquid crystals may be, for example, nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, or the like.
  • Organic EL display The organic EL display of the invention is produced using the color filter of the invention.
  • a color filter is prepared by forming a resin black matrix (not shown) provided between the pixels 20, and an organic light emitter 500 is formed on the color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween.
  • the organic EL element 100 can be produced by laminating the .
  • At least one of the pixels 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention.
  • the transparent anode 50, the hole injection layer 51, the hole transport layer 52, the light emitting layer 53, the electron injection layer 54, and the cathode 55 are sequentially formed on the upper surface of the color filter.
  • organic EL element 100 for example, the method described in "Organic EL Display” (Ohmsha, Aug. 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata). can produce an organic EL display.
  • the color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.
  • TMP trimethylolpropane
  • BPDA biphenyltetracarboxylic dianhydride
  • THPA tetrahydrophthalic anhydride
  • the constituent components of the pigment dispersion liquid and the photosensitive resin composition used in the following examples and comparative examples are as follows.
  • Sulfonic acid group-containing compound A electrical conductivity 2080 ⁇ S/cm, acid value 80 mgKOH/g Sulfonic acid group-containing compound B: electrical conductivity 5100 ⁇ S/cm, acid value 81 mgKOH/g Sulfonic acid group-containing compound C: electrical conductivity 9012 ⁇ S/cm, acid value 83 mgKOH/g Sulfonic acid group-containing compound D: electrical conductivity 1420 ⁇ S/cm, acid value 40 mgKOH/g
  • Compound E C.I. I. Pigment Blue 15:6 (electrical conductivity 0 ⁇ S/cm, acid value 0 mgKOH/g)
  • Alkali-soluble resin-1 Resin described in Synthesis Example
  • DPHA "KAYARAD DPHA” (polyfunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.
  • TR-PBG-304 "TR-PBG-304" (an oxime ester compound having a carbazole skeleton) manufactured by Changzhou Power Electronics New Materials Co., Ltd.
  • X-12-1048 Shin-Etsu Chemical Co., Ltd. "X-12-1048" (polyfunctional acrylic silane)
  • a photosensitive resin composition was coated on a glass substrate with a spin coater so that the film thickness after heat curing was 1.2 ⁇ m, dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 100 ° C. for 120 seconds. bottom.
  • a photomask having a line width opening of 1 ⁇ m to 20 ⁇ m in increments of 1 ⁇ m is used as a photomask for the resulting coating film, and ultraviolet rays having a wavelength of 365 nm and an intensity of 60 mW/cm 2 are used to expose the coating film. Exposure processing was carried out so as to obtain 40 mJ/cm 2 .
  • a photosensitive resin composition was coated on a glass substrate with a spin coater so that the film thickness after heat curing was 1.2 ⁇ m, dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 100 ° C. for 120 seconds. bottom.
  • a photomask having a line width opening of 1 ⁇ m to 20 ⁇ m in increments of 1 ⁇ m is used as a photomask for the resulting coating film, and ultraviolet rays having a wavelength of 365 nm and an intensity of 60 mW/cm 2 are used to expose the coating film. Exposure processing was carried out so as to obtain 40 mJ/cm 2 .
  • a substrate was prepared in the same manner as the thin line adhesion evaluation substrate, and the linearity of the pattern corresponding to the 6 ⁇ m opening of the photomask was measured using an optical microscope.
  • Example 1 From Example 1, Example 2, and Comparative Example 1, when the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 ⁇ S/cm or less and the acid value is 40 mgKOH/g or more, the solubility in development is excellent and the fine line adhesion is good. It was shown to be superior in terms of performance. On the other hand, when the electrical conductivity of (C) the sulfonic acid group-containing compound exceeds 9000 ⁇ S/cm, that is, when the electrical conductivity increases, the amount of free acid due to poor pigment adsorption of the (C) sulfonic acid group-containing compound increases. It is thought that the dissolution time was shortened and the undercut was emphasized, which deteriorated the fine wire adhesion.
  • Example 3 and Comparative Example 1 if the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 ⁇ S / cm or less, the amount of (C) the sulfonic acid group-containing compound relative to the amount of pigment Even when the content was increased from 2% to 10%, the fine wire adhesion did not deteriorate, and the dissolution rate did not change significantly. From Example 1, Example 4 and Comparative Example 1, if the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 ⁇ S / cm or less, the amount of dispersant is changed from 20% to 25% with respect to the amount of pigment. Even if it was increased, the fine wire adhesion did not deteriorate, and the dissolution rate did not change significantly.
  • Example 1 and Comparative Example 2 when the electrical conductivity of (C) the sulfonic acid group-containing compound is less than 2000 ⁇ S/cm, the acid value around the pigment is significantly decreased, resulting in a long dissolution time and poor fine line adhesion. was shown. It was also shown that the linearity deteriorated and it became difficult to form thin lines. From Example 1, Comparative Example 2, and Comparative Example 3, when the electrical conductivity of (C) the sulfonic acid group-containing compound is less than 2000 ⁇ S/cm and the acid value is less than 40 mgKOH/g, the pigment adsorption capacity is lost.
  • the sulfonic acid group-containing compound has an electrical conductivity of 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less and an acid value of 40 mgKOH/g or more, thereby minimizing the influence of the free acid. It was shown that the fine wire adhesion and linearity were improved, and the amount of change in dissolution time could be reduced.

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Abstract

Provided are a pigment dispersion from which a photosensitive resin composition having exceptional solubility and fine-line adhesiveness is obtained, and a photosensitive resin composition in which the pigment dispersion is used. This pigment dispersion contains (A) a pigment, (B) a dispersant, and (C) a sulfonate-group-containing compound. The electrical conductivity of the (C) sulfonate-group-containing compound is 2000-9000 μS/cm inclusive, and the acid value of the (C) sulfonate-group-containing compound is 40 mg KOH/g or greater.

Description

顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置Pigment dispersion liquid, photosensitive resin composition, cured product, black matrix and image display device
　本発明は、顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス（Ｂｌａｃｋ　Ｍａｔｒｉｘ。以下「ＢＭ」と略称することがある。）及び画像表示装置に関する。
　本願は、２０２１年１０月２０日に日本出願された特願２０２１－１７１５６６号、及び２０２１年１２月９日に日本出願された特願２０２１－１９９７７３号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a pigment dispersion, a photosensitive resin composition, a cured product, a black matrix (hereinafter sometimes abbreviated as "BM"), and an image display device.
This application claims priority based on Japanese Patent Application No. 2021-171566 filed in Japan on October 20, 2021 and Japanese Patent Application No. 2021-199773 filed in Japan on December 9, 2021. incorporated here.
　カラーフィルターは、通常、ガラス、プラスチック等の透明基板の表面に、黒色のブラックマトリックスを形成し、続いて、赤、緑、青等の３種以上の異なる色の画素を順次、格子状、ストライプ状またはモザイク状等のパターンで形成したものである。パターンサイズはカラーフィルターの用途並びにそれぞれの色により異なるが通常５～７００μｍ程度である。 A color filter is usually formed by forming a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially forming pixels of three or more different colors such as red, green, and blue in a lattice or stripe pattern. It is formed in a pattern such as a shape or a mosaic shape. The pattern size varies depending on the application of the color filter and each color, but is usually about 5 to 700 μm.
　カラーフィルターの代表的な製造方法として、顔料分散法が知られている。顔料分散法によりカラーフィルターを製造する場合、まずカーボンブラック等の黒色顔料を含有する感光性樹脂組成物を透明基板上に塗布した後に真空乾燥装置にて減圧乾燥し、その後ホットプレートにて加熱乾燥させ、さらに画像露光、現像した後、２００℃以上の高温処理により硬化（キュア）させることでＢＭを形成し、これを赤、緑、青等の各色ごとに繰り返し、画素を形成することで、ＢＭ及び画素を有するカラーフィルターを形成する。しかし、上記のホットプレートでの加熱乾燥が不均一に進行すると膜厚均一性が悪化し、ＢＭ及び画素上に現像ムラが発生することがあり、特に過現像されてしまう部分においてＢＭの密着性が大幅に悪化する問題があった。 The pigment dispersion method is known as a representative manufacturing method for color filters. When producing a color filter by a pigment dispersion method, first, a photosensitive resin composition containing a black pigment such as carbon black is applied on a transparent substrate, dried under reduced pressure in a vacuum drying apparatus, and then heated and dried on a hot plate. Further, after image exposure and development, the BM is formed by curing by high temperature treatment at 200° C. or higher, and this is repeated for each color such as red, green, and blue to form pixels. A color filter with BM and pixels is formed. However, if the drying by heating on the hot plate progresses unevenly, the film thickness uniformity deteriorates, and uneven development may occur on the BM and pixels. There was a problem that was greatly exacerbated.
　ＢＭは、赤、緑、青等の画素の間に格子状、ストライプ状またはモザイク状に配置するのが一般的であり、各画素間の混色抑制によるコントラスト向上あるいは光漏れを防止する役目がある。このため、ＢＭには高い遮光性が要求される。また、ＢＭ形成後に形成する赤、緑、青等の画素のエッジ部は、このＢＭと一部が重なるため、ＢＭの膜厚の影響を受けて、重なり部分で段差が形成される。この重なり部分では、画素の平坦性が損なわれ、液晶セルギャップの不均一化あるいは液晶の配向の乱れが発生して、表示能力低下の原因となる。そこで近年は特にＢＭの膜厚を細線化及び薄膜化することが求められており、薄膜化した際でも十分な遮光性を発現するために、ＢＭ中の顔料濃度が高くなる方向にあり、現像ムラが発生すると特にＢＭの密着性の悪化が顕著になる。 BM is generally arranged between red, green, and blue pixels in a grid, stripe, or mosaic pattern, and has the role of improving contrast by suppressing color mixing between pixels and preventing light leakage. . Therefore, BM is required to have a high light shielding property. In addition, since the edges of pixels such as red, green, and blue formed after forming the BM partially overlap with the BM, a step is formed at the overlapping portion due to the influence of the film thickness of the BM. In this overlapping portion, the flatness of the pixels is impaired, and the liquid crystal cell gap becomes nonuniform or the orientation of the liquid crystal is disturbed, resulting in deterioration of the display performance. Therefore, in recent years, there has been a particular demand for thinning and thinning the film thickness of the BM. If unevenness occurs, deterioration in adhesion of the BM becomes particularly noticeable.
　加えて、省エネルギー化やモバイルバッテリーの長寿命化のため、バックライトの出力は低くなる方向にあり、そのような条件下にあっても高輝度で画像表示できるよう、遮光部であるＢＭの細線化が進められている。また、近年では、液晶ディスプレイの市場において、タブレットなどのような小型化が主流となってきている一方で、大型のテレビにおいては高解像度の要求が高くなってきている。これらの理由からも、ＢＭの高精細化の要望が高くなってきており、近年では、従来の１０μｍ前後の線幅から、現在では６～８μｍ前後の線幅のＢＭ細線が求められるようになってきている。 In addition, in order to save energy and extend the life of mobile batteries, the output of backlights tends to be low. transformation is in progress. In recent years, in the liquid crystal display market, miniaturization such as tablets has become mainstream, while demand for high resolution is increasing in large-sized televisions. For these reasons as well, the demand for higher definition of BM has increased, and in recent years, BM fine lines with a line width of about 6 to 8 μm have been demanded from the conventional line width of about 10 μm. is coming.
　また、露光後の現像においては、残渣を無くすために現像時間を長めに設定するのが一般的であるが、これにより基板との界面部分のＢＭの溶解（差込み） が進行し、ＢＭ細線ラインパターンの剥離が起こりやすくなる。パターン線幅が１０μｍ以上の場合はＢＭ細線片側に約１～２μｍの差込み（細線ライン両側の合計で約２～４μｍ）が生じても基板との細線密着性を維持できるが、線幅が１０μｍ未満の細線パターンではＢＭ／基板界面の密着面積が小さくなるため、線幅を１μｍ狭めるごとのパターン密着性の低下幅が顕著に大きくなってくる。 In addition, in the development after exposure, it is common to set the development time longer in order to eliminate the residue, but this causes the dissolution (insertion) of BM at the interface with the substrate to proceed, resulting in fine BM lines. Peeling of the pattern is likely to occur. When the pattern line width is 10 μm or more, even if one side of the BM thin line is inserted by about 1 to 2 μm (the total of both sides of the thin line is about 2 to 4 μm), the thin line adhesion to the substrate can be maintained, but the line width is 10 μm. Since the adhesion area at the BM/substrate interface becomes small in a fine line pattern having a thickness of less than 1 μm, the degree of reduction in pattern adhesion increases remarkably every time the line width is narrowed by 1 μm.
　こうした背景から、細線密着性及び現像溶解性に優れた感光性樹脂組成物が求められており、細線特性及び現像溶解性に影響を与える顔料分散液の改良が進められている。
　例えば、顔料分散液に分散助剤を用いることが知られており、分散助剤としては、例えば、カルボキシ基、スルホン酸基、又はリン酸基を含有する化合物が挙げられるが、顔料分散性や工業利用性の観点から、スルホン酸基含有化合物が用いられる場合がある。
　例えば、特許文献１には、特定のアルカリ可溶性樹脂に酸価が０～３０の分散助剤（スルホン酸基含有化合物）を用いた分散顔料を配合することで現像密着性及び残渣が改善されたカラーフィルター用感光性樹脂組成物が記載されている。 Against this background, there is a demand for a photosensitive resin composition that is excellent in fine line adhesion and development solubility, and efforts are being made to improve pigment dispersions that affect fine line properties and development solubility.
For example, it is known to use a dispersing aid in a pigment dispersion, and examples of the dispersing aid include compounds containing a carboxy group, a sulfonic acid group, or a phosphoric acid group. From the viewpoint of industrial applicability, a sulfonic acid group-containing compound may be used.
For example, in Patent Document 1, development adhesion and residue are improved by blending a dispersion pigment using a dispersing aid (sulfonic acid group-containing compound) having an acid value of 0 to 30 in a specific alkali-soluble resin. A photosensitive resin composition for color filters is described.
日本国特開２００８－１６４９３７号公報Japanese Patent Application Laid-Open No. 2008-164937
　本発明者らが、特許文献１に記載の感光性樹脂組成物を用いてＢＭ評価を行ったところ、溶解性及び細線密着性が十分ではないことが分かった。 When the present inventors performed BM evaluation using the photosensitive resin composition described in Patent Document 1, it was found that the solubility and fine line adhesion were not sufficient.
　そこで本発明は、溶解性及び細線密着性に優れた感光性樹脂組成物が得られる顔料分散液、ならびにそれを用いた感光性樹脂組成物を提供することを目的とする。 Accordingly, an object of the present invention is to provide a pigment dispersion from which a photosensitive resin composition having excellent solubility and fine line adhesion can be obtained, and a photosensitive resin composition using the same.
　本発明者らが鋭意検討した結果、特定の化合物を用いることで前記課題を解決できることを見出した。即ち本発明の要旨は以下に存する。 As a result of intensive studies by the present inventors, they have found that the above problems can be solved by using a specific compound. That is, the gist of the present invention resides in the following.
［１］　（Ａ）顔料、（Ｂ）分散剤及び（Ｃ）スルホン酸基含有化合物を含有する顔料分散液であって、前記（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下であり、前記（Ｃ）スルホン酸基含有化合物の酸価が４０ｍｇＫＯＨ／ｇ以上である、顔料分散液。
［２］　前記（Ｃ）スルホン酸基含有化合物が、フタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体及びジオキサジンのスルホン酸誘導体からなる群から選ばれる少なくとも一つを含む、［１］に記載の顔料分散液。
［３］　前記（Ｃ）スルホン酸基含有化合物が銅フタロシアニンスルホン酸誘導体を含む、［１］に記載の顔料分散液。
［４］　前記（Ａ）顔料と前記（Ｃ）スルホン酸基含有化合物との、質量基準における含有比率（（Ａ）顔料／（Ｃ）スルホン酸基含有化合物）が１０以上である、［１］～［３］のいずれかに記載の顔料分散液。
［５］　前記（Ａ）顔料と前記（Ｂ）分散剤との、質量基準における含有比率（（Ａ）顔料／（Ｂ）分散剤）が４以上である、［１］～［４］のいずれかに記載の顔料分散液。
［６］　前記（Ａ）顔料がカーボンブラックを含有する、［１］～［５］のいずれかに記載の顔料分散液。
［７］　（Ａ）顔料、（Ｂ）分散剤、（Ｃ）スルホン酸基含有化合物、（Ｄ）アルカリ可溶性樹脂、（Ｅ）光重合性化合物及び（Ｆ）光重合開始剤を含有する感光性樹脂組成物であって、前記（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下であり、前記（Ｃ）スルホン酸基含有化合物の酸価が４０ｍｇＫＯＨ／ｇ以上である、感光性樹脂組成物。
［８］　前記（Ｃ）スルホン酸基含有化合物が、フタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体及びジオキサジンのスルホン酸誘導体からなる群から選ばれる少なくとも一つを含む、［７］に記載の感光性樹脂組成物。
［９］　前記（Ｃ）スルホン酸基含有化合物が銅フタロシアニンスルホン酸誘導体を含む、［７］に記載の感光性樹脂組成物。
［１０］　前記（Ａ）顔料がカーボンブラックを含有する、［７］～［９］のいずれかに記載の感光性樹脂組成物。
［１１］　［７］～［１０］のいずれかに記載の感光性樹脂組成物を硬化させた硬化物。
［１２］　［１１］に記載の硬化物からなるブラックマトリックス。
［１３］　［１１］に記載の硬化物を有する画像表示装置。 [1] A pigment dispersion containing (A) a pigment, (B) a dispersant, and (C) a sulfonic acid group-containing compound, wherein the (C) sulfonic acid group-containing compound has an electrical conductivity of 2000 μS/cm or more. 9000 μS/cm or less, and the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
[2] The (C) sulfonic acid group-containing compound is a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfone. The pigment dispersion according to [1], containing at least one selected from the group consisting of acid derivatives.
[3] The pigment dispersion according to [1], wherein the (C) sulfonic acid group-containing compound contains a copper phthalocyanine sulfonic acid derivative.
[4] The content ratio of the (A) pigment and the (C) sulfonic acid group-containing compound on a mass basis ((A) pigment/(C) sulfonic acid group-containing compound) is 10 or more [1] The pigment dispersion liquid according to any one of to [3].
[5] Any of [1] to [4], wherein the content ratio ((A) pigment/(B) dispersant) on a mass basis of the (A) pigment and the (B) dispersant is 4 or more The pigment dispersion according to 1.
[6] The pigment dispersion according to any one of [1] to [5], wherein the pigment (A) contains carbon black.
[7] Photosensitive containing (A) pigment, (B) dispersant, (C) sulfonic acid group-containing compound, (D) alkali-soluble resin, (E) photopolymerizable compound and (F) photopolymerization initiator In the resin composition, the (C) sulfonic acid group-containing compound has an electrical conductivity of 2000 μS/cm or more and 9000 μS/cm or less, and the (C) sulfonic acid group-containing compound has an acid value of 40 mgKOH/g or more. A photosensitive resin composition.
[8] The (C) sulfonic acid group-containing compound is a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfone. The photosensitive resin composition according to [7], containing at least one selected from the group consisting of acid derivatives.
[9] The photosensitive resin composition according to [7], wherein the (C) sulfonic acid group-containing compound comprises a copper phthalocyanine sulfonic acid derivative.
[10] The photosensitive resin composition according to any one of [7] to [9], wherein the pigment (A) contains carbon black.
[11] A cured product obtained by curing the photosensitive resin composition according to any one of [7] to [10].
[12] A black matrix comprising the cured product of [11].
[13] An image display device comprising the cured product of [11].
　本発明によれば、溶解性及び細線密着性に優れた感光性樹脂組成物が得られる顔料分散液、ならびにそれを用いた感光性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a pigment dispersion from which a photosensitive resin composition having excellent solubility and fine line adhesion can be obtained, and a photosensitive resin composition using the same.
図１は、本発明のカラーフィルターを有する有機ＥＬ素子の一例を示す断面概略図である。FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device having a color filter of the present invention.
　以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。
　なお、本発明において、「（メタ）アクリル」とは「アクリル及び／又はメタクリル」を意味し、「（メタ）アクリレート」、「（メタ）アクリロイル」についても同様である。 Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".
　本発明において「全固形分」とは、感光性樹脂組成物中又は顔料分散液中に含まれる、溶剤以外の全成分を意味し、溶剤以外の成分が室温で液体であっても、固形分に含める。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）を指す。
　本発明において、「アミン価」とは、特に断りのない限り、有効固形分換算のアミン価を表し、分散剤の固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表される値である。なお、測定方法については後述する。
　本発明において、酸価とは、有効固形分換算の酸価を表し、中和滴定により算出される。 In the present invention, "total solid content" means all components other than the solvent contained in the photosensitive resin composition or the pigment dispersion, even if the components other than the solvent are liquid at room temperature, the solid content include in
In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
In the present invention, the "amine value" represents the amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. . In addition, the measuring method will be described later.
In the present invention, the acid value represents an acid value in terms of effective solid content, and is calculated by neutralization titration.
［顔料分散液］
　本発明の顔料分散液は、（Ａ）顔料、（Ｂ）分散剤及び（Ｃ）スルホン酸基含有化合物を含有する顔料分散液であって、前記（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下であり、前記（Ｃ）スルホン酸基含有化合物の酸価が４０ｍｇＫＯＨ／ｇ以上であることを特徴とする。
　所定の電気伝導度及び酸価に調節または組み合わせたスルホン酸基含有化合物を用いることにより、本発明の顔料分散液を用いて感光性樹脂組成物を調製した場合、溶解性及び細線密着性に優れた感光性樹脂組成物を得ることができる。 [Pigment dispersion]
The pigment dispersion of the present invention is a pigment dispersion containing (A) a pigment, (B) a dispersant and (C) a sulfonic acid group-containing compound, wherein the electrical conductivity of the (C) sulfonic acid group-containing compound is 2000 μS/cm or more and 9000 μS/cm or less, and the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
By using a sulfonic acid group-containing compound adjusted to or combined with a predetermined electrical conductivity and acid value, when a photosensitive resin composition is prepared using the pigment dispersion of the present invention, the solubility and fine line adhesion are excellent. A photosensitive resin composition can be obtained.
　本発明の顔料分散液は、必要に応じてさらにその他の成分を含んでいてもよく、例えば、溶剤、アルカリ可溶性樹脂、染料を含んでいてもよい。
　溶剤、アルカリ可溶性樹脂については、後述する本発明の感光性樹脂組成物で用いられる溶剤、アルカリ可溶性樹脂を好ましく用いることができる。 The pigment dispersion of the present invention may further contain other components as necessary, such as solvents, alkali-soluble resins, and dyes.
As the solvent and alkali-soluble resin, the solvent and alkali-soluble resin used in the photosensitive resin composition of the present invention, which will be described later, can be preferably used.
＜（Ａ）顔料＞
　本発明の顔料分散液は（Ａ）顔料を含む。（Ａ）顔料は本発明の顔料分散液、感光性樹脂組成物を着色するものをいう。 <(A) Pigment>
The pigment dispersion of the present invention contains (A) a pigment. (A) Pigment refers to a pigment that colors the pigment dispersion and the photosensitive resin composition of the present invention.
　（Ａ）顔料としては青色顔料、緑色顔料、赤色顔料、黄色顔料、紫色顔料、オレンジ顔料、ブラウン顔料、黒色顔料等各種の色の顔料を使用することができる。また、その構造としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系等の有機顔料の他に種々の無機顔料等も利用可能である。 (A) As pigments, pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments can be used. In addition to organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments, various inorganic pigments can also be used. is.
　以下に、本発明に使用できる顔料の具体例をピグメントナンバーで示す。なお、以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。
　赤色顔料としては、例えば、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１２、１４、１５、１６、１７、２１、２２、２３、３１、３２、３７、３８、４１、４７、４８、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５０：１、５２：１、５２：２、５３、５３：１、５３：２、５３：３、５７、５７：１、５７：２、５８：４、６０、６３、６３：１、６３：２、６４、６４：１、６８、６９、８１、８１：１、８１：２、８１：３、８１：４、８３、８８、９０：１、１０１、１０１：１、１０４、１０８、１０８：１、１０９、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４７、１４９、１５１、１６６、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７７、１７８、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１６８、１７７、２０２、２０６、２０７、２０９、２２４、２４２、２５４、さらに好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。 Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. In addition, terms such as "C.I. Pigment Red 2" mentioned below mean a color index (C.I.).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, C.I. I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.
　青色顔料としては、例えば、Ｃ．Ｉ．ピグメントブルー１、１：２、９、１４、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、１９、２５、２７、２８、２９、３３、３５、３６、５６、５６：１、６０、６１、６１：１、６２、６３、６６、６７、６８、７１、７２、７３、７４、７５、７６、７８、７９を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、６０、さらに好ましくはＣ．Ｉ．ピグメントブルー１５：６、６０を挙げることができる。 As a blue pigment, for example, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6,60 may be mentioned.
　緑色顔料としては、例えば、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５、５８、５９を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントグリーン７、３６、５８、５９を挙げることができる。 As a green pigment, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 . Among these, C.I. I. Pigment Green 7, 36, 58, 59 can be mentioned.
　黄色顔料としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、さらに好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０、１８５を挙げることができる。 As a yellow pigment, for example, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180, 185 can be mentioned.
　オレンジ顔料としては、例えば、Ｃ．Ｉ．ピグメントオレンジ１、２、５、１３、１６、１７、１９、２０、２１、２２、２３、２４、３４、３６、３８、３９、４３、４６、４８、４９、６１、６２、６４、６５、６７、６８、６９、７０、７１、７２、７３、７４、７５、７７、７８、７９を挙げることができる。この中でも、好ましくは、Ｃ．Ｉ．ピグメントオレンジ３８、６４、７１を挙げることができる。 As an orange pigment, for example, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, C.I. I. Pigment Orange 38, 64, 71 may be mentioned.
　紫色顔料としては、例えば、Ｃ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９、５０を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、２９さらに好ましくはＣ．Ｉ．ピグメントバイオレット２３、２９を挙げることができる。 As a purple pigment, for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23, 29 may be mentioned.
　また、本発明の顔料分散液を用いた感光性樹脂組成物が、カラーフィルターのブラックマトリックス用感光性樹脂組成物である場合、（Ａ）顔料としては、黒色の顔料を用いることができる。黒色顔料は、黒色顔料単独としてもよく、赤、緑、青等の混合としてもよい。また、これら顔料は無機又は有機の顔料から適宜選択することができる。
　黒色顔料を調製するために混合使用可能な顔料としては、例えば、ビクトリアピュアブルー（４２５９５）、オーラミンＯ（４１０００）、カチロンブリリアントフラビン（ベーシック１３）、ローダミン６ＧＣＰ（４５１６０）、ローダミンＢ（４５１７０）、サフラニンＯＫ７０：１００（５０２４０）、エリオグラウシンＸ（４２０８０）、Ｎｏ．１２０／リオノールイエロー（２１０９０）、リオノールイエローＧＲＯ（２１０９０）、シムラーファーストイエロー８ＧＦ（２１１０５）、ベンジジンイエロー４Ｔ－５６４Ｄ（２１０９５）、シムラーファーストレッド４０１５（１２３５５）、リオノールレッド７Ｂ４４０１（１５８５０）、ファーストゲンブルーＴＧＲ－Ｌ（７４１６０）、リオノールブルーＳＭ（２６１５０）、リオノールブルーＥＳ（ピグメントブルー１５：６）、リオノーゲンレッドＧＤ（ピグメントレッド１６８）、リオノールグリーン２ＹＳ（ピグメントグリーン３６）が挙げられる（なお、上記の（　）内の数字は、カラーインデックス（Ｃ．Ｉ．）を意味する。）。 When the photosensitive resin composition using the pigment dispersion of the present invention is a photosensitive resin composition for a black matrix of a color filter, a black pigment can be used as the pigment (A). The black pigment may be a black pigment alone or a mixture of red, green, blue, and the like. Moreover, these pigments can be appropriately selected from inorganic or organic pigments.
Pigments that can be mixed to prepare black pigments include, for example, Victoria Pure Blue (42595), Auramine O (41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). , Safranin OK 70:100 (50240), Erioglaucine X (42080), No. 120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), First Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36) (Note that the numbers in ( ) above mean the color index (C.I.).).
　また、さらに他の混合使用可能な顔料についてＣ．Ｉ．ナンバーにて示すと、例えば、Ｃ．Ｉ．黄色顔料２０、２４、８６、９３、１０９、１１０、１１７、１２５、１３７、１３８、１４７、１４８、１５３、１５４、１６６、Ｃ．Ｉ．オレンジ顔料３６、４３、５１、５５、５９、６１、６４、Ｃ．Ｉ．赤色顔料９、９７、１２２、１２３、１４９、１６８、１７７、１８０、１９２、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２５４、Ｃ．Ｉ．バイオレット顔料１９、２３、２９、３０、３７、４０、５０、Ｃ．Ｉ．青色顔料１５、１５：１、１５：４、２２、６０、６４、Ｃ．Ｉ．緑色顔料７、Ｃ．Ｉ．ブラウン顔料２３、２５、２６を挙げることができる。 Also, regarding other pigments that can be mixed, see C.I. I. When indicated by number, for example, C.I. I. yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. orange pigments 36, 43, 51, 55, 59, 61, 64, C.I. I. red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, C.I. I. violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. blue pigment 15, 15:1, 15:4, 22, 60, 64, C.I. I. green pigment 7, C.I. I. Brown pigments 23, 25, 26 may be mentioned.
　また、単独使用可能な黒色顔料としては、例えば、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、アニリンブラック、シアニンブラック、チタンブラック、ペリレンブラック、ラクタムブラックが挙げられる。
　これらの（Ａ）顔料の中で黒色の顔料を用いる場合には、遮光率、画像特性の観点から前述した単独使用可能な黒色顔料が好ましく、カーボンブラックが特に好ましい。カーボンブラックの例としては、以下のようなカーボンブラックが挙げられる。 Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
Among these (A) pigments, when a black pigment is used, the above-described black pigment that can be used alone is preferable from the viewpoint of light shielding rate and image characteristics, and carbon black is particularly preferable. Examples of carbon black include the following carbon blacks.
　三菱ケミカル社製：ＭＡ７、ＭＡ７７、ＭＡ８、ＭＡ１１、ＭＡ１００、ＭＡ１００Ｒ、ＭＤ１２０、ＭＤ１３０、ＭＡ６００、＃５、＃１０、＃２０、＃２５、＃３０、＃３２、＃３３、＃４０、＃４４、＃４５、＃４７、＃５０、＃５２、＃５５、＃６５０、＃７５０、＃８５０、＃９５０、＃９６０、＃９７０、＃９８０、＃９９０、＃１０００、＃２２００、＃２３００、＃２３５０、＃２４００、＃２６００、＃３０５０、＃３１５０、＃３２５０、＃３６００、＃３７５０、＃３９５０、＃４０００、＃４０１０、ＯＩＬ７Ｂ、ＯＩＬ９Ｂ、ＯＩＬ１１Ｂ、ＯＩＬ３０Ｂ、ＯＩＬ３１Ｂ
　デグサ社製：Ｐｒｉｎｔｅｘ（登録商標。以下同じ。）３、Ｐｒｉｎｔｅｘ３ＯＰ、Ｐｒｉｎｔｅｘ３０、Ｐｒｉｎｔｅｘ３０ＯＰ、Ｐｒｉｎｔｅｘ４０、Ｐｒｉｎｔｅｘ４５、Ｐｒｉｎｔｅｘ５５、Ｐｒｉｎｔｅｘ６０、Ｐｒｉｎｔｅｘ７５、Ｐｒｉｎｔｅｘ８０、Ｐｒｉｎｔｅｘ８５、Ｐｒｉｎｔｅｘ９０、Ｐｒｉｎｔｅｘ　Ａ、Ｐｒｉｎｔｅｘ　Ｌ、Ｐｒｉｎｔｅｘ　Ｇ、Ｐｒｉｎｔｅｘ　Ｐ、Ｐｒｉｎｔｅｘ　Ｕ、Ｐｒｉｎｔｅｘ　Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２Ｖ、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２００、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１６０、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１７０
　キャボット社製：Ｍｏｎａｒｃｈ（登録商標。以下同じ。）１２０、Ｍｏｎａｒｃｈ２８０、Ｍｏｎａｒｃｈ４６０、Ｍｏｎａｒｃｈ８００、Ｍｏｎａｒｃｈ８８０、Ｍｏｎａｒｃｈ９００、Ｍｏｎａｒｃｈ１０００、Ｍｏｎａｒｃｈ１１００、Ｍｏｎａｒｃｈ１３００、Ｍｏｎａｒｃｈ１４００、Ｍｏｎａｒｃｈ４６３０、ＲＥＧＡＬ（登録商標。以下同じ。）９９、ＲＥＧＡＬ９９Ｒ、ＲＥＧＡＬ４１５、ＲＥＧＡＬ４１５Ｒ、ＲＥＧＡＬ２５０、ＲＥＧＡＬ２５０Ｒ、ＲＥＧＡＬ３３０、ＲＥＧＡＬ４００Ｒ、ＲＥＧＡＬ５５０Ｒ、ＲＥＧＡＬ６６０Ｒ、ＢＬＡＣＫ　ＰＥＡＲＬＳ４８０、ＰＥＡＲＬＳ１３０、ＶＵＬＣＡＮ（登録商標）　ＸＣ７２Ｒ、ＥＬＦＴＥＸ（登録商標）－８
　ビルラー社製：ＲＡＶＥＮ１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２、ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ、ＲＡＶＥＮ１１７０、ＲＡＶＥＮ１１９０Ｕ、ＲＡＶＥＮ１２５０、ＲＡＶＥＮ１５００、ＲＡＶＥＮ２０００、ＲＡＶＥＮ２５００Ｕ、ＲＡＶＥＮ３５００、ＲＡＶＥＮ５０００、ＲＡＶＥＮ５２５０、ＲＡＶＥＮ５７５０、ＲＡＶＥＮ７０００ Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MD120, MD130, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350 , #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Degussa: Printex (registered trademark; hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, PrintexPrintx G, PrintexPrintx L, intex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color F W Black 2 Black , Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark; the same shall apply hereinafter) 99, REGAL45REGAL99 REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL550R, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8
RAVEN 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890 H, RAVEN 1 VEN 1 VEN 2, RAVEN 1000 0, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
　また、顔料として、例えば、硫酸バリウム、硫酸鉛、酸化チタン、黄色鉛、ベンガラ、酸化クロムを用いることもできる。これら各種の顔料は、複数種を併用することもできる。例えば、色度の調整のために、緑色顔料と黄色顔料とを併用したり、青色顔料と紫色顔料とを併用したりすることができる。 Also, as pigments, for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide can be used. These various pigments can also be used in combination of multiple types. For example, a green pigment and a yellow pigment can be used together, or a blue pigment and a violet pigment can be used together for chromaticity adjustment.
　本発明に用いられる（Ａ）顔料の平均粒径としては、例えばカラーフィルターのブラックマトリックスとした場合に、所望の発色が可能なものであればよく、特に限定されず、用いる顔料の種類によっても異なるが、１０～１００ｎｍであることが好ましく、１０～７０ｎｍであることがより好ましい。該顔料の平均粒径が上記範囲であることにより、本発明の顔料分散液を用いて製造された液晶表示装置の色特性を高品質なものとすることができる傾向がある。
　また、顔料がカーボンブラックの場合の平均粒径は、６０ｎｍ以下が好ましく、５０ｎｍ以下がさらに好ましく、また、２０ｎｍ以上が好ましい。例えば、２０～６０ｎｍが好ましく、２０～５０ｎｍがより好ましい。平均粒径を前記上限値以下とすることで、散乱が小さくなり、遮光性やコントラストなどの色特性の低下を抑制できる傾向がある。また、平均粒径を前記下限値以上とすることで、分散剤の量が過度に多くならずに済み、分散性が良好となる傾向がある。
　なお、上記顔料の平均粒径は、電子顕微鏡写真から一次粒子の大きさを直接計測する方法で求めることができる。具体的には、個々の一次粒子の短軸径と長軸径を計測し、その平均をその粒子の粒径とする。次に、１００個以上の粒子について、それぞれの粒子の体積（質量）を、求めた粒径の直方体と近似して求め、体積平均粒径を求めそれを平均粒径とする。なお、透過型電子顕微鏡（ＴＥＭ）または走査型電子顕微鏡（ＳＥＭ）のいずれを用いても同じ結果を得ることができる。 The average particle size of the pigment (A) used in the present invention is not particularly limited as long as it can develop a desired color when used as a black matrix for a color filter, for example, and is also dependent on the type of pigment used. Although different, it is preferably 10 to 100 nm, more preferably 10 to 70 nm. When the average particle diameter of the pigment is within the above range, the color characteristics of the liquid crystal display device manufactured using the pigment dispersion of the present invention tend to be of high quality.
When the pigment is carbon black, the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more. For example, 20 to 60 nm is preferable, and 20 to 50 nm is more preferable. By setting the average particle size to the above upper limit or less, there is a tendency that scattering is reduced and deterioration of color characteristics such as light shielding properties and contrast can be suppressed. Further, by setting the average particle size to the above lower limit or more, the amount of the dispersant is not excessively increased, and the dispersibility tends to be improved.
The average particle size of the pigment can be obtained by directly measuring the size of primary particles from an electron micrograph. Specifically, the short axis diameter and long axis diameter of each primary particle are measured, and the average thereof is taken as the particle size of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating the rectangular parallelepiped of the obtained particle diameter, and the volume average particle diameter is obtained and taken as the average particle diameter. The same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).
　また、本発明の顔料分散液は、（Ａ）顔料以外にも、本発明の効果に影響を及ぼさない範囲で染料を併用してもよい。併用できる染料としては、例えば、アゾ系染料、アントラキノン系染料、フタロシアニン系染料、キノンイミン系染料、キノリン系染料、ニトロ系染料、カルボニル系染料、メチン系染料が挙げられる。 In addition to (A) the pigment, the pigment dispersion of the present invention may also contain a dye as long as the effect of the present invention is not affected. Dyes that can be used in combination include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
　アゾ系染料としては、例えば、Ｃ．Ｉ．アシッドイエロー１１、Ｃ．Ｉ．アシッドオレンジ７、Ｃ．Ｉ．アシッドレッド３７、Ｃ．Ｉ．アシッドレッド１８０、Ｃ．Ｉ．アシッドブルー２９、Ｃ．Ｉ．ダイレクトレッド２８、Ｃ．Ｉ．ダイレクトレッド８３、Ｃ．Ｉ．ダイレクトイエロー１２、Ｃ．Ｉ．ダイレクトオレンジ２６、Ｃ．Ｉ．ダイレクトグリーン２８、Ｃ．Ｉ．ダイレクトグリーン５９、Ｃ．Ｉ．リアクティブイエロー２、Ｃ．Ｉ．リアクティブレッド１７、Ｃ．Ｉ．リアクティブレッド１２０、Ｃ．Ｉ．リアクティブブラック５、Ｃ．Ｉ．ディスパースオレンジ５、Ｃ．Ｉ．ディスパースレッド５８、Ｃ．Ｉ．ディスパースブルー１６５、Ｃ．Ｉ．ベーシックブルー４１、Ｃ．Ｉ．ベーシックレッド１８、Ｃ．Ｉ．モルダントレッド７、Ｃ．Ｉ．モルダントイエロー５、Ｃ．Ｉ．モルダントブラック７が挙げられる。 Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. Mordant Black 7 is mentioned.
　アントラキノン系染料としては、例えば、Ｃ．Ｉ．バットブルー４、Ｃ．Ｉ．アシッドブルー４０、Ｃ．Ｉ．アシッドグリーン２５、Ｃ．Ｉ．リアクティブブルー１９、Ｃ．Ｉ．リアクティブブルー４９、Ｃ．Ｉ．ディスパースレッド６０、Ｃ．Ｉ．ディスパースブルー５６、Ｃ．Ｉ．ディスパースブルー６０が挙げられる。 Examples of anthraquinone dyes include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 may be mentioned.
　この他、フタロシアニン系染料として、例えば、Ｃ．Ｉ．バットブルー５が、キノンイミン系染料として、例えば、Ｃ．Ｉ．ベーシックブルー３、Ｃ．Ｉ．ベーシックブルー９が、キノリン系染料として、例えば、Ｃ．Ｉ．ソルベントイエロー３３、Ｃ．Ｉ．アシッドイエロー３、Ｃ．Ｉ．ディスパースイエロー６４が、ニトロ系染料として、例えば、Ｃ．Ｉ．アシッドイエロー１、Ｃ．Ｉ．アシッドオレンジ３、Ｃ．Ｉ．ディスパースイエロー４２が挙げられる。 In addition, as a phthalocyanine dye, for example, C.I. I. Vat Blue 5 can be used as a quinoneimine dye, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 can be used as a quinoline dye, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 can be used as a nitro dye, for example C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 is mentioned.
　本発明の顔料分散液を用いた感光性樹脂組成物は、後述する種々な用途に使用することができるが、優れた画像形成性は、カラーフィルター用ブラックマトリックスの形成に使用した場合に、特に効果的である。ブラックマトリックスの形成に使用する場合には（Ａ）顔料として、前述したカーボンブラックやチタンブラック等の黒色顔料を使用するか、黒色以外の顔料を複数種類混合し黒色に調整して使用すればよい。その中でも分散安定性及び遮光性の観点から、カーボンブラックを使用することが、特に好ましい。 The photosensitive resin composition using the pigment dispersion of the present invention can be used for various applications described later, but the excellent image formability is particularly high when it is used to form a black matrix for color filters. Effective. When used to form a black matrix, as the pigment (A), a black pigment such as the carbon black or titanium black described above may be used, or a plurality of types of pigments other than black may be mixed and adjusted to black. . Among them, it is particularly preferable to use carbon black from the viewpoint of dispersion stability and light-shielding properties.
　後述する本発明の感光性樹脂組成物は、顔料濃度が大きくなる領域で細線密着性の効果が大きい。特に近年は遮光度を上げるために顔料濃度を多くする必要がある。このように効果が大きくなる領域における（Ａ）顔料の含有割合は、感光性樹脂組成物の全固形分に対し３０質量％以上であり、４０質量％以上が好ましく、５０質量％以上がより好ましく、５２質量％以上が特に好ましい。また、画像形成性能の観点からは、７０質量％以下が好ましく、６５質量％以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、３０～７０質量％が好ましく、４０～７０質量％がより好ましく、５０～６５質量％がさらに好ましく、５２～６５質量％が特に好ましい。 The photosensitive resin composition of the present invention, which will be described later, has a large effect on fine line adhesion in a region where the pigment concentration is high. Especially in recent years, it is necessary to increase the pigment concentration in order to increase the degree of light blocking. The content of the pigment (A) in such a region where the effect is increased is 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, relative to the total solid content of the photosensitive resin composition. , 52% by mass or more is particularly preferred. From the viewpoint of image forming performance, it is preferably 70% by mass or less, more preferably 65% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 30 to 70% by mass is preferable, 40 to 70% by mass is more preferable, 50 to 65% by mass is even more preferable, and 52 to 65% by mass is particularly preferable.
　本発明の感光性樹脂組成物において、顔料の含有割合が上記範囲内であることにより、遮光性（光学濃度、ＯＤ値）の高い感光性樹脂組成物を得ることができる。具体的には、感光性樹脂組成物の全固形分に対する（Ａ）顔料の含有割合を５０質量％以上とすることにより、本発明の感光性樹脂組成物を用いて厚さ１μｍのブラックマトリックスを形成した場合における光学濃度を４．０以上の値とすることができる。光学濃度はより好ましくは４．１以上であり、さらに好ましくは４．２以上である。遮光性が高い領域では現像によるパターニングの剥離が観察されやすいが、本発明の顔料分散液を用いた感光性樹脂組成物を使用した場合は、特に（Ａ）顔料の含有割合が大きい場合に、本発明の細線密着効果をよく確認できる。 In the photosensitive resin composition of the present invention, a photosensitive resin composition with high light-shielding properties (optical density, OD value) can be obtained by setting the pigment content within the above range. Specifically, by setting the content of the pigment (A) to 50% by mass or more relative to the total solid content of the photosensitive resin composition, a black matrix having a thickness of 1 μm is formed using the photosensitive resin composition of the present invention. The optical density when formed can be set to a value of 4.0 or more. The optical density is more preferably 4.1 or higher, still more preferably 4.2 or higher. In areas with high light-shielding properties, peeling of the patterning due to development is likely to be observed. The thin wire adhesion effect of the present invention can be well confirmed.
　本発明の感光性樹脂組成物において、（Ａ）顔料の含有割合は、特に限定されないが、（Ｄ）アルカリ可溶性樹脂１００質量部あたり、好ましくは２０質量部以上、より好ましくは５０質量部以上、さらに好ましくは１００質量部以上、よりさらに好ましくは１２０質量部以上、ことさらに好ましくは１５０質量部以上、特に好ましくは１８０質量部以上であり、また、好ましくは５００質量部以下、より好ましくは３００質量部以下、さらに好ましくは２５０質量部以下である。（Ａ）顔料の含有割合を前記下限値以上とすることで未露光部の現像液に対する溶解性の低下を抑制しやすい傾向があり、また、前記上限値以下とすることで現像時の細線密着性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは２０～５００質量部、より好ましくは５０～５００質量部、さらに好ましくは１００～３００質量部、よりさらに好ましくは１２０～３００質量部、ことさらに好ましくは１５０～２５０質量部、特に好ましくは１８０～２５０質量部である。 In the photosensitive resin composition of the present invention, the content of (A) pigment is not particularly limited, but (D) per 100 parts by mass of alkali-soluble resin, preferably 20 parts by mass or more, more preferably 50 parts by mass or more, More preferably 100 parts by mass or more, still more preferably 120 parts by mass or more, even more preferably 150 parts by mass or more, particularly preferably 180 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass parts or less, more preferably 250 parts by mass or less. (A) When the content of the pigment is equal to or higher than the lower limit, it tends to suppress the deterioration of the solubility of the unexposed area in the developing solution. tend to improve. The above upper and lower limits can be combined arbitrarily. For example, preferably 20 to 500 parts by mass, more preferably 50 to 500 parts by mass, still more preferably 100 to 300 parts by mass, even more preferably 120 to 300 parts by mass, even more preferably 150 to 250 parts by mass, particularly preferably is 180 to 250 parts by mass.
＜（Ｂ）分散剤＞
　本発明の顔料分散液は、（Ａ）顔料を微細に分散させ、且つその分散状態を安定化させることが品質の安定性確保には重要なため、（Ｂ）分散剤を含む。
　（Ｂ）分散剤としては、官能基を有する高分子分散剤が好ましく、さらには、分散安定性の面からカルボキシ基；リン酸基；スルホン酸基；又はこれらの塩基；一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を有する高分子分散剤が好ましい。中でも特に、一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤が特に好ましい。これら塩基性官能基を有する高分子分散剤を使用することにより、分散性を良好にでき、高い遮光性を達成できる傾向がある。 <(B) Dispersant>
The pigment dispersion liquid of the present invention contains (B) a dispersant because it is important to finely disperse (A) the pigment and stabilize the dispersion state in order to ensure the stability of the quality.
(B) As the dispersant, a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxy group; Polymeric dispersants having functional groups such as primary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred. Among them, polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are particularly preferred. By using a polymer dispersant having these basic functional groups, there is a tendency that dispersibility can be improved and high light-shielding properties can be achieved.
　また高分子分散剤としては、例えば、ウレタン系分散剤、アクリル系分散剤、ポリエチレンイミン系分散剤、ポリアリルアミン系分散剤、アミノ基を持つモノマーとマクロモノマーからなる分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンジエステル系分散剤、ポリエーテルリン酸系分散剤、ポリエステルリン酸系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤を挙げることができる。 Examples of polymer dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples include system dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
　このような分散剤の具体例としては、例えば、商品名で、ＥＦＫＡ（登録商標。エフカーケミカルズビーブイ（ＥＦＫＡ）社製。）、Ｄｉｓｐｅｒｂｙｋ（登録商標。ビックケミー社製。）、ディスパロン（登録商標。楠本化成社製。）、ＳＯＬＳＰＥＲＳＥ（登録商標。ルーブリゾール社製。）、ＫＰ（信越化学工業社製。）、ポリフロー又はフローレン（登録商標。共栄社化学社製。）、アジスパー（登録商標。味の素ファインテクノ社製。）を挙げることができる。
　これらの高分子分散剤は１種を単独で使用してもよく、又は２種以上を併用してもよい。 Specific examples of such dispersants include trade names of EFKA (registered trademark, manufactured by EFKA Chemicals B.V. (EFKA)), Disperbyk (registered trademark, manufactured by BYK-Chemie), and Disparon (registered trademark). Kusumoto Kasei Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Floren (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, Ajinomoto Fine) manufactured by Techno Co., Ltd.).
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.
　これらの内、細線密着性及び直線性の面から、（Ｂ）分散剤として、塩基性官能基を有するウレタン系高分子分散剤及び／又はアクリル系高分子分散剤を含むことが、特に好ましい。特にはウレタン系高分子分散剤が細線密着性の面で好ましい。また分散性、保存性の面から、塩基性官能基を有し、ポリエステル及び／又はポリエーテル結合を有する高分子分散剤が好ましい。 Among these, it is particularly preferable to include a urethane polymer dispersant and/or an acrylic polymer dispersant having a basic functional group as the (B) dispersant in terms of fine line adhesion and linearity. In particular, urethane-based polymer dispersants are preferred from the standpoint of fine wire adhesion. Polymeric dispersants having basic functional groups and polyester and/or polyether bonds are preferred from the standpoint of dispersibility and storage stability.
　高分子分散剤の重量平均分子量（Ｍｗ）は好ましくは７００以上、より好ましくは１０００以上であり、また、好ましくは１０００００以下、より好ましくは５００００以下、さらに好ましくは３００００以下である。前記上限値以下とすることで、顔料濃度が高い時でもアルカリ現像性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは７００～１０００００、より好ましくは７００～５００００、さらに好ましくは１０００～３００００である。
　ウレタン系及びアクリル系高分子分散剤としては、例えばＤｉｓｐｅｒｂｙｋ１６０～１６７、１８２シリーズ（いずれもウレタン系）、Ｄｉｓｐｅｒｂｙｋ２０００，２００１等（いずれもアクリル系）（以上すべてビックケミー社製）が挙げられる。上記の塩基性官能基を有し、ポリエステル及び／又はポリエーテル結合を有するウレタン系高分子分散剤で重量平均分子量３００００以下の特に好ましいものとして、例えば、Ｄｉｓｐｅｒｂｙｋ１６７、１８２が上げられる。 The weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less. By adjusting the content to the above upper limit or less, there is a tendency that the alkali developability becomes good even when the pigment concentration is high. The above upper and lower limits can be combined arbitrarily. For example, it is preferably from 700 to 100,000, more preferably from 700 to 50,000, even more preferably from 1,000 to 30,000.
Examples of urethane-based and acrylic polymer dispersants include Disperbyk 160-167, 182 series (all of which are urethane-based), Disperbyk 2000, 2001, etc. (both of which are acrylic-based) (all of which are manufactured by BYK-Chemie). Disperbyk 167 and 182 are particularly preferred urethane polymer dispersants having a polyester and/or polyether bond and having a weight average molecular weight of 30,000 or less.
＜ウレタン系高分子分散剤＞
　ウレタン系高分子分散剤として、例えば、ポリイソシアネート化合物と、分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物と、同一分子内に活性水素と３級アミノ基を有する化合物とを反応させることによって得られる、重量平均分子量１０００～２０００００の分散樹脂が挙げられる。 <Urethane Polymer Dispersant>
Urethane polymer dispersants include, for example, polyisocyanate compounds, compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, and compounds having active hydrogen and a tertiary amino group in the same molecule. and a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting with.
　上記のポリイソシアネート化合物としては、例えば、パラフェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４′－ジフェニルメタンジイソシアネート、ナフタレン－１，５－ジイソシアネート、トリジンジイソシアネート等の芳香族ジイソシアネート、ヘキサメチレンジイソシアネート、リジンメチルエステルジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート等の脂肪族ジイソシアネート、イソホロンジイソシアネート、４，４′－メチレンビス（シクロヘキシルイソシアネート）、ω，ω′－ジイソシネートジメチルシクロヘキサン等の脂環族ジイソシアネート、キシリレンジイソシアネート、α，α，α′，α′－テトラメチルキシリレンジイソシアネート等の芳香環を有する脂肪族ジイソシアネート、リジンエステルトリイソシアネート、１，６，１１－ウンデカントリイソシアネート、１，８－ジイソシアネート－４－イソシアネートメチルオクタン、１，３，６－ヘキサメチレントリイソシアネート、ビシクロヘプタントリイソシアネート、トリス（イソシアネートフェニルメタン）、トリス（イソシアネートフェニル）チオホスフェート等のトリイソシアネート、及びこれらの三量体、水付加物、及びこれらのポリオール付加物が挙げられる。ポリイソシアネートとして好ましいのは有機ジイソシアネートの三量体で、最も好ましいのはトリレンジイソシアネートの三量体とイソホロンジイソシアネートの三量体である。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω Alicyclic diisocyanates such as ′-diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thiophosphate and triisocyanates such as triisocyanates, trimers thereof, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.
　イソシアネートの三量体の製造方法としては、前記ポリイソシアネート類を適当な三量化触媒、例えば第３級アミン類、ホスフィン類、アルコキシド類、金属酸化物、カルボン酸塩類等を用いてイソシアネート基の部分的な三量化を行い、触媒毒の添加により三量化を停止させた後、未反応のポリイソシアネートを溶剤抽出、薄膜蒸留により除去して目的のイソシアヌレート基含有ポリイソシアネートを得る方法が挙げられる。 As a method for producing a trimer of isocyanate, the above-mentioned polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part After the trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
　同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物としては、ポリエーテルグリコール、ポリエステルグリコール、ポリカーボネートグリコール、ポリオレフィングリコール等、及びこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化されたもの及びこれら２種類以上の混合物が挙げられる。 Examples of compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has 1 to 1 carbon atoms. Those alkoxylated with 25 alkyl groups and mixtures of two or more thereof are included.
　ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジオール、及びこれら２種類以上の混合物が挙げられる。ポリエーテルジオールとしては、アルキレンオキシドを単独又は共重合させて得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリエチレン－プロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシヘキサメチレングリコール、ポリオキシオクタメチレングリコール及びそれらの２種以上の混合物が挙げられる。 Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of
　ポリエーテルエステルジオールとしては、エーテル基含有ジオールもしくは他のグリコールとの混合物をジカルボン酸又はそれらの無水物と反応させるか、又はポリエステルグリコールにアルキレンオキシドを反応させることによって得られるもの、例えば、ポリ（ポリオキシテトラメチレン）アジペートが挙げられる。ポリエーテルグリコールとして最も好ましいのはポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール又はこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化された化合物である。 Polyether ester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly( polyoxytetramethylene)adipate. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
　ポリエステルグリコールとしては、ジカルボン酸（コハク酸、グルタル酸、アジピン酸、セバシン酸、フマル酸、マレイン酸、フタル酸等）又はそれらの無水物とグリコール（エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２－プロピル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２，５－ジメチル－２，５－ヘキサンジオール、１，８－オクタメチレングリコール、２－メチル－１，８－オクタメチレングリコール、１，９－ノナンジオール等の脂肪族グリコール、ビスヒドロキシメチルシクロヘキサン等の脂環族グリコール、キシリレングリコール、ビスヒドロキシエトキシベンゼン等の芳香族グリコール、Ｎ－メチルジエタノールアミン等のＮ－アルキルジアルカノールアミン等）とを重縮合させて得られたもの、例えばポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリエチレン／プロピレンアジペート等、又は前記ジオール類又は炭素数１～２５の１価アルコールを開始剤として用いて得られるポリラクトンジオール又はポリラクトンモノオール、例えばポリカプロラクトングリコール、ポリメチルバレロラクトン及びこれらの２種以上の混合物が挙げられる。ポリエステルグリコールとして最も好ましいのはポリカプロラクトングリコール又は炭素数１～２５のアルコールを開始剤としたポリカプロラクトンである。 Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 ,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic glycols; bishydroxymethylcyclohexane and other aliphatic glycols; aromatic glycols such as lenglycol and bishydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine; , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol, polymethylvalerolactone and these Mixtures of two or more are included. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.
　ポリカーボネートグリコールとしては、ポリ（１，６－ヘキシレン）カーボネート、ポリ（３－メチル－１，５－ペンチレン）カーボネート等、ポリオレフィングリコールとしてはポリブタジエングリコール、水素添加型ポリブタジエングリコール、水素添加型ポリイソプレングリコール等が挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. is mentioned.
These may be used individually by 1 type, and may use 2 or more types together.
　同一分子内に水酸基を１個又は２個有する化合物の数平均分子量は、好ましくは３００～１００００、より好ましくは５００～６０００、さらに好ましくは１０００～４０００である。 The compound having one or two hydroxyl groups in the same molecule preferably has a number average molecular weight of 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000.
　本発明に用いられる同一分子内に活性水素と３級アミノ基を有する化合物を説明する。
　活性水素、即ち、酸素原子、窒素原子又はイオウ原子に直接結合している水素原子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中でもアミノ基、特に１級のアミノ基の水素原子が好ましい。
　３級アミノ基は、特に限定されないが、例えば炭素数１～４のアルキル基を有するアミノ基、又はヘテロ環構造、より具体的にはイミダゾール環又はトリアゾール環、などが挙げられる。
　このような同一分子内に活性水素と３級アミノ基を有する化合物としては、例えば、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジプロピル－１，３－プロパンジアミン、Ｎ，Ｎ－ジブチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ－ジプロピルエチレンジアミン、Ｎ，Ｎ－ジブチルエチレンジアミン、Ｎ，Ｎ－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジプロピル－１，４－ブタンジアミン、Ｎ，Ｎ－ジブチル－１，４－ブタンジアミンが挙げられる。 A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be explained.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of the amino group of is preferred.
The tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N- dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1, 4-butanediamine may be mentioned.
　また、３級アミノ基が含窒素ヘテロ環構造である場合の該含窒素ヘテロ環としては、例えば、ピラゾール環、イミダゾール環、トリアゾール環、テトラゾール環、インドール環、カルバゾール環、インダゾール環、ベンズイミダゾール環、ベンゾトリアゾール環、ベンゾオキサゾール環、ベンゾチアゾール環、ベンゾチアジアゾール環等のＮ含有ヘテロ５員環、ピリジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、アクリジン環、イソキノリン環等の含窒素ヘテロ６員環が挙げられる。これらの含窒素ヘテロ環のうち好ましいものはイミダゾール環又はトリアゾール環である。 When the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes, for example, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, and benzimidazole ring. , N-containing hetero five-membered rings such as benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, nitrogen-containing hetero ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A 6-membered ring is mentioned. Preferred among these nitrogen-containing heterocycles are imidazole rings and triazole rings.
　これらのイミダゾール環とアミノ基を有する化合物としては、例えば、１－（３－アミノプロピル）イミダゾール、ヒスチジン、２－アミノイミダゾール、１－（２－アミノエチル）イミダゾールが挙げられる。また、トリアゾール環とアミノ基を有する化合物としては、例えば、３－アミノ－１，２，４－トリアゾール、５－（２－アミノ－５－クロロフェニル）－３－フェニル－１Ｈ－１，２，４－トリアゾール、４－アミノ－４Ｈ－１，２，４－トリアゾール－３，５－ジオール、３－アミノ－５－フェニル－１Ｈ－１，３，４－トリアゾール、５－アミノ－１，４－ジフェニル－１，２，３－トリアゾール、３－アミノ－１－ベンジル－１Ｈ－２，４－トリアゾールが挙げられる。中でも、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、１－（３－アミノプロピル）イミダゾール、３－アミノ－１，２，４－トリアゾールが好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole and 1-(2-aminoethyl)imidazole. Examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4 -triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl -1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable.
These may be used individually by 1 type, and may use 2 or more types together.
　ウレタン系高分子分散剤を製造する際の原料の配合比率はポリイソシアネート化合物１００質量部に対し、同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物が、好ましくは１０～２００質量部、より好ましくは２０～１９０質量部、さらに好ましくは３０～１８０質量部、同一分子内に活性水素と３級アミノ基を有する化合物が、好ましくは０．２～２５質量部、より好ましくは０．３～２４質量部である。 The compounding ratio of raw materials when producing a urethane polymer dispersant is 100 parts by mass of a polyisocyanate compound, and a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule, preferably 10. ~ 200 parts by mass, more preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, a compound having active hydrogen and a tertiary amino group in the same molecule, preferably 0.2 to 25 parts by mass, more It is preferably 0.3 to 24 parts by mass.
　ウレタン系高分子分散剤の製造はポリウレタン樹脂製造の公知の方法に従って行われる。製造する際の溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、イソホロン等のケトン類、酢酸エチル、酢酸ブチル、酢酸セロソルブ等のエステル類、ベンゼン、トルエン、キシレン、ヘキサン等の炭化水素類、ダイアセトンアルコール、イソプロパノール、第二ブタノール、第三ブタノール等一部のアルコール類、塩化メチレン、クロロホルム等の塩化物、テトラヒドロフラン、ジエチルエーテル等のエーテル類、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキサイド等の非プロトン性極性溶媒が用いられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 　Urethane-based polymer dispersants are produced according to known methods for producing polyurethane resins. Solvents for production include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane. Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.
　上記製造に際して、ウレタン化反応触媒を用いてもよい。この触媒としては、例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクトエート、スタナスオクトエート等の錫系触媒、鉄アセチルアセトナート、塩化第二鉄等の鉄系触媒、トリエチルアミン、トリエチレンジアミン等の３級アミン系触媒が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 A urethanization reaction catalyst may be used in the above production. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; triethylamine and triethylenediamine; and a tertiary amine-based catalyst. These may be used individually by 1 type, and may use 2 or more types together.
＜アミン価の測定方法＞
　分散剤のアミン価は、分散剤試料中の溶剤を除いた固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表し、次の方法により測定することができる。
　１００ｍＬのビーカーに分散剤試料の０．５～１．５ｇを精秤し、５０ｍＬの酢酸で溶解する。ｐＨ電極を備えた自動滴定装置を使って、この溶液を０．１ｍｏｌ／ＬのＨＣｌＯ4（過塩素酸）酢酸溶液にて中和滴定する。滴定ｐＨ曲線の変曲点を滴定終点とし次式によりアミン価を求める。
　アミン価［ｍｇＫＯＨ／ｇ］＝（５６１×Ｖ）／（Ｗ×Ｓ）
〔但し、Ｗ：分散剤試料秤取量［ｇ］、Ｖ：滴定終点での滴定量［ｍＬ］、Ｓ：分散剤試料の固形分濃度［質量％］を表す。〕 <Method for measuring amine value>
The amine value of the dispersant is expressed by the mass of KOH equivalent to the amount of base per 1 g of the solid content excluding the solvent in the dispersant sample, and can be measured by the following method.
Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO 4 (perchloric acid) acetic acid solution. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.
Amine value [mgKOH/g] = (561 x V)/(W x S)
[However, W: Amount of weighed dispersant sample [g], V: Amount of titration [mL] at the end point of titration, S: Solid content concentration [% by mass] of dispersant sample. ]
　同一分子内に活性水素と３級アミノ基を有する化合物の導入量は反応後のアミン価で１～１００ｍｇＫＯＨ／ｇに制御するのが好ましい。より好ましくは５～９５ｍｇＫＯＨ／ｇである。アミン価は、塩基性アミノ基を酸により中和滴定し、酸価に対応させてＫＯＨのｍｇ数で表した値である。アミン価を前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。 The introduction amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled to 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably 5 to 95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. When the amine value is above the lower limit, the dispersibility tends to be good, and when the amine value is below the upper limit, the developability tends to be good.
　なお、以上の反応で高分子分散剤にイソシアネート基が残存する場合にはさらに、アルコールやアミノ化合物でイソシアネート基を消費すると生成物の経時安定性が高くなるので好ましい。
　ウレタン系高分子分散剤の重量平均分子量（Ｍｗ）は、好ましくは１０００～２０００００、より好ましくは２０００～１０００００、さらに好ましくは３０００～５００００である。ウレタン系高分子分散剤の重量平均分子量（Ｍｗ）は、特に３００００以下が好ましい。例えば、１０００～３００００が好ましく、２０００～３００００がより好ましく、３０００～３００００がさらに好ましい。前記下限値以上とすることで分散性及び分散安定性が良好となる傾向があり、前記上限値以下とすることで溶解性が良好となる傾向がある。分子量が３００００以下であると、特に顔料濃度の高い場合でも、アルカリ現像性が良好となる傾向がある。このような特に好ましい市販のウレタン分散剤として、例えば、Ｄｉｓｐｅｒｂｙｋ１６７、１８２（ビックケミー社製）が挙げられる。 When the isocyanate groups remain in the polymer dispersant after the reaction described above, it is preferable to further consume the isocyanate groups with an alcohol or an amino compound, since the stability of the product over time increases.
The weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 50,000. The weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 30,000 or less. For example, 1,000 to 30,000 is preferred, 2,000 to 30,000 is more preferred, and 3,000 to 30,000 is even more preferred. The dispersibility and dispersion stability tend to be improved by setting the amount to the lower limit or more, and the solubility tends to be improved by setting the amount to the upper limit or less. When the molecular weight is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is particularly high. Such particularly preferred commercially available urethane dispersants include, for example, Disperbyk 167 and 182 (manufactured by BYK-Chemie).
　本発明の顔料分散液において、（Ａ）顔料と（Ｂ）分散剤との質量基準における含有比率（（Ａ）顔料／（Ｂ）分散剤）は１以上が好ましく、３以上がより好ましく、４以上がさらに好ましく、５以上が特に好ましい。また、５０以下が好ましく、３０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで現像溶解性が良好となる傾向がある。また、前記上限値以下とすることで分散安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１～５０が好ましく、３～５０がより好ましく、４～３０がさらに好ましく、５～１５が特に好ましい。 In the pigment dispersion of the present invention, the content ratio ((A) pigment/(B) dispersant) based on mass of (A) pigment and (B) dispersant is preferably 1 or more, more preferably 3 or more, and 4 More preferably, 5 or more is particularly preferable. Moreover, it is preferably 50 or less, more preferably 30 or less, and particularly preferably 15 or less. When the content is at least the above lower limit, the development solubility tends to be good. Moreover, there exists a tendency for dispersion stability to improve by making it below the said upper limit. The above upper and lower limits can be combined arbitrarily. For example, 1 to 50 are preferred, 3 to 50 are more preferred, 4 to 30 are even more preferred, and 5 to 15 are particularly preferred.
　本発明の感光性樹脂組成物における、後述する（Ｂ）分散剤の含有割合は、特に限定されないが、感光性樹脂組成物の全固形分中、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、また、好ましくは１質量％以上、より好ましくは３質量％以上、さらに好ましくは５質量％以上、よりさらに好ましくは７質量％以上、特に好ましくは１０質量％以上である。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは１～５０質量％、より好ましくは３～５０質量％、さらに好ましくは５～３０質量％、よりさらに好ましくは７～３０質量％、特に好ましくは１０～２０質量％である。
　また、本発明の感光性樹脂組成物における、後述する（Ｂ）分散剤の含有割合は、（Ａ）顔料１００質量部に対して、好ましくは５質量部以上、より好ましくは１０質量部以上、さらに好ましくは１５質量部以上であり、また、好ましくは２００質量部以下、より好ましくは８０質量部以下、さらに好ましくは５０質量部以下である。前記下限値以上とすることで十分な分散性を確保しやすい傾向がある。また、前記上限値以下とすることで他の成分の割合を減らすことなく、色濃度、感度、成膜性などを十分なものとしやすい傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは５～２００質量部、より好ましくは１０～８０質量部、さらに好ましくは１５～５０質量部である。 The content of the dispersant (B) described later in the photosensitive resin composition of the present invention is not particularly limited, but the total solid content of the photosensitive resin composition is preferably 50% by mass or less, more preferably 30% by mass. % or less, more preferably 20% by mass or less, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass % or more. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, still more preferably 5 to 30% by mass, still more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass.
Further, the content ratio of the dispersant (B) described later in the photosensitive resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the (A) pigment. More preferably 15 parts by mass or more, preferably 200 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 50 parts by mass or less. By making it equal to or higher than the lower limit, there is a tendency to easily ensure sufficient dispersibility. In addition, by setting the content to the above upper limit or less, there is a tendency to easily achieve sufficient color density, sensitivity, film formability, etc., without reducing the ratio of other components. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 200 parts by mass, more preferably 10 to 80 parts by mass, still more preferably 15 to 50 parts by mass.
＜（Ｃ）スルホン酸基含有化合物＞
　本発明の顔料分散液には、分散性、保存性向上のため、（Ｃ）スルホン酸基含有化合物を含有させる。（Ｃ）スルホン酸基含有化合物としては、例えば、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、キノフタロン系、イソインドリノン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系化合物の誘導体が挙げられる。中でもフタロシアニン系、キノフタロン系化合物の誘導体が好ましい。 <(C) Sulfonic Acid Group-Containing Compound>
The pigment dispersion liquid of the present invention contains (C) a sulfonic acid group-containing compound in order to improve dispersibility and storage stability. Examples of the (C) sulfonic acid group-containing compound include azo compounds, phthalocyanine compounds, quinacridone compounds, benzimidazolone compounds, quinophthalone compounds, isoindolinone compounds, dioxazine compounds, anthraquinone compounds, indanthrene compounds, perylene compounds, and perinone compounds. derivatives of diketopyrrolopyrrole-based and dioxazine-based compounds. Among them, derivatives of phthalocyanine-based and quinophthalone-based compounds are preferred.
　（Ｃ）スルホン酸基含有化合物はスルホン酸基を有し、他の置換基として、例えば、スルホンアミド基及びその４級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシ基、アミド基が化合物の骨格に直接又は、例えば、アルキル基、アリール基、複素環基を介して結合していてもよい化合物が挙げられる。（Ｃ）スルホン酸基含有化合物はスルホン酸基の他、他の置換基として、例えば、スルホンアミド基及びその４級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシ基、アミド基が化合物の骨格に直接又は、例えば、アルキル基、アリール基、複素環基を介して結合していることが好ましい。これらの他の置換基は一つの化合物の骨格に複数置換していてもよい。
　（Ｃ）スルホン酸基含有化合物は、フタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体、ジオキサジンのスルホン酸誘導体を含むことが好ましく、フタロシアニンのスルホン酸誘導体を含むことがより好ましく、銅フタロシアニンスルホン酸誘導体を含むことがさらに好ましい。また、（Ｃ）スルホン酸基含有化合物としては、フタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体、又はジオキサジンのスルホン酸誘導体であることが好ましく、フタロシアニンのスルホン酸誘導体であることがより好ましく、銅フタロシアニンスルホン酸誘導体であることがさらに好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 (C) The sulfonic acid group-containing compound has a sulfonic acid group, and other substituents include, for example, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. Examples thereof include compounds that may be bonded directly to the skeleton of the compound or via, for example, an alkyl group, an aryl group, or a heterocyclic group. (C) the sulfonic acid group-containing compound has, in addition to the sulfonic acid group, other substituents such as a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. directly or via, for example, an alkyl group, an aryl group, or a heterocyclic group. These other substituents may be plurally substituted on the skeleton of one compound.
(C) Sulfonic acid group-containing compounds include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. more preferably a phthalocyanine sulfonic acid derivative, and even more preferably a copper phthalocyanine sulfonic acid derivative. In addition, the (C) sulfonic acid group-containing compound includes a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, or a dioxazine sulfonic acid derivative. Acid derivatives are preferred, phthalocyanine sulfonic acid derivatives are more preferred, and copper phthalocyanine sulfonic acid derivatives are even more preferred.
These may be used individually by 1 type, and may use 2 or more types together.
　本発明の顔料分散液に含まれる（Ｃ）スルホン酸基含有化合物の含有割合は特に限定されないが、顔料分散液の全質量中、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１．０質量％以上がさらに好ましく、また、２０質量％以下が好ましく、１０質量％以下がより好ましく、５．０質量％以下がさらに好ましい。前記下限値以上とすることで分散安定性が向上する傾向がある。また、前記上限値以下とすることで顔料凝集を抑制し塗膜面が均一となる傾向がある。 The content of (C) the sulfonic acid group-containing compound contained in the pigment dispersion of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the pigment dispersion. It is more preferably 1.0% by mass or more, more preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5.0% by mass or less. When the content is equal to or higher than the lower limit, there is a tendency that the dispersion stability is improved. Further, when the content is equal to or less than the above upper limit, there is a tendency that the pigment aggregation is suppressed and the coated film surface becomes uniform.
　本発明の顔料分散液において、（Ａ）顔料と（Ｃ）スルホン酸基含有化合物との、質量基準における含有比率（（Ａ）顔料／（Ｃ）スルホン酸基含有化合物）は１０以上が好ましく、２０以上がさらに好ましく、２５以上が特に好ましい。また、２００以下が好ましく、１５０以下がより好ましく、１００以下がさらに好ましく、５０以下が特に好ましい。前記下限値以上とすることで基板密着性が向上する傾向がある。また、前記上限値以下とすることで分散安定性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１０～２００が好ましく、１０～１５０がより好ましく、２０～１００がさらに好ましく、２５～５０が特に好ましい。 In the pigment dispersion of the present invention, the content ratio ((A) pigment/(C) sulfonic acid group-containing compound) of (A) pigment and (C) sulfonic acid group-containing compound on a mass basis is preferably 10 or more. 20 or more is more preferable, and 25 or more is particularly preferable. Also, it is preferably 200 or less, more preferably 150 or less, still more preferably 100 or less, and particularly preferably 50 or less. When the content is equal to or higher than the lower limit, there is a tendency that the adhesion to the substrate is improved. Moreover, there exists a tendency for dispersion stability to improve by making it below the said upper limit. The above upper and lower limits can be combined arbitrarily. For example, 10 to 200 are preferred, 10 to 150 are more preferred, 20 to 100 are even more preferred, and 25 to 50 are particularly preferred.
　後述する本発明の感光性樹脂組成物に含まれる（Ｃ）スルホン酸基含有化合物の含有割合は特に限定されないが、感光性樹脂組成物の全固形分に対して０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１．０質量％以上がさらに好ましく、また、１０質量％以下が好ましく、５質量％以下がより好ましい。前記下限値以上とすることで現像溶解性が向上する傾向がある。また、前記上限値以下とすることで現像性が安定し、パターニング密着性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、０．１～１０質量％が好ましく、０．５～１０質量％がより好ましく、１．０～５質量％がさらに好ましい。 The content ratio of (C) the sulfonic acid group-containing compound contained in the photosensitive resin composition of the present invention, which will be described later, is not particularly limited, but is preferably 0.1% by mass or more relative to the total solid content of the photosensitive resin composition. , 0.5% by mass or more is more preferable, 1.0% by mass or more is more preferable, and 10% by mass or less is preferable, and 5% by mass or less is more preferable. When the content is at least the above lower limit, there is a tendency that the development solubility is improved. Further, when the content is set to the upper limit value or less, the developability tends to be stable and the patterning adhesion tends to be good. The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferable, 0.5 to 10% by mass is more preferable, and 1.0 to 5% by mass is even more preferable.
＜電気伝導度の測定方法＞
　（Ｃ）スルホン酸基含有化合物の電気伝導度は、２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下である。
　（Ｃ）スルホン酸基含有化合物の電気伝導度は、（Ｃ）スルホン酸基含有化合物を５％溶液となるように超純水に攪拌した時の導電率で表し、電気伝導率計で測定することができる。単位はμＳ／ｃｍで記載することができる。
　（Ｃ）スルホン酸基含有化合物の電気伝導度は２０００μＳ／ｃｍ以上であり、２５００μＳ／ｃｍ以上が好ましく、３０００μＳ／ｃｍ以上がより好ましく、また、９０００μＳ／ｃｍ以下であり、８０００μＳ／ｃｍ以下が好ましく、７０００μＳ／ｃｍ以下がより好ましい。前記下限値以上とすることで分散安定性が向上する傾向がある。また、前記上限値以下とすることでアンダーカットが抑制され現像密着性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、２０００～９０００μＳ／ｃｍであり、２５００～８０００μＳ／ｃｍが好ましく、３０００～７０００μＳ／ｃｍがより好ましい。 <Method for measuring electrical conductivity>
(C) The electrical conductivity of the sulfonic acid group-containing compound is 2000 μS/cm or more and 9000 μS/cm or less.
The electrical conductivity of the (C) sulfonic acid group-containing compound is expressed by the electrical conductivity when the (C) sulfonic acid group-containing compound is stirred in ultrapure water so as to form a 5% solution, and is measured with an electrical conductivity meter. be able to. The unit can be described in μS/cm.
(C) The electrical conductivity of the sulfonic acid group-containing compound is 2000 μS/cm or more, preferably 2500 μS/cm or more, more preferably 3000 μS/cm or more, and 9000 μS/cm or less, preferably 8000 μS/cm or less. , 7000 μS/cm or less. When the content is equal to or higher than the lower limit, there is a tendency that the dispersion stability is improved. In addition, when the content is equal to or less than the above upper limit, there is a tendency that undercut is suppressed and development adhesion is improved. The above upper and lower limits can be combined arbitrarily. For example, it is 2000 to 9000 μS/cm, preferably 2500 to 8000 μS/cm, more preferably 3000 to 7000 μS/cm.
　（Ｃ）スルホン酸基含有化合物の酸価は４０ｍｇＫＯＨ／ｇ以上であり、６０ｍｇＫＯＨ／ｇ以上が好ましく、８０ｍｇＫＯＨ／ｇ以上がより好ましく、９０ｍｇＫＯＨ／ｇ以上がさらに好ましく、１００ｍｇＫＯＨ／ｇ以上が特に好ましく、また、５００ｍｇＫＯＨ／ｇ以下が好ましく、３００ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下がさらに好ましく、１５０ｍｇＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで溶解性が向上する傾向がある。また、前記上限値以下とすることでアンダーカットが抑制され細線密着性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、４０～５００ｍｇＫＯＨ／ｇが好ましく、６０～５００ｍｇＫＯＨ／ｇがより好ましく、８０～３００ｍｇＫＯＨ／ｇがさらに好ましく、９０～２００ｍｇＫＯＨ／ｇがよりさらに好ましく、１００～１５０ｍｇＫＯＨ／ｇが特に好ましい。 (C) the acid value of the sulfonic acid group-containing compound is 40 mgKOH/g or more, preferably 60 mgKOH/g or more, more preferably 80 mgKOH/g or more, still more preferably 90 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more; Also, it is preferably 500 mgKOH/g or less, more preferably 300 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less. The solubility tends to be improved by adjusting the content to be equal to or higher than the above lower limit. Further, when the content is equal to or less than the above upper limit, there is a tendency that undercutting is suppressed and fine line adhesion is improved. The above upper and lower limits can be combined arbitrarily. For example, 40 to 500 mgKOH/g is preferred, 60 to 500 mgKOH/g is more preferred, 80 to 300 mgKOH/g is still more preferred, 90 to 200 mgKOH/g is even more preferred, and 100 to 150 mgKOH/g is particularly preferred.
　本発明の顔料分散液は、例えば、（Ａ）顔料、（Ｂ）分散剤及び（Ｃ）スルホン酸基含有化合物や、必要に応じて使用される各種材料が、溶剤に溶解又は分散した状態で使用される。
　溶剤としては、水や後述する本発明の感光性樹脂組成物で用いられる有機溶剤を好適に用いることができる。 In the pigment dispersion of the present invention, for example, (A) a pigment, (B) a dispersant and (C) a sulfonic acid group-containing compound, and optionally various materials used are dissolved or dispersed in a solvent. used.
As the solvent, water or an organic solvent used in the photosensitive resin composition of the present invention, which will be described later, can be suitably used.
　本発明の顔料分散液が有機溶剤を含む場合、有機溶剤の含有割合は特に限定されないが、塗布し易さや粘度安定性の観点から、顔料分散液中の全固形分が好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは２０質量％以上、また、好ましくは５０質量％以下、より好ましくは４５質量％以下、さらに好ましくは４０質量％以下、特に好ましくは３５質量％以下である。前記下限値以上とすることで着色力が向上し、光学濃度（ＯＤ値）を上げやすくなる傾向がある。また、前記上限値以下とすることで分散安定性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは５～５０質量％、より好ましくは５～４５質量％、さらに好ましくは１０～４０質量％、特に好ましくは２０～３５質量％である。 When the pigment dispersion of the present invention contains an organic solvent, the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the pigment dispersion is preferably 5% by mass or more. , More preferably 10% by mass or more, still more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, particularly preferably 35% by mass or less be. When the content is at least the lower limit, the coloring power is improved, and the optical density (OD value) tends to be easily increased. Further, when the amount is equal to or less than the above upper limit, there is a tendency that the dispersion stability becomes good. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 50% by mass, more preferably 5 to 45% by mass, even more preferably 10 to 40% by mass, particularly preferably 20 to 35% by mass.
［感光性樹脂組成物］
　本発明の感光性樹脂組成物は（Ａ）顔料、（Ｂ）分散剤、（Ｃ）スルホン酸基含有化合物、（Ｄ）アルカリ可溶性樹脂、（Ｅ）光重合性化合物及び（Ｆ）光重合開始剤を含有する感光性樹脂組成物であって、前記（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下であり、前記（Ｃ）スルホン酸基含有化合物の酸価が４０ｍｇＫＯＨ／ｇ以上であることを特徴とする。
　所定の電気伝導度及び酸価に調節または組み合わせたスルホン酸基含有化合物を用いることにより、溶解性及び細線密着性に優れた感光性樹脂組成物を得ることができる。 [Photosensitive resin composition]
The photosensitive resin composition of the present invention includes (A) a pigment, (B) a dispersant, (C) a sulfonic acid group-containing compound, (D) an alkali-soluble resin, (E) a photopolymerizable compound and (F) a photopolymerization initiator. wherein the (C) sulfonic acid group-containing compound has an electrical conductivity of 2000 μS/cm or more and 9000 μS/cm or less, and the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
By using a sulfonic acid group-containing compound adjusted to or combined with a predetermined electrical conductivity and acid value, a photosensitive resin composition excellent in solubility and fine line adhesion can be obtained.
　本発明の感光性樹脂組成物に含有される（Ａ）顔料、（Ｂ）分散剤、（Ｃ）スルホン酸基含有化合物としては、上述の顔料分散液で挙げた（Ａ）顔料、（Ｂ）分散剤、（Ｃ）スルホン酸基含有化合物を好ましく用いることができる。 As the (A) pigment, (B) dispersant, and (C) sulfonic acid group-containing compound contained in the photosensitive resin composition of the present invention, the (A) pigment, (B) A dispersant and (C) a sulfonic acid group-containing compound can be preferably used.
＜（Ｄ）アルカリ可溶性樹脂＞
　（Ｄ）アルカリ可溶性樹脂としては、感光性樹脂組成物を塗布、乾燥して得られる塗膜を露光後、露光部と非露光部のアルカリ現像に対する溶解性が変化するようなものであれば特に限定されてないが、カルボキシ基を有するアルカリ可溶性樹脂であるのが好ましい。また、エチレン性不飽和基を有するものが好ましく、エチレン性不飽和基とカルボキシ基を有するアルカリ可溶性樹脂が、さらに好ましい。
　以下にその一例を示す。 <(D) Alkali-soluble resin>
(D) As the alkali-soluble resin, especially if the solubility of the exposed area and the non-exposed area in alkali development changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed. Although not limited, it is preferably an alkali-soluble resin having a carboxy group. Moreover, those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxyl group are more preferable.
An example is shown below.
＜アルカリ可溶性樹脂（ｄ１）＞
　本発明における（Ｄ）アルカリ可溶性樹脂には、下記一般式（ｄ１－１）で表される部分構造を有するアルカリ可溶性樹脂（ｄ１）を含むことが好ましい。アルカリ可溶性樹脂（ｄ１）を含むことにより、密着性が良好となる傾向がある。 <Alkali-soluble resin (d1)>
The (D) alkali-soluble resin in the present invention preferably contains an alkali-soluble resin (d1) having a partial structure represented by the following general formula (d1-1). Including the alkali-soluble resin (d1) tends to improve adhesion.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ｄ１－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。Ｒ７は各々独立に、水素原子又はメチル基を表す。Ｘは各々独立に、Ｏ、Ｓ、ＣＯ、又は直接結合を示す。＊は各々結合手を表す。ｎは０～４の整数を表す。 The benzene ring in formula (d1-1) may be further substituted with any substituent. Each R7 independently represents a hydrogen atom or a methyl group. Each X independently represents O, S, CO, or a direct bond. Each * represents a bond. n represents an integer of 0 to 4;
　上記一般式（ｄ１－１）において、感度の観点からはｎは３以下が好ましく、２以下がより好ましく、０であることがさらに好ましい。
　Ｒ７は水素原子であることが好ましい。 In general formula (d1-1) above, n is preferably 3 or less, more preferably 2 or less, and even more preferably 0 from the viewpoint of sensitivity.
R7 is preferably a hydrogen atom.
　上記一般式（ｄ１－１）において、感度の観点からは、Ｘは直接結合が好ましい。 In the above general formula (d1-1), X is preferably a direct bond from the viewpoint of sensitivity.
　式（ｄ１－１）で表される部分構造を有するアルカリ可溶性樹脂（ｄ１）は、例えば、下記式（ｄ７－１）で表されるカルド骨格を有するエポキシ樹脂に（メタ）アクリル酸を付加させ、さらに、多塩基酸及び／又はその無水物を反応させることによって得られたアルカリ可溶性樹脂であることが好ましい。 Alkali-soluble resin (d1) having a partial structure represented by formula (d1-1) is obtained, for example, by adding (meth)acrylic acid to an epoxy resin having a cardo skeleton represented by formula (d7-1) below. Furthermore, it is preferably an alkali-soluble resin obtained by reacting a polybasic acid and/or its anhydride.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（ｄ７－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。Ｘは各々独立に、Ｏ、Ｓ、ＣＯ、または直接結合を示す。ｎは０～４の整数を表す。 The benzene ring in formula (d7-1) may be further substituted with any substituent. Each X independently represents O, S, CO, or a direct bond. n represents an integer of 0 to 4;
　上記一般式（ｄ７－１）において、ｎは０～４の整数を表し、ｎは３以下が好ましく、２以下がより好ましく、０であることがさらに好ましい。 In the above general formula (d7-1), n represents an integer of 0 to 4, preferably 3 or less, more preferably 2 or less, and even more preferably 0.
　エポキシ樹脂に（メタ）アクリル酸を付加させる方法としては、公知の手法を用いることができる。例えば、エステル化触媒の存在下、５０～１５０℃の温度で、反応させることができる。ここで用いる触媒としては、トリエチルホスフィン、トリブチルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン等の３級ホスフィン、トリエチルアミン、トリメチルアミン、ベンジルジメチルアミン、ベンジルジエチルアミン等の３級アミン、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド等の４級アンモニウム塩を用いることができる。 As a method for adding (meth)acrylic acid to the epoxy resin, a known technique can be used. For example, the reaction can be carried out at a temperature of 50-150° C. in the presence of an esterification catalyst. The catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. , dodecyltrimethylammonium chloride and the like can be used.
　（メタ）アクリル酸の使用量は、エポキシ樹脂のエポキシ基１当量に対し０．５～１．２当量の範囲が好ましく、０．７～１．１当量の範囲がより好ましい。
　（メタ）アクリル酸の使用量を前記下限値以上とすることで不飽和基の導入量が十分となり、引き続く多塩基酸及び／又はその無水物との反応も十分となり、また、多量のエポキシ基の残存を抑制できる傾向がある。一方で、前記使用量を前記上限値以下とすることで（メタ）アクリル酸が未反応物として残存するのを抑制できる傾向がある。 The amount of (meth)acrylic acid used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the epoxy resin.
By setting the amount of (meth)acrylic acid to be at least the above lower limit, the amount of unsaturated groups introduced is sufficient, the subsequent reaction with polybasic acid and / or its anhydride is sufficient, and a large amount of epoxy groups It tends to be possible to suppress the remaining of On the other hand, by setting the amount to be the upper limit or less, there is a tendency that (meth)acrylic acid can be suppressed from remaining as an unreacted product.
　多塩基酸及び／又はその無水物としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸、及びこれらの無水物から選ばれた、１種又は２種以上が挙げられる。 Examples of polybasic acids and/or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexacarboxylic acid, One or more selected from hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof can be mentioned.
　多塩基酸及び／又はその無水物の付加反応に関しても、公知の手法を用いることができ、（メタ）アクリル酸の付加反応と同様な条件下で、継続反応させて目的物を得ることができる。 For the addition reaction of polybasic acid and/or its anhydride, a known method can be used, and the desired product can be obtained by continuous reaction under the same conditions as the addition reaction of (meth)acrylic acid. .
　アルカリ可溶性樹脂（ｄ１）の多塩基酸及び／又はその無水物の付加反応合成時に、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールなどの多価アルコールを添加し、多分岐構造を導入したものとしてもよい。 Polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol are added during the addition reaction synthesis of the alkali-soluble resin (d1) polybasic acid and/or its anhydride to introduce a multibranched structure. good.
　アルカリ可溶性樹脂（ｄ１）は、例えば、エポキシ樹脂と（メタ）アクリル酸との反応物に、多塩基酸及び／又はその無水物を混合した後、もしくは、エポキシ樹脂と（メタ）アクリル酸との反応物に、多塩基酸及び／又はその無水物及び多価アルコールを混合した後に、加温することにより得られる。この場合、多塩基酸及び／又はその無水物と多価アルコールの混合順序に、特に制限はない。加温により、（メタ）アクリル酸との反応物と多価アルコールとの混合物中に存在するいずれかの水酸基に対して多塩基酸及び／又はその無水物が付加反応する。 Alkali-soluble resin (d1), for example, after mixing a reaction product of epoxy resin and (meth)acrylic acid with polybasic acid and / or its anhydride, or after mixing epoxy resin and (meth)acrylic acid It is obtained by heating after mixing a polybasic acid and/or its anhydride and a polyhydric alcohol with a reactant. In this case, the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. By heating, the polybasic acid and/or its anhydride undergo an addition reaction with any hydroxyl group present in the mixture of the reaction product with (meth)acrylic acid and the polyhydric alcohol.
　多価アルコールの使用量は、増粘やゲル化を抑制しつつ効果を発現するとの観点から、エポキシ樹脂と（メタ）アクリル酸との反応物と、多塩基酸及び／又はその無水物との反応物に対して、通常０．０１～０．５質量倍程度、好ましくは０．０２～０．２質量倍程度である。 The amount of the polyhydric alcohol used is the amount of the reaction product of the epoxy resin and (meth)acrylic acid and the polybasic acid and / or its anhydride from the viewpoint of exhibiting the effect while suppressing thickening and gelation. It is usually about 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight, the reactant.
　アルカリ可溶性樹脂（ｄ１）は、１種を単独で用いても、２種以上の樹脂を混合して用いてもよい。 The alkali-soluble resin (d1) may be used alone, or two or more resins may be mixed and used.
　アルカリ可溶性樹脂（ｄ１）の酸価は、１０ｍｇＫＯＨ／ｇ以上が好ましく、５０ｍｇＫＯＨ／ｇ以上がより好ましく、８０ｍｇＫＯＨ／ｇ以上がさらに好ましく、８０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１５０ｍｇＫＯＨ／ｇ以下であることがより好ましく、１２０ｍｇＫＯＨ／ｇ以下であることがさらに好ましい。前記下限値以上とすることで残渣が低減する傾向がある。また、前記上限値以下とすることで細線密着性を良好にすることができる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１０～２００ｍｇＫＯＨ／ｇが好ましく、５０～２００ｍｇＫＯＨ／ｇがより好ましく、８０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、８０～１２０ｍｇＫＯＨ／ｇが特に好ましい。 The acid value of the alkali-soluble resin (d1) is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, and 200 mgKOH/g or less. is preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. Residue tends to be reduced by making it equal to or higher than the lower limit. Moreover, there is a tendency that fine wire adhesion can be improved by adjusting the content to be equal to or less than the above upper limit. The above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH/g is preferred, 50 to 200 mgKOH/g is more preferred, 80 to 150 mgKOH/g is even more preferred, and 80 to 120 mgKOH/g is particularly preferred.
　アルカリ可溶性樹脂（ｄ１）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算の重量平均分子量（Ｍｗ）は、１０００以上が好ましく、２０００以上がより好ましく、４０００以上がさらに好ましく、５０００以上が特に好ましい。また、２００００以下が好ましく、１５０００以下がより好ましく、１００００以下がさらに好ましく、８０００以下がよりさらに好ましく、７０００以下が特に好ましい。前記下限値以上とすることで細線密着性が良好となる傾向がある。また、前記上限値以下とすることで現像溶解性や再溶解性を良好なものとすることができる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～２００００が好ましく、１０００～１５０００がより好ましく、２０００～１００００がさらに好ましく、４０００～８０００がよりさらに好ましく、５０００～７０００が特に好ましい。 The polystyrene equivalent weight average molecular weight (Mw) of the alkali-soluble resin (d1) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 2000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. . Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 7,000 or less. By making it more than the said lower limit, there exists a tendency for thin line|wire adhesiveness to become favorable. Moreover, there is a tendency that development solubility and re-solubility can be improved by making the amount equal to or less than the above upper limit. The above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,000 to 15,000 is more preferred, 2,000 to 10,000 is even more preferred, 4,000 to 8,000 is even more preferred, and 5,000 to 7,000 is particularly preferred.
　本発明の感光性樹脂組成物は（Ｄ）アルカリ可溶性樹脂として、アルカリ可溶性樹脂（ｄ１）以外のアルカリ可溶性樹脂を含有してもよい。
　アルカリ可溶性樹脂（ｄ１）以外のアルカリ可溶性樹脂としては、感光性樹脂組成物を塗布、乾燥して得られる塗膜を露光後、露光部と非露光部のアルカリ現像に対する溶解性が変化するようなものであれば特に限定されてないが、カルボキシ基を有するアルカリ可溶性樹脂であるのが好ましい。また、エチレン性不飽和基を有するものが好ましく、エチレン性不飽和基とカルボキシ基を有するアルカリ可溶性樹脂が、さらに好ましい。
　具体的には、アルカリ可溶性樹脂（ｄ１）以外のカルボキシ基を有するエポキシ（メタ）アクリレート樹脂（ｄ２）、アクリル共重合樹脂（ｄ３）、それ以外の樹脂（ｄ４）が挙げられる。 The photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the alkali-soluble resin (d1) as the (D) alkali-soluble resin.
As the alkali-soluble resin other than the alkali-soluble resin (d1), after the coating film obtained by applying and drying the photosensitive resin composition is exposed, the solubility of the exposed area and the non-exposed area in alkali development changes. Although it is not particularly limited as long as it is a substance, it is preferably an alkali-soluble resin having a carboxy group. Moreover, those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxy group are more preferable.
Specific examples include an epoxy (meth)acrylate resin (d2) having a carboxy group other than the alkali-soluble resin (d1), an acrylic copolymer resin (d3), and other resins (d4).
＜アルカリ可溶性樹脂（ｄ１）以外のカルボキシ基を有するエポキシ（メタ）アクリレート樹脂（ｄ２）＞
　アルカリ可溶性樹脂（ｄ１）以外のカルボキシ基を有するエポキシ（メタ）アクリレート樹脂（ｄ２）としては、例えば、以下のエポキシ（メタ）アクリレート樹脂（ｄ２－１）、エポキシ（メタ）アクリレート樹脂（ｄ２－２）が挙げられる。 <Epoxy (meth)acrylate resin (d2) having a carboxy group other than alkali-soluble resin (d1)>
As the epoxy (meth)acrylate resin (d2) having a carboxy group other than the alkali-soluble resin (d1), for example, the following epoxy (meth)acrylate resin (d2-1), epoxy (meth)acrylate resin (d2-2 ).
　＜エポキシ（メタ）アクリレート樹脂（ｄ２－１）＞
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多塩基酸及び／又はその無水物を反応させることによって得られたアルカリ可溶性樹脂。 <Epoxy (meth)acrylate resin (d2-1)>
Obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin and further reacting a polybasic acid and / or its anhydride. Alkali-soluble resin.
　＜エポキシ（メタ）アクリレート樹脂（ｄ２－２）＞
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多価アルコール、及び多塩基酸及び／又はその無水物と反応させることによって得られたアルカリ可溶性樹脂。 <Epoxy (meth)acrylate resin (d2-2)>
An α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and/or its anhydride. Alkali-soluble resin obtained by
＜エポキシ（メタ）アクリレート樹脂（ｄ２－１）、エポキシ（メタ）アクリレート樹脂（ｄ２－２）＞
　原料となるエポキシ樹脂として、例えば、ビスフェノールＡ型エポキシ樹脂（例えば、三菱ケミカル社製の「ｊＥＲ（登録商標。以下同じ。）８２８」、「ｊＥＲ１００１」、「ｊＥＲ１００２」、「ｊＥＲ１００４」等）、ビスフェノールＡ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ（例えば、日本化薬社製の「ＮＥＲ－１３０２」（エポキシ当量３２３，軟化点７６℃））、ビスフェノールＦ型樹脂（例えば、三菱ケミカル社製の「ｊＥＲ８０７」、「ＥＰ－４００１」、「ＥＰ－４００２」、「ＥＰ－４００４等」）、ビスフェノールＦ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ樹脂（例えば、日本化薬社製の「ＮＥＲ－７４０６」（エポキシ当量３５０，軟化点６６℃））、ビスフェノールＳ型エポキシ樹脂、ビフェニルグリシジルエーテル（例えば、三菱ケミカル社製の「ＹＸ－４０００」）、フェノールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ－２０１」、三菱ケミカル社製の「ＥＰ－１５２」、「ＥＰ－１５４」、ダウケミカル社製の「ＤＥＮ－４３８」）、（ｏ，ｍ，ｐ－）クレゾールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＯＣＮ（登録商標。以下同じ。）－１０２Ｓ」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」）、トリグリシジルイソシアヌレート（例えば、日産化学社製の「ＴＥＰＩＣ（登録商標）」）、トリスフェノールメタン型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ（登録商標。以下同じ。）－５０１」、「ＥＰＰＮ－５０２」、「ＥＰＰＮ－５０３」）、脂環式エポキシ樹脂（ダイセル社製の「セロキサイド（登録商標。以下同じ。）２０２１Ｐ」、「セロキサイドＥＨＰＥ」）、ジシクロペンタジエンとフェノールの反応によるフェノール樹脂をグリシジル化したエポキシ樹脂（例えば、ＤＩＣ社製の「ＥＸＡ－７２００」、日本化薬社製の「ＮＣ－７３００」）、下記一般式（ｄ２－ａ）～（ｄ２－ｅ）で表されるエポキシ樹脂を好適に用いることができる。具体的には、例えば、下記一般式（ｄ２－ａ）で表されるエポキシ樹脂として日本化薬社製の「ＸＤ－１０００」、下記一般式（ｄ２－ｂ）で表されるエポキシ樹脂として日本化薬社製の「ＮＣ－３０００」が挙げられる。 <Epoxy (meth)acrylate resin (d2-1), epoxy (meth)acrylate resin (d2-2)>
Examples of epoxy resins used as raw materials include bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corp.'s "jER (registered trademark; the same shall apply hereinafter) 828", "jER1001", "jER1002", "jER1004", etc.), bisphenol Epoxy obtained by reaction of alcoholic hydroxyl group of A-type epoxy resin and epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point: 76 ° C.)), bisphenol F-type resin (for example, Mitsubishi "JER807", "EP-4001", "EP-4002", "EP-4004, etc." manufactured by Chemical Co., Ltd.), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (for example, Japan Kayaku Co., Ltd. "NER-7406" (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, Mitsubishi Chemical Co., Ltd. "YX-4000"), phenol novolac type epoxy Resin (e.g., Nippon Kayaku "EPPN-201", Mitsubishi Chemical "EP-152", "EP-154", Dow Chemical "DEN-438"), (o, m, p-) cresol novolac type epoxy resin (e.g., Nippon Kayaku Co., Ltd. "EOCN (registered trademark; hereinafter the same)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (e.g. , “TEPIC (registered trademark)” manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resin (for example, “EPPN (registered trademark) -501”, “EPPN-502” manufactured by Nippon Kayaku Co., Ltd., "EPPN-503"), alicyclic epoxy resins ("Celoxide (registered trademark) 2021P" and "Celoxide EHPE" manufactured by Daicel), and glycidylated phenolic resins by the reaction of dicyclopentadiene and phenol. Epoxy resins (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (d2-a) to (d2-e) are preferred. can be used for Specifically, for example, as an epoxy resin represented by the following general formula (d2-a), "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and as an epoxy resin represented by the following general formula (d2-b), Japan "NC-3000" manufactured by Kayaku Co., Ltd. can be mentioned.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（ｄ２－ａ）において、ｂ１１は平均値を示し０～１０の数を示す。Ｒ11は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ11は互いに同一であっても異なっていてもよい。 In the formula (d2-a), b11 indicates an average value and indicates a number from 0 to 10. R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. A plurality of R 11 present in one molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（ｄ２－ｂ）において、ｂ１２は平均値を示し０～１０の数を示す。Ｒ21は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ21は互いに同一であっても異なっていてもよい。 In the formula (d2-b), b12 represents an average value and represents a number from 0 to 10. R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 21 in one molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（ｄ２－ｃ）において、Ｘは下記一般式（ｄ２－ｃ－１）又は（ｄ２－ｃ－２）で表される連結基を示す。但し、分子構造中に１つ以上のアダマンタン構造を含む。ｂ１３は２又は３の整数を示す。 In formula (d2-c), X represents a linking group represented by general formula (d2-c-1) or (d2-c-2) below. However, it contains one or more adamantane structures in its molecular structure. b13 represents an integer of 2 or 3;
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（ｄ２－ｃ－１）及び（ｄ２－ｃ－２）において、Ｒ31～Ｒ34及びＲ35～Ｒ37は、各々独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数１～１２のアルキル基、又は置換基を有していてもよいフェニル基を示す。また、式中の＊印は（ｄ２－ｃ）中の結合部位を表す。 In formulas (d2-c-1) and (d2-c-2), R 31 to R 34 and R 35 to R 37 each independently represent an optionally substituted adamantyl group, a hydrogen atom, It represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. The * mark in the formula represents the binding site in (d2-c).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（ｄ２－ｄ）において、Ｒ51～Ｒ54は各々独立に、水素原子、炭素数１～２０のアルキル基、炭素原子６～２０のアリール基、又は、炭素原子７～２０のアラルキル基であり、Ｒ55は各々独立に炭素数１～２０のアルキル基、炭素数６～２０のアリール基、又は炭素数７～２０のアラルキル基であり、Ｒ56は各々独立に炭素数１～５のアルキレン基である。ｋは１～５の整数であり、ｌは０～１３の整数であり、ｍは各々独立に０～５の整数である。 In formula (d2-d), each of R 51 to R 54 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. each R 55 is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; It is an alkylene group. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is each independently an integer of 0 to 5.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記一般式（ｄ２－ｅ）において、ｎ及びｏは各々独立に１～９の整数である。
　Ｒ23は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ23は互いに同一であっても異なっていてもよい。 In the above general formula (d2-e), n and o are each independently an integer of 1-9.
R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. A plurality of R 23 present in one molecule may be the same or different.
　これらの中で、一般式（ｄ２－ａ）～（ｄ２－ｅ）のいずれかで表されるエポキシ樹脂を用いるのが好ましい。 Among these, it is preferable to use epoxy resins represented by any of general formulas (d2-a) to (d2-e).
　α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルとしては、例えば、（メタ）アクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸、（メタ）アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体などのモノカルボン酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルアジピン酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルマレイン酸、２－（メタ）アクリロイロキシプロピルコハク酸、２－（メタ）アクリロイロキシプロピルアジピン酸、２－（メタ）アクリロイロキシプロピルテトラヒドロフタル酸、２－（メタ）アクリロイロキシプロピルフタル酸、２－（メタ）アクリロイロキシプロピルマレイン酸、２－（メタ）アクリロイロキシブチルコハク酸、２－（メタ）アクリロイロキシブチルアジピン酸、２－（メタ）アクリロイロキシブチルヒドロフタル酸、２－（メタ）アクリロイロキシブチルフタル酸、２－（メタ）アクリロイロキシブチルマレイン酸、
　（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸にε－カプロラクトン、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン等のラクトン類を付加させ末端に１個の水酸基を有する単量体や、
　或いはヒドロキシアルキル（メタ）アクリレートのような末端に１個の水酸基を有する単量体や、ペンタエリスリトールトリ（メタ）アクリレートのような末端に１個の水酸基を有する化合物に、（無水）コハク酸、（無水）フタル酸、（無水）マレイン酸などの酸（無水物）を付加させ、１個以上のエチレン不飽和基と末端に１個のカルボキシ基を有する（メタ）アクリル酸エステルが挙げられる。また、（メタ）アクリル酸ダイマーが挙げられる。 Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 - (meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2 - (meth) acryloyloxypropyl adipate, 2-(meth) acryloyloxypropyl tetrahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) acryloyloxypropyl maleate, 2- (Meth) acryloyloxybutyl succinate, 2-(meth) acryloyloxybutyl adipate, 2-(meth) acryloyloxybutyl hydrophthalate, 2-(meth) acryloyloxybutyl phthalate, 2-( meth) acryloyloxybutyl maleate,
(Meth)acrylic acid esters include, for example, lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone added to (meth)acrylic acid and having one hydroxyl group at the end. a monomer or
Alternatively, a monomer having one hydroxyl group at the terminal such as hydroxyalkyl (meth)acrylate, or a compound having one hydroxyl group at the terminal such as pentaerythritol tri(meth)acrylate, (anhydrous) succinic acid, Examples include (meth)acrylic esters to which an acid (anhydride) such as (anhydride) phthalic acid and (anhydride) maleic acid is added and which has one or more ethylenically unsaturated groups and one carboxyl group at the end. (Meth)acrylic acid dimers are also included.
　これらの内、感度の点から、特に好ましいものは（メタ）アクリル酸である。
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルを付加させる方法としては、公知の手法を用いることができる。例えば、エステル化触媒の存在下、５０～１５０℃の温度で、α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルとエポキシ樹脂とを反応させることができる。
　ここで用いる触媒としては、トリエチルホスフィン、トリブチルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン等の３級ホスフィン、トリエチルアミン、トリメチルアミン、ベンジルジメチルアミン、ベンジルジエチルアミン等の３級アミン、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド等の４級アンモニウム塩を用いることができる。 Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method for adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, a known technique can be used. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. can.
The catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. , dodecyltrimethylammonium chloride and the like can be used.
　なお、エポキシ樹脂、α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステル、及びエステル化触媒は、いずれも１種を単独で用いてもよく、２種以上を併用してもよい。
　α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルの使用量は、エポキシ樹脂のエポキシ基１当量に対し０．５～１．２当量の範囲が好ましく、０．７～１．１当量の範囲がより好ましい。
　α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルの使用量を前記下限値以上とすることで不飽和基の導入量が十分となり、引き続く多塩基酸及び／又はその無水物との反応も十分となり、また、多量のエポキシ基の残存を抑制できる傾向がある。一方で、前記使用量を前記上限値以下とすることでα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルが未反応物として残存するのを抑制できる傾向がある。 The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may be used singly, or two kinds may be used. You may use the above together.
The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. , 0.7 to 1.1 equivalents is more preferred.
By setting the amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the amount of the unsaturated group introduced becomes sufficient, and the subsequent polybasic acid And/or the reaction with its anhydride becomes sufficient, and there is a tendency that a large amount of epoxy groups can be suppressed from remaining. On the other hand, by setting the amount to be equal to or less than the upper limit, it is possible to suppress the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group from remaining as an unreacted product. Tend.
　多塩基酸及び／又はその無水物、多価アルコールとしては、アルカリ可溶性樹脂（ｄ１）と同様の化合物を使用することができる。また合成法もアルカリ可溶性樹脂（ｄ１）と同様の合成方法を用いることができる。 As the polybasic acid and/or its anhydride and polyhydric alcohol, the same compound as the alkali-soluble resin (d1) can be used. Also, the same synthetic method as that for the alkali-soluble resin (d1) can be used.
　このようにして得られるエポキシ（メタ）アクリレート樹脂（ｄ２－１、ｄ２－２）の酸価は、１０ｍｇＫＯＨ／ｇ以上が好ましく、５０ｍｇＫＯＨ／ｇ以上がより好ましく、８０ｍｇＫＯＨ／ｇ以上がさらに好ましい。また、２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１５０ｍｇＫＯＨ／ｇ以下であることがより好ましい。前記下限値以上とすることで細線密着性が良好となる傾向がある。また、前記上限値以下とすることで現像溶解性を良好にすることができる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１０～２００ｍｇＫＯＨ／ｇが好ましく、５０～２００ｍｇＫＯＨ／ｇがより好ましく、８０～１５０ｍｇＫＯＨ／ｇがさらに好ましい。 The acid value of the epoxy (meth)acrylate resins (d2-1, d2-2) thus obtained is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 80 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less. By making it more than the said lower limit, there exists a tendency for thin line|wire adhesiveness to become favorable. Further, there is a tendency that developing solubility can be improved by adjusting the content to be equal to or less than the above upper limit. The above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH/g is preferred, 50 to 200 mgKOH/g is more preferred, and 80 to 150 mgKOH/g is even more preferred.
　エポキシ（メタ）アクリレート樹脂（ｄ２－１、ｄ２－２）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算の重量平均分子量（Ｍｗ）は、１０００以上が好ましく、１５００以上がより好ましく、２０００以上がさらに好ましく、２３００以上が特に好ましい。また、２００００以下が好ましく、１５０００以下がより好ましく、１００００以下がさらに好ましく、８０００以下がよりさらに好ましく、６０００以下が特に好ましい。前記下限値以上とすることで感度、塗膜強度、アルカリ耐性が良好となる傾向がある。また、前記上限値以下とすることで現像性や再溶解性を良好なものとすることができる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～２００００が好ましく、１０００～１５０００がより好ましく、１５００～１００００がさらに好ましく、２０００～８０００がよりさらに好ましく、２３００～６０００が特に好ましい。 The polystyrene equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resins (d2-1, d2-2) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, and 2000 or more. is more preferable, and 2300 or more is particularly preferable. Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less. When the content is at least the above lower limit, sensitivity, coating film strength and alkali resistance tend to be improved. Moreover, there is a tendency that the developability and the re-solubility can be improved by adjusting the content to the above upper limit or less. The above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,000 to 15,000 is more preferred, 1,500 to 10,000 is even more preferred, 2,000 to 8,000 is even more preferred, and 2,300 to 6,000 is particularly preferred.
＜アクリル共重合樹脂（ｄ３）＞
　アクリル共重合樹脂（ｄ３）としては、例えば、日本国特開平７－２０７２１１号公報、日本国特開平８－２５９８７６号公報、日本国特開平１０－３００９２２号公報、日本国特開平１１－１４０１４４号公報、日本国特開平１１－１７４２２４号公報、日本国特開２０００－５６１１８号公報、日本国特開２００３－２３３１７９号公報、日本国特開２００７－２７０１４７号公報などの各公報に記載された様々な高分子化合物を使用することができる。好ましくは、下記アクリル共重合樹脂（ｄ３－１）～（ｄ３－４）が挙げられる。中でも、アクリル共重合樹脂（ｄ３－１）が特に好ましい。 <Acrylic copolymer resin (d3)>
Examples of the acrylic copolymer resin (d3) include Japanese Patent Laid-Open Nos. 7-207211, 8-259876, 10-300922, and 11-140144. Publications, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2003-233179, Japanese Patent Application Publication No. 2007-270147, etc. Any polymeric compound can be used. Preferred are the following acrylic copolymer resins (d3-1) to (d3-4). Among them, the acrylic copolymer resin (d3-1) is particularly preferred.
　アクリル共重合樹脂（ｄ３－１）：エポキシ基含有（メタ）アクリレートと、他のラジカル重合性単量体との共重合体に対し、当該共重合体が有するエポキシ基の少なくとも一部に不飽和一塩基酸を付加させてなる樹脂、或いは当該付加反応により生じた水酸基の少なくとも一部に多塩基酸無水物を付加させて得られる樹脂。
　アクリル共重合樹脂（ｄ３－２）：主鎖にカルボキシ基を含有する直鎖状アルカリ可溶性樹脂。
　アクリル共重合樹脂（ｄ３－３）：前記アクリル共重合樹脂（ｄ３－２）のカルボキシ基部分に、エポキシ基含有不飽和化合物を付加させた樹脂。
　アクリル共重合樹脂（ｄ３－４）：（メタ）アクリル系樹脂。 Acrylic copolymer resin (d3-1): for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, at least some of the epoxy groups of the copolymer are unsaturated A resin obtained by adding a monobasic acid, or a resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction.
Acrylic copolymer resin (d3-2): Linear alkali-soluble resin containing a carboxy group in the main chain.
Acrylic copolymer resin (d3-3): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of the acrylic copolymer resin (d3-2).
Acrylic copolymer resin (d3-4): (meth)acrylic resin.
＜その他のアルカリ可溶性樹脂（ｄ４）＞
　その他のアルカリ可溶性樹脂（ｄ４）は、アルカリ可溶性樹脂（ｄ１）、アルカリ可溶性樹脂（ｄ１）以外のカルボキシ基を有するエポキシ（メタ）アクリレート樹脂（ｄ２）及びアクリル共重合樹脂（ｄ３）を除くアルカリ可溶性樹脂であれば特に制限は無く、カラーフィルター用感光性樹脂組成物に通常使用される樹脂から選択すればよい。例えば、日本国特開２００７－２７１７２７号公報や、日本国特開２００７－３１６６２０号公報、日本国特開２００７－３３４２９０号公報に記載のアルカリ可溶性樹脂が挙げられる。 <Other alkali-soluble resin (d4)>
Other alkali-soluble resins (d4) are alkali-soluble resins (d1), epoxy (meth)acrylate resins (d2) having carboxy groups other than alkali-soluble resins (d1), and alkali-soluble resins (d3) other than acrylic copolymer resins (d3). There is no particular limitation as long as it is a resin, and it may be selected from resins commonly used in photosensitive resin compositions for color filters. Examples thereof include the alkali-soluble resins described in JP-A-2007-271727, JP-A-2007-316620, and JP-A-2007-334290.
　（Ｄ）アルカリ可溶性樹脂の含有割合は、特に限定されないが、本発明の感光性樹脂組成物の全固形分に対して、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは１５質量％以上であり、特に好ましくは２０質量％以上であり、好ましくは９０質量％以下、より好ましくは７０質量％以下、さらに好ましくは５０質量％以下、よりさらに好ましくは３０質量％以下、特に好ましくは２５質量％以下である。前記下限値以上とすることで未露光部分の現像液に対する溶解性が良好となる傾向がある。また、前記上限値以下とすることで露光部への現像液の過剰な浸透を抑制することができ、画像のシャープ性や細線密着性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは５～９０質量％、より好ましくは５～７０質量％、さらに好ましくは１０～５０質量％、よりさらに好ましくは１５～３０質量％、特に好ましくは２０～２５質量％である。 (D) The content of the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably, based on the total solid content of the photosensitive resin composition of the present invention. 15% by mass or more, particularly preferably 20% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, especially Preferably, it is 25% by mass or less. When the amount is at least the above lower limit, the solubility of the unexposed portion in the developer tends to be good. In addition, by making it equal to or less than the above upper limit, excessive permeation of the developer into the exposed area can be suppressed, and there is a tendency that the sharpness of the image and the fine line adhesion are improved. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, still more preferably 10 to 50% by mass, even more preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass.
　本発明の感光性樹脂組成物において、（Ｅ）光重合性化合物１００質量部に対する（Ｄ）アルカリ可溶性樹脂の含有量は、１００質量部以上が好ましく、１５０質量部以上がより好ましく、２００質量部以上がさらに好ましい。また、１０００質量部以下が好ましく、８００質量部以下がより好ましく、６００質量部以下がさらに好ましく、４００質量部以下が特に好ましい。前記下限値以上であることで、未露光部分の現像液に対する溶解性が良好となる傾向がある。また、前記上限値以下であることで、露光部への現像液の過剰な浸透を抑制することができ、画像のシャープ性や細線密着性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１００～１０００質量部が好ましく、１００～８００質量部がより好ましく、１５０～６００質量部がさらに好ましく、２００～４００質量部が特に好ましい。 In the photosensitive resin composition of the present invention, the content of (D) alkali-soluble resin relative to 100 parts by mass of (E) photopolymerizable compound is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and 200 parts by mass. The above is more preferable. Also, it is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, still more preferably 600 parts by mass or less, and particularly preferably 400 parts by mass or less. When it is at least the above lower limit, there is a tendency that the unexposed portion has good solubility in a developer. Moreover, when it is not more than the above upper limit, it is possible to suppress excessive permeation of the developer into the exposed area, and there is a tendency that the sharpness of the image and the fine line adhesion are improved. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 1000 parts by mass, more preferably 100 to 800 parts by mass, even more preferably 150 to 600 parts by mass, and particularly preferably 200 to 400 parts by mass.
＜（Ｅ）光重合性化合物＞
　本発明の感光性樹脂組成物は、感度等の点から（Ｅ）光重合性化合物を含有する。
　（Ｅ）光重合性化合物としては、１分子中にエチレン性不飽和基を２個以上有する多官能エチレン性単量体を使用することが好ましい。多官能エチレン性単量体におけるエチレン性不飽和基の数は好ましくは２個以上、より好ましくは３個以上、さらに好ましくは４個以上、また、好ましくは１０個以下、より好ましくは８個以下である。前記下限値以上とすることで感光性樹脂組成物が高感度となる傾向があり、また、前記上限値以下とすることで重合時の硬化収縮が小さくなる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは２～１０個、より好ましくは３～１０個、さらに好ましくは４～８個である。
　多官能エチレン性単量体の例としては、例えば、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げられ、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましい。 <(E) Photopolymerizable compound>
The photosensitive resin composition of the present invention contains (E) a photopolymerizable compound in terms of sensitivity and the like.
(E) As the photopolymerizable compound, it is preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. is. The sensitivity of the photosensitive resin composition tends to be high when it is equal to or higher than the lower limit, and shrinkage on curing during polymerization tends to be small when it is equal to or lower than the upper limit. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 2 to 10, more preferably 3 to 10, still more preferably 4 to 8.
Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Polyvalent hydroxy compounds such as polyhydroxy compounds, esters obtained by esterification reaction with unsaturated carboxylic acids and polybasic carboxylic acids, etc., and esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. .
　前記脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル、これら例示化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル、同様にイタコネートに代えたイタコン酸エステル、クロネートに代えたクロトン酸エステルもしくはマレエートに代えたマレイン酸エステル等が挙げられ、脂肪族ポリヒドロキシ化合物のアクリル酸エステル、脂肪族ポリヒドロキシ化合物のメタアクリル酸エステルが好ましい。 Examples of the ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Acrylic acid esters of aliphatic polyhydroxy compounds such as acrylates, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylics obtained by replacing the acrylates of these exemplary compounds with methacrylates Acid esters, similarly, itaconic acid esters instead of itaconates, crotonic acid esters instead of clonates, and maleic acid esters instead of maleates are mentioned, and acrylic acid esters of aliphatic polyhydroxy compounds and meta-esters of aliphatic polyhydroxy compounds. Acrylic acid esters are preferred.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステル等が挙げられる。
　多塩基性カルボン酸及び不飽和カルボン酸と、多価ヒドロキシ化合物のエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物が挙げられる。 Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. and acid esters.
A polybasic carboxylic acid and an unsaturated carboxylic acid and an ester obtained by an esterification reaction of a polyhydric hydroxy compound are not necessarily single substances, but typical examples include acrylic acid, phthalic acid, and Condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol.
　その他、本発明に用いられる多官能エチレン性単量体の例としては、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物とヒドロキシ（メタ）アクリレート又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物等が有用である。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Other examples of polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester. urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful.
These may be used individually by 1 type, and may use 2 or more types together.
　（Ｅ）光重合性化合物の含有割合は、特に限定されないが、感光性樹脂組成物の全固形分に対して、好ましくは９０質量％以下、より好ましくは７０質量％以下、さらに好ましくは５０質量％以下、よりさらに好ましくは３０質量％以下、ことさらに好ましくは２０質量％以下、特に好ましくは１０質量％以下である。光重合性化合物の含有量が上記上限値以下であることで、露光部への現像液の浸透性が適度となり良好な画像を得ることができる傾向にある。
　（Ｅ）光重合性化合物の含有割合の下限は、特に制限されないが、好ましくは１質量％以上、より好ましくは５質量％以上である。上記下限値以上であることで、紫外線照射による光硬化を向上させるとともに細線密着性も良好となる傾向にある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは１～９０質量％、より好ましくは１～７０質量％、さらに好ましくは１～５０質量％、よりさらに好ましくは５～３０質量％、ことさらに好ましくは５～２０質量％、特に好ましくは５～１０質量％である。 (E) The content of the photopolymerizable compound is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass, based on the total solid content of the photosensitive resin composition. %, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the content of the photopolymerizable compound is equal to or less than the above upper limit, there is a tendency that the penetration of the developer into the exposed area becomes moderate and good images can be obtained.
Although the lower limit of the content of (E) the photopolymerizable compound is not particularly limited, it is preferably 1% by mass or more, more preferably 5% by mass or more. When it is at least the above lower limit, there is a tendency that photocuring by ultraviolet irradiation is improved and fine line adhesion is also improved. The above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 90% by mass, more preferably 1 to 70% by mass, still more preferably 1 to 50% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, particularly preferably is 5 to 10% by mass.
＜（Ｆ）光重合開始剤＞
　本発明の感光性樹脂組成物は（Ｆ）光重合開始剤を含む。（Ｆ）光重合開始剤は光を直接吸収し、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分である。必要に応じて増感色素等の付加剤を添加して使用してもよい。 <(F) Photoinitiator>
The photosensitive resin composition of the present invention contains (F) a photopolymerization initiator. (F) The photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. If necessary, an additive such as a sensitizing dye may be added for use.
　（Ｆ）光重合開始剤としては、例えば、日本国特開昭５９－１５２３９６号公報、日本国特開昭６１－１５１１９７号各公報に記載のチタノセン化合物を含むメタロセン化合物；日本国特開２０００－５６１１８号公報に記載のヘキサアリールビイミダゾール誘導体；日本国特開平１０－３９５０３号公報記載のハロメチル化オキサジアゾール誘導体、ハロメチル－ｓ－トリアジン誘導体、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α－アミノアルキルフェノン誘導体；日本国特開２０００－８００６８号公報、日本国特開２００６－３６７５０号公報等に記載されているオキシムエステル誘導体が挙げられる。 (F) Photopolymerization initiators include, for example, Japanese Patent Laid-Open Nos. 59-152396 and 61-151197, metallocene compounds containing titanocene compounds; Hexaarylbiimidazole derivatives described in JP-A-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl-α-amino acids such as N-phenylglycine described in JP-A-10-39503 Radical activators such as N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples thereof include oxime ester derivatives described in JP-A-2003-201215 and the like.
　チタノセン誘導体類としては、例えば、ジシクロペンタジエニルチタニウムジクロライド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６－テトラフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，４，６－トリフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，４－ジフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウム〔２，６－ジ－フルオロ－３－（ピロ－１－イル）－フェニ－１－イル〕が挙げられる。 Titanocene derivatives include, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl-1-yl), Dicyclopentadienyl titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium [ 2,6-di-fluoro-3-(pyro-1-yl)-phenyl-1-yl].
　また、ビイミダゾール誘導体類としては、例えば、２－（２’－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（２’－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－メトキシフエニル）－４，５－ジフェニルイミダゾール２量体、（４’－メトキシフエニル）－４，５－ジフェニルイミダゾール２量体が挙げられる。 Biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl ) imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′ -methoxyphenyl)-4,5-diphenylimidazole dimer.
　また、ハロメチル化オキサジアゾール誘導体類としては、例えば、２－トリクロロメチル－５－（２’－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－（６”－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－フリル－１，３，４－オキサジアゾールが挙げられる。 Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole , 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
　また、ハロメチル－ｓ－トリアジン誘導体類としては、例えば、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジンが挙げられる。 Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloro methyl)-s-triazine.
　また、α－アミノアルキルフェノン誘導体類としては、例えば、２－メチル－１〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル)ブタン－１－オン、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル)シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコンが挙げられる。 Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1 ,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone.
　（Ｆ）光重合開始剤としては、特に、感度の点でオキシムエステル誘導体類（オキシムエステル系化合物及びケトオキシムエステル系化合物）が有効であり、フェノール性水酸基を含むアルカリ可溶性樹脂を用いる場合などは、感度の点で不利になる場合があるため、特にこのような感度に優れたオキシムエステル誘導体類（オキシムエステル系化合物及びケトオキシムエステル系化合物）が有用である。オキシムエステル誘導体類の中でも、基板との密着性の観点から、オキシムエステル系化合物が好ましい。 (F) As the photopolymerization initiator, oxime ester derivatives (oxime ester compounds and keto oxime ester compounds) are particularly effective in terms of sensitivity. In particular, oxime ester derivatives (oxime ester compounds and keto oxime ester compounds) having excellent sensitivity are useful. Among the oxime ester derivatives, oxime ester compounds are preferred from the viewpoint of adhesion to substrates.
　オキシムエステル系化合物の光重合開始剤は、その構造の中に紫外線を吸収する構造と光エネルギーを伝達する構造とラジカルを発生する構造を併せ持っているために、少量で感度が高く、かつ熱反応に対しては安定であり、少量で高感度な感光性樹脂組成物の設計が可能である。特に、露光光源のｉ線（３６５ｎｍ）に対する光吸収性の観点から、置換されていてもよいカルバゾリル基（置換されていてもよいカルバゾール環を有する基）を含有するオキシムエステル系化合物の場合に、この構造特性が良好に発現され、より好ましい。現在、市場では、遮光度が高く、薄膜なＢＭ（ブラックマトリックス）が要求されており、顔料濃度も、ますます大きくなっている。このような状況においては、特に有効である。 The photopolymerization initiator of the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so it is highly sensitive even in a small amount and can react with heat. It is stable against , and it is possible to design a highly sensitive photosensitive resin composition in a small amount. In particular, in the case of an oxime ester compound containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring), from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, This structural characteristic is well expressed, which is more preferable. At present, there is a demand in the market for a thin BM (black matrix) with a high degree of light shielding, and the pigment concentration is also increasing more and more. It is particularly effective in such circumstances.
　オキシムエステル系化合物としては、下記一般式（２２）で示される構造部分を含む化合物が挙げられ、好ましくは、下記一般式（２３）で示されるオキシムエステル系化合物が挙げられる。 Examples of the oxime ester-based compound include compounds containing a structural moiety represented by the following general formula (22), preferably oxime ester-based compounds represented by the following general formula (23).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（２２）中、Ｒ22は、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数３～２０のアルコキシカルボニルアルカノイル基、炭素数８～２０のフェノキシカルボニルアルカノイル基、炭素数３～２０のヘテロアリ－ルオキシカルボニルアルカノイル基、炭素数２～１０のアミノアルキルカルボニル基、炭素数７～２０のアロイル基、炭素数１～２０のヘテロアロイル基、炭素数２～１０のアルコキシカルボニル基、又は炭素数７～２０のアリールオキシカルボニル基を示す。 In formula (22), R 22 is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, or 3 carbon atoms. ~8 cycloalkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxycarbonylalkanoyl group, C2-C10 amino It represents an alkylcarbonyl group, an aroyl group having 7 to 20 carbon atoms, a heteroaroyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（２３）中、Ｒ21aは、水素、またはそれぞれ置換されていてもよい、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアロイル基、炭素数１～２０のヘテロアロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、又は炭素数１～１０のシクロアルキルアルキル基を示す。
　Ｒ21bは芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。 In formula (23), R 21a is hydrogen, or an optionally substituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 25 carbon atoms, heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, aminoalkyl group having 1 to 20 carbon atoms , a C2-12 alkanoyl group, a C3-25 alkenoyl group, a C3-8 cycloalkanoyl group, a C7-20 aroyl group, a C1-20 heteroaroyl group, a C2 1 to 10 alkoxycarbonyl groups, aryloxycarbonyl groups having 7 to 20 carbon atoms, or cycloalkylalkyl groups having 1 to 10 carbon atoms.
R 21b represents any substituent containing an aromatic or heteroaromatic ring.
　なお、Ｒ21aはＲ21bと共に環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）r－）、ポリエチニレン基（－（Ｃ≡Ｃ）r－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。
　Ｒ22aは、式（２２）のおけるＲ22と同様の基を示す。
　式（２２）におけるＲ22及び式（２３）におけるＲ22aとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基が挙げられる。 Incidentally, R 21a may form a ring together with R 21b , and the linking group thereof is an alkylene group having 1 to 10 carbon atoms each optionally having a substituent, a polyethylene group (-(CH=CH) r -), a polyethylene group (-(C≡C) r -), or a group formed by combining these (where r is an integer of 0 to 3).
R 22a represents the same group as R 22 in formula (22).
R 22 in formula (22) and R 22a in formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a cycloalkanoyl group having 3 to 8 carbon atoms. are mentioned.
　式（２３）におけるＲ21aとしては、好ましくは無置換のメチル基、エチル基、プロピル基などの直鎖アルキル基又はシクロアルキルアルキル基や、Ｎ－アセチル－Ｎ－アセトキシアミノ基で置換されたプロピル基が挙げられる。
　また、式（２３）におけるＲ21bとしては、好ましくは置換されていてもよいカルバゾリル基、置換されていてもよいチオキサントニル基、置換されていてもよいフェニルスルフィド基が挙げられる。 R 21a in formula (23) is preferably an unsubstituted straight-chain alkyl group such as methyl, ethyl or propyl, or a cycloalkylalkyl group, or propyl substituted with an N-acetyl-N-acetoxyamino group. groups.
R 21b in formula (23) preferably includes an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenylsulfide group.
　オキシムエステル系化合物の光重合開始剤としては、式（２３）におけるＲ21bが、置換されていてもよいカルバゾリル基であるものが、前述の理由からより好ましい。さらに、置換されていてもよい炭素数６～２５のアリール基、置換されていてもよい炭素数７～２５のアリールカルボニル基、置換されていてもよい炭素数５～２５のヘテロアリール基、置換されていてもよい炭素数６～２５のヘテロアリールカルボニル基、及びニトロ基からなる群から選ばれる少なくとも１種の基を有するカルバゾール基が好ましい。特に、ベンゾイル基、トルオイル基、ナフトイル基、チエニルカルボニル基、及びニトロ基からなる群から選ばれる少なくとも１種の基を有するカルバゾリル基が好ましい。また、これらの基はカルバゾリル基の３位に結合していることが望ましい。 As the photopolymerization initiator for the oxime ester compound, those in which R 21b in formula (23) is an optionally substituted carbazolyl group are more preferable for the reasons described above. Furthermore, optionally substituted aryl groups having 6 to 25 carbon atoms, optionally substituted arylcarbonyl groups having 7 to 25 carbon atoms, optionally substituted heteroaryl groups having 5 to 25 carbon atoms, substituted A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms which may be substituted and a nitro group is preferred. A carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group and a nitro group is particularly preferred. Moreover, it is desirable that these groups are bonded to the 3-position of the carbazolyl group.
　このようなオキシムエステル系化合物の光重合開始剤の市販品として、ＢＡＳＦ社製のＯＸＥ－０２、常州強力電子社製のＴＲ－ＰＢＧ－３０４やＴＲ－ＰＢＧ－３１４などがある。 Commercially available photopolymerization initiators for such oxime ester compounds include OXE-02 manufactured by BASF and TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics.
　本発明に好適なオキシムエステル系化合物の光重合開始剤として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 Specific examples of the photopolymerization initiator of the oxime ester compound suitable for the present invention include the compounds exemplified below, but are not limited to these compounds.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　ケトオキシムエステル系化合物としては、下記一般式（２４）で示される構造部分を含む化合物が挙げられ、好ましくは、下記一般式（２５）で示されるケトオキシムエステル系化合物が挙げられる。 The ketoxime ester-based compound includes a compound containing a structural moiety represented by the following general formula (24), preferably a ketoxime ester-based compound represented by the following general formula (25).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（２４）において、Ｒ24は、式（２２）におけるＲ22と同義である。 In formula (24), R 24 has the same definition as R 22 in formula (22).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（２５）において、Ｒ23aは、それぞれ置換されていてもよい、フェニル基、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数２～２０のアルキルチオアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアロイル基、炭素数１～２０のヘテロアロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、又は炭素数１～１０のシクロアルキルアルキル基を示す。 In formula (25), R 23a is an optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms , an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aroyl group having 7 to 20 carbon atoms, a carbon number It represents a heteroaroyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms.
　Ｒ23bは芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。
　なお、Ｒ23aはＲ23bと共に環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）r－）、ポリエチニレン基（－（Ｃ≡Ｃ）r－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。 R 23b represents any substituent containing an aromatic or heteroaromatic ring.
R 23a may form a ring together with R 23b , and the linking group may be an alkylene group having 1 to 10 carbon atoms which may have a substituent, or a polyethylene group (-(CH=CH) r -), a polyethylene group (-(C≡C) r -), or a group formed by combining these (where r is an integer of 0 to 3).
　Ｒ24aは、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数４～８のシクロアルカノイル基、炭素数７～２０のベンゾイル基、炭素数３～２０のヘテロアロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、炭素数２～２０のヘテロアリール基、又は炭素数２～２０のアルキルアミノカルボニル基を表す。
　式（２４）におけるＲ24及び上記一般式（２５）におけるＲ24aとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアロイル基が挙げられる。 R 24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a carbon heteroaroyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylaminocarbonyl group having 2 to 20 carbon atoms represents
R 24 in formula (24) and R 24a in general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a cyclo An alkanoyl group and an aroyl group having 7 to 20 carbon atoms can be mentioned.
　式（２５）におけるＲ23aとしては、好ましくは無置換のエチル基、プロピル基、ブチル基や、メトキシカルボニル基で置換されたエチル基またはプロピル基が挙げられる。
　また、式（２５）におけるＲ23bとしては、好ましくは置換されていてもよいカルバゾイル基、置換されていてもよいフェニルスルフィド基が挙げられる。
　本発明に好適なケトオキシムエステル系化合物として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 R 23a in formula (25) preferably includes an unsubstituted ethyl group, propyl group, butyl group, and an ethyl group or propyl group substituted with a methoxycarbonyl group.
R 23b in formula (25) preferably includes an optionally substituted carbazolyl group and an optionally substituted phenylsulfide group.
Specific examples of the ketoxime ester compounds suitable for the present invention include compounds as exemplified below, but are not limited to these compounds.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　このようなケトオキシムエステル系化合物の光重合開始剤の市販品として、ＢＡＳＦ社製のＯＸＥ－０１、常州強力電子社製のＴＲ－ＰＢＧ－３０５などがある。 Commercially available photopolymerization initiators for such ketoxime ester compounds include OXE-01 manufactured by BASF Corporation and TR-PBG-305 manufactured by Changzhou Power Electronics Co., Ltd.
　これらのオキシムエステル系化合物及びケトオキシムエステル系化合物は、それ自体公知の化合物であり、例えば、日本国特開２０００－８００６８号公報や、日本国特開２００６－３６７５０号公報に記載されている一連の化合物の一種である。
　上記光重合開始剤は１種を単独で用いてもよく、２種以上を併用してもよい。 These oxime ester compounds and keto oxime ester compounds are themselves known compounds. is a kind of compound of
One type of the photopolymerization initiator may be used alone, or two or more types may be used in combination.
　その他に、例えば、ベンゾインメチルエーテル、ベンゾインフェニルエーテル、ベンゾインイソブチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインアルキルエーテル類；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノン等のアントラキノン誘導体類；ベンゾフェノン、ミヒラーズケトン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、２－クロロベンゾフェノン、４－ブロモベンゾフェノン、２－カルボキシベンゾフェノン等のベンゾフェノン誘導体類；２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシアセトフェノン、１－ヒドロキシシクロへキシルフェニルケトン、α－ヒドロキシ－２－メチルフェニルプロパノン、１－ヒドロキシ－１－メチルエチル－（ｐ－イソプロピルフェニル）ケトン、１－ヒドロキシ－１－（ｐ－ドデシルフェニル）ケトン、２－メチル－（４’－メチルチオフェニル）－２－モルホリノ－１－プロパノン、１，１，１－トリクロロメチル－（ｐ－ブチルフェニル）ケトン等のアセトフェノン誘導体類；チオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン誘導体類；ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジエチルアミノ安息香酸エチル等の安息香酸エステル誘導体類；９－フェニルアクリジン、９－（ｐ－メトキシフェニル）アクリジン等のアクリジン誘導体類；９，１０－ジメチルベンズフェナジン等のフェナジン誘導体類；ベンズアンスロン等のアンスロン誘導体類が挙げられる。 In addition, for example, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone anthraquinone derivatives; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2 -phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1 -hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)ketone, etc. Acetophenone derivatives of; Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; p- Benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazines such as 9,10-dimethylbenzphenazine Derivatives; includes anthrone derivatives such as benzanthrone.
＜増感色素＞
　（Ｆ）光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素を併用させることができる。これら増感色素としては、例えば、日本国特開平４－２２１９５８号公報、日本国特開平４－２１９７５６号公報に記載のキサンテン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、その他、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、日本国特開平４－２８８８１８号公報に記載のジアルキルアミノベンゼン骨格を有する色素を挙げることができる。 <Sensitizing dye>
If necessary, the photopolymerization initiator (F) can be combined with a sensitizing dye corresponding to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include, for example, JP-A-4-221958, xanthene dyes described in JP-A-4-219756, JP-A-3-239703, JP-A-5- A coumarin dye having a heterocycle described in JP-A-289335, a 3-ketocoumarin compound described in JP-A-3-239703, a 3-ketocoumarin compound described in JP-A-5-289335, and a JP-A-6-19240 The pyrromethene dyes described above, Japanese Patent Laid-Open Nos. 47-2528, 54-155292, 45-37377, 48-84183, Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2- 69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, dialkylaminobenzenes described in JP-A-4-288818 Pigments having a skeleton can be mentioned.
　これらの増感色素のうち、アミノ基含有増感色素が好ましく、さらにアミノ基及びフェニル基を同一分子内に有する化合物がより好ましく、例えば、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、２－アミノベンゾフェノン、４－アミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、３，４－ジアミノベンゾフェノン等のベンゾフェノン系化合物；２－（ｐ－ジメチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［４，５］ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［６，７］ベンゾオキサゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）１，３，４－オキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニル）ベンズイミダゾール、２－（ｐ－ジエチルアミノフェニル）ベンズイミダゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）１，３，４－チアジアゾール、（ｐ－ジメチルアミノフェニル）ピリジン、（ｐ－ジエチルアミノフェニル）ピリジン、（ｐ－ジメチルアミノフェニル）キノリン、（ｐ－ジエチルアミノフェニル）キノリン、（ｐ－ジメチルアミノフェニル）ピリミジン、（ｐ－ジエチルアミノフェニル）ピリミジン等のｐ－ジアルキルアミノフェニル基含有化合物が挙げられる。４，４’－ジアルキルアミノベンゾフェノンが特に好ましい。
　増感色素は１種を単独で用いてもよく、２種以上を併用してもよい。 Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. Benzophenone compounds such as diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl) benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl) ) benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine , (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, and other p-dialkylaminophenyl group-containing compounds. 4,4'-dialkylaminobenzophenones are particularly preferred.
The sensitizing dyes may be used singly or in combination of two or more.
　（Ｆ）光重合開始剤の含有割合は、特に限定されないが、本発明の感光性樹脂組成物の全固形分に対して、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは３質量％以上、特に好ましくは４質量％以上であり、また、好ましくは３０質量％以下、より好ましくは２０質量％以下、さらに好ましくは１５質量％以下、よりさらに好ましくは１０質量％以下、特に好ましくは８質量％以下である。前記下限値以上とすることで感度が向上する傾向がある。また、前記上限値以下とすることで基板との密着応力が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは１～３０質量％、より好ましくは１～２０質量％、さらに好ましくは２～１５質量％、よりさらに好ましくは３～１０質量％、特に好ましくは４～８質量％である。 (F) The content of the photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 2% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. is 3% by mass or more, particularly preferably 4% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less, Particularly preferably, it is 8% by mass or less. Sensitivity tends to be improved by making it equal to or higher than the lower limit. Further, when the content is equal to or less than the above upper limit, there is a tendency that the adhesion stress with the substrate is improved. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass, still more preferably 3 to 10% by mass, and particularly preferably 4 to 8% by mass.
　本発明の感光性樹脂組成物が（Ｆ）光重合開始剤としてオキシムエステル系化合物を含有する場合、オキシムエステル系化合物の含有割合は、特に限定されないが、本発明の感光性樹脂組成物の全固形分に対して、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは３質量％以上、特に好ましくは４質量％以上である。また、好ましくは３０質量％以下、より好ましくは２０質量％以下、さらに好ましくは１５質量％以下、よりさらに好ましくは１０質量％以下、特に好ましくは８質量％以下である。前記下限値以上とすることで感度が向上する傾向があり、細線密着性が良好となる。また、前記上限値以下とすることで未露光部分の現像液に対する溶解性が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。好ましくは１～３０質量％、より好ましくは１～２０質量％、さらに好ましくは２～１５質量％、よりさらに好ましくは３～１０質量％、特に好ましくは４～８質量％である。 When the photosensitive resin composition of the present invention contains (F) an oxime ester compound as a photopolymerization initiator, the content of the oxime ester compound is not particularly limited. It is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more, relative to the solid content. Also, it is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. When the content is equal to or higher than the lower limit, the sensitivity tends to be improved, and fine line adhesion is improved. Further, when the amount is not more than the above upper limit, there is a tendency that the solubility of the unexposed portion in the developing solution is improved. The above upper and lower limits can be combined arbitrarily. It is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass, even more preferably 3 to 10% by mass, and particularly preferably 4 to 8% by mass.
　また、増感色素を用いる場合、増感色素の含有割合は、感光性樹脂組成物の全固形分中、好ましくは０～２０質量％、より好ましくは０～１５質量％、さらに好ましくは０～１０質量％である。 Further, when a sensitizing dye is used, the content of the sensitizing dye is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, more preferably 0 to 15% by mass, in the total solid content of the photosensitive resin composition. 10% by mass.
＜界面活性剤＞
　本発明の感光性樹脂組成物は、塗布性を調整する目的で界面活性剤を含有していてもよい。
　界面活性剤としては、例えば、ＢＹＫ－３３０（ビックケミー社製、表面張力２４．４ｍＮ／ｍ）、Ｆ－４７５（ＤＩＣ社製、表面張力２５．４ｍＮ／ｍ）、Ｆ－５５４（ＤＩＣ社製、表面張力２３．３ｍＮ／ｍ）が挙げられる。なお、界面活性剤は、１種を用いてもよく、２種以上を任意の組み合わせ及び比率で併用してもよい。 <Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant for the purpose of adjusting coatability.
Examples of surfactants include BYK-330 (manufactured by BYK-Chemie, surface tension 24.4 mN/m), F-475 (manufactured by DIC, surface tension 25.4 mN/m), F-554 (manufactured by DIC, surface tension of 23.3 mN/m). In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and ratios.
　本発明の感光性樹脂組成物が界面活性剤を含有する場合、界面活性剤の含有割合は特に限定されないが、感光性樹脂組成物の全固形分中、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上がさらに好ましく、０．１５質量％以上が特に好ましい。また、１．０質量％以下が好ましく、０．７質量％以下がより好ましく、０．５質量％以下がさらに好ましく、０．３質量％以下が特に好ましい。前記下限値以上とすることで塗膜均一性が向上し、細線密着性が向上できる傾向があり、また、前記上限値以下とすることで感度が向上する傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～１．０質量％が好ましく、０．０５～０．７質量％がより好ましく、０．１～０．５質量％がさらに好ましく０．１５～０．３質量％が特に好ましい。 When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is not particularly limited. 05% by mass or more is more preferable, 0.1% by mass or more is even more preferable, and 0.15% by mass or more is particularly preferable. Also, it is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. When the content is at least the above lower limit, the coating film uniformity tends to be improved and the fine line adhesion tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1.0% by mass is preferable, 0.05 to 0.7% by mass is more preferable, 0.1 to 0.5% by mass is more preferable, and 0.15 to 0.3% by mass is particularly preferable.
＜溶剤＞
　本発明の感光性樹脂組成物は、例えば、（Ｄ）アルカリ可溶性樹脂、（Ｅ）光重合性化合物及び（Ｆ）光重合開始剤及び必要に応じて使用される各種材料が、有機溶剤に溶解又は分散した状態で使用される。
　有機溶剤としては、沸点（圧力１０１３．２５［ｈＰａ］条件下。以下、沸点に関しては全て同様。）が１００～３００℃の範囲の有機溶剤を選択するのが好ましく、１２０～２８０℃の沸点を有機溶剤がより好ましい。 <Solvent>
In the photosensitive resin composition of the present invention, for example, (D) an alkali-soluble resin, (E) a photopolymerizable compound and (F) a photopolymerization initiator and various materials used as necessary are dissolved in an organic solvent. Or used in a distributed state.
As the organic solvent, it is preferable to select an organic solvent having a boiling point (under a pressure of 1013.25 [hPa]; hereinafter, the same applies to all boiling points) in the range of 100 to 300°C. Organic solvents are more preferred.
　有機溶剤としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、メトキシメチルペンタノール、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類； Examples of organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, and propylene glycol-t. -butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl glycol monoalkyl ethers such as ethers, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
　エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類；
　エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、３－メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートのようなグリコールアルキルエーテルアセテート類； glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
　エチレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテートなどのグリコールジアセテート類；
　シクロヘキサノールアセテートなどのアルキルアセテート類；
　アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類；
　アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；
　エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；
　ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；
　シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類； Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethyl pentanone ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
　ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；
　アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、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、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；
　３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類； aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
　ブチルクロライド、アミルクロライドのようなハロゲン化炭化水素類；
　メトキシメチルペンタノンのようなエーテルケトン類；
　アセトニトリル、ベンゾニトリルのようなニトリル類；が挙げられる。
　市販の溶剤としては、例えば、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１及びＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ（「セロソルブ」は登録商標。以下同じ。）、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）が挙げられる。 Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile;
Examples of commercially available solvents include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve ("Cellosolve" is a registered trademark. The same shall apply hereinafter.), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (any are also trade names).
　これらの有機溶剤は、単独で用いてもよく、２種以上を併用してもよい。
　フォトリソグラフィー法にてカラーフィルターの画素又はブラックマトリックスを形成する場合、有機溶剤としては沸点が１００～２５０℃の有機溶剤を選択するのが好ましく、１２０～２３０℃の沸点を持つ有機溶剤がより好ましい。
　塗布性、表面張力などのバランスがよく、感光性樹脂組成物の各構成成分の溶解度が比較的大きい点から、有機溶剤としては、グリコールアルキルエーテルアセテート類が好ましい。 These organic solvents may be used alone or in combination of two or more.
When forming pixels of a color filter or a black matrix by photolithography, it is preferable to select an organic solvent having a boiling point of 100 to 250°C, more preferably an organic solvent having a boiling point of 120 to 230°C. .
Glycol alkyl ether acetates are preferable as the organic solvent because they have a good balance of coatability, surface tension, etc., and the solubility of each component of the photosensitive resin composition is relatively high.
　グリコールアルキルエーテルアセテート類は、単独で使用してもよく、他の有機溶剤と併用してもよい。併用してもよい他の有機溶剤としては、グリコールモノアルキルエーテル類が好ましく、組成物中の構成成分の溶解性から、プロピレングリコールモノメチルエーテルが好ましい。得られる感光性樹脂組成物の保存安定性の観点から、有機溶剤中のグリコールモノアルキルエーテル類の割合は５質量％～３０質量％が好ましく、５質量％～２０質量％がより好ましい。 The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As other organic solvents that may be used in combination, glycol monoalkyl ethers are preferred, and propylene glycol monomethyl ether is preferred in view of the solubility of the components in the composition. From the viewpoint of storage stability of the resulting photosensitive resin composition, the proportion of the glycol monoalkyl ether in the organic solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.
　また、２００℃以上の沸点をもつ有機溶剤（以下「高沸点溶剤」と称す場合がある。）を併用してもよい。高沸点溶剤を併用することにより、感光性樹脂組成物は乾きにくくなるが、組成物中における顔料の均一な分散状態が、急激な乾燥により破壊されることを防止する効果がある。すなわち、例えばスリットノズル先端における、色材などの析出・固化による異物欠陥の発生を防止する効果がある。このような効果が高い点から、高沸点溶剤としては、ジプロピレングリコールメチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、１，４－ブタンジオールジアセテート、１，３－ブチレングリコールジアセテート、トリアセチン、１，６－ヘキサンジオールジアセテートが好ましい。 Also, an organic solvent having a boiling point of 200°C or higher (hereinafter sometimes referred to as a "high boiling point solvent") may be used together. The combined use of a high boiling point solvent makes the photosensitive resin composition difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to the deposition and solidification of the coloring material at the tip of the slit nozzle. From the point that such an effect is high, as a high boiling point solvent, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene Glycol diacetate, triacetin, 1,6-hexanediol diacetate are preferred.
　有機溶剤が高沸点溶剤を含有する場合、有機溶剤中の高沸点溶剤の含有割合は、０～５０質量％が好ましく、０．５～４０質量％がより好ましく、１～３０質量％が特に好ましい。前記下限値以上とすることで、例えばスリットノズル先端で色材などが析出・固化して異物欠陥を惹き起こすことを抑制できる傾向がある。また前記上限値以下とすることで組成物の乾燥温度が遅くなってカラーフィルター製造工程における、減圧乾燥プロセスのタクト不良や、プリベークのピン跡といった問題の発生を抑制できる傾向がある。 When the organic solvent contains a high-boiling solvent, the content of the high-boiling solvent in the organic solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass. . When the value is equal to or higher than the lower limit, it tends to be possible to suppress, for example, the deposition and solidification of the coloring material at the tip of the slit nozzle and the occurrence of foreign matter defects. Further, when the drying temperature is set to the above upper limit or less, the drying temperature of the composition tends to be slowed, which tends to suppress the occurrence of problems such as tact failure in the reduced pressure drying process and pin marks during prebaking in the color filter manufacturing process.
　本発明の感光性樹脂組成物が有機溶剤を含む場合、有機溶剤の含有割合は特に限定されないが、塗布し易さや粘度安定性の観点から、感光性樹脂組成物中の全固形分が好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上、また、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２５質量％以下、特に好ましくは２０質量％以下となるように添加する。上記の上限及び下限は任意に組み合わせることができる。例えば、感光性樹脂組成物中の全固形分が、好ましくは５～４０質量％、より好ましくは５～３０質量％、さらに好ましくは８～２５質量％、特に好ましくは１０～２０質量％となるように添加してよい。 When the photosensitive resin composition of the present invention contains an organic solvent, the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, particularly preferably 20% by mass It is added so that it becomes the mass % or less. The above upper and lower limits can be combined arbitrarily. For example, the total solid content in the photosensitive resin composition is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 8 to 25% by mass, and particularly preferably 10 to 20% by mass. may be added as follows.
＜感光性樹脂組成物のその他の配合成分＞
　本発明の感光性樹脂組成物には、上述の成分の他、例えば、チオール類、添加剤、現像改良剤、紫外線吸収剤、酸化防止剤を適宜配合することができる。 <Other compounding components of the photosensitive resin composition>
In the photosensitive resin composition of the present invention, in addition to the components described above, for example, thiols, additives, development modifiers, ultraviolet absorbers, and antioxidants can be appropriately blended.
＜チオール類＞
　本発明の感光性樹脂組成物は、高感度化、基板への密着性の向上のため、チオール類を含有してもよい。チオール類としては、例えば、ヘキサンジチオール、デカンジチオール、１，４－ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、エチレングリコールビス（３－メルカプトブチレート）、プロピレングリコールビス（３－メルカプトブチレート）（ＰＧＭＢ），ブタンジオールビス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン；（商品名；カレンズＭＴ　ＢＤ１、昭和電工（株）製）、ブタンジオールトリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）；（商品名；カレンズＭＴ　ＰＥ１、昭和電工（株）製）、ペンタエリスリトールトリス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトイソブチレート）、ブタンジオールビス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）（ＴＰＭＢ）トリメチロールプロパントリス（２－メルカプトイソブチレート）（ＴＰＭＩＢ）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン；（商品名；カレンズＭＴ　ＮＲ１、昭和電工（株）製）が挙げられ、これらは１種を単独で、或いは２種以上を混合して使用できる。ＰＧＭＢ、ＴＰＭＢ、ＴＰＭＩＢ、カレンズＭＴ　ＢＤ１、カレンズＭＴ　ＰＥ１、カレンズＭＴ　ＮＲ１などの多官能チオールが好ましく、カレンズＭＴ　ＢＤ１、カレンズＭＴ　ＰＥ１、カレンズＭＴ　ＮＲ１がより好ましく、カレンズＭＴ　ＰＥ１がさらに好ましい。 <Thiols>
The photosensitive resin composition of the present invention may contain thiols in order to increase sensitivity and improve adhesion to substrates. Thiols include, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate. , butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane (trade name; Karenz MT BD1, manufactured by Showa Denko KK), butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT PE1, Showa Denko Co., Ltd.), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3- mercaptoisobutyrate), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB), 1,3,5-tris(3-mercaptobutyloxyethyl )-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.); or a mixture of two or more. Polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are preferred, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are more preferred, and Karenz MT PE1 is even more preferred.
　本発明の感光性樹脂組成物がチオール類を含む場合、チオール類の含有割合は、本発明の感光性樹脂組成物の全固形分に対して、好ましくは０．１質量％以上、より好ましくは０．３質量％以上、さらに好ましくは０．５質量％以上であり、また、好ましくは１０質量％以下、より好ましくは５質量％以下である。前記下限値以上とすることで感度低下を抑制できる傾向がある。また、前記上限値以下とすることで保存安定性を良好なものとしやすい傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは０．１～１０質量％、より好ましくは０．３～１０質量％、さらに好ましくは０．５～５質量％である。 When the photosensitive resin composition of the present invention contains thiols, the content of the thiols is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, more preferably It is 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less. By making it more than the said lower limit, there exists a tendency which can suppress a sensitivity fall. In addition, when the content is equal to or less than the above upper limit, there is a tendency that the storage stability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 10% by mass, more preferably 0.3 to 10% by mass, still more preferably 0.5 to 5% by mass.
＜添加剤＞
　基板との密着性を改善するため、添加剤を含有させてもよい。例えば、シランカップリング剤、チタンカップリング剤が挙げられる。特にシランカップリング剤が好ましい。
　シランカップリング剤としては、例えば、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＭ－５０２、ＫＢＭ－５１０３、ＫＢＥ－９００７、Ｘ－１２－１０４８、Ｘ－１２－１０５０（信越シリコーン社製）、Ｚ－６０４０、Ｚ－６０４３、Ｚ－６０６２（東レ・ダウコーニング社製）が挙げられる。シランカップリング剤は、１種を用いてもよく、２種以上を併用してもよい。
　さらに、シランカップリング剤以外の添加剤を本発明の感光性樹脂組成物に含有させてもよく、例えば、リン酸系添加剤、その他の添加剤が挙げられる。 <Additive>
Additives may be added to improve adhesion to the substrate. Examples include silane coupling agents and titanium coupling agents. A silane coupling agent is particularly preferred.
Silane coupling agents include, for example, KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040. , Z-6043 and Z-6062 (manufactured by Dow Corning Toray). One type of silane coupling agent may be used, or two or more types may be used in combination.
Further, additives other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, examples of which include phosphoric acid-based additives and other additives.
　リン酸系添加剤としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましい。中でも下記一般式（ｇ１）、（ｇ２）、（ｇ３）で表されるものが好ましい。 As the phosphoric acid additive, (meth)acryloyloxy group-containing phosphates are preferred. Among them, those represented by the following general formulas (g1), (g2) and (g3) are preferable.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式（ｇ１）、（ｇ２）、（ｇ３）において、Ｒ51は各々独立に水素原子又はメチル基を示し、ｌ及びｌ’は各々独立に１～１０の整数、ｍは各々独立に１、２又は３である。
　その他の添加剤としては、例えば、ＴＥＧＯ*Ａｄｄ　Ｂｏｎｄ　ＬＴＨ（Ｅｖｏｎｉｋ社製）挙げられる。これらの燐酸基含有化合物やその他の密着剤は１種類を単独で用いても、２種以上を併用してもよい。 In formulas (g1), (g2) and (g3), R 51 each independently represents a hydrogen atom or a methyl group, l and l′ each independently represent an integer of 1 to 10, m each independently represents 1, 2 or 3.
Other additives include, for example, TEGO * Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesion agents may be used alone or in combination of two or more.
　本発明の感光性樹脂組成物が添加剤を含む場合、添加剤の含有割合は特に限定されないが、感光性樹脂組成物の全固形分中、０．０１質量％以上が好ましく、０．１０質量％以上がより好ましく、０．５０質量％以上がさらに好ましく、また、５．０質量％以下が好ましく、３．０質量％以下がより好ましく、２．０質量％以下がさらに好ましく、１．５質量％以下が特に好ましい。前記下限値以上とすることで密着力が向上する傾向がある。また、前記上限値以下とすることで現像性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～５．０質量％が好ましく、０．０１～３．０質量％がより好ましく、０．１０～２．０質量％がさらに好ましく、０．５０～１．５質量％が特に好ましい。 When the photosensitive resin composition of the present invention contains an additive, the content of the additive is not particularly limited, but the total solid content of the photosensitive resin composition is preferably 0.01% by mass or more, and 0.10% by mass. % or more, more preferably 0.50% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 2.0% by mass or less, and 1.5% by mass or less. % by mass or less is particularly preferred. Adhesion tends to be improved by making it more than the said lower limit. Further, when the content is set to the upper limit value or less, the developability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5.0% by mass is preferable, 0.01 to 3.0% by mass is more preferable, 0.10 to 2.0% by mass is more preferable, and 0.50 to 1.5% by mass is Especially preferred.
＜感光性樹脂組成物の物性＞
　本発明の感光性樹脂組成物は、ブラックマトリックス形成用に好適に使用することができる。係る観点からは黒色を呈していることが好ましい。また、その硬化した塗膜の膜厚１．０μｍ当たりの光学濃度（ＯＤ値）が４．０以上であることが好ましい。４．１以上であることがより好ましく、４．２以上であることがさらに好ましく、また、好ましくは６．０以下である。前記下限値以上とすることで十分な遮光性が確保できる傾向がある。例えば、４．０～６．０が好ましく、４．１～６．０がより好ましく、４．２～６．０がさらに好ましい。
　光学濃度とは、受光部の分光感度特性がＩＳＯ　５－３規格におけるＩＳＯ　ｖｉｓｕａｌ　ｄｅｎｓｉｔｙで示される透過光学濃度をいう。通常、光源としては、ＣＩＥ（国際照明委員会）が規定するＡ光源が用いられる。透過光学濃度の測定に用いることができる測定器としては、例えば、サカタインクスエンジニアリング社のＸ－Ｒｉｔｅ　３６１Ｔ（Ｖ）を挙げることができる。 <Physical properties of the photosensitive resin composition>
The photosensitive resin composition of the present invention can be suitably used for black matrix formation. From this point of view, it is preferable that the color is black. Moreover, it is preferable that the optical density (OD value) per 1.0 μm of film thickness of the cured coating film is 4.0 or more. It is more preferably 4.1 or more, further preferably 4.2 or more, and preferably 6.0 or less. By making it equal to or higher than the lower limit, there is a tendency that sufficient light shielding properties can be ensured. For example, 4.0 to 6.0 is preferred, 4.1 to 6.0 is more preferred, and 4.2 to 6.0 is even more preferred.
The optical density is the transmission optical density in which the spectral sensitivity characteristic of the light receiving portion is indicated by ISO visual density in the ISO 5-3 standard. Normally, the A light source defined by CIE (International Commission on Illumination) is used as the light source. An example of a measuring instrument that can be used to measure transmission optical density is X-Rite 361T(V) manufactured by Sakata Inx Engineering.
＜顔料分散液の製造方法＞
　本発明の顔料分散液は、常法によって製造される。（Ａ）顔料は、例えば、ペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザーを用いて予め分散処理することが好ましい。分散処理により（Ａ）顔料が微粒子化されるため、感光性樹脂組成物の塗布特性が向上する。（Ａ）顔料として黒色顔料を使用した場合は遮光能力の向上に寄与する。 <Method for producing pigment dispersion>
The pigment dispersion of the present invention is produced by a conventional method. (A) The pigment is preferably dispersed in advance using, for example, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, or homogenizer. Since the pigment (A) is finely divided by the dispersion treatment, the application properties of the photosensitive resin composition are improved. (A) When a black pigment is used as the pigment, it contributes to the improvement of the light shielding ability.
　分散処理は、通常、（Ａ）顔料、（Ｂ）分散剤、（Ｃ）スルホン酸基含有化合物、溶剤、及び必要に応じて（Ｄ）アルカリ可溶性樹脂の一部又は全部を併用した系にて行うことが好ましい（以下、分散処理に供する混合物、及び分散処理にて得られた顔料分散液を「インク」と称することがある。）。分散剤として高分子分散剤を用いると、得られたインクの経時の増粘が抑制される（分散安定性に優れる。）ので好ましい。 Dispersion treatment is usually carried out in a system in which (A) a pigment, (B) a dispersant, (C) a sulfonic acid group-containing compound, a solvent, and optionally (D) some or all of an alkali-soluble resin are used in combination. (The mixture subjected to the dispersing treatment and the pigment dispersion obtained by the dispersing treatment are hereinafter sometimes referred to as "ink".). It is preferable to use a polymeric dispersant as the dispersant, since the thickening of the obtained ink over time is suppressed (they are excellent in dispersion stability).
　サンドグラインダーで（Ａ）顔料を分散させる場合には、０．１～８ｍｍ程度の径のガラスビーズ、ジルコンビーズ、又はジルコニアビーズが好ましく用いられる。分散処理の温度条件は、０℃から１００℃が好ましく、室温（２５℃）から８０℃がより好ましい。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。感光性樹脂組成物の２０度鏡面光沢度（ＪＩＳ　Ｚ８７４１）が１００～２００の範囲となるように、インクの光沢を制御するのが分散の目安である。感光性樹脂組成物の２０度鏡面光沢度が１００以上であれば、分散処理が十分となり、荒い顔料（色材）粒子の残存が抑制され、十分な現像性、密着性、解像性が得られやすい。また、２０度鏡面光沢値が２００以下であれば、顔料が破砕されすぎず、多数の超微粒子の生成が抑制され、分散安定性が損なわれにくい。 When dispersing the (A) pigment with a sand grinder, glass beads, zircon beads, or zirconia beads with a diameter of about 0.1 to 8 mm are preferably used. The temperature condition of the dispersion treatment is preferably 0°C to 100°C, more preferably room temperature (25°C) to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate. The aim of dispersion is to control the glossiness of the ink so that the 20° specular glossiness (JIS Z8741) of the photosensitive resin composition is in the range of 100-200. If the 20° specular glossiness of the photosensitive resin composition is 100 or more, the dispersion treatment is sufficient, residual coarse pigment (coloring material) particles are suppressed, and sufficient developability, adhesion, and resolution are obtained. easy to get Further, when the 20-degree specular gloss value is 200 or less, the pigment is not excessively crushed, the production of a large number of ultrafine particles is suppressed, and the dispersion stability is less likely to be impaired.
＜感光性樹脂組成物の製造方法＞
　本発明の感光性樹脂組成物は、常法によって製造される。例えば、上述した分散処理により得られたインクと、感光性樹脂組成物中に含まれる他の成分を混合して均一な溶液とすることができる。感光性樹脂組成物の製造工程においては、微細なゴミが液中に混じることが多いため、得られた感光性樹脂組成物はフィルター等により濾過処理することが望ましい。 <Method for producing a photosensitive resin composition>
The photosensitive resin composition of the present invention is produced by a conventional method. For example, the ink obtained by the dispersion treatment described above and other components contained in the photosensitive resin composition can be mixed to form a uniform solution. In the production process of the photosensitive resin composition, fine dust is often mixed in the liquid, so it is desirable to filter the obtained photosensitive resin composition with a filter or the like.
［硬化物］
　本発明の硬化物は、本発明の感光性樹脂組成物を硬化させることで得ることができる。本発明の感光性樹脂組成物を硬化させた硬化物は、画素、ブラックマトリックスや着色スペーサーなどのカラーフィルターを構成する部材として好適に用いることができる。 [Cured product]
The cured product of the invention can be obtained by curing the photosensitive resin composition of the invention. A cured product obtained by curing the photosensitive resin composition of the present invention can be suitably used as a member constituting a color filter such as a pixel, a black matrix or a colored spacer.
［ブラックマトリックス］
　本発明のブラックマトリックスは、本発明の硬化物からなる。 [Black Matrix]
The black matrix of the invention consists of the cured product of the invention.
　（１）　支持体
　ブラックマトリックスを形成するための支持体としては、適度の強度があれば、その材質は特に限定されるものではない。透明基板が使用されることが好ましい。透明基板の材質としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォンなどの熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ（メタ）アクリル系樹脂などの熱硬化性樹脂シート、各種ガラスが挙げられる。耐熱性の観点からガラス、耐熱性樹脂が好ましい。
　基板の表面にＩＴＯ、ＩＺＯ等の透明電極が成膜されていてもよい。
　透明基板以外では、ＴＦＴアレイ上に透明電極を形成してもよい。 (1) Support The material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength. Preferably, a transparent substrate is used. Materials for the transparent substrate include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, epoxy resins, unsaturated polyester resins, Examples include thermosetting resin sheets such as poly(meth)acrylic resins and various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resin are preferable.
A transparent electrode such as ITO or IZO may be deposited on the surface of the substrate.
Other than the transparent substrate, a transparent electrode may be formed on the TFT array.
　支持体には、接着性などの表面物性の改良のため、必要に応じ、例えば、コロナ放電処理、オゾン処理、大気圧プラズマ処理、シランカップリング剤やウレタン系樹脂などの各種樹脂の薄膜形成処理を行ってもよい。
　支持体の厚さは、好ましくは０．０５～１０ｍｍ、より好ましくは０．１～７ｍｍである。各種樹脂の薄膜形成処理を行う場合、その膜厚は、好ましくは０．０１～１０μｍ、より好ましくは０．０５～５μｍである。 In order to improve surface physical properties such as adhesiveness, the support may be subjected, if necessary, to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, and thin film formation treatment using various resins such as silane coupling agents and urethane resins. may be performed.
The thickness of the support is preferably 0.05-10 mm, more preferably 0.1-7 mm. In the case of performing thin film formation processing of various resins, the film thickness is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.
　（２）　ブラックマトリックス
　本発明の感光性樹脂組成物により、ブラックマトリックスを形成するには、透明基板上に感光性樹脂組成物を塗布して、乾燥した後、感光性樹脂組成物が塗布、乾燥された透明基板上に配置されたフォトマスクを介して画像露光、現像、必要に応じて熱硬化若しくは光硬化することによりブラックマトリックスを形成することができる。 (2) Black Matrix In order to form a black matrix using the photosensitive resin composition of the present invention, the photosensitive resin composition is applied onto a transparent substrate, dried, and then the photosensitive resin composition is applied and dried. A black matrix can be formed by imagewise exposure through a photomask placed on a transparent substrate, development, and thermal curing or photocuring as necessary.
　（３）　ブラックマトリックスの形成
　（３－１）　感光性樹脂組成物の塗布
　ブラックマトリックス用の感光性樹脂組成物の透明基板上への塗布は、例えば、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法によって行うことができる。中でも、ダイコート法によれば、塗布液使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響がなく、異物発生が抑制されるなどの観点から好ましい。 (3) Formation of Black Matrix (3-1) Coating of Photosensitive Resin Composition The coating of the photosensitive resin composition for the black matrix onto the transparent substrate can be performed by, for example, spinner method, wire bar method, flow coating method, It can be carried out by a die coating method, a roll coating method, or a spray coating method. Among them, the die-coating method is preferable from the viewpoints that the amount of the coating liquid used is significantly reduced, and the mist that adheres when the spin-coating method is used does not have an effect, and the generation of foreign matter is suppressed.
　塗膜の厚さは、乾燥後の膜厚として、０．２～１０μｍが好ましく、０．５～６μｍがより好ましく、１～４μｍがさらに好ましい。前記上限値以下とすることで、パターン現像が容易となり、液晶セル化工程でのギャップ調整も容易となる傾向がある。前記下限値以上とすることで、所望の色発現が容易となる傾向がある。 The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, even more preferably 1 to 4 μm. By making it below the said upper limit, there exists a tendency for pattern development to become easy and to become easy to adjust the gap in a liquid-crystal cell-forming process. By making it more than the said lower limit, there exists a tendency for desired color expression to become easy.
　（３－２）　塗膜の乾燥
　基板に感光性樹脂組成物を塗布した後の塗膜の乾燥は、真空乾燥装置を使用した減圧乾燥法、及びホットプレート、ＩＲオーブン、又はコンベクションオーブンを使用した加熱乾燥法によることが好ましい。ホットプレートを用いた加熱乾燥法の場合、基板を裏面からピンで支えてもよい。加熱乾燥の条件は、有機溶剤の種類、使用する乾燥機の性能などに応じて適宜選択することができる。好ましくは、４０～２００℃の温度で１５秒～５分間、より好ましくは５０～１３０℃の温度で３０秒～３分間である。 (3-2) Drying of the coating film Drying of the coating film after applying the photosensitive resin composition to the substrate was performed using a vacuum drying method using a vacuum drying apparatus, and a hot plate, IR oven, or convection oven. Heat drying is preferred. In the case of the heat drying method using a hot plate, the substrate may be supported by pins from the rear surface. The conditions for heat drying can be appropriately selected according to the type of organic solvent, the performance of the dryer to be used, and the like. Preferably, the temperature is 40 to 200° C. for 15 seconds to 5 minutes, more preferably 50 to 130° C. for 30 seconds to 3 minutes.
　乾燥温度は、高いほど透明基板に対する塗膜の接着性が向上する。前記上限値以下であれば、透明基板に対する塗膜の十分な接着性を確保しつつ、アルカリ可溶性樹脂が分解し、熱重合を誘発して現像不良を生ずるおそれを抑制できる傾向がある。また、乾燥温度を前記上限値以下とすることで、膜厚が均一に収縮し、塗膜表面のムラを抑制できる傾向がある。 The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. If it is not more than the above upper limit, there is a tendency that it is possible to suppress the possibility of decomposing the alkali-soluble resin and inducing thermal polymerization to cause poor development while ensuring sufficient adhesion of the coating film to the transparent substrate. In addition, by setting the drying temperature to the above upper limit or less, there is a tendency that the film thickness shrinks uniformly and the unevenness of the coating film surface can be suppressed.
　（３－３）　露光
　画像露光は、感光性樹脂組成物の塗膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外域から可視域に至る波長の光を照射して行うことができる。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、光重合性の塗膜上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ってもよい。上記の画像露光に使用される光源は、特に限定されるものではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアークなどのランプ光源が挙げられる。特定の波長の光を照射して使用する場合には、光学フィルターを利用することもできる。 (3-3) Exposure Imagewise exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating light of wavelengths from the ultraviolet region to the visible region through this mask pattern. can be done. In this case, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the above image exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arcs. An optical filter can also be used when using it by irradiating the light of a specific wavelength.
　（３－４）　現像
　本発明のブラックマトリックスは、感光性樹脂組成物による塗膜を、上記の光源によって画像露光を行った後、有機溶剤、又は、界面活性剤とアルカリ性化合物とを含む水溶液を用いる現像によって、基板上に画像を形成して作製することができる。この水溶液は、さらに有機溶剤、緩衝剤、錯化剤、染料、顔料を含んでいてもよい。 (3-4) Development The black matrix of the present invention is prepared by subjecting a coating film made of a photosensitive resin composition to imagewise exposure with the light source described above, followed by an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. The development used can be used to form an image on the substrate. This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes and pigments.
　アルカリ性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化アンモニウムなどの無機アルカリ性化合物や、モノ－、ジ－又はトリエタノールアミン、モノ－、ジ－又はトリメチルアミン、モノ－、ジ－又はトリエチルアミン、モノ－又はジイソプロピルアミン、ｎ－ブチルアミン、モノ－、ジ－又はトリイソプロパノールアミン、エチレンイミン、エチレンジイミン、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリンなどの有機アルカリ性化合物が挙げられる。これらのアルカリ性化合物は、１種を単独で用いてもよく、２種以上を併用してもよい。 Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine , mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. compound. These alkaline compounds may be used singly or in combination of two or more.
　界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノニオン系界面活性剤、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのアニオン性界面活性剤、アルキルベタイン類、アミノ酸類などの両性界面活性剤が挙げられる。 Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.
　有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコールが挙げられる。有機溶剤は、単独で用いてもよく、また、水溶液と併用してもよい。
　現像処理の条件に特に制限はない。現像温度は１０～５０℃が好ましく、１５～４５℃がより好ましく、２０～４０℃がさらに好ましい。現像方法は、例えば、浸漬現像法、スプレー現像法、ブラシ現像法、超音波現像法であってよい。 Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions for development processing. The developing temperature is preferably 10 to 50°C, more preferably 15 to 45°C, even more preferably 20 to 40°C. The development method may be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
　（３－５）　熱硬化処理
　現像の後の基板には、熱硬化処理又は光硬化処理、好ましくは熱硬化処理を施す。温度は、好ましくは１００～２８０℃、より好ましくは１５０～２５０℃である。時間は５～６０分間が好ましい。
　以上のようにして形成させたブラックマトリックスの高さは、好ましくは０．５～５μｍ、より好ましくは０．８～４μｍである。 (3-5) Heat Curing Treatment The substrate after development is subjected to heat curing treatment or photocuring treatment, preferably heat curing treatment. The temperature is preferably 100-280°C, more preferably 150-250°C. The time is preferably 5 to 60 minutes.
The height of the black matrix formed as described above is preferably 0.5 to 5 μm, more preferably 0.8 to 4 μm.
［その他のカラーフィルターの形成］
　ブラックマトリックスを設けた透明基板上に、上記（３－１）～（３－５）と同じプロセスで赤色、緑色、青色のうち一色の色材を含有する感光性樹脂組成物を塗布し、乾燥した後、塗膜の上にフォトマスクを重ね、このフォトマスクを介して画像露光、現像、必要に応じて熱硬化又は光硬化により画素画像を形成させ、着色層を作成する。この操作を、赤色、緑色、青色（順序は任意であってよい。）の三色の感光性樹脂組成物についてそれぞれ行うことによって、カラーフィルターを形成することができる。 [Formation of other color filters]
On a transparent substrate provided with a black matrix, a photosensitive resin composition containing a coloring material of one of red, green, and blue is applied in the same process as (3-1) to (3-5) above, and dried. After that, a photomask is overlaid on the coating film, imagewise exposure through the photomask, development, and if necessary, thermal curing or photocuring are performed to form a pixel image, thereby forming a colored layer. A color filter can be formed by performing this operation for each of the three photosensitive resin compositions of red, green, and blue (the order may be arbitrary).
［着色スペーサー］
　本発明の感光性樹脂組成物は、ブラックマトリックス以外に着色スペーサー用の感光性樹脂組成物として使用することも可能である。スペーサーをＴＦＴ型ＬＣＤに使用する場合、ＴＦＴに入射する光によりスイッチング素子としてＴＦＴが誤作動を起こすことがあり、着色スペーサーはこれを防止するために用いられ、例えば、日本国特開平８－２３４２１２号公報にスペーサーを遮光性とすることが記載されている。着色スペーサーは着色スペーサー用のマスクを用いる以外は前述のブラックマトリックスと同様の方法で形成することができる。 [Colored spacer]
The photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for colored spacers in addition to the black matrix. When spacers are used in TFT-type LCDs, the TFTs may malfunction as switching elements due to light incident on the TFTs. Colored spacers are used to prevent this. JP-A-2004-110003 describes that the spacer is light-shielding. The colored spacers can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.
　（３－６）　透明電極の形成
　カラーフィルターは、このままの状態で画像上にＩＴＯなどの透明電極を形成して、カラーディスプレー、液晶表示装置などの部品の一部として使用される。カラーフィルターの表面平滑性や耐久性を高めるため、必要に応じ、画像上にポリアミド、ポリイミドなどのトップコート層を設けてもよい。例えば、平面配向型駆動方式（ＩＰＳモード）の用途においては、透明電極を形成しなくてもよい。 (3-6) Formation of Transparent Electrode The color filter is used as a part of a color display, a liquid crystal display device, or the like by forming a transparent electrode such as ITO on an image as it is. In order to improve the surface smoothness and durability of the color filter, a top coat layer such as polyamide or polyimide may be provided on the image, if necessary. For example, in the application of the planar orientation driving system (IPS mode), it is not necessary to form the transparent electrode.
［画像表示装置］
　本発明の画像表示装置は、本発明硬化物を有する。画像表示装置としては、画像や映像を表示する装置であれば特に限定されないが、例えば、液晶表示装置や有機ＥＬディスプレイが挙げられる。 [Image display device]
The image display device of the present invention has the cured product of the present invention. The image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display.
［液晶表示装置］
　本発明の液晶表示装置は、本発明の硬化物、特にブラックマトリックスを有するものであり、カラー画素やブラックマトリックスの形成順序や形成位置等、特に制限を受けるものではない。 [Liquid crystal display device]
The liquid crystal display device of the present invention has the cured product of the present invention, particularly the black matrix, and the order and positions of forming the color pixels and the black matrix are not particularly limited.
　液晶表示装置は、カラーフィルター上に配向膜を形成し、この配向膜上にスペーサーを散布した後、対向基板と貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入し、対向電極に結線して製造することができる。配向膜としては、例えば、ポリイミド等の樹脂膜が好適である。配向膜の形成には、グラビア印刷法及び／又はフレキソ印刷法を採用することができ、配向膜の厚さは数１０ｎｍであってよい。熱焼成によって配向膜の硬化処理を行った後、紫外線の照射やラビング布による処理によって表面処理し、液晶の傾きを調整しうる表面状態に加工してもよい。 In a liquid crystal display device, an alignment film is formed on a color filter, spacers are sprinkled on the alignment film, and then a counter substrate is attached to form a liquid crystal cell. can be manufactured by connecting to As the alignment film, for example, a resin film such as polyimide is suitable. A gravure printing method and/or a flexographic printing method can be employed for forming the alignment film, and the thickness of the alignment film may be several tens of nm. After hardening the alignment film by heat baking, the surface may be processed by irradiating with ultraviolet rays or by treatment with a rubbing cloth so as to obtain a surface state capable of adjusting the tilt of the liquid crystal.
　スペーサーとしては、対向基板とのギャップ（隙間）に応じた大きさのものが用いられ、２～８μｍのスペーサーが好適である。カラーフィルター基板上に、フォトリソグラフィー法によって透明樹脂膜のフォトスペーサー（ＰＳ）を形成し、これをスペーサーの代わりに活用することもできる。対向基板としては、アレイ基板を用いることができ、特にＴＦＴ（薄膜トランジスタ）基板が好適である。 As the spacer, a spacer having a size corresponding to the gap (clearance) with the counter substrate is used, and a spacer of 2 to 8 μm is suitable. A photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer. An array substrate can be used as the opposing substrate, and a TFT (thin film transistor) substrate is particularly suitable.
　対向基板との貼り合わせのギャップは、液晶表示装置の用途によって異なるが、２～８μｍであってよい。対向基板と貼り合わせた後、液晶注入口以外の部分は、エポキシ樹脂等のシール材によって封止する。シール材は、ＵＶ照射及び／又は加熱することによって硬化させ、液晶セル周辺がシールされる。
　周辺をシールされた液晶セルは、パネル単位に切断した後、真空チャンバー内で減圧とし、上記液晶注入口を液晶に浸漬した後、チャンバー内をリークすることによって、液晶を液晶セル内に注入する。液晶セル内の減圧度は、好ましくは１×１０-2～１×１０-7Ｐａ、より好ましくは１×１０-3～１×１０-6Ｐａである。また、減圧時に液晶セルを加温するのが好ましく、加温温度は、好ましくは３０～１００℃、より好ましくは５０～９０℃である。減圧時の加温保持は、１０～６０分間であってよく、その後液晶中に浸漬される。液晶を注入した液晶セルは、液晶注入口を、ＵＶ硬化樹脂を硬化させて封止することによって、液晶表示装置（パネル）が完成する。 The gap between the substrate and the opposing substrate may be 2 to 8 μm, depending on the application of the liquid crystal display device. After bonding to the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.
After the liquid crystal cell with its periphery sealed is cut into panels, the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell. . The degree of pressure reduction in the liquid crystal cell is preferably 1×10 -2 to 1×10 -7 Pa, more preferably 1×10 -3 to 1×10 -6 Pa. Further, it is preferable to heat the liquid crystal cell when the pressure is reduced, and the heating temperature is preferably 30 to 100°C, more preferably 50 to 90°C. Heating and holding at reduced pressure may be for 10 to 60 minutes, and then immersed in liquid crystal. A liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curing resin.
　液晶の種類には特に制限がなく、例えば、芳香族系、脂肪族系、多環状化合物等、従来から知られている液晶であって、例えば、リオトロピック液晶、サーモトロピック液晶であってよい。サーモトロピック液晶としては、例えば、ネマティック液晶、スメスティック液晶、コレステリック液晶等、いずれであってもよい。 The type of liquid crystal is not particularly limited. For example, it may be a conventionally known liquid crystal such as an aromatic system, an aliphatic system, or a polycyclic compound, such as a lyotropic liquid crystal or a thermotropic liquid crystal. Thermotropic liquid crystals may be, for example, nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, or the like.
［有機ＥＬディスプレイ］
　本発明の有機ＥＬディスプレイは、本発明のカラーフィルターを用いて作製される。 [Organic EL display]
The organic EL display of the invention is produced using the color filter of the invention.
　本発明のカラーフィルターを用いて有機ＥＬディスプレイを作製する場合、例えば図１に示すように、まず透明支持基板１０上に、感光性樹脂組成物により形成されたパターン（すなわち、画素２０、及び隣接する画素２０の間に設けられた樹脂ブラックマトリックス（図示せず））が形成されてなるカラーフィルターを作製し、該カラーフィルター上に有機保護層３０及び無機酸化膜４０を介して有機発光体５００を積層することによって、有機ＥＬ素子１００を作製することができる。なお、画素２０及び樹脂ブラックマトリックスの内、少なくとも一つは本発明の感光性樹脂組成物を用いて作製されたものである。
　有機発光体５００の積層方法としては、例えば、カラーフィルター上面へ透明陽極５０、正孔注入層５１、正孔輸送層５２、発光層５３、電子注入層５４、及び陰極５５を逐次形成していく方法や、別基板上へ形成した有機発光体５００を無機酸化膜４０上に貼り合わせる方法が挙げられる。
　このようにして作製された有機ＥＬ素子１００を用い、例えば、「有機ＥＬディスプレイ」（オーム社，２００４年８月２０日発光，時任静士、安達千波矢、村田英幸著）に記載された方法で有機ＥＬディスプレイを作製することができる。 When producing an organic EL display using the color filter of the present invention, for example, as shown in FIG. A color filter is prepared by forming a resin black matrix (not shown) provided between the pixels 20, and an organic light emitter 500 is formed on the color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween. The organic EL element 100 can be produced by laminating the . At least one of the pixels 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention.
As a method of stacking the organic light emitter 500, for example, the transparent anode 50, the hole injection layer 51, the hole transport layer 52, the light emitting layer 53, the electron injection layer 54, and the cathode 55 are sequentially formed on the upper surface of the color filter. method, and a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40 .
Using the organic EL element 100 thus produced, for example, the method described in "Organic EL Display" (Ohmsha, Aug. 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata). can produce an organic EL display.
　本発明のカラーフィルターは、パッシブ駆動方式の有機ＥＬディスプレイにも、アクティブ駆動方式の有機ＥＬディスプレイにも適用可能である。 The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.
　合成例、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 Although the present invention will be described more specifically with reference to synthesis examples, examples, and comparative examples, the present invention is not limited to the following examples as long as it does not exceed the gist thereof.
＜合成例：アルカリ可溶性樹脂の合成＞ <Synthesis Example: Synthesis of alkali-soluble resin>
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記構造のエポキシ化合物（エポキシ当量２６４）２４０質量部、メタクリル酸８１．６質量部、メトキシブチルアセテート２６３．１質量部、トリフェニルホスフィン６．４質量部、及びパラメトキシフェノール０．１６質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら９０℃で酸価が５ｍｇＫＯＨ／ｇ以下になるまで１２時間反応させた。
　次いで、上記反応により得られた反応液にトリメチロールプロパン（ＴＭＰ）８．３質量部、ビフェニルテトラカルボン酸２無水物（ＢＰＤＡ）８０．７質量部、テトラヒドロフタル酸無水物（ＴＨＰＡ）５１．６質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら１０５℃までゆっくり昇温し反応させ、固形分酸価１１２ｍｇＫＯＨ／ｇ、ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）２５００であるアルカリ可溶性樹脂を得た。 240 parts by mass of the epoxy compound having the above structure (epoxy equivalent weight: 264), 81.6 parts by mass of methacrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol , a thermometer, a stirrer, and a flask equipped with a cooling tube, and reacted with stirring at 90° C. for 12 hours until the acid value became 5 mgKOH/g or less.
Next, 8.3 parts by mass of trimethylolpropane (TMP), 80.7 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 51.6 parts by mass of tetrahydrophthalic anhydride (THPA) were added to the reaction solution obtained by the above reaction. The mass part is placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature is slowly raised to 105 ° C. while stirring to react. An alkali-soluble resin with Mw) of 2500 was obtained.
　以下の実施例及び比較例で用いた顔料分散液、感光性樹脂組成物の構成成分は、次の通りである。 The constituent components of the pigment dispersion liquid and the photosensitive resin composition used in the following examples and comparative examples are as follows.
＜顔料－１＞
　Ｒ１０６０：ＢＩＲＬＡ　ＣＡＲＢＯＮ社製「ＲＡＶＥＮ１０６０」（カーボンブラック） <Pigment-1>
R1060: BIRLA CARBON "RAVEN1060" (carbon black)
＜分散剤－１＞
　ＢＹＫ１６７：ビックケミー社製「ＤＩＳＰＥＲＢＹＫ－１６７」（ウレタン系高分子分散剤） <Dispersant-1>
BYK167: "DISPERBYK-167" manufactured by BYK Chemie (urethane polymer dispersant)
＜スルホン酸基含有化合物Ａ～Ｄ、化合物Ｅ＞
　Ｓ１２０００－Ｓ：ルーブリゾール社製「Ｓ１２０００－Ｓ」（銅フタロシアニンスルホン酸誘導体）
　製造時の酸添加量および洗浄の工程を変更することにより電気伝導度を変更したＳ１２０００－Ｓをスルホン酸基含有化合物Ａ～Ｄとして用いた。化合物Ｅは銅フタロシアニン顔料を用いた。
　スルホン酸基含有化合物Ａ：電気伝導度２０８０μＳ／ｃｍ、酸価８０ｍｇＫＯＨ／ｇ
　スルホン酸基含有化合物Ｂ：電気伝導度５１００μＳ／ｃｍ、酸価８１ｍｇＫＯＨ／ｇ
　スルホン酸基含有化合物Ｃ：電気伝導度９０１２μＳ／ｃｍ、酸価８３ｍｇＫＯＨ／ｇ
　スルホン酸基含有化合物Ｄ：電気伝導度１４２０μＳ／ｃｍ、酸価４０ｍｇＫＯＨ／ｇ
　化合物Ｅ：Ｃ．Ｉ．ピグメントブルー１５：６（電気伝導度０μＳ／ｃｍ、酸価０ｍｇＫＯＨ／ｇ） <Sulfonic Acid Group-Containing Compounds A to D, Compound E>
S12000-S: “S12000-S” manufactured by Lubrizol (copper phthalocyanine sulfonic acid derivative)
S12000-S, whose electrical conductivity was changed by changing the amount of acid added and the washing process during production, was used as sulfonic acid group-containing compounds A to D. Compound E used a copper phthalocyanine pigment.
Sulfonic acid group-containing compound A: electrical conductivity 2080 µS/cm, acid value 80 mgKOH/g
Sulfonic acid group-containing compound B: electrical conductivity 5100 µS/cm, acid value 81 mgKOH/g
Sulfonic acid group-containing compound C: electrical conductivity 9012 μS/cm, acid value 83 mgKOH/g
Sulfonic acid group-containing compound D: electrical conductivity 1420 μS/cm, acid value 40 mgKOH/g
Compound E: C.I. I. Pigment Blue 15:6 (electrical conductivity 0 μS/cm, acid value 0 mgKOH/g)
＜アルカリ可溶性樹脂－１＞
　アルカリ可溶性樹脂－１：合成例に記載の樹脂 <Alkali-soluble resin-1>
Alkali-soluble resin-1: Resin described in Synthesis Example
＜光重合性化合物－１＞
　ＤＰＨＡ　：日本化薬社製「ＫＡＹＡＲＡＤ　ＤＰＨＡ」（多官能アクリレート） <Photopolymerizable compound-1>
DPHA: "KAYARAD DPHA" (polyfunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.
＜光重合開始剤－１＞
　ＴＲ－ＰＢＧ－３０４：常州強力電子新材料社製「ＴＲ－ＰＢＧ－３０４」（カルバゾール骨格を有するオキシムエステル系化合物） <Photoinitiator-1>
TR-PBG-304: "TR-PBG-304" (an oxime ester compound having a carbazole skeleton) manufactured by Changzhou Power Electronics New Materials Co., Ltd.
＜添加剤－１＞
　Ｘ－１２－１０４８：信越化学工業社製「Ｘ－１２－１０４８」（多官能アクリルシラン） <Additive-1>
X-12-1048: Shin-Etsu Chemical Co., Ltd. "X-12-1048" (polyfunctional acrylic silane)
＜界面活性剤－１＞
　Ｆ－５５４：ＤＩＣ社製「メガファックＦ５５４」（フッ素系界面活性剤） <Surfactant-1>
F-554: "Megafac F554" manufactured by DIC (fluorosurfactant)
＜溶剤＞
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート <Solvent>
PGMEA: propylene glycol monomethyl ether acetate
＜分散液１～７の調製＞
　表１に記載の顔料－１、分散剤－１、スルホン酸基含有化合物Ａ～Ｄ、化合物Ｅ及び溶剤を、表１に記載の質量比となるように混合して混合液を得た。なお表１中の溶剤の配合割合には、分散剤、及び化合物由来の溶剤の量も含まれる。
　この混合液をペイントシェーカーにより２５～４５℃の範囲で６時間分散処理を行った。ビーズとしては、０．５ｍｍφのジルコニアビーズを用い、分散液の２．５倍の質量を加えた。分散終了後、フィルターによりビーズと分散液を分離して、分散液１～７を調製した。
　この顔料分散液（分散液１～分散液７）は増粘もなく分散性が良好であった。 <Preparation of Dispersions 1 to 7>
Pigment-1, dispersant-1, sulfonic acid group-containing compounds A to D, compound E and a solvent shown in Table 1 were mixed at the mass ratio shown in Table 1 to obtain a mixture. The mixing ratio of the solvent in Table 1 also includes the amount of the dispersant and the solvent derived from the compound.
This mixture was subjected to dispersion treatment for 6 hours at a temperature of 25 to 45° C. using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After completion of the dispersion, the beads and dispersion liquid were separated by a filter to prepare dispersion liquids 1 to 7.
These pigment dispersions (dispersions 1 to 7) did not thicken and had good dispersibility.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
＜感光性樹脂組成物の調製＞
［実施例１～４及び比較例１～３］
　上記調製した分散液１～７を用いて、感光性樹脂組成物の全固形分における各成分の固形分比率が表２の配合割合となるように各成分を加え、さらに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）、３－メトキシブチルアセテート（ＭＢＡ）、及びジエチレングリコールモノエチルエーテルアセテート（ＥＤＧＡＣ）を、感光性樹脂組成物の全固形分の含有割合が１４質量％となり、さらには溶剤中の比率がＰＧＭＥＡ／ＭＢＡ／ＥＤＧＡＣが６８／３０／２質量％となるように加え、攪拌、溶解させて、感光性樹脂組成物を調製した。得られた各感光性樹脂組成物を用いて、後述する方法で評価を行った。 <Preparation of photosensitive resin composition>
[Examples 1 to 4 and Comparative Examples 1 to 3]
Using dispersions 1 to 7 prepared above, each component was added so that the solid content ratio of each component in the total solid content of the photosensitive resin composition was the mixing ratio shown in Table 2, and propylene glycol monomethyl ether acetate ( PGMEA), 3-methoxybutyl acetate (MBA), and diethylene glycol monoethyl ether acetate (EDGAC), the total solid content of the photosensitive resin composition is 14% by mass, and the ratio in the solvent is PGMEA / A photosensitive resin composition was prepared by adding MBA/EDGAC to 68/30/2% by mass and stirring and dissolving. Using each of the obtained photosensitive resin compositions, evaluation was performed by the method described later.
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
（感光性樹脂組成物の評価）
＜溶解時間の測定＞
　ガラス基板上に感光性樹脂組成物を加熱硬化後の膜厚が１．２μｍとなるようにスピンコーターにて塗布し、１００Ｐａで６０秒間減圧乾燥した後に、ホットプレートで１００℃にて１２０秒間乾燥した。得られた塗膜に、フォトマスクとして、１μｍ刻みで１μｍ～２０μｍの線幅開口を有するフォトマスクを使用して、波長３６５ｎｍでの強度が６０ｍＷ／ｃｍ２である紫外線を用いて、露光量が４０ｍＪ／ｃｍ２となるよう露光処理を施した。
　続いて、０．０４質量％のＫＯＨ（水酸化カリウム）水溶液よりなる現像液を用い、２３℃において水圧０．０５ＭＰａのシャワー現像を施したのち、純水にて現像を停止し、水洗スプレーにて洗浄した。シャワー現像時にパターニングが目視できた時間を溶解時間として測定した。 (Evaluation of photosensitive resin composition)
<Measurement of dissolution time>
A photosensitive resin composition was coated on a glass substrate with a spin coater so that the film thickness after heat curing was 1.2 μm, dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 100 ° C. for 120 seconds. bottom. A photomask having a line width opening of 1 μm to 20 μm in increments of 1 μm is used as a photomask for the resulting coating film, and ultraviolet rays having a wavelength of 365 nm and an intensity of 60 mW/cm 2 are used to expose the coating film. Exposure processing was carried out so as to obtain 40 mJ/cm 2 .
Subsequently, using a developer consisting of a 0.04% by mass KOH (potassium hydroxide) aqueous solution, shower development was performed at 23 ° C. with a water pressure of 0.05 MPa, and then development was stopped with pure water. was washed. The dissolution time was measured as the time during which the patterning was visible during shower development.
＜細線密着性の評価＞
　ガラス基板上に感光性樹脂組成物を加熱硬化後の膜厚が１．２μｍとなるようにスピンコーターにて塗布し、１００Ｐａで６０秒間減圧乾燥した後に、ホットプレートで１００℃にて１２０秒間乾燥した。得られた塗膜に、フォトマスクとして、１μｍ刻みで１μｍ～２０μｍの線幅開口を有するフォトマスクを使用して、波長３６５ｎｍでの強度が６０ｍＷ／ｃｍ２である紫外線を用いて、露光量が４０ｍＪ／ｃｍ２となるよう露光処理を施した。
　続いて、０．０４質量％のＫＯＨ（水酸化カリウム）水溶液よりなる現像液を用い、２３℃において水圧０．０５ＭＰａのシャワー現像を溶解時間の２倍施したのち、純水にて現像を停止し、水洗スプレーにて洗浄、２３０℃で２５分間加熱硬化（ポストベーク）させたて、細線密着性評価用基板を作成した。
　得られた基板の線形パターンを光学顕微鏡（ニコン社製　Ｅｃｌｉｐｓｅ　Ｌ２００ＮＤ）により観察し、欠けずに残った最小のパターンのフォトマスク開口サイズを最小密着（細線密着性）として測定した。 <Evaluation of thin line adhesion>
A photosensitive resin composition was coated on a glass substrate with a spin coater so that the film thickness after heat curing was 1.2 μm, dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 100 ° C. for 120 seconds. bottom. A photomask having a line width opening of 1 μm to 20 μm in increments of 1 μm is used as a photomask for the resulting coating film, and ultraviolet rays having a wavelength of 365 nm and an intensity of 60 mW/cm 2 are used to expose the coating film. Exposure processing was carried out so as to obtain 40 mJ/cm 2 .
Subsequently, using a developer consisting of a 0.04% by mass KOH (potassium hydroxide) aqueous solution, shower development was performed at 23° C. under a water pressure of 0.05 MPa twice as long as the dissolution time, and then the development was stopped with pure water. Then, the substrate was washed with a water washing spray and cured by heating (post-baking) at 230° C. for 25 minutes to prepare a substrate for fine line adhesion evaluation.
The resulting linear pattern on the substrate was observed with an optical microscope (Nikon Eclipse L200ND), and the photomask opening size of the smallest remaining pattern without chipping was measured as the minimum adhesion (fine line adhesion).
＜直線性＞
　細線密着性評価用基板と同様の方法で基板を作成し、フォトマスクの６μｍ開口部に対応するパターンの直線性を、光学顕微鏡を用いて測定した。
　Ａ：カケが無い。
　Ｂ：２～３個のカケが見られるが、カラーフィルターの製造には問題はない。
　Ｃ：多くのカケが見られ、カラーフィルターの製造には不適切である。 <Linearity>
A substrate was prepared in the same manner as the thin line adhesion evaluation substrate, and the linearity of the pattern corresponding to the 6 μm opening of the photomask was measured using an optical microscope.
A: There is no chip.
B: Two or three chips are observed, but there is no problem in producing a color filter.
C: A lot of chips are observed, and it is unsuitable for manufacturing color filters.
　実施例１、実施例２及び比較例１より、（Ｃ）スルホン酸基含有化合物の電気伝導度が９０００μＳ／ｃｍ以下で、酸価が４０ｍｇＫＯＨ／ｇ以上あれば、現像溶解性に優れ、細線密着性に優れることが示された。
　一方で、（Ｃ）スルホン酸基含有化合物の電気伝導度が９０００μＳ／ｃｍを超える、すなわち、電気伝導度が高くなると、（Ｃ）スルホン酸基含有化合物の顔料吸着不良による遊離酸量が増加したと考えられ、溶解時間が早くなり、アンダーカットが強調されることで、細線密着性が悪化したと考えられる。
　実施例１、実施例３及び比較例１より、（Ｃ）スルホン酸基含有化合物の電気伝導度が９０００μＳ／ｃｍ以下であれば、（Ｃ）スルホン酸基含有化合物の量を顔料量に対して２％から１０％に増やしても細線密着性は悪化せず、溶解速度も大きく変化することは無かった。
　実施例１、実施例４及び比較例１より、（Ｃ）スルホン酸基含有化合物の電気伝導度が９０００μＳ／ｃｍ以下であれば、分散剤の量を顔料量に対して２０％から２５％に増やしても細線密着性は悪化せず、溶解速度も大きく変化することは無かった。 From Example 1, Example 2, and Comparative Example 1, when the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 μS/cm or less and the acid value is 40 mgKOH/g or more, the solubility in development is excellent and the fine line adhesion is good. It was shown to be superior in terms of performance.
On the other hand, when the electrical conductivity of (C) the sulfonic acid group-containing compound exceeds 9000 μS/cm, that is, when the electrical conductivity increases, the amount of free acid due to poor pigment adsorption of the (C) sulfonic acid group-containing compound increases. It is thought that the dissolution time was shortened and the undercut was emphasized, which deteriorated the fine wire adhesion.
From Example 1, Example 3 and Comparative Example 1, if the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 μS / cm or less, the amount of (C) the sulfonic acid group-containing compound relative to the amount of pigment Even when the content was increased from 2% to 10%, the fine wire adhesion did not deteriorate, and the dissolution rate did not change significantly.
From Example 1, Example 4 and Comparative Example 1, if the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 μS / cm or less, the amount of dispersant is changed from 20% to 25% with respect to the amount of pigment. Even if it was increased, the fine wire adhesion did not deteriorate, and the dissolution rate did not change significantly.
　実施例１及び比較例２より、（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ未満となると、顔料周辺の酸価が大きく下がるため、溶解時間が長く、細線密着性も悪化することが示された。直線性も悪化し、細線は作り難くなっていることも示された。
　実施例１、比較例２及び比較例３より、（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ未満であり、酸価が４０ｍｇＫＯＨ／ｇ未満となると、顔料吸着能は失われるため、分散液の安定性が悪化することで、さらに溶解時間がさらに長く、細線密着性および直線性もさらに悪化することが示された。
　以上の結果より、（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下であり、酸価が４０ｍｇＫＯＨ／ｇ以上であることで、遊離酸の影響を最小限にとどめることが可能となり、細線密着性及び直線性が良化し、溶解時間の変化量も小さくできることが示された。 According to Example 1 and Comparative Example 2, when the electrical conductivity of (C) the sulfonic acid group-containing compound is less than 2000 μS/cm, the acid value around the pigment is significantly decreased, resulting in a long dissolution time and poor fine line adhesion. was shown. It was also shown that the linearity deteriorated and it became difficult to form thin lines.
From Example 1, Comparative Example 2, and Comparative Example 3, when the electrical conductivity of (C) the sulfonic acid group-containing compound is less than 2000 μS/cm and the acid value is less than 40 mgKOH/g, the pigment adsorption capacity is lost. , the deterioration of the stability of the dispersion resulted in a longer dissolution time and further deterioration of fine line adhesion and linearity.
From the above results, (C) the sulfonic acid group-containing compound has an electrical conductivity of 2000 μS/cm or more and 9000 μS/cm or less and an acid value of 40 mgKOH/g or more, thereby minimizing the influence of the free acid. It was shown that the fine wire adhesion and linearity were improved, and the amount of change in dissolution time could be reduced.
　１０　透明支持基板
　２０　画素
　３０　有機保護層
　４０　無機酸化膜
　５０　透明陽極
　５１　正孔注入層
　５２　正孔輸送層
　５３　発光層
　５４　電子注入層
　５５　陰極
　１００　有機ＥＬ素子
　５００　有機発光体 REFERENCE SIGNS LIST 10 transparent support substrate 20 pixel 30 organic protective layer 40 inorganic oxide film 50 transparent anode 51 hole injection layer 52 hole transport layer 53 light emitting layer 54 electron injection layer 55 cathode 100 organic EL element 500 organic light emitter

Claims (13)

  1. 　（Ａ）顔料、（Ｂ）分散剤及び（Ｃ）スルホン酸基含有化合物を含有する顔料分散液であって、
    　前記（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下であり、
    　前記（Ｃ）スルホン酸基含有化合物の酸価が４０ｍｇＫＯＨ／ｇ以上である、顔料分散液。     A pigment dispersion containing (A) a pigment, (B) a dispersant and (C) a sulfonic acid group-containing compound,
    (C) the sulfonic acid group-containing compound has an electrical conductivity of 2000 μS/cm or more and 9000 μS/cm or less;
    The pigment dispersion liquid, wherein the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
  2. 　前記（Ｃ）スルホン酸基含有化合物が、フタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体及びジオキサジンのスルホン酸誘導体からなる群から選ばれる少なくとも一つを含む、請求項１に記載の顔料分散液。 The (C) sulfonic acid group-containing compound is selected from phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. The pigment dispersion according to claim 1, comprising at least one selected from the group consisting of:
  3. 　前記（Ｃ）スルホン酸基含有化合物が銅フタロシアニンスルホン酸誘導体を含む、請求項１に記載の顔料分散液。 The pigment dispersion according to claim 1, wherein the (C) sulfonic acid group-containing compound contains a copper phthalocyanine sulfonic acid derivative.
  4. 　前記（Ａ）顔料と前記（Ｃ）スルホン酸基含有化合物との、質量基準における含有比率（（Ａ）顔料／（Ｃ）スルホン酸基含有化合物）が１０以上である、請求項１～３のいずれか１項に記載の顔料分散液。 Claims 1 to 3, wherein the content ratio ((A) pigment/(C) sulfonic acid group-containing compound) on a mass basis of the (A) pigment and the (C) sulfonic acid group-containing compound is 10 or more. The pigment dispersion according to any one of items 1 and 2.
  5. 　前記（Ａ）顔料と前記（Ｂ）分散剤との、質量基準における含有比率（（Ａ）顔料／（Ｂ）分散剤）が４以上である、請求項１～４のいずれか１項に記載の顔料分散液。 The content ratio ((A) pigment/(B) dispersant) on a mass basis of the (A) pigment and the (B) dispersant is 4 or more, according to any one of claims 1 to 4. pigment dispersion.
  6. 　前記（Ａ）顔料がカーボンブラックを含有する、請求項１～５のいずれか１項に記載の顔料分散液。 The pigment dispersion liquid according to any one of claims 1 to 5, wherein the pigment (A) contains carbon black.
  7. 　（Ａ）顔料、（Ｂ）分散剤、（Ｃ）スルホン酸基含有化合物、（Ｄ）アルカリ可溶性樹脂、（Ｅ）光重合性化合物及び（Ｆ）光重合開始剤を含有する感光性樹脂組成物であって、
    　前記（Ｃ）スルホン酸基含有化合物の電気伝導度が２０００μＳ／ｃｍ以上９０００μＳ／ｃｍ以下であり、
    　前記（Ｃ）スルホン酸基含有化合物の酸価が４０ｍｇＫＯＨ／ｇ以上である、感光性樹脂組成物。     A photosensitive resin composition containing (A) a pigment, (B) a dispersant, (C) a sulfonic acid group-containing compound, (D) an alkali-soluble resin, (E) a photopolymerizable compound, and (F) a photopolymerization initiator and
    (C) the sulfonic acid group-containing compound has an electrical conductivity of 2000 μS/cm or more and 9000 μS/cm or less;
    The photosensitive resin composition, wherein (C) the sulfonic acid group-containing compound has an acid value of 40 mgKOH/g or more.
  8. 　前記（Ｃ）スルホン酸基含有化合物が、フタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体及びジオキサジンのスルホン酸誘導体からなる群から選ばれる少なくとも一つを含む、請求項７に記載の感光性樹脂組成物。 The (C) sulfonic acid group-containing compound is selected from phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. The photosensitive resin composition according to claim 7, comprising at least one selected from the group consisting of:
  9. 　前記（Ｃ）スルホン酸基含有化合物が銅フタロシアニンスルホン酸誘導体を含む、請求項７に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 7, wherein the (C) sulfonic acid group-containing compound contains a copper phthalocyanine sulfonic acid derivative.
  10. 　前記（Ａ）顔料がカーボンブラックを含有する、請求項７～９のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 7 to 9, wherein the pigment (A) contains carbon black.
  11. 　請求項７～１０のいずれか１項に記載の感光性樹脂組成物を硬化させた硬化物。 A cured product obtained by curing the photosensitive resin composition according to any one of claims 7 to 10.
  12. 　請求項１１に記載の硬化物からなるブラックマトリックス。 A black matrix made of the cured product according to claim 11.
  13. 　請求項１１に記載の硬化物を有する画像表示装置。 An image display device having the cured product according to claim 11.
PCT/JP2022/038423 2021-10-20 2022-10-14 Pigment dispersion, photosensitive resin composition, cured product, black matrix, and image display device WO2023068201A1 (en)

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