KR20180135935A - Curable composition, cured film, color filter, light-shielding film, solid-state imaging element, image display, and method of manufacturing cured film - Google Patents

Abstract

A curable composition, a cured film, a color filter, a light-shielding film, a solid-state image pickup device, an image display, and a method for producing a cured film which can obtain a cured film having an excellent pattern shape while maintaining excellent light shielding property. The curable composition is a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound and a polyfunctional thiol compound, wherein the optical density per film thickness of 1.5 占 퐉 in the visible light region of the cured film obtained by curing the curable composition is , 4.0 or more.

Description

Curable composition, cured film, color filter, light-shielding film, solid-state imaging element, image display, and method of manufacturing cured film

The present invention relates to a curable composition, a cured film, a color filter, a light-shielding film, a solid-state imaging device, an image display device, and a method for producing a cured film.

A color filter used in a liquid crystal display device is provided with a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.

Also in the solid-state image pickup device, a light-shielding film is provided for the purpose of preventing noise generation and improving image quality. 2. Description of the Related Art Presently, a portable terminal of an electronic device such as a cellular phone and a PDA (Personal Digital Assistant) is equipped with a small and thin imaging unit. Such an image pickup unit generally includes a solid-state image pickup device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor and a lens for forming a subject image on the solid-state image pickup device have.

Patent Document 1 discloses a method for forming a light-shielding film, which comprises a black coloring agent having an average particle size of 40 nm or less and a resin component capable of forming a coating film disposed on the periphery of an effective pixel region (image pickup section) of a solid- Quot; composition for forming a light-shielding film " wherein the black colorant contains at least one of carbon black and titanium black.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-156801

The inventors of the present invention have studied the light-shielding film obtained by curing the composition for forming a light-shielding film described in Patent Document 1 and have found that there is room for further improvement in the obtained pattern shape although it has excellent light-shielding properties. Specifically, the light-shielding film obtained by curing the composition for forming a light-shielding film described in Patent Document 1 revealed that the film thickness of the end portion may be smaller than the thickness of the central portion.

Accordingly, it is an object of the present invention to provide a curable composition capable of obtaining a cured film having an excellent pattern shape while maintaining excellent light-shielding properties.

It is another object of the present invention to provide a cured film obtained by using the curable composition, a color filter, a light-shielding film, a solid-state image pickup device and an image display device including the cured film, and a method of manufacturing a cured film.

The inventors of the present invention have made extensive studies in order to achieve the above-described object. As a result, it was found that a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound was obtained by curing a cured film obtained by curing a curable composition in an optical density of 1.5 Or more, and the curable composition can solve the above problems, thus completing the present invention.

That is, it has been found that the above problems can be achieved by the following constitution.

[1] A curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound and a polyfunctional thiol compound, wherein the optical density per film thickness of 1.5 μm in the visible light region of the cured film obtained by curing the curable composition, 4.0 or more.

[2] The curable composition according to [1], wherein the content of the colorant is 55% by mass or more based on the total solid content of the curable composition.

[3] The curable composition according to [1] or [2], wherein the content of the polyfunctional thiol compound is 1 to 5.5% by mass with respect to the content of the colorant.

[4] The curable composition according to any one of [1] to [3], which further contains a polymerization inhibitor.

[5] The curable composition according to [4], wherein the content of the polymerization inhibitor is 0.1 to 1.5% by mass with respect to the content of the polyfunctional thiol compound.

[6] The curable composition according to [4] or [5], wherein the polymerization inhibitor contains a phenol compound.

[7] The curable composition according to any one of [4] to [6], wherein the polymerization inhibitor contains two or more phenolic compounds.

[8] The curable composition according to any one of [4] to [7], wherein the polymerization inhibitor contains a hindered amine compound.

[9] The curable composition according to any one of [1] to [8], wherein the colorant is an inorganic pigment.

[10] The image forming method according to any one of [1] to [10], wherein the inorganic pigment is at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver or tin-containing metal pigments, Wherein the curable composition is a curable composition.

[11] The curable composition according to any one of [1] to [10], wherein the polyfunctional thiol compound is a compound having two or more groups represented by formula (1).

[12] The curable composition according to any one of [1] to [11], wherein the polyfunctional thiol compound is trifunctional or more.

Wherein the polyfunctional thiol compound is at least one selected from the group consisting of pentaerythritol tetra (3-mercaptopropionate), and trimethylol propanol (3-mercaptopropionate) The curable composition according to any one of [1] to [12].

[14] The curable composition according to any one of [1] to [13], wherein the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass with respect to the total solid content of the curable composition.

[15] The curable composition according to any one of [1] to [14], wherein the content of the polymerizable compound is more than 3.5 mass% and less than 20 mass% with respect to the total solid content of the curable composition.

[16] The curable composition according to any one of [1] to [15], which further contains a dispersant and the content of the dispersant is 17 mass% or more based on the total solid content of the curable composition.

[17] The curable composition according to any one of [1] to [16], wherein the photopolymerization initiator is an oxime compound.

[18] A cured film obtained by curing the curable composition according to any one of [1] to [17].

[19] A color filter comprising the cured film according to [18].

[20] A light-shielding film containing the cured film according to [18].

[21] A solid-state imaging element comprising the cured film according to [18].

[22] An image display device comprising the cured film according to [18].

[23] A curable composition comprising a curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of [1] to [17], and a curing composition including an exposure step of exposing the curable composition layer ≪ / RTI >

[24] The method for producing a cured film according to [23], wherein an exposure amount of the curable composition layer in the exposure step is 200 mJ / cm ² or more.

[25] The method for producing a cured film according to [23] or [24], wherein the step of forming a curable composition layer comprises a coating step of directly applying a curable composition on a support and forming a layer of the curable composition on the support.

[26] The method for producing a cured film according to any one of [23] to [25], further comprising a development step of developing the exposed curable composition layer and a cleaning step of cleaning the developed curable composition layer.

According to the present invention, it is possible to provide a curable composition capable of obtaining a cured film having an excellent pattern shape while maintaining excellent light shielding properties.

According to the present invention, it is possible to provide a cured film obtained by using the curable composition, a color filter, a light shielding film, a solid-state image pickup device, an image display device including the cured film, and a method of manufacturing the cured film.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing a process for producing a cured film using a curable composition containing no polyfunctional thiol compound.
2 is a cross-sectional view schematically showing a process for producing a cured film using a curable composition containing no polyfunctional thiol compound for each process.
3 is a cross-sectional view schematically showing a process for producing a cured film using a curable composition containing no polyfunctional thiol compound for each process.
4 is a cross-sectional view schematically showing a step of manufacturing a cured film using the curable composition according to the embodiment of the present invention.
5 is a cross-sectional view schematically showing a process for producing a cured film using the curable composition according to the embodiment of the present invention.
6 is a cross-sectional view schematically showing a process for producing a cured film using the curable composition according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

Descriptions of the constituent elements described below may be made based on the exemplary embodiments of the present invention, but the present invention is not limited to these embodiments.

In the present specification, the numerical value range indicated by "~" means a range including numerical values written before and after "~" as a lower limit value and an upper limit value.

In the notation of the group (atomic group) in the present specification, the notations in which substitution and non-substitution are not described include those which do not contain a substituent and also contain a substituent. For example, the "alkyl group" includes an alkyl group (substituted alkyl group) containing a substituent as well as an alkyl group (unsubstituted alkyl group) containing no substituent.

The term " actinic ray " or " radiation " in the present specification includes, for example, a line spectrum of a mercury lamp, and deep ultraviolet rays (Extreme ultra violet lithography) And the like. In the present specification, the term " light " means an actinic ray and radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays, X-rays, EUV light, etc. represented by mercury-free spectral lines of mercury and excimer lasers but also by exposure to particle beams such as electron beams and ion beams It also includes drawing.

In the present specification, "(meth) acrylate" refers to acrylate and methacrylate. In the present specification, "(meth) acryl" refers to acrylic and methacrylic. In the present specification, "(meth) acryloyl" represents acryloyl and methacryloyl. In the present specification, "(meth) acrylamide" refers to acrylamide and methacrylamide. In the present specification, the terms " monomer " and " monomer " are synonyms. A monomer is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group means a group involved in the polymerization reaction.

[Curable composition]

The curable composition preferably has an optical density of not less than 4.0 per 1.5 탆 of the film thickness in a visible light region of a cured film containing a colorant, a photopolymerization initiator, a polymerizable compound and a polyfunctional thiol compound, and curing the curable composition .

According to the curable composition having such a constitution, a cured film having an excellent pattern shape can be obtained while maintaining excellent light shielding property (hereinafter, also referred to as " effect of the present invention ").

The mechanism by which the effect of the present invention is obtained by the curable composition is not necessarily clear, but the present inventors have assumed the following. In addition, by the following conjecture, the curable composition is not limited to the component showing the effect of the present invention.

Conventionally known curable compositions containing a colorant such as carbon black and not containing a polyfunctional thiol compound are widely used because they can obtain a high shielding concentration over a wide wavelength range. However, the optical density (OD: also referred to as optical density) of the curable composition layer gradually increases from the long wavelength side to the short wavelength side, and the optical density in the short wavelength region is very high as compared with the long wavelength side. Thus, when the curable composition layer is pattern-exposed to light in the ultraviolet region such as g-line, h-line, and i-line, for example, light does not reach the inside of the curable composition layer, exposure becomes insufficient, .

1 to 6 schematically showing the manufacturing process of the cured film for each process will be described below. First, Figs. 1 to 3 are cross-sectional views schematically showing a process for producing a cured film using a curable composition containing no polyfunctional thiol for each process.

First, as shown in Fig. 1, a curable composition layer 102 is formed on a support 101 using a curable composition. Next, the curable composition layer 102 is exposed through the opening of the photomask 103 (the arrow in FIG. 1 indicates the direction of light irradiation, and the line AB is an extension of the end of the opening of the photomask) ). Next, the exposed curable composition layer 102 is developed to form a patterned cured film 201.

Since the optical density of the curable composition layer 102 is high at the time of exposure in the above procedure, light hardly reaches the inside of the curable composition layer 102 at the time of exposure, and the exposure becomes insufficient at the bottom of the curable composition layer 102. Then, when the development is carried out, the curable composition is eluted at a portion where the exposure of the curable composition layer 102 is insufficient (Fig. 2). In such a state, when the post-baking treatment for heating the cured film 201 is performed, there arises a problem called " thermal deflection " in the portion eluted at the time of development. That is, it is presumed that the thickness of the end portion of the obtained post-baked cured film 301 is reduced compared to the central portion (FIG. 3).

Figs. 4 to 6 are cross-sectional views schematically showing steps of manufacturing a cured film using the curable composition of the present invention.

First, as shown in Fig. 4, the curable composition layer 401 is formed on the support 101 by using the curable composition of the present invention. Next, the curable composition layer 401 is exposed through the opening of the photomask 103. Next,

At this time, since the curable composition layer 401 contains a polyfunctional thiol compound, it is presumed that the curable composition layer 401 is sufficiently cured to the inside of the curable composition layer 401 for the following reasons.

Inside the exposed curable composition layer 401, the radical polymerization reaction is initiated by the photopolymerization initiator. At this time, the radicals generated by the photopolymerization initiator may react with oxygen in the curable composition layer 401 to generate peroxy radicals. Since the peroxy radical does not have a function of promoting the polymerization reaction, the polymerization reaction is thus stopped.

On the other hand, in the case where a polyfunctional thiol compound is present in the curable composition layer 401, a thiol group in the polyfunctional thiol compound donates hydrogen to the peroxy radical, thereby generating a tile radical that is less susceptible to polymerization deactivation by oxygen , The polymerization reaction proceeds. Therefore, it is presumed that the curable composition containing the polyfunctional thiol compound is easily cured sufficiently to the inside of the curable composition layer 401.

The optical density of the cured film obtained by curing the curable composition is 1.5 or more in the visible light region of 4.0 or more, and the curable composition layer 401 is high in light shielding property.

The light irradiated to the curable composition layer 401 through the opening of the photomask 103 is diffracted at the opening of the photomask 103 and is also irradiated to the outside mask shielding portion 402 by the AB line &Quot; leak light "). If the light shielding property of the curable composition layer is low, the leakage of the light up to the layer of the curable composition of the mask light shielding portion leads to deterioration of the pattern shape.

However, since the curable composition layer 401 has high light shielding property, the leaked light is absorbed without exposing the mask shielding portion 402 (Fig. 4).

Therefore, when the cured film after exposure is developed, the cured film 501 is sufficiently cured to the inside and the light diffracted at the opening portion of the photomask is absorbed, whereby a cured film 501 having an excellent pattern shape is obtained (Fig. 5). Since the cured film 501 hardly causes "thermal deflection" even after the post-baking process, the difference in film thickness between the central portion and the end portion of the post-baked cured film 601 becomes small, (Fig. 6).

[Optical density (OD value)]

The optical density per film thickness of 1.5 占 퐉 in the visible light region of the cured film obtained by curing the curable composition is 4.0 or more. Among them, the optical density is more preferably 4.1 or more, and more preferably 4.3 or more, from the standpoint of obtaining a curable composition having a better effect of the present invention. The upper limit value is not particularly limited, but is generally preferably 8.0 or less.

In the present specification, the optical density means the optical density measured by the method described in the embodiment, and the visible light region means light with a wavelength of 400 to 800 nm. Therefore, in the case where the optical density per film thickness of 1.5 占 퐉 in the visible light region is 4.0 or more, the optical density per film thickness of 1.5 占 퐉 throughout the wavelength range of 400 to 800 nm is intended to be 4.0 or more.

Hereinafter, each component included in the curable composition will be described in detail.

〔coloring agent〕

The curable composition contains a colorant. The colorant is at least one selected from the group consisting of pigments and dyes.

The content of the colorant is preferably 55% by mass or more, more preferably 56% by mass or more, and still more preferably 58% by mass or more based on the total solid content of the curable composition.

When the content of the colorant is 55 mass% or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent.

The upper limit value of the content of the colorant is not particularly limited, but is generally 70% by mass or less based on the total solid content of the curable composition. When the content of the coloring agent is not more than the upper limit, the curable composition has more excellent applicability.

<Pigment>

The pigment is not particularly limited, and known inorganic pigments and / or organic pigments can be used. Among them, the pigment is preferably an inorganic pigment in that a curable composition having a better effect of the present invention can be obtained.

(Inorganic pigment)

The inorganic pigment is not particularly limited, and a known inorganic pigment can be used.

Examples of the inorganic pigments include inorganic pigments such as zinc oxide, white pig iron, lysophone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead titanate, red iron oxide, Prussian blue, Prussian blue (ferrocyanide potassium) zircon gray, Praseodymium yellow, Chromium titanium yellow, Chromium green, Peacock, Victorian green, Prussian blue (irrelevant to prussian blue) Vanadium zirconium blue, chromium tin pink, manganese pink, and salmon pink. Examples of the black inorganic pigment include metal oxides containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti and Ag, .

As the inorganic pigment, carbon black, titanium black, metal pigments, etc. (hereinafter, also referred to as " black pigment ") are preferable in that a curable composition capable of forming a cured film having a high optical density at least in content can be obtained. Examples of the metallic pigment include metal oxides containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Or metal nitrogen.

Examples of the inorganic pigment include at least one kind selected from the group consisting of a metal pigment containing titanium nitride, titanium oxide, niobium nitride, vanadium nitride, silver or tin, and a metallic pigment containing tin And more preferably at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, and vanadium nitride.

As the inorganic pigment, carbon black may also be used. Specific examples of the carbon black include commercially available inorganic pigments such as C.I. Pigment Black 1 and C.I. Pigment Black 7, but are not limited thereto.

As the curable composition, a pigment having infrared absorbing property other than the pigment described as a black pigment may be used.

As the pigment having infrared ray absorbency, a tungsten compound, a metal boride and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light shielding property in the wavelength region in the infrared region. Particularly, a tungsten compound is preferable from the viewpoint of the light absorption wavelength range of the photopolymerization initiator and the light transmittance of the visible light region, which are related to the curing efficiency by exposure.

These pigments may be used in combination of two or more, and may be used in combination with the dyes described later. Colored pigments such as red, green, yellow, orange, purple, and blue or pigments having a light-shielding property, such as red, green, And an embodiment in which the dye is mixed. It is preferable to mix a red pigment or a dye or a purple pigment or a dye into a pigment having black or infrared ray shielding property and more preferably to mix a red pigment with a pigment having black or infrared ray shielding property.

Further, a near infrared absorbent and an infrared absorbent described later may be added.

The black pigment preferably contains titanium black and / or niobium oxynitride. Titanium black is a black particle containing a titanium atom. Preferably titanium oxide, titanium oxynitride, titanium nitride or the like. The surface of the titanium black particles can be modified as needed for the purpose of improving dispersibility and inhibiting cohesiveness. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and it is also possible to perform treatment with a water repellent material as disclosed in Japanese Patent Application Laid-Open No. 2007-302836 Do.

Titanium black is typically a titanium black particle, and it is preferable that the primary particle diameter and the average primary particle diameter of each particle are small. Niobium oxynitride is also the same.

Concretely, it is preferable that the average primary particle diameter is in the range of 10 nm to 45 nm.

The average primary particle size of the pigment can be measured using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission type microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.

(D max: maximum length at two points on the outline of the particle image) obtained by using a transmission electron microscope, and maximum length and vertical length (DV-max: images between two straight lines parallel to the maximum length (The shortest length connecting two straight lines vertically when placed) was measured, and the rising average value (Dmax x DV-max) 1/2 was taken as the particle diameter. The particle diameters of 100 particles were measured by this method, and the arithmetic average value was taken as the average particle diameter, and the average primary particle diameter of the pigment was determined.

The specific surface area of the titanium black and the niobium oxynitride is not particularly limited. However, since the water repellency after the surface treatment of the titanium black and the niobium oxynitride with the water repellent agent has a predetermined performance, it is preferable to use a BET (Brunauer, Emmett, Teller) The measured value is preferably 5 m ² / g or more and 150 m ² / g or less, and more preferably 20 m ² / g or more and 120 m ² / g or less.

Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N and 13M-T (trade names, manufactured by Mitsubishi Materials Corporation), Tilack D (Trade name, manufactured by Wako Pure Chemical Industries, Ltd.) and 50 nm of titanium nitride (trade name, manufactured by Wako Pure Chemical Industries, Ltd.).

As the colorant, it is preferable to use titanium oxynitride, titanium nitride, or niobium oxynitride and more preferably titanium nitride or niobium oxynitride because the resulting cured film has better moisture resistance, and niobium oxynitride More preferable. This is presumably because these colorants are hydrophobic.

It is also preferable to further contain titanium black as a pigment dispersion containing titanium black and Si atoms.

In this embodiment, the titanium black is contained as a dispersoid in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersoid is preferably 0.05 or more, more preferably 0.05 to 0.5 More preferably 0.07 to 0.4.

Here, the above-described dispersed body includes both of titanium black as primary particles and agglomerates (secondary particles).

In order to change the Si / Ti of the object to be dispersed (for example, to be 0.05 or more), the following means can be used.

First, a dispersion is obtained by dispersing titanium oxide and silica particles using a dispersing machine, and the dispersion is subjected to a reduction treatment at a high temperature (for example, 850 to 1,000 ° C) to obtain a titanium black particle as a main component, And the like can be obtained. The reduction treatment may be performed in an atmosphere of a reducing gas such as ammonia.

Examples of the titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).

Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name, manufactured by Evonik).

A dispersion agent may be used for the dispersion of the titanium oxide and the silica particles. As the dispersing agent, those described in the section of the dispersing agent to be described later can be mentioned.

The above dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. Include those described in the column of organic solvents to be described later.

Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, can be produced by a method described in, for example, Japanese Patent Laid-Open Publication No. 2008-266045 and paragraphs [0016] to [0021] Can be produced.

(Si / Ti) of the Si atoms and the Ti atoms in the dispersoid containing titanium black and Si atoms to a suitable range (for example, 0.05 or more). By using the curable composition containing the dispersoid, When the film is formed, residues derived from the curable composition outside the region where the cured film is formed are reduced. In addition, the residue includes a component derived from a curable composition such as titanium black particles and a resin component.

The reason why the residue is reduced is still unclear. However, the particle size of such an object tends to be small (for example, a particle size of 30 nm or less) and the content of Si atoms in the object is increased, The adsorbability of the whole to the base is reduced. This is presumed to contribute to the improvement of the developing ability of the uncured curable composition (particularly, titanium black) in the formation of the cured film.

Titanium black is preferably an object to be dispersed (preferably Si / Ti in terms of mass) as the titanium black and the Si atom in view of the excellent light shielding property against light in the wavelength region over a wide range from ultraviolet light to infrared light 0.05 or more) exhibits excellent light shielding property.

Further, the content ratio (Si / Ti) of Si atoms and Ti atoms in the target dispersion can be measured by using the method (1-1) or the method (1-2) described in paragraph 0033 of Japanese Laid-Open Patent Publication No. 2013-249417 .

When judging whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the object to be dispersed is 0.05 or more with respect to the object to be dispersed contained in the cured film obtained by curing the curable composition, JP-A-2013-249417 The method (2) described in paragraph [0035] of the present application may be used.

In the pigment dispersion containing titanium black and Si atoms, the above-mentioned titanium black can be used.

In order to adjust the dispersibility, coloring property and the like with the titanium black, the pigment to be used is preferably a composite oxide of Cu, Fe, Mn, V, Ni or the like, a black oxide such as cobalt oxide, iron oxide, carbon black, One or more pigments may be used in combination. In this case, it is preferable that 50% by mass or more of the entire dispersoid is occupied by the to-be-dispersed body made of titanium black.

In the pigment dispersion, other colorants (organic pigments and / or dyes, etc.) may be used in combination with the titanium black in accordance with the object, so long as the effect of the present invention is not impaired.

Hereinafter, a material used for introducing Si atoms into the object to be dispersed will be described. When a Si atom is introduced into the object to be dispersed, a Si-containing substance such as silica may be used.

Examples of usable silica include precipitated silica, fumed silica, colloidal silica, synthetic silica and the like, and these may be appropriately selected and used.

Further, it is preferable to use fine particle type silica because the particle size of the silica particles is smaller than the film thickness when the cured film is formed, so that the light shielding property is better. Further, as an example of the particulate type silica, there may be mentioned, for example, the silica described in paragraph 0039 of Japanese Laid-Open Patent Publication No. 2013-249417, the contents of which are incorporated herein.

The curable composition may use a tungsten compound and / or a metal boride as a pigment.

Tungsten compounds and metal borides are infrared shielding materials that have high absorption (that is, high shielding property against infrared rays) for infrared rays (light having a wavelength of about 800 to 1,200 nm) and low absorption for visible light. Thus, the curable composition of the present invention contains a tungsten compound and / or a metal boride, thereby forming a pattern having high light-shielding property in the infrared region and high transparency in the visible light region.

The tungsten compound and the metal boride are less absorbed by light of shorter wavelength than the visible region used for exposure of high-pressure mercury lamp, KrF, ArF, etc. used for image formation. Thus, when combined with a polymerizable compound, an alkali-soluble resin, and a photopolymerization initiator, which will be described later, an excellent pattern can be obtained and the development residue can be further suppressed in pattern formation.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, and a tungsten sulphide compound, and a tungsten oxide compound represented by the following formula (composition formula) (I) is preferable.

M_xW_yO_z ... (I)

M represents a metal, W represents tungsten, and O represents oxygen.

0.001? X / y?

2.2? Z / y? 3.0

As the metal of M, for example, an alkali metal, an alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, , Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, Rb and Cs. The metal of M may be one kind or two kinds or more.

M is preferably an alkali metal, more preferably Rb or Cs, and more preferably Cs.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided.

When z / y is 2.2 or more, the chemical stability as a material can be further improved. When the ratio z / y is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , and Ba _0.33 WO ₃ , and Cs _0.33 WO ₃ or Rb _0.33 WO ₃ , And Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably a fine particle. The average primary particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average primary particle diameter falls within this range, the tungsten fine particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be more surely obtained. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better, but the average primary particle diameter of the tungsten fine particles is usually 1 nm or more for ease of handling at the time of production.

It is possible to use two or more kinds of tungsten compounds.

Tungsten compounds are commercially available. When the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained by a heat treatment of the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent Publication No. 4096205).

The tungsten oxide-based compound is also available as a dispersion of tungsten microparticles such as YMF-02 manufactured by Sumitomo Chemical Co., Ltd.

Examples of the metal boride include LaB ₆ , PrB ₆ , NdB ₆ , CeB ₆ , YB ₆ , TiB ₂ , zirconium boride (ZrB _2), boride, hafnium (HfB _2), boride, vanadium (VB _2), boride, tantalum (TaB _2), boride, chromium (CrB, CrB _2), boride, molybdenum _{(MoB 2, Mo 2 B 5} , MoB ), Tungsten boride (W ₂ B ₅ ), and the like, and it is preferable to use lanthanum boride (LaB ₆ ).

The metal boride is preferably fine particles. The average primary particle size of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and most preferably 100 nm or less. When the average primary particle size falls within this range, the light transmittance in the visible light region can be further ensured because the metal boride fine particles are less likely to block visible light due to light scattering. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better, but the average primary particle diameter of the metal boride fine particles is usually 1 nm or more for ease of handling at the time of production and so on.

It is possible to use two or more metal borides.

The metal boride is available as a commercially available product, and is also available as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo 3M Kogyo Kogyo Co., Ltd.

(Titanium nitride-containing particles)

As the inorganic pigment, titanium nitride-containing particles containing Fe atoms may be used. In the production of the titanium nitride-containing particles, a gas phase reaction method is usually used, and specifically, an electric furnace method and a thermal plasma method can be mentioned. Among these methods, the thermal plasma method is preferable because of the low content of impurities, easy preparation of the particle diameter, high productivity, and the like.

Examples of the method of generating the thermal plasma include a DC arc discharge, a polyphase arc discharge, a high frequency (RF) plasma, a hybrid plasma, and the like, and a high frequency plasma in which impurities are rarely mixed from the electrode is preferable. As a specific method for producing the titanium nitride-containing fine particles by the thermal plasma method, for example, a titanium powder is vaporized by a high-frequency thermal plasma to introduce nitrogen into the apparatus as a carrier gas, and the titanium powder is nitrided in the cooling process, Containing particles are synthesized. The thermal plasma method is not limited to the above.

The method for producing the titanium nitride-containing particles is not particularly limited, but the manufacturing method described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, instead of the Ag powder of International Patent Publication No. 2010/147098, a component containing Fe and / or a component containing Si, which will be described later, and a titanium powder material (titanium particle) , The titanium nitride-containing particles contained in the curable composition of the present invention can be produced.

The titanium powder material (titanium particle) used for producing the titanium nitride-containing particles is preferably high purity. The titanium powder material is not particularly limited, but the purity of the titanium element is preferably 99.99% or more, more preferably 99.999% or more.

Titanium powder materials (titanium particles) used for producing titanium nitride-containing particles sometimes contain atoms other than titanium atoms. Other atoms that may be included in the titanium powder material include, for example, Fe atoms and Si atoms.

When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001 mass% with respect to the total mass of the titanium powder material.

In the case where the titanium powder material contains Si atoms, the content of Si atoms is preferably from 0.002 to less than 0.3% by mass, more preferably from 0.01 to 0.15% by mass, more preferably from 0.02 to 0.25% by mass based on the total mass of the titanium powder material. By mass to 0.1% by mass. When the Si atom content exceeds 0.002 mass%, the patterning property of the cured film is further improved. When the Si atom content is less than 0.3 mass%, the polarity of the outermost layer of the resulting titanium nitride-containing particles is more stabilized. Thus, it is considered that when the titanium nitride-containing particles are dispersed, the adsorbability of the dispersant to the titanium nitride-containing particles is improved, the fine dispersion of the titanium nitride-containing particles is reduced, and the generation of particles is suppressed.

The water content in the titanium powder material (titanium particles) used for the production of the titanium nitride-containing particles is preferably less than 1% by mass, more preferably less than 0.1% by mass with respect to the total mass of the titanium powder material, It is more preferable not to.

The titanium nitride-containing particles are obtained by using the thermal plasma method so that the diffraction angle 2? Of the peak derived from the (200) plane (details will be described later) when the CuK? Ray is an X-ray source is more than 42.6 degrees and not more than 43.5 degrees In the range of &lt; / RTI &gt;

The method of incorporating Fe atoms in the titanium nitride-containing particles is not particularly limited, and for example, a method of introducing Fe atoms in the step of obtaining titanium particles (titanium powder) used as a raw material of the titanium nitride- And the like. More specifically, when titanium is produced by a crawling method or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel (SUS) may be used, or a material of a press and a pulverizer for crushing titanium Fe atoms can be attached to the surface of the titanium particles by using Fe atoms.

In the case of using the thermal plasma method for the production of the titanium nitride-containing particles, it is possible to add Fe atoms, Fe oxide and other components in addition to the titanium particles as the raw material, and nitridize them by the thermal plasma method to form Fe atoms in the titanium nitride- .

The Fe atoms contained in the titanium nitride-containing particles may be in any form such as ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides, May be included. The Fe atoms contained in the titanium nitride-containing particles may be present as impurities at crystal lattice positions, or may exist as impurities in an amorphous state at grain boundaries.

As a result of intensive studies, the inventors of the present invention have found that the content of Fe atoms in the titanium nitride-containing particles is related to the patterning properties and the corrosion resistance of the electrodes. It is considered that the Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and that the titanium nitride in the titanium nitride-containing particles adheres to the electrode and the substrate through Fe atoms. After the patterning of the cured film, such as development processing, the Fe atoms remain on the electrodes and the substrate, and titanium nitride is likely to be removed. Accordingly, it is presumed that the content of Fe atoms in the titanium nitride-containing particles is set to a predetermined amount or more so that the patternability of the cured film is improved. On the other hand, if the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrodes and the substrate increases, which is considered to cause corrosion of the electrodes. Therefore, it is presumed that the corrosion resistance of the electrode is improved if the content of Fe atoms in the titanium nitride-containing particles is set to a predetermined amount or less.

It is preferable that the content of Fe atoms in the titanium nitride-containing particles is more than 0.001 mass% and less than 0.4 mass% with respect to the total mass of the titanium nitride-containing particles. In particular, it is more preferably 0.01 to 0.2% by mass, and still more preferably 0.02 to 0.1% by mass. When the Fe atom content exceeds 0.001 mass%, the patterning property of the cured film is further improved. If the Fe atom content is less than 0.4 mass%, the corrosion resistance of the electrode due to the cured film is further improved (the cured film can suppress corrosion of the electrode). That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above range, excellent patterning properties of the cured film and corrosion resistance of the electrode can be obtained.

The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectroscopy.

It is preferable that the titanium nitride-containing particles further contain a Si atom (silicon atom). This further improves the patterning property of the cured film. The reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-mentioned Fe atoms.

The content of Si atoms in the titanium nitride-containing particles is preferably in the range of more than 0.002 mass% to less than 0.3 mass%, more preferably in the range of 0.01 to 0.15 mass%, more preferably in the range of 0.02 to 0.1 mass% Is more preferable. When the Si atom content exceeds 0.002 mass%, the patterning property of the cured film is further improved. When the Si atom content is less than 0.3 mass%, the polarity of the outermost layer of the titanium nitride-containing particles is more stabilized. Thus, it is considered that when the titanium nitride-containing particles are dispersed, the adsorbability of the dispersant to the titanium nitride-containing particles is improved, the fine dispersion of the titanium nitride-containing particles is reduced, and the generation of particles is suppressed.

The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as the above-described Fe atoms.

The method of incorporating Si atoms into the titanium nitride-containing particles is not particularly limited and, for example, a method of introducing Si atoms in the step of obtaining titanium particles (titanium powder) used as a raw material of the titanium nitride- And the like. More specifically, in the production of titanium by the crawling method or the like, a material comprising a Si atom as a reaction vessel may be used, or a material containing Si atoms may be used as a material for the press and grinder when crushing titanium , It is possible to attach Si atoms to the surface of the titanium particles.

In the case of using the thermal plasma method in the production of the titanium nitride-containing particles, Si particles, Si oxide and the like are added in addition to the titanium particles as the raw material, and these are nitrided by the thermal plasma method, .

The Si atoms contained in the titanium nitride-containing particles may be in any form such as an ion, a metal compound (including a complex compound), an intermetallic compound, an alloy, an oxide, a composite oxide, a nitride, an oxynitride, a sulfide, do. The Si atoms contained in the titanium nitride-containing particles may be present as an impurity at a crystal lattice position or may exist as an impurity in an amorphous state at grain boundaries.

The content of the titanium atom (Ti atom) in the titanium nitride-containing particles is preferably 10 to 85 mass%, more preferably 15 to 75 mass%, and more preferably 20 to 70 mass%, based on the total mass of the titanium nitride- % Is more preferable. The content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectroscopy.

The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60 mass%, more preferably 5 to 50 mass%, and more preferably 10 to 40 mass%, based on the total mass of the titanium nitride- % Is more preferable. The content of nitrogen atoms can be analyzed by inert gas fusion-thermal conductivity method.

The titanium nitride-containing particles include titanium nitride (TiN) as a main component, and are usually remarkable when oxygen is mixed in the synthesis and when the particle diameter is small. However, by oxidizing the surface of the particles, .

The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40 mass%, more preferably 1 to 35 mass%, and more preferably 5 to 30 mass%, based on the total mass of the titanium nitride- desirable. The content of oxygen atoms can be analyzed by an inert gas melting-infrared absorption method.

From the viewpoint of dispersion stability, and light shielding property, it is the specific surface area of the titanium nitride-containing particles is more preferably 5m ² / g more than 100m ² / g or less is preferred, and 10m ² / g more than 60m ² / g or less. The specific surface area can be determined by the BET (Brunauer, Emmett, Teller) method.

The titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.

The composite fine particles refer to particles in which titanium nitride particles and metal fine particles are combined or highly dispersed. Here, " composite " means that particles are constituted by both titanium nitride and metal components, and " highly dispersed state " means that titanium nitride particles and metal particles are individually present, It means that the particles of a small amount of component are dispersed uniformly and uniformly without aggregation.

The metal fine particles are not particularly limited and examples thereof include metals such as copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, Calcium, titanium, bismuth, antimony and lead, and alloys thereof. Among them, at least one selected from among copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium and alloys thereof is preferable and copper, silver, gold, platinum and tin, And more preferably at least one kind selected from alloys. From the standpoint of better moisture resistance, silver is preferable.

The content of the metal fine particles in the titanium nitride-containing particles is preferably 5 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 30 mass% or less, with respect to the total mass of the titanium nitride-containing particles.

Peak diffraction angle 2 &amp;thetas; of titanium nitride-

It is preferable that the titanium nitride-containing particles have a diffraction angle 2 &amp;thetas; of a peak derived from the (200) plane when the CuK alpha ray is an X-ray source, from 42.6 DEG to 43.5 DEG. A cured film (for example, a black matrix or the like) obtained by using the curable composition containing the titanium nitride-containing particles having such characteristics can achieve a high OD value.

When the X-ray diffraction spectrum of the titanium compound was measured using the CuK? Line as an X-ray source, the peak having the strongest intensity was found to have a peak derived from the (200) plane in the vicinity of 2? = 42.5 占 TiO2 in the Peak is observed in the vicinity of 2? = 43.4 占. On the other hand, the peaks derived from the (200) plane of the anatase type TiO ₂ are in the vicinity of 2? = 48.1 ° and the peaks derived from the (200) plane of the rutile TiO ₂ are in the vicinity of 2? = 39.2 ° Lt; / RTI &gt; Accordingly, the peak position shifts toward the high angle side with respect to 42.5 DEG in the crystalline state containing a large amount of oxygen atoms.

The diffraction angle 2? Of the peak originating from the (200) plane of the titanium nitride-containing particles is preferably from 42.6 DEG to less than 43.5 DEG from the viewpoint of the stability with time of the particles, and furthermore, from the viewpoint of excellent process margin at the time of production, More preferably 42.7 DEG to less than 43.5 DEG, and further preferably 42.7 DEG to less than 43.4 DEG from the viewpoint of excellent reproducibility of particle performance. The case of containing the titanium dioxide TiO ₂ as an auxiliary component, the strength is a strong peak in the vicinity of the peak of 2θ = 25.3 ° derived from anatase-type TiO ₂ (101), a peak derived from the rutile type TiO ₂ (110) 2θ = 27.4 °. However, since TiO ₂ is white and is a factor for lowering the light shielding property of the black matrix, it is preferable that TiO ₂ is reduced to such an extent that it can not be observed as a peak.

The crystallite size constituting the titanium nitride-containing particles can be obtained from the half width of the X-ray diffraction peak, and is calculated using the Scherr's equation.

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. By forming the black matrix using the titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film has a peak wavelength of 475 nm or less and exhibits a bluish purple color, and a black matrix having high light shielding and ultraviolet sensitivity can be obtained. When the crystallite size is 20 nm or more, the ratio of the surface of the active particles to the volume of the particles becomes small, so that the titanium nitride-containing particles have excellent heat resistance and / or durability.

(Metal nitride-containing particles containing atom A)

As the inorganic pigment, metal nitride-containing particles containing a predetermined atom A in the metal nitride-containing particles may be used as the metal nitride-containing particles.

Examples of the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W and Re. The curable composition , Nb, or V is more preferable.

Examples of the atom A include B, Al, Si, Mn, Fe, Ni, and Ag.

When the metal-nitride-containing particles contain the atom A, the content thereof is not particularly limited, but the content of the atom A in the metal-nitride-containing particles is preferably 0.00005 to 10 mass%.

The method for producing the metal nitride-containing particles containing the atom A is not particularly limited and a known method can be used.

In the production of the metal nitride-containing particles, a gas phase reaction method is usually used, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these methods, the thermal plasma method is preferable because of the low content of impurities, easy preparation of the particle diameter, high productivity, and the like.

As a specific method for producing the metal nitride-containing particles by the thermal plasma method, for example, a method using a metal fine particle production apparatus (the same apparatus as the "black composite fine particle production apparatus" described later) can be mentioned. The apparatus for producing fine metal particles includes, for example, a plasma torch for generating a thermal plasma, a material supply device for supplying the metal raw material powder into the plasma torch, a chamber containing a cooling function, a cyclone for classifying the produced metal fine particles, And a recovery unit for recovery.

In the present specification, the metal fine particles are intended to mean particles having a primary particle size of 20 nm to 40 μm containing a metal element.

The method for producing the metal nitride-containing particles using the metal fine particle production apparatus is not particularly limited and a known method can be used. Among them, the method for producing the metal nitride-containing particles by using the metal fine particle production apparatus preferably includes the following steps in that the yield of the metal nitride-containing particles having a predetermined average primary particle diameter is increased.

Process A: A process of generating a thermal plasma salt by supplying an inert gas containing no nitrogen gas as a plasma gas into a plasma torch.

Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma salt in a plasma torch and evaporating the metal raw material powder to obtain a raw material metal in a gaseous phase.

Step C: A step of cooling the gaseous raw material metal to obtain metal fine particles containing a transition metal.

Step D: A process of generating a thermal plasma salt by supplying an inert gas containing nitrogen gas as a plasma gas into the plasma torch.

Step E: A step of supplying fine metal particles containing a transition metal to a thermal plasma salt in a plasma torch and evaporating the fine metal particles to obtain a raw material metal in a gaseous phase.

Step F: A step of cooling the raw material metal in the vapor phase to obtain metal nitride-containing particles.

The method for producing the metal nitride-containing particles may contain the following step G according to the purpose after the step C and / or the step F described above.

Step G: Classifying the obtained particles.

Between Step A and Step B, before Step A, between Step C and Step D, or between Step D and Step E, the following Step A2 may be further contained.

Step A2: A step of mixing atom A with a metal raw material powder containing a transition metal.

Before the step A2, the following steps A3-1 to A3-3 may further be contained.

Step A3-1: A process for generating a thermal plasma salt by supplying an inert gas not containing nitrogen gas as a plasma gas into the plasma torch.

Step A3-2: A step of supplying a raw material powder containing an atom A to a thermal plasma salt in a plasma torch and evaporating the raw material powder to obtain a gaseous atom A;

Step A3-3: A step of cooling the gaseous atom A to obtain atomized atom A;

Step G3 may further be added after step A3-3.

Further, in the present specification, the atomized atom A is intended to mean particles having a primary particle diameter of 20 nm to 40 μm containing an atom A.

It is preferable that the method for producing the metal nitride-containing particles further contains the following step H after step F (when step G includes the step G, after step G after step F).

Step H: A step of nitriding the metal nitride-containing particles obtained in step F (or step G) by exposing them to a mixed atmosphere of water vapor and nitrogen gas.

Further, depending on the purpose, the method for producing the metal nitride-containing particles may further contain Step G after Step H. Hereinafter, a preferable mode of each process will be described in detail.

· Process A

Process A is a process of generating a thermal plasma salt by supplying an inert gas containing no nitrogen gas as a plasma gas into a plasma torch. The method of generating the thermal plasma salt is not particularly limited, and examples thereof include a direct current arc discharge method, a polyphase arc discharge method, a high frequency plasma method and a hybrid plasma method, and a high frequency plasma method in which impurities are rarely mixed from the electrode is preferable .

The method of generating the thermal plasma salt by the high-frequency plasma method is not particularly limited. For example, a plasma gas is supplied into a plasma torch containing a high-frequency oscillation coil and a quartz tube, and a high-frequency current is applied to the high- A method of obtaining a thermal plasma salt can be mentioned.

As the plasma gas in the process A, an inert gas containing no nitrogen gas may be mentioned. Examples of the inert gas that does not contain nitrogen gas include argon gas, hydrogen gas, and the like. The inert gas containing no nitrogen gas may be used singly or in combination of two or more species.

Process A2

Step A2 is a step of mixing atom A with a metal raw material powder containing a transition metal. The mixing method of the raw metal powder and the atom A is not particularly limited and a known method can be used. For example, the material supply device for supplying the metal raw material powder into the plasma torch may contain a mixing and dispersing function. Specifically, it is possible to use the material feeding device described in paragraphs 0047 to 0058 of International Publication No. 2010/147098, the contents of which are incorporated herein by reference. The method for producing a metal nitride-containing particle may further contain the following steps A3-1 to A3-3 before step A2.

· Process B

Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma salt in a plasma torch and evaporating the metal raw material powder to obtain a gaseous raw metal. The method of supplying the metal raw material powder to the thermal plasma salt in the plasma torch is not particularly limited, but it is preferable to spray using the carrier gas since the obtained gaseous starting material metal becomes more uniform. As the carrier gas, it is preferable to use an inert gas that does not contain nitrogen gas. The aspect of the inert gas not containing the nitrogen gas is as described above.

In the case where the method for producing the metal nitride-containing particles contains the step A2, it is preferable that the metal raw material powder is maintained in a uniformly dispersed state until the supply of the metal raw material powder into the plasma torch is reached.

Process C

Step C is a step of cooling the raw material metal in the gaseous phase to obtain metal fine particles containing a transition metal. The cooling method is not particularly limited, but it is preferable to use a chamber containing a cooling function. By introducing the gaseous raw metal obtained in the step B into the chamber containing the cooling function and rapidly quenching in the chamber, metal fine particles having the following desired particle diameters can be produced. The produced fine metal particles are recovered, for example, by a recovery section. As the atmosphere in the chamber, an inert gas containing no nitrogen gas is preferable. The aspect of the inert gas not containing the nitrogen gas is as described above.

Further, by passing through the above steps A to C, metal fine particles containing a transition metal can be obtained. The fine metal particles containing a transition metal are liable to evaporate in the step E. Even when the metal raw material powder contains impurities, the impurities can be removed by going through steps A to C above.

· Process D

Step D is a step of generating a thermal plasma salt by supplying an inert gas containing nitrogen gas as a plasma gas into the plasma torch. Examples of the nitrogen-containing inert gas include a nitrogen gas and a nitrogen gas containing an inert gas. Examples of the inert gas include argon gas and hydrogen gas. The nitrogen gas containing the inert gas is not particularly limited, but the nitrogen gas content is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. The other aspect is the same as the step A.

Process E

Step E is a step of supplying metal fine particles containing a transition metal to a thermal plasma salt in a plasma torch and evaporating the metal fine particles to obtain a gaseous starting metal. The method of supplying the metal fine particles to the thermal plasma salt in the plasma torch is the same as described above, but as the carrier gas, an inert gas containing nitrogen is preferable. The aspect of the inert gas containing nitrogen is as described above.

In the step E, since the raw metal which has become the metal fine particles by the steps A to C is supplied to the thermal plasma salt, the raw metal of the vapor phase tends to be obtained, and the state of the raw metal of the vapor phase tends to become more uniform.

· Process F

Step F is a step of cooling the raw material metal in the gaseous phase to obtain metal nitride-containing particles containing nitride of a transition metal. The preferred mode of cooling is as described above, but an inert gas containing nitrogen gas is preferable as the atmosphere in the chamber. The preferred embodiment of the inert gas containing nitrogen gas is as described above.

· Process G

Step G is a step of classifying the obtained fine metal particles and / or metal nitride-containing particles. The classification method is not particularly limited, but cyclone can be used, for example. The cyclone has a conical container, and has a function of generating a swirling flow in the container and classifying the particles using centrifugal force. Classification is preferably carried out in an atmosphere of an inert gas. The aspect of the inert gas is as described above.

· Process H

Step H is a step of nitriding the metal nitride-containing particles by exposing them to a mixed atmosphere of water vapor and nitrogen gas. By carrying out this step, the content of the metal nitride in the metal nitride-containing particles can be further increased. The method of exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas is not particularly limited. For example, metal nitride-containing particles may be introduced into a constant temperature chamber filled with a gas mixture of water vapor and nitrogen gas, Or stirring. More preferably, the surface of the metal nitride-containing particles and the crystal boundary are more stabilized.

The mixing ratio of water vapor and nitrogen gas is preferably such that the relative humidity is 25 to 95% in the atmosphere. The stirring or stirring time is preferably 0.5 to 72 hours, and the temperature is preferably 10 to 40 占 폚.

Processes A3-1 to A3-3

The steps A3-1 to A3-3 are the steps (A3-1) of supplying an inert gas containing no nitrogen gas into the plasma torch as a plasma gas to generate a thermal plasma salt, (A3-2) of supplying a raw material powder containing A and evaporating the raw powder to obtain gaseous atom A, and a step (A3-2) of cooling the gaseous atom A to obtain fine particles of atom A -3). In each of the steps, the step A and the step B (using the raw material powder containing the atom A instead of the metal raw material powder containing the transition metal) and the step C (substituting the metal fine particles containing the transition metal , The atomized atom A is obtained).

By the above process, the atom A is made into fine particles, and the atom A is easily evaporated in the step E. In addition, impurities (metal components other than the atom A) contained in the raw material powder containing the atom A can be removed by passing through the above-described steps.

A preferred mode of production of metal nitride-containing particles containing atom A

As a preferred embodiment of the method for producing the metal nitride-containing particles containing the atom A, the following processes can be mentioned in order.

Process A: A process of generating a thermal plasma salt by supplying an inert gas containing no nitrogen gas as a plasma gas into a plasma torch.

Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma salt in a plasma torch and evaporating the metal raw material powder to obtain a raw material metal in a gaseous phase.

Step C: A step of cooling the raw material metal in the gaseous phase to obtain metal fine particles containing a transition metal.

Step G: A step of classifying the obtained particles.

Step A3-1: A process of generating a thermal plasma salt by supplying an inert gas containing no nitrogen gas as a plasma gas into the plasma torch

Step A3-2: A step of supplying a raw material powder containing an atom A to a thermal plasma salt in a plasma torch and evaporating the raw material powder to obtain a gaseous atom A

Step A3-3: a step of cooling the gaseous atom A to obtain atomized atom A

Step G: A step of classifying the obtained particles.

Step A2: A step of mixing atom A (in this case, atomized atom A) into a metal raw material powder containing a transition metal (metal fine particles in this case).

Step D: A process of generating a thermal plasma salt by supplying an inert gas containing nitrogen gas as a plasma gas into the plasma torch.

Step E: A step of supplying fine metal particles containing a transition metal to a thermal plasma salt in a plasma torch and evaporating the fine metal particles to obtain a raw material metal in a gaseous phase.

Step F: A step of cooling the raw material metal of the vapor phase to obtain metal nitride-containing particles.

Step G: A step of classifying the obtained particles.

Step H: A step of nitriding the metal nitride-containing particles obtained in step G by exposing them to a mixed atmosphere of water vapor and nitrogen gas.

In the series of steps, steps A to C and steps A3-1 to A3-3 may be changed. That is, after the steps A3-1 to A3-3, the steps A to C may be performed.

According to the preferred embodiment of the method for producing a metal nitride-containing particle containing the atom A, the metal nitride powder and the metal-nitride-containing particles having impurities contained in the raw material particles can be removed and a desired average primary particle diameter can be obtained Can be manufactured. The reason is that the transition metal, atom A, and / or atom A are ionized by the plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurity are considered to be microparticles reflecting their respective melting points. At this time, atoms having a low melting point are quick to be granulated, and atoms having a high melting point are delayed in grain formation. As described above, it is assumed that the fine particles once subjected to the plasma treatment (the steps B and C and the steps A3-2 and A3-3) tend to become a single component (single crystal). By classifying the single-component particles thus obtained, the impurity particles can be removed by the difference in the density and / or the particle diameter of the particles of the transition metal and / or the particles of the atom A and the impurity particles. The classification can be performed by suitably setting the classification conditions using, for example, a cyclone.

· Purification of metal raw material powder and raw material powder

As a raw material powder containing a transition metal-containing metal raw material powder (hereinafter simply referred to as "metal raw material powder") and an atom A (hereinafter simply referred to as "raw material powder") usable in the step B, Although not limited, high purity is preferable. The content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more, more preferably 99.999% or more. The content of atom A in the raw material powder is also the same.

The metal raw material powder and / or the raw material powder sometimes contain atoms other than the desired transition metal and / or atom A as impurities. Examples of the impurities contained in the metal raw material powder include boron, aluminum, silicon, manganese, iron, nickel and silver. Examples of the impurities contained in the raw material powder include metal elements and the like.

The method for producing a metal nitride-containing particle may further contain the following step A0 in the step B before the step B (when the step A2 contains the step A2, before step A2).

Step A0: A step of removing impurities from the metal raw material powder and / or the raw material powder.

Process A0

The method (separation and purification method) for removing impurities from the metal raw material powder and / or the raw material powder in the step A0 is not particularly limited, but for example, in Japanese Patent Application Laid-Open Publication No. 2012-211048, paragraphs 0013 to 0030 The method described above can be used, and other metal raw material powders and / or raw material powders can be used.

Cladding of metal nitride-containing particles

The metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be a coated metal nitride-containing particle having a metal nitride-containing particle and a coating layer formed by using an inorganic compound which covers the metal nitride-containing particle. The curable composition containing metal nitride-containing particles coated with an inorganic compound has better dispersion stability.

The inorganic compound is not particularly limited, and oxides such as SiO ₂ , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ and P ₂ O ₅ , and hydroxides such as aluminum hydroxide and zirconium hydroxide . Of these, aluminum hydroxide is preferable in that it is easy to form a thinner film and to easily form a film with a higher coating ratio.

When it is intended to control the refractive index of the metal nitride-containing particles, silicon oxide is preferable as the low refractive index coating film and zirconium hydroxide is preferable as the high refractive index coating film.

The method for coating the metal nitride-containing particles with the inorganic compound is not particularly limited, but it is preferable that the method for producing the metal nitride-containing particles includes the following inorganic compound coating process.

· Inorganic compound coating process

The inorganic compound coating step is a step of coating the metal nitride-containing particles with oxides and / or hydroxides. The coating method is not particularly limited, and for example, the following wet coating method and the like can be mentioned.

As the first wet coating method, first, the above-described metal nitride-containing particles are mixed with water to prepare a slurry. Next, a water-soluble compound (for example, sodium silicate) containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y and P is caused to react with the slurry to remove excess alkali ions Decantation and / or ion exchange resin. Thereafter, the slurry is dried to obtain oxide-coated metal nitride-containing particles.

As the second wet coating method, first, the above-mentioned metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry. Next, an organometallic compound such as an alkoxide containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y and P is produced in the slurry, and the slurry is calcined at a high temperature. When the slurry is calcined at a high temperature, the sol-gel reaction proceeds to obtain a metal nitride-containing particle coated with an oxide.

As the third wet coating method, a slurry containing an ionic liquid is prepared by using urea and aluminum chloride in the presence of metal nitride-containing particles. The metal nitride-containing particles are taken out from the slurry and dried, and then the metal nitride-containing particles are fired to obtain metal nitride-containing particles coated with hydroxides containing aluminum hydroxide.

(Organic pigment)

Examples of the organic pigments include color index (CI) pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31 , 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, , 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126 , 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.;

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 73;

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 175, 176, 177, 178, 179, 170, 176, 168, 169, 170, 171, 172, 175, 176, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272,

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc.;

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc.; And

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79,

. The pigments may be used singly or in combination of two or more kinds.

<Dye>

As the dyes, for example, Japanese Unexamined Patent Application Publication No. 64-090403, Japanese Unexamined Patent Publication No. 64-091102, Japanese Unexamined Patent Publication No. 1-094301, Japanese Unexamined Patent Publication No. 6-011614, Japanese Patent No. 2592207 , U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 5,05950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, A dye disclosed in JP-A-6-194828 can be used. The chemical structures of the compounds include pyrazole compounds, pyromethene compounds, anilino compounds, triphenylmethane compounds, anthraquinone compounds, benzilidene compounds, oxolin compounds, pyrazolotriazoazo compounds, pyridone azo compounds, A cyanine compound, a phenothiazine compound, a pyrrolopyrazolequamethane compound, and the like can be used. As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097. Polymerizable dyes having polymerizability in the molecule may also be used. Examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.

<Infrared absorbent>

The colorant may further contain an infrared absorbing agent.

The infrared absorbing agent means a compound having absorption in a wavelength region of an infrared region (preferably a wavelength of 650 to 1,300 nm). Preferably, the infrared absorbing agent is a compound having a maximum absorption wavelength in a wavelength range of 675 to 900 nm.

Examples of the colorant having such spectroscopic characteristics include a pyrrolopyrrole compound, a copper compound, a cyanide compound, a phthalocyanine compound, an iminium compound, a thiol complex compound, a transition metal oxide compound, a squarylium compound , Naphthalocyanine compounds, quaternary compounds, dithiol metal complex compounds, and croconium compounds.

The phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanide compound, the squarylium compound and the croconium compound may use the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750, The contents of which are incorporated herein by reference. Cyanine compounds can be referred to, for example, as " functional coloring matter, Makawa Ogawa / Masaru Matsuoka / Gitao Daiziro / Hirashimatsuaki Aichi, Kodansha Scientific ", which contents are incorporated herein by reference.

As the colorant having the spectroscopic characteristics, compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Laid-Open No. 2002-146254, Near-infrared absorbing particles composed of a crystallite of an oxide including Cu and / or P and having a number-average agglomerated particle size of 5 to 200 nm as disclosed in paragraphs [0034] to [0067]

As the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm, at least one compound selected from the group consisting of a cyanide compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound Paper is preferable.

The infrared absorbing agent is preferably a compound dissolving at least 1% by mass in water at 25 ° C, more preferably a compound dissolving at least 10% by mass in water at 25 ° C. By using such a compound, solvent resistance is improved.

The pyrrolopyrrole compound can be referred to Japanese Patent Application Laid-Open No. 2010-222557, paragraphs 0049 to 0062, the content of which is incorporated herein by reference. Cyanide compounds and squarylium compounds are disclosed in International Publication No. WO 01/088063, paragraphs 0022 to 0063, International Publication No. WO 201/030628, paragraphs 0053 to 0118, Japanese Patent Laid-Open Publication No. 2014-059550, paragraphs 0028 to 0074, Paragraphs 0013 to 0091 of International Publication No. 2012/169447, paragraphs 0019 to 0033 of Japanese Patent Laid-Open Publication No. 2015-176046, paragraphs 0053 to 0099 of Japanese Laid-Open Patent Publication No. 2014-063144, paragraphs of Japanese Laid-Open Patent Publication No. 2014-052431 No. 0085 to 0150, paragraphs Nos. 0076 to 0124 of JP-A No. 2014-044301, paragraphs No. 0045 to 0078 of JP-A No. 2012-008532, paragraphs No. 0027 to 0067 of JP-A No. 2015-172102, Paragraph Nos. 0029 to 0067 of Publication No. 2015-172004, Paragraph Nos. 0029 to 0085 of Japanese Patent Laid-Open Publication No. 2015-040895, Paragraph Nos. 0022 to 0036 of Japanese Laid-Open Patent Publication No. 2014-126642, Paragraph No. of Japanese Laid-Open Patent Publication No. 2014-148567 ~ 0 017, paragraphs 0010 to 0025 of JP-A-2015-157893, paragraphs 0013 to 0026 of JP-A-2014-095007, paragraphs 0013 to 0047 of JP-A-2014-080487, -227403, and the contents of which are incorporated herein by reference.

The infrared absorbing agent is preferably at least one member selected from the group consisting of compounds represented by the following general formulas (1) to (3).

1

[Chemical Formula 1]

In the general formula (1), A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the following general formula 1-A.

In general formula 1-A

(2)

In the general formula 1-A, Z ^1A represents a nonmetal atomic group forming a nitrogen-containing heterocycle, R ^2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, .

Formula 2

(3)

In the general formula (2), R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group,

R ² to R ⁵ each independently represents a hydrogen atom or a substituent, R ² and R ³ , and R ⁴ and R ⁵ may be bonded to each other to form a ring,

R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^A R ^B or a metal atom, R ^A and R ^B each independently represent a hydrogen atom or a substituent,

R ⁶ may be covalently bonded or coordinated to R ^1a or R ³ ,

R ⁷ may be covalently bonded or coordinated to R ^1b or R ⁵ .

Formula 3

[Chemical Formula 4]

In the general formula (3), Z ¹ and Z ² are each a non-metallic atomic group which forms a 5-membered or 6-membered nitrogen-containing heterocycle which may be independently and independently bonded,

R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group,

L ¹ represents meta-printing consisting of an odd number of meta in,

a and b are each independently 0 or 1,

When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded in a single bond,

When the moiety represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a necessary number for taking charge balance, and when the moiety represented by Cy in the formula is an anion moiety, X ¹ represents a cation and c Represents the number required to balance the charge, and when the charge of the site represented by Cy in the formula is neutralized in the molecule, c is zero.

<Pigment Derivative>

The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group or a phthalimide methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable from the viewpoints of the dispersibility and the dispersion stability of the colorant A. It is particularly preferable that the pigment derivative has a basic group. The combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Examples of the organic pigments for constituting the pigment derivative include pigments such as diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perynone pigments, , Thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, metal complex pigments, and the like.

The acidic group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group or a salt thereof, more preferably a carboxylic acid group or a sulfonic acid group, and more preferably a sulfonic acid group. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable.

When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 30 mass%, more preferably from 3 to 20 mass%, based on the mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

[Photopolymerization initiator]

The photopolymerization initiator is not particularly limited as long as polymerization of the polymerizable compound can be initiated, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, it is preferable that the photopolymerization initiator has photosensitivity to the visible light ray region from the ultraviolet ray region. It may also be an activator which generates active radicals by generating some action with a photoexcited sensitizer, or an initiator which initiates cationic polymerization depending on the type of the polymerizable compound.

The photopolymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 in a wavelength region of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 1% by mass or more, relative to the total solid content of the curable composition, By mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 10% by mass or less.

When the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass based on the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.

The photopolymerization initiator may be used alone or in combination of two or more. When two or more photopolymerization initiators are used in combination, the total amount is preferably within the above range.

Examples of the photopolymerization initiator include acylphosphine compounds such as halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton and an oxadiazole skeleton), acylphosphine oxides and the like, Oxime compounds such as arylimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

Examples of the halogenated hydrocarbon compound containing the triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Compounds described in GB-A-5313428, compounds described in German Patent Publication No. 3337024, compounds described in J. Org., &Lt; RTI ID = 0.0 &gt; . Chem .; 29, 1527 (1964), compounds described in JP-A-62-058241, compounds described in JP-A-5-281728, compounds described in JP-A-5-034920, Compounds described in Japanese Patent Publication No. 4212976, and the like.

From the viewpoint of exposure sensitivity, it is preferable to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, , Triallyl imidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound and 3- Aryl-substituted coumarin compounds are preferable.

Among them, a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound or an acetophenone compound More preferred are at least one compound selected from the group consisting of a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

Particularly, when the curable composition is used in the production of a light-shielding film, it is necessary to form a fine pattern in a sharp shape, and therefore it is important that the curable composition is developed without residue on the unexposed portion with curing property. From this viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. Particularly, in the case of forming a fine pattern, although stepper exposure is used for curing exposure, this exposure apparatus may be damaged by halogen, and it is also necessary to suppress the addition amount of the photopolymerization initiator to a low level. Taking this into consideration, it is particularly preferable to use an oxime compound as the photopolymerization initiator when forming a fine pattern.

As specific examples of the photopolymerization initiator, reference can be made, for example, to paragraphs 0265 to 0268 of Japanese Laid-Open Patent Publication No. 2013-029760, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969 and the acylphosphine-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used.

As the aminoacetophenone compound, commercial products IRGACURE-907, IRGACURE-369, IRGACURE-379EG (trade names, all manufactured by BASF) can be used. As the aminoacetophenone compound, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm can be used.

As the acylphosphine compound, commercially available IRGACURE-819 or DAROCUR-TPO (trade name, all manufactured by BASF) can be used.

<Oxime compound>

The photopolymerization initiator is more preferably an oxime compound (oxime-based initiator). In particular, an oxime compound is preferable because it has high sensitivity and high polymerization efficiency, can cure the curable composition layer regardless of the concentration of the colorant, and can easily design the concentration of the colorant.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-80068, and compounds disclosed in Japanese Laid-Open Patent Publication No. 2006-342166.

Examples of the oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan- And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

J. C. S. Perkin II (1979) pp. Pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. The compounds described in the respective publications of JP-A-202-232, JP-A 2000-066385, JP-A 2000-080068, JP-A 2004-534797 and JP-A 2006-342166 .

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) are also suitably used as commercially available products. ADEKA ACKNES NCI-831 and ADEKA ACKLS NCI-930 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) , Or N-1919 (a photoinitiator containing a carbazole oxime ester skeleton (manufactured by ADEKA)).

As the oxime compounds other than the above-mentioned materials, the compounds described in JP-A-2009-519904 in which oxime is linked to carbazole N; Compounds described in U.S. Patent No. 7626957 to which a hetero substituent is introduced at a benzophenone moiety; The compounds described in JP-A-2010-015025 and U.S. Patent Publication No. 2009-292039 wherein a nitro group is introduced at a pigment site; Ketoxime compounds described in International Patent Publication No. 2009-131189; A compound described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; A compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and a good sensitivity to a g-ray light source; Or the like may be used.

Preferably, for example, reference can be made to paragraphs 0274 to 0275 of JP-A-2013-029760, the contents of which are incorporated herein by reference.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N-O bond of the oxime compound may be an oxime compound of the (E) form or an oxime compound of the (Z) form, or a mixture of the form (E) form and the form (Z) form.

[Chemical Formula 5]

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of the monovalent nonmetal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The above-mentioned substituent may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, there may be mentioned the above substituents.

In the formula (OX-1), as the divalent organic group represented by A, an alkylene group, a cycloalkylene group or an alkane-ylene group having 1 to 12 carbon atoms is preferable. These groups may have one or more substituents. As the substituent, there may be mentioned the above substituents.

As the photopolymerization initiator, an oxime compound containing a fluorine atom may be used. Specific examples of the oxime compound containing a fluorine atom include the compounds described in JP-A-2010-262028; Compounds 24, 36 to 40 described in Japanese Patent Publication No. 2014-500852; The compound (C-3) described in JP-A-2013-164471; And the like. The contents of which are incorporated herein by reference.

As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) may be used.

[Chemical Formula 6]

(7)

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms If an aryl group, R ¹ and R ² is a phenyl group, by combining a phenyl group with each other and to form an fluorene, R ³ and R ⁴ are, each independently, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, having a carbon number of 6 An aryl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

In the formula (2), R ^1, R ^2, R ³ and R ^4, and R ^1, R ^2, R ³ and R ⁴ with the consent of the formula (1), R ⁵ is -R ^{6, -OR 6, -SR 6, -COR 6} , -CONR 6 R 6, -NR 6 COR 6, -OCOR 6, -COOR 6, -SCOR 6, -OCSR 6, -COSR 6, -CSOR 6, -CN , A halogen atom or a hydroxyl group, and R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, Or a carbonyl group, and a represents an integer of 0 to 4.

In formula (3), R ¹ represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ³ And R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, Carbonyl group.

In the formula ^{(4), R 1, R} 3 and R ^4, and R ^1, R ³ and R ⁴ with the consent of the formula (3), R ⁵ is -R ^6, -OR ^6, -SR ^{6, -COR 6, -CONR 6 R} 6, -NR 6 COR 6, -OCOR 6, -COOR 6, -SCOR 6, -OCSR 6, -COSR 6, -CSOR 6, -CN, a halogen atom or a hydroxyl group , R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X is a direct bond or a carbonyl group, a represents an integer of 0 to 4;

In the formulas (1) and (2), R ¹ and R ² are each independently preferably a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.

In the formulas (3) and (4), R ¹ is preferably independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.

Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. The contents of which are incorporated herein by reference.

Specific examples of the oxime compounds preferably used in the curable composition are shown below.

[Chemical Formula 8]

The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and more preferably a high absorbance at 365 nm and 405 nm.

The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and still more preferably 5,000 to 200,000 from the viewpoint of sensitivity.

The molar extinction coefficient of the compound can be measured by a known method. For example, it is preferable that the molar extinction coefficient of the compound is measured with an ultraviolet visible spectrophotometer (Cary-5 spactrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L .

The photopolymerization initiator may be used in combination of two or more as necessary.

[Polymerizable compound]

The curable composition contains a polymerizable compound.

The content of the polymerizable compound is preferably 0.1 to 40% by mass relative to the total solid content of the curable composition. The lower limit is, for example, more preferably 1.0% by mass or more, still more preferably 3.5% by mass or more, and particularly preferably 3.5% by mass or more. The upper limit is more preferably 30 mass% or less, more preferably 20 mass% or less, particularly preferably 20 mass% or less.

When the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass based on the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.

The polymerizable compound may be used alone or in combination of two or more. When two or more kinds of polymerizable compounds are used in combination, the total amount is preferably within the above range.

The polymerizable compound is preferably a compound containing at least one group containing an ethylenically unsaturated bond, more preferably a compound containing two or more, more preferably at least three, and at least five Particularly preferred. The upper limit is, for example, 15 or less. Examples of the group containing an ethylenic unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The polymerizable compound may be, for example, a monomer, a prepolymer, an oligomer, a mixture thereof, or a chemical form such as a multimer thereof, and is preferably a monomer.

The molecular weight of the polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500.

The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functional groups, and more preferably a (meth) acrylate compound having 3 to 6 functional groups.

Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, amides and their oligomers , Preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and oligomers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide containing a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxy group, and an unsaturated carboxylic acid ester or an unsaturated carboxylic acid ester A dehydration condensation reaction product of an amide and a monofunctional or polyfunctional carboxylic acid is suitably used. In addition, an unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as an isocyanate group or an epoxy group may be reacted with a monofunctional or polyfunctional alcohol, amine or thiol reactant, a halogen group or a tosyloxy group Unsaturated carboxylic acid esters or amides containing a clearing substituent such as an acid or a functional group, and a reaction product of monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. It is also possible to use a group of compounds substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like in place of the above unsaturated carboxylic acid.

As specific compounds of these, the compounds described in paragraphs 0095 to 0108 of JP-A No. 2009-288705 can be suitably used in the present invention.

The polymerizable compound is also preferably a compound containing at least one group containing an ethylenic unsaturated bond and having a boiling point of 100 캜 or more at normal pressure. For example, reference can be made to the compounds described in paragraphs 0227 to 027 of Japanese Patent Application Laid-Open No. 2013-029760 and Japanese Patent Application Laid-Open No. 2008-292970, the contents of which are incorporated herein by reference.

Examples of the polymerizable compound include dipentaerythritol triacrylate (trade name: KAYARAD D-330, manufactured by Nippon Kayaku), dipentaerythritol tetraacrylate (commercial product: KAYARAD D-320, manufactured by Nippon Kayaku), dipentaerythritol Acrylate (KAYARAD DPHA; A-DPH-12E manufactured by Nippon Kayaku Co., Ltd., Shin Nakamura Co., Ltd.) as a commercially available product (trade name: KAYARAD D-310 manufactured by Nippon Kayaku Co., (For example, SR454 and SR499 commercially available from Satomaru Co., Ltd.) in which the (meth) acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue Do. These oligomer types can also be used. NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Kagaku Co., Ltd.) and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) may also be used.

Preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound containing an acid group, an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid are preferable, and a polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride More preferably, in the ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Doagosei Co.,

The acid value of the polymerizable compound containing an acid group is preferably from 0.1 to 40 mgKOH / g, and more preferably from 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, in the above range, the photopolymerization performance is good and the curability is excellent.

As the polymerizable compound, a compound containing a caprolactone structure is also a preferred embodiment.

The compound containing the caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as pentaerythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylol melamine with And polyfunctional (meth) acrylates. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.

[Chemical Formula 9]

In the formula (Z-1), all six R's are groups represented by the following formula (Z-2), or one to five of the six R's are groups represented by the following formula (Z-2) Is a group represented by the formula (Z-3).

[Chemical formula 10]

In the formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bond.

(11)

In the formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and * represents a bond.

The polymerizable compound containing a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku. DPCA-20 (in the formulas (Z-1) to (Z-3) (Wherein R ¹ is a hydrogen atom), DPCA-30 (in the same formula, m is 1, the number of groups represented by the formula (Z-2) is 3, and R ¹ is DPCA-120 (a compound in which m is 1, the number of groups represented by formula (Z-2) is 6 and R ¹ are all hydrogen atoms), DPCA-120 M is 2, the number of groups represented by the formula (Z-2) is 6, and R ¹ is a hydrogen atom).

The polymerizable compound may be a compound represented by the following formula (Z-4) or (Z-5).

[Chemical Formula 12]

E in the formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) _y CH ₂ O) - or ((CH ₂ ) _y CH (CH ₃ ) , Y represents independently an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.

The total number of (meth) acryloyl groups in the formula (Z-4) is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40.

The total number of (meth) acryloyl groups in the formula (Z-5) is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.

In the formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.

- ((CH ₂ ) _y CH ₂ O) - or ((CH ₂ ) _y CH (CH ₃ ) O) - in the formula (Z-4) or the formula (Z- Is preferable.

The compounds represented by the formula (Z-4) or (Z-5) may be used singly or in combination of two or more. In particular, in the formula (Z-5), all of the six Xs are acryloyl groups, and in the formula (Z-5), at least one of the compounds in which all six Xs are acryloyl groups, Hydrogen atom is preferable. With such a configuration, the developability can be further improved.

The total content of the compound represented by the formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the formula (Z-4) or (Z-5) can be produced by a process known in the art, such as pentaerythritol or dipentaerythritol, in which ethylene oxide or propylene oxide is subjected to ring- And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride to the terminal hydroxyl group of the ring opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the formula (Z-4) or (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

(A), (b), (f), (f), and (f) are examples of the compounds represented by the following formulas , (e) and (f) are preferable.

[Chemical Formula 13]

[Chemical Formula 14]

Examples of commercial products of the polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate containing four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate containing 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate containing three isobutyleneoxy chains.

As the polymerizable compound, there may be mentioned, for example, the compounds described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 2-032293, Japanese Patent Publication No. 2-016765, Rheology; Japanese Patent Publication No. 58-049860, Japanese Examined Patent Publication No. 56-017654, Japanese Examined Patent Publication No. 62-039417, and Japanese Examined Patent Publication No. 62-039418 disclose an oil containing an ethylene oxide skeleton Latex compounds are also suitable. Further, it is also possible to use an addition polymerizable compound having an amino structure and / or a sulfide structure in the molecule, which is described in JP-A-63-277653, JP-A-63-260909 and JP- By using the compounds, a curable composition having a very high photosensitive speed can be obtained.

(Commercially available from Shin-Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

The polymerizable compound preferably has a SP (Solubility Parameter) value of 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more.

In this specification, the SP value is obtained by the Hoy method (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118) unless otherwise specified. The unit of the SP value is omitted, but the unit is cal ^1/2 cm ^-3/2 .

It is also preferable that the curable composition contains a polymerizable compound containing a cardo framework from the viewpoint of development residue remediation.

As the polymerizable compound containing a cardo framework, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

In equation (Q3)

[Chemical Formula 15]

In the formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a broken line. X ¹ to X ⁴ each independently represent a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted by a heteroatom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 5. E, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h may be Ar ¹¹ to Ar ¹⁴ , respectively, and R ¹ to R ⁴ each independently represent a substituent; Is the value obtained by subtracting a, b, c, or d from the number of substituents present. When Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ¹ to X ⁴ and R ¹ to R ⁴ are each independently a benzene ring surrounded by a dashed line Or may be substituted with a ring other than a benzene ring surrounded by a broken line.

In the formula (Q3), the aryl group containing a benzene ring surrounded by the broken line represented by Ar ¹¹ to Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (e.g., More preferably a phenyl group (benzene ring surrounded by a broken line).

In the formula (Q3), X ¹ to X ⁴ each independently represent a substituent containing a polymerizable group, and the carbon atoms in the substituent may be substituted by a hetero atom. The substituent containing a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but is preferably an aliphatic group containing a polymerizable group.

The aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, more preferably an alkylene group having 2 to 10 carbon atoms And more preferably an alkylene group having 2 to 5 carbon atoms.

In the aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ , when the aliphatic group is substituted by a hetero atom, it is preferably substituted by -NR- (R is a substituent), an oxygen atom and a sulfur atom more preferably optionally substituted with an oxygen atom or a sulfur atom, -CH ₂ that are not adjacent to each other in the aliphatic group - -, -CH ₂ that are not adjacent to each other in the aliphatic group is more preferred that the optionally substituted oxygen atom. The aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ is preferably substituted by 1 to 2 substituents selected from the group consisting of a heteroatom, more preferably one substituent by a heteroatom, more preferably Ar ¹¹ to Ar ¹⁴ It is more preferable that one adjacent to an aryl group containing a benzene ring surrounded by a broken line represents a heteroatom.

As the polymerizable group contained in the aliphatic group containing a polymerizable group represented by X ¹ to X ⁴ , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter also referred to as a radical polymerizable group and a cationic polymerizable group, respectively) is preferable.

Suitable radically polymerizable groups include polymerizable groups containing radically polymerizable ethylenically unsaturated bonds, which are generally known, and specific examples thereof include a vinyl group, a (meth) acryloyloxy group, etc. . Among them, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.

As the cationic polymerizable group, generally known cationic polymerizability can be used. Specific examples thereof include aliphatic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spirooxoester groups, . Among them, alicyclic ethers and vinyloxy groups are suitable, and epoxy groups, oxetanyl groups and vinyloxy groups are particularly preferred.

The polymerizable group contained in the substituent group contained in Ar ¹¹ to Ar ¹⁴ is preferably a radical polymerizable group.

Of Ar ¹¹ ~ Ar 2 or more of the ¹⁴ are preferably comprising a substituent containing a polymerizable group, and containing a substituent of the dog Ar ¹¹ ~ Ar 2 ~ 4 of ¹⁴ containing a polymerizable group, Ar ¹¹ ~ Ar ¹⁴ 2 Or three of them contain a substituent group containing a polymerizable group, and more preferably two of Ar ¹¹ to Ar ¹⁴ contain a substituent group containing a polymerizable group.

When Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ¹ to X ⁴ may be independently substituted with a benzene ring surrounded by a broken line, May be substituted by a ring other than a benzene ring.

In formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.

In formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably all of c and d are 0.

In the formula (Q3), R ¹ to R ⁴ each independently represents a substituent. The substituent represented by R ¹ to R ⁴ is not particularly limited and examples thereof include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, Groups, and vicinal groups. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group, more preferably a methyl group, More preferable.

In the formula (Q3), when Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as a condensed ring, R ¹ to R ⁴ are each independently a benzene ring surrounded by a dashed line Or may be substituted with a ring other than a benzene ring surrounded by a broken line.

In the formula (Q3), each of e, f, g and h independently represents an integer of 0 or more, and the upper limit values of e, f, g and h are, from the number of substituents that Ar ¹¹ to Ar ¹⁴ can contain, b, c, or d.

e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, still more preferably 0.

When Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1, and more preferably 0 .

Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. As the polymerizable compound containing a 9,9-bisarylfluorene skeleton, the compounds described in JP-A-2010-254732 can also be suitably used.

Examples of the polymerizable compound containing such a cardo framework include, but are not limited to, Oncoat EX series (manufactured by Nagase Sansan Co., Ltd.) and Oglesol (manufactured by Osaka Gas Chemicals Co., Ltd.).

[Polyfunctional thiol compound]

The curable composition contains a polyfunctional thiol compound. In the present specification, the polyfunctional thiol compound is intended to contain two or more thiol groups (i.e., groups represented by -SH) in the same molecule.

The content of the polyfunctional thiol compound is not particularly limited, but is usually from 1 to 10% by mass based on the content of the colorant. Among them, the curable composition is preferably 1 to 5.5% by mass, and more preferably 1.5 to 3.5% by mass in view of better effect of the present invention.

The content of the polyfunctional thiol compound is preferably 0.55 to 3.5 mass%, more preferably 0.8 to 2.0 mass%, based on the total solid content of the curable composition.

The polyfunctional thiol compound may be used singly or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.

The polyfunctional thiol compound is preferably a low molecular weight compound having a molecular weight of 100 or more, and more preferably a molecular weight of 100 to 1,500, and more preferably 150 to 1,000.

The polyfunctional thiol compound preferably contains two or more thiol groups in the molecule and preferably contains three or more, more preferably 10 or less, more preferably 6 or less, and no more than 4 . Among them, the polyfunctional thiol compound is preferably trifunctional or more, and more preferably trifunctional or tetrafunctional.

When the multifunctional thiol compound has three or more functional groups, the curable composition has a better effect of the present invention.

The polyfunctional thiol compound is preferably a compound having two or more groups represented by the following formula (1).

[Chemical Formula 16]

In the formula (1), L ¹ represents a single bond or -CO-, and L ² represents a single bond or a divalent linking group.

The polyfunctional thiol compound is preferably a compound containing 2 to 6 groups per molecule represented by the formula (1), more preferably a compound containing 2 to 4, and more preferably 3 or 4 Do.

Examples of the divalent linking group in L ² in the formula (1) include divalent linking groups such as divalent aliphatic groups (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, ), a divalent aromatic group (for example, an aryl group, a substituted arylene group), a divalent heterocyclic group, an oxygen atom (-O-), imino group (-NH-), a substituted imino group (-NR ³¹ -, where , R ³¹ represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.

When the divalent linking group is an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 5, more preferably from 1 to 2.

As the polyfunctional thiol compound, a compound represented by the following formula (2) having two or more groups represented by the formula (1) is more preferable.

[Chemical Formula 17]

In the formula (1), L ¹ represents a single bond or -CO-, and L ² represents a single bond or a divalent linking group. X represents a linking group of n, and n represents an integer of 2 to 6. The plurality of L ¹ and L ² may be the same or different.

The aspects of L ¹ and L ^{2 in} the formula (2) are the same as those in the formula (1).

In the formula (2), n is preferably 2 to 4, and more preferably 3 or 4.

Examples of X as a linking group of n in the formula (2) include divalent linking groups such as - (CH ₂ ) _m - (m represents an integer of 2 to 6); A tri-methylol propane residue, and an isocyanuric ring having three - (CH ₂ ) _p - (p represents an integer of 2 to 6); Tetravalent linking groups such as pentaerythritol residue; Or a pentavalent linkage; And a dipentaerythritol residue.

Specific examples of the polyfunctional thiol compound include 1,4-butenediol bis (thioglycolate), pentaerythritol tetra (3-mercaptopropionate), trimethylol propanol (3 Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto Propionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutylate), butane diol bis (3-mercaptobutylate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 5-triazine-2,4,6 (1H, 3H, 5H) -tione.

Among them, the polyfunctional thiol compound is preferably selected from the group consisting of pentaerythritol tetra (3-mercaptopropionate), and trimethylol propanol (3-mercapto Propionate) is more preferable.

[Optional Components]

<Polymerization inhibitor>

The curable composition preferably contains a polymerization inhibitor. By containing a polymerization inhibitor, the curable composition has better stability with time. Further, in the present specification, the aging stability means that a cured film having a good pattern shape can be obtained even when the curable composition is prepared and stored for a predetermined period of time.

It is presumed that the polymerization inhibitor has an effect of suppressing the progress of the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition in storage, and the above effect can be obtained.

The content of the polymerization inhibitor is preferably 0.1 to 1.5% by mass, more preferably 0.3 to 1.0% by mass based on the content of the polyfunctional thiol compound.

When the content of the polymerization inhibitor is within the above range, the curable composition has better stability over time.

The content of the polymerization inhibitor is preferably 0.00055 to 0.055 mass%, more preferably 0.0015 to 0.01 mass%, based on the total solid content of the curable composition.

The polymerization inhibitor is not particularly limited, and known compounds used as polymerization inhibitors can be used. Examples of the compound used as the polymerization inhibitor include phenol compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds. These compounds may be used alone or in combination of two or more.

Examples of the phenol compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert- Di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl- Tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol and 1,4-dihydroxynaphthalene.

As the phenol compound, a phenol compound represented by the formula (IH-1) is preferable.

[Chemical Formula 18]

In formula (IH-1), R ₁ to R ₅ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an amino group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group . R ₁ to R ₅ may be connected to form a ring.

Examples of R ₁ to R ₅ in the formula (IH-1) include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (such as methyl and ethyl), an alkoxy group having 1 to 5 carbon atoms (for example, An alkenyl group having 2 to 4 carbon atoms (e.g., a vinyl group), or a phenyl group.

Among them, R ₁ and R ₅ are each independently preferably a hydrogen atom or a tert-butyl group, R ₂ and R ₄ are more preferably a hydrogen atom, and R ₃ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, More preferably an alkoxy group of 1 to 5 carbon atoms.

Examples of the quinone-based compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.

As the hindered amine-based compound, for example, a polymerization inhibitor represented by the following formula (IH-2) can be mentioned.

[Chemical Formula 19]

R ₆ in the formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group or an acyl group. Among them, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.

R ₇ to R ₁₀ in the formula (IH-2) each independently represent a hydrogen atom or an alkyl group. As the alkyl group represented by R ₇ to R ₁₀ , an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

As the polymerization inhibitor, each of the above-described compounds may be used singly, or two or more of them may be used in combination.

The polymerization inhibitor preferably contains a phenol compound. Among them, the polymerization inhibitor preferably contains two or more phenolic compounds. The curable composition containing other phenolic compounds has a better effect of the present invention.

The polymerization inhibitor preferably contains a phenolic compound and a hindered amine compound. The curable composition containing a phenolic compound and a hindered amine compound has a better effect of the present invention.

<Solvent>

The curable composition preferably contains a solvent. As the solvent, water and an organic solvent can be mentioned. The curable composition preferably contains an organic solvent.

When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 40% by mass. If the solid content of the curable composition is the lower limit value or more, the viscosity is low and the coatability becomes good. In addition, since the concentration of the highly reactive compound is lowered, the stability over time is improved. If the solid content of the curable composition is not more than the upper limit value, the viscosity is kept low and the coatability becomes good. Further, the coloring agent having a high specific gravity is hardly settled, and the stability with time is improved.

(Organic solvent)

When the curable composition contains an organic solvent, the content of the organic solvent is preferably 60 to 90% by mass based on the total mass of the curable composition.

The organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total amount is preferably in the above range.

Examples of the organic solvent include, but are not limited to, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, But are not limited to, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether Acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, gamma -butyrolactone, methyl 3-ethoxypropionate, 3- Ethyl propionate, ethyl cellosolve acetate, methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate.

When two or more organic solvents are contained, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, Which is composed of methyl methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate And the like.

(water)

The curable composition may contain water. The water may be intentionally added or may be inevitably contained in the curable composition by adding each component contained in the curable composition.

The content of water is preferably 0.01 to 1% by mass based on the total mass of the curable composition. When the content of water is within the above range, the occurrence of pinholes is suppressed when the cured film is produced, and the moisture resistance of the cured film is further improved.

<Dispersant>

The curable composition preferably contains a dispersant. The dispersant contributes to the improvement of the dispersibility of the colorant. In the present specification, the dispersant and the binder resin described later are different components.

When the curable composition contains a dispersant, the content of the dispersant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 5% by mass or more, and still more preferably 5% by mass or more based on the total solid content of the curable composition. By mass or more, particularly preferably 17% by mass or more. The upper limit of the content of the dispersant is preferably 50 mass% or less, more preferably 30 mass% or less, and most preferably 22 mass% or less, based on the total solid content of the curable composition.

When the content of the dispersant is 17 mass% or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent.

The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total amount is preferably within the above range.

As the dispersing agent, for example, a known pigment dispersing agent can be suitably selected and used. Among them, a polymer compound is preferable.

Examples of the dispersing agent include polymer dispersing agents such as polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, Acrylic copolymer, naphthalenesulfonic acid-formalin condensate], polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, and pigment derivative.

The polymer compound can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer from the structure.

(Polymer compound)

The polymer compound is adsorbed on the surface of an object to be dispersed of a colorant (for example, an inorganic pigment) and functions to prevent re-aggregation of the object to be dispersed. For this reason, end-modified polymers, graft-type polymers, and block-type polymers containing anchor sites on the pigment surface are preferred.

The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, the term "structural unit" is synonymous with "repeating unit".

Such a polymer compound containing a structural unit containing a graft chain is excellent in dispersibility of a coloring agent such as a black pigment and dispersion stability (aged stability) after aging since it has affinity with a solvent by a graft chain . The polymer compound containing a structural unit containing a graft chain has affinity with a polymerizable compound or other compatible resin or the like due to the presence of a graft chain. As a result, it is difficult to generate residues by the alkali phenomenon.

As the graft chain becomes longer, the effect of steric repulsion increases, and the dispersibility of the black pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorption force against the color pigment such as a black pigment decreases, and the dispersibility of the black pigment tends to decrease. Therefore, the number of atoms other than hydrogen atoms is preferably 40 to 10,000, more preferably 50 to 2,000 atoms other than hydrogen atoms, and more preferably 60 to 500 atoms other than hydrogen atoms in the graft chain .

Here, the graft chain indicates from the base of the main chain of the copolymer (the atom bonding to the main chain in the group branching from the main chain) to the end of the group branching from the main chain.

The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, Structure, a polyurea structure, a polyamide structure, and a polyether structure.

The graft chain is preferably at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interactivity of the graft chain and the solvent and thereby increase the dispersibility of the black pigment and the like. Is preferably a graft chain containing at least one of a polyester structure and a polyether structure, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.

The macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bond group can be suitably used.

Examples of commercially available macromonomers suitable for the synthesis of polymeric compounds corresponding to structural units containing a graft chain contained in the polymer compound include AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, AA-714 (trade name, product of Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS- AKY-70 (trade name, manufactured by Toagosei Co., Ltd.), AY-714 (trade name, manufactured by Toagosei Co., Ltd.) (Trade name, manufactured by Toagosei Co., Ltd.), BLEMMER PP-100 (trade name, manufactured by NICHI CO., LTD.), BLEMMER PP- ), Blemmer PP-1000 (trade name, manufactured by Niches), Blemmer 55-PET-800 (trade name, 00 (trade name, manufactured by Nichite Corporation), Blemmer PSE-1300 (trade name, manufactured by Nichicon Corporation), and Blemmer 43PAPE-600B (trade name, manufactured by Nichia Corporation). Of these, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB- (Trade name, manufactured by Toagosei Co., Ltd.) and Blemmer PME-4000 (trade name, manufactured by Nichia Corporation).

The dispersing agent preferably contains at least one structure selected from the group consisting of methyl polyacrylate, methyl polymethacrylate, and cyclic or straight-chain polyesters. It is more preferable that the dispersing agent contains at least one structure selected from the group consisting of methyl polyacrylate, methyl polymethacrylate, and chain polyester. It is more preferable that the dispersing agent contains at least one structure selected from the group consisting of a polyacrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalero lactone structure. The dispersing agent may contain the above structure alone in one dispersing agent or may contain a plurality of such structures in one dispersing agent.

Here, the polycaprolactone structure refers to a structure containing a structure in which? -Caprolactone is replaced by a repeating unit. The polyvalero lactone structure refers to a structure containing a structure in which? -Valerolactone is introduced as a repeating unit.

Specific examples of the dispersant containing a polycaprolactone structure include those wherein j and k in the following formulas (1) and (2) are 5. Specific examples of the dispersing agent containing a polyvalero lactone structure include those in which j and k in the following formulas (1) and (2) are 4.

As specific examples of the dispersing agent containing a polyacrylate structure, X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. Specific examples of the dispersant containing a polymethylmethacrylate structure include those in which X ⁵ in the following formula (4) is a methyl group and R ⁴ is a methyl group.

Structural unit containing graft chain

The polymer compound is preferably a structural unit containing a graft chain and contains a structural unit represented by any one of the following formulas (1) to (4), and is preferably a structural unit represented by the following formula (1A) (3A), the following formula (3B), and the following formula (4).

[Chemical Formula 20]

In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH 2. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.

In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (in terms of synthetic limitations) A hydrogen atom or a methyl group is more preferable, and a methyl group is more preferable.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include linking groups represented by the following (Y-1) to (Y-21). In the structures shown below, A and B each mean a bonding site. Among the structures shown below, from the simplicity of synthesis, it is more preferable to be (Y-2) or (Y-13).

[Chemical Formula 21]

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, but specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl thioether group, an aryl thioether group, a heteroaryl thioether group, . Among them, as an organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , from the viewpoint of improving the dispersibility, it is preferable to contain a steric repulsion effect, and each independently represents an alkyl group or alkoxy group having 5 to 24 carbon atoms More preferably a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms, independently of each other. The alkyl group contained in the alkoxy group may be any of linear, branched and cyclic.

In the formulas (1) to (4), n, m, p and q are each independently an integer of 1 to 500.

In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably an integer of 4 to 6, and most preferably 5 from the viewpoints of stability with time and developability of the curable composition.

In the formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R ³ may be the same or different.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and a straight chain alkyl group having 1 to 20 carbon atoms is more preferable. More preferably a straight-chain alkyl group having 1 to 6 carbon atoms. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ existing in the graft copolymer may be the same or different.

The polymer compound may contain a structural unit containing a graft chain having two or more different structures. That is, the molecules of the polymer compound may include structural units represented by the formulas (1) to (4) having different structures from each other, and n, m, p, and q in the formulas (1) (1) and (2) may include a structure in which j and k are different from each other in the side chain, and in the formulas (3) and (4) The plurality of R ³ , R ⁴ and X ^{5 present} may be the same or different.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of stability with time and developability of the curable composition.

The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of stability with time and developability of the curable composition.

[Chemical Formula 22]

Formula (1A) of the, X ^1, Y ^1, Z ¹ and n is ¹ and X, Y ^1, Z ¹ and n and the consent of the formula (1), are also the same preferable range. In the formula ^{(2A), X 2, Y} 2, Z 2 and m is ^2, and X, Y ^2, Z ² and m and consent of the formula (2) are also the same preferable range.

The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or (3B) from the viewpoint of stability with time and developability of the curable composition.

(23)

In the formula (3A) or ^{(3B), X 3, Y} 3, Z 3 , and p is ^3, and X, Y ^3, Z ^3, and p and consent of the formula (3) it is also the same preferable range.

The polymer compound is a structural unit containing a graft chain and more preferably contains a structural unit represented by the formula (1A).

In the polymer compound, the structural unit containing the graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is preferably 2 to 90% of the total mass of the polymer compound , And more preferably in the range of 5 to 30%. When the structural unit containing the graft chain is contained within this range, the dispersibility of the black pigment is high, and the developability in forming the cured film is good.

· Hydrophobic structural units

The polymer compound preferably contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (i.e., does not correspond to the structural unit containing the graft chain). However, in this specification, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

The hydrophobic structural unit is preferably a structural unit derived from a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a structural unit derived from a compound having a ClogP value of 1.2 to 8. As a result, the effect of the present invention can be more reliably expressed.

The ClogP value was calculated using the method of Daylight Chemical Information System, Inc. Quot; CLOGP " which can be obtained from the program " CLOGP " This program provides the value of "computed logP" calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of the compound and estimates the logP value of the compound by dividing the chemical structure into partial structures (fragments) and summing the logP contributions assigned to the fragments. The details thereof are described in the following documents. In this specification, the ClogP value is intended to be the value calculated by the program CLOGP v 4.82.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990 C. Hansch &amp; A. J. Leo. Substituent Constants for Correlation Analysis in Chemistry and Biology. John Wiley &amp; Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306,1993.

logP means the common logarithm of the partition coefficient P and is a quantitative measure of how organic compounds are distributed in the equilibrium of the two-phase system of oil (usually 1-octanol) with water And is expressed by the following equation.

logP = log (Coil / Cwater)

In the formula, Coil represents the molar concentration of the compound in the oil phase and Cwater represents the molar concentration of the compound in the aqueous phase.

When the value of logP is increased to 0 on the positive side, the oil solubility is increased and when the negative value is increased, the water solubility is increased. The water solubility of the organic compound is negatively correlated with that of the organic compound. And is widely used as a parameter for evaluating the hydrophilicity.

The polymer compound preferably contains at least one structural unit selected from the structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.

&Lt; EMI ID =

In the formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) Represents an alkyl group having 1 to 6 (e.g., methyl, ethyl, propyl, etc.).

R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. It is more preferable that R ² and R ³ are hydrogen atoms.

X represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group), a divalent aromatic group (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, where R is a substituted or unsubstituted aryl group), a divalent heterocyclic group, ³¹ represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, or a heterocyclic group.

L is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by - (OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

Z represents an aliphatic group (e.g., an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (e.g., an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) . &Lt; / RTI &gt; These groups include an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, wherein R ³¹ represents an aliphatic group, ), Or a carbonyl group (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. Examples of the cyclic hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenylene group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the cyclic hydrocarbon group include a cyclic hydrocarbon group and a cyclic hydrocarbon group, do. As the bridged cyclic hydrocarbon ring, there may be mentioned, for example, phenane, bonene, nopine, novone, bicyclooctane ring (bicyclo [2.2.2] octane ring and bicyclo [3.2.1] 2, 3, 4, ^{5, 8} ] undecane rings such as homocyclododecane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] Cyclic hydrocarbon rings such as tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane and perhydro-1,4-methano-5,8-methanonaphthalene ring, And the like. Examples of the bridged cyclic hydrocarbon ring include condensed cyclic hydrocarbon rings such as perhydro- naphthalene (decalin), perhydroanthracene, perhydro- phenanthrene, perhydro-acenaphthene, perhydrofluorene, perhydroindene, And a condensed ring in which a plurality of 5- to 8-membered cycloalkene rings such as a benzene ring are condensed.

The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. Provided that the aliphatic group does not have an acid group as a substituent.

The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group and a heterocyclic group. Provided that the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Provided that the heterocyclic group does not have an acid group as a substituent.

In formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) An alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), Z, or LZ. Wherein L and Z are the same as those in the above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

A monomer represented by the formula (i) wherein R ¹ , R ² and R ³ are each a hydrogen atom or a methyl group, L is a divalent linking group containing a single bond or an alkylene group or an oxyalkylene structure, X is an oxygen atom or An imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group.

As the monomer represented by the formula (ii), a compound wherein R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.

As the monomer represented by the formula (iii), a compound wherein R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom or a methyl group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.

Examples of representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrene, and the like.

As an example of representative compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP-A No. 2013-249417, the contents of which are incorporated herein by reference.

In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably 20 to 80%, in terms of mass, based on the total mass of the polymer compound. When the content is within the above range, a satisfactory pattern formation can be obtained.

· Functional groups capable of forming an interaction with a coloring agent such as a black pigment

The polymer compound can introduce a functional group capable of forming an interaction with a coloring agent such as a black pigment. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a coloring agent such as a black pigment.

Examples of the functional group capable of forming an interaction with a coloring agent such as a black pigment include an acid group, a basic group, a coordinating group, and a functional group having reactivity.

When the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, it is possible to use a structural unit containing an acid group, a structural unit containing a basic group, a structural unit containing a coordinating group, Unit is preferable.

In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided with developability for forming a pattern by an alkali development.

That is, by introducing an alkali-soluble group into the polymer compound, the curable composition contains the alkali-soluble polymer compound as a dispersing agent contributing to the dispersion of the coloring agent such as a black pigment. The curable composition containing such a polymer compound is excellent in the light shielding property of the exposed portion and improves the alkali developing property of the unexposed portion.

Since the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be easily compatible with the solvent, and the coating property tends to be improved.

This is because the acid group in the structural unit containing an acid group is likely to interact with a coloring agent such as a black pigment and that the polymer compound stably disperses a coloring agent such as a black pigment and also a polymer compound for dispersing a coloring agent such as a black pigment The viscosity of the polymer compound itself is lowered, and the polymer compound itself is likely to be stably dispersed.

The structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or may be another structural unit, but is a structural unit different from the above-mentioned hydrophobic structural unit (that is, It does not correspond to the structural unit).

Examples of the acid group that is a functional group capable of forming an interaction with a coloring agent such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and at least one of a carboxylic acid group, a sulfonic acid group, , And a carboxylic acid group is more preferable because it has good adsorption ability to a coloring agent such as a black pigment and a high dispersibility of a colorant.

That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may contain one or more structural units containing an acid group.

The polymer compound may or may not contain a structural unit containing an acid group, but if contained, the content of the structural unit containing an acid group is preferably 5 to 100 mass%, based on the mass of the polymer compound, And more preferably from 10 to 60% from the viewpoint of suppressing the damage of the image strength due to the alkali development.

Examples of the basic group which is a functional group capable of forming an interaction with a coloring agent such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, It is preferably a tertiary amino group in view of good adsorption ability to a colorant such as a black pigment and high dispersibility of the colorant. The polymer compound may contain one or more of these basic groups.

The polymer compound may or may not contain a structural unit containing a basic group, but when contained, the content of the structural unit containing a basic group is 0.01% or more and 50% or less, Or less, more preferably 0.01% or more and 30% or less from the viewpoint of inhibiting developmental inhibition.

Examples of the coordinating group that is a functional group capable of forming an interaction with a coloring agent such as a black pigment and the reactive functional group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, . It is preferably an acetyl acetoxy group in view of good adsorption ability to a colorant such as a black pigment and high dispersibility of a colorant. The polymer compound may have one or more of these groups.

The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a functional group having a reactivity, but if contained, the content of such a structural unit may be, in terms of mass, Is preferably 10% or more and 80% or less with respect to the total mass, and more preferably 20% or more and 60% or less from the viewpoint of suppressing development inhibition.

When the polymer compound contains, in addition to the graft chain, a functional group capable of forming an interaction with a coloring agent such as a black pigment, it may contain a functional group capable of forming an interaction with a coloring agent such as various black pigments, The manner in which these functional groups are introduced is not particularly limited, but it is preferable that the polymer compound contains at least one structural unit selected from the structural units derived from the monomers represented by the following general formulas (iv) to (vi).

(25)

In the formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) An alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, etc.).

In the formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently hydrogen An atom or a methyl group. In the formula (iv), it is particularly preferable that R ¹² and R ¹³ are each a hydrogen atom.

X ₁ in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

Y in the formula (v) represents a metha-popular or nitrogen atom.

L ₁ in formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, and a substituted alkenylene group) (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ^{31 '} ), a substituted or unsubstituted arylene group -, wherein R ^{31 '} is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with one or more of other heterocyclic, aliphatic or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L ₁ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by - (OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

In the formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a coloring agent such as a black pigment in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group. Is more preferable.

In formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) An alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), -Z ₁ , or L ₁ -Z ₁ . Here, L ₁ and Z ₁ is, and L ₁ and Z ₁ and copper in the above, preferred examples are the same. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

A monomer represented by the formula ^{(iv), R 11, R} 12, and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is a divalent linking group containing an alkylene group or an oxyalkylene structure, X ₁ is oxygen An atom or an imino group, and Z &lt; _{1 &gt;} is a carboxylic acid group.

As the monomer represented by the formula (v), a compound wherein R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a meta-group is preferable.

As the monomer represented by the formula (vi), a compound wherein R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z ₁ is a carboxylic acid group is preferable.

Representative examples of the monomers (compounds) represented by the formulas (iv) to (vi) are shown below.

Examples of the monomer include a reaction product of a compound containing methacrylic acid, crotonic acid, isocrotonic acid, addition polymerizable double bond and hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride, A reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group and a phthalic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in a molecule and a tetrahydrophthalic anhydride, an addition polymerizable double bond in the molecule and a hydroxyl group A reaction product of a compound containing an acid anhydride and trimellitic anhydride, a reaction product of a compound containing an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, -Vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide. There.

The content of the structural unit containing a functional group capable of forming an interaction with a coloring agent such as a black pigment is preferably from 1 to 100 parts by weight based on 100 parts by weight of the total mass of the polymer compound By mass, more preferably from 1.0% by mass to 80% by mass, and still more preferably from 10% by mass to 70% by mass.

· Other structural units

In order to improve all the performances such as the image strength, the polymer compound is required to have an interaction with a coloring agent such as a structural unit containing a graft chain, a hydrophobic structural unit, and a black pigment as long as the effect of the present invention is not impaired (For example, a structural unit containing a functional group having affinity with a dispersion medium used in a dispersion), which is different from the structural unit containing a functional group capable of forming do.

Examples of such another structural unit include a structural unit derived from a radically polymerizable compound selected from acrylonitrile, methacrylonitrile, and the like.

The polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less, more preferably 10% or more and 60% or less, % Or less is more preferable. When the content is within the above range, sufficient pattern formation property is maintained.

· Properties of polymer compounds

The acid value of the polymer compound is preferably in a range of from 0 mgKOH / g to 250 mgKOH / g, more preferably from 10 mgKOH / g to 200 mgKOH / g, and still more preferably from 20 mgKOH / g to 120 mgKOH / g.

When the acid value of the polymer compound is 160 mgKOH / g or less, the pattern peeling at the time of development when the cured film is formed is more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability is better. When the acid value of the macromolecular compound is 20 mgKOH / g or more, precipitation of the coloring agent such as black pigment can be further suppressed, the number of coarse particles can be further reduced, and the stability over time of the curable composition can be further improved have.

The acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. In addition, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group, which is a component of the polymer compound.

The weight average molecular weight of the polymer compound is preferably from 4,000 to less than 300,000 as a polystyrene reduced value by GPC (Gel Permeation Chromatography) method from the viewpoint of suppressing pattern peeling at the time of development and developing property at the time of forming a cured film More preferably 5,000 or more and 200,000 or less, still more preferably 6,000 or more and 100,000 or less, particularly preferably 10,000 or more and 50,000 or less.

The GPC method was a method using HLC-8020 GPC (a plasticizer), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (plasticizer, 4.6 mm ID x 15 cm) as columns and THF (tetrahydrofuran) Based.

The polymer compound can be synthesized on the basis of known methods. Examples of the solvent used in synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylethanolamine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound include DA-7301 manufactured by Goosumoto Chemical Co., Ltd., Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group) BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ", EFKA " EFKA4047 " (Modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (polyacrylate), 4050 to 4010 to 4165 (polyurethane resin), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (Azo pigment), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "manufactured by Ajinomoto Fine Techno Co., Ltd." Ajisper PB821, PB822, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co., 8750, 873, 874, 871, 871, 873, 873, 873, 871, 705, DA-725 ", Daido RN, N (naphthalene sulfonic acid-formaldehyde polycondensate), MS, 9, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ", " C, SN-B (aromatic sulfonic acid formalin polycondensate) ", " Homogenol L- 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene sorbitan monooleate) manufactured by Nippon Kayaku Co., Ltd., " Monostearate "manufactured by Shin-Etsu Chemical Co., Ltd., Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd., Shinano Etsu Chemical Co., Ltd., organosiloxane polymer KP341, , Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene 46, EFKA-47, EFKA-47EA, EFKA-47, anionic surfactants such as " W004, W005 and W017 ", and nonionic surface active agents such as glycerol monostearate, Polymer dispersants such as Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", Sanofucose" Disperse 6, Disperse 8, Disperse 15, Disperse 9100 " P143, F108, L121, P-123 ", and Sanyo Gasset now " Ionet (" Trade name " S-20 "). In addition, Acrybee FFS-6752, Acrybee FFS-187, Acricheter RD-F8, and Cyclamer P may be used.

DISPERBYK-140, DISPERBYK-140, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010 and DISPERBYK-130 DISPERBYK- -2012, DISPERBYK-2025, BYK-9076, Ajisper PB821 manufactured by Ajinomoto Fine Techno, Ajisper PB822, Ajisper PB881 and the like.

These polymer compounds may be used singly or in combination of two or more.

As specific examples of the polymer compound, reference may be made to the polymer compounds described in paragraphs 0127 to 0129 of Japanese Laid-Open Patent Publication No. 2013-249417, the contents of which are incorporated herein by reference.

As the dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of JP-A No. 2010-106268, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011 / 0124824), may be used , Incorporated herein by reference.

In addition to the above, a polymer compound containing a constituent component containing a side chain structure formed by bonding an acidic group of the paragraphs 0028 to 0084 (corresponding to paragraphs 0075 to 0133 of US2011 / 0279759) of JP-A No. 2011-153283 via a linking group The contents of which are expressly incorporated herein by reference.

<Binder Resin>

The curable composition preferably contains a binder resin.

The content of the binder resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.9% by mass or more, particularly preferably 1.9% by mass or more, and most preferably 30% by mass or more, based on the total solid content of the curable composition. By mass or less, more preferably 25% by mass or less, further preferably 18% by mass or less, and particularly preferably 10% by mass or less.

When the content of the binder resin is 1.9 mass% or more and 10 mass% or less, the pattern shape of the cured film obtained by curing the curable composition is more excellent.

One kind of binder resin may be used alone, or two or more kinds of binder resins may be used in combination. When two or more kinds of binder resins are used in combination, it is preferable that the total amount is within the above range.

As the binder resin, it is preferable to use a linear organic polymer. As such a linear organic polymer, any known one can be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline development. Among them, an alkali-soluble resin (a resin containing a group capable of promoting alkali solubility) is particularly preferable as the binder resin.

As the binder resin, it is preferable to use, as the linear organic polymer, an alkali-soluble resin containing at least one group capable of promoting alkali solubility among molecules (preferably, a (meth) acrylic copolymer or a styrene- You can choose. (Meth) acrylic resin, (meth) acrylamide resin, (meth) acrylic / (meth) acrylamide copolymer resin, epoxy resin and polyimide resin are preferable from the viewpoint of heat resistance. (Meth) acrylic resin, (meth) acrylamide resin, (meth) acrylic / (meth) acrylamide copolymer resin or polyimide resin is more preferable from the viewpoint of development control .

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as acid group) include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, those soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution are preferable, and alkali-soluble resins containing structural units derived from (meth) acrylic acid are more preferable. These acid groups may be one kind or two or more kinds.

As the binder resin, there can be mentioned, for example, a radical polymer containing a carboxylic acid group in the side chain. Examples of the radical polymer containing a carboxylic acid group in the side chain include those described in JP-A-59-044615, JP-A-54-034327, JP-A-58-012577, JP- 025957, JP-A-54-092723, JP-A-59-053836, and JP-A-59-071048. Examples of the radical polymer containing a carboxylic acid group in the side chain include a resin obtained by singly or copolymerizing a monomer containing a carboxylic acid group or an acid anhydride unit obtained by copolymerizing monomers containing an acid anhydride either by hydrolysis, Resins, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides.

Examples of the monomer containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Acidic cellulose derivatives containing a carboxylic acid group in the side chain are also exemplified.

Monomers containing an acid anhydride include maleic anhydride and the like. In addition, it is useful to add a cyclic acid anhydride to a polymer containing a hydroxyl group.

Acetal-modified polyvinyl alcohol-based binder resins containing an acid group are described in publications such as European Patent Publication No. 993966, European Patent Publication No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463. The acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because of excellent balance of film strength and developability.

As the water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide and the like are useful. In addition, in order to increase the strength of the cured coating, alcohol-soluble nylon and a polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

The polyimide resin described in International Publication No. 2008/123097 is also useful.

Among them, a copolymer of [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition polymerizable vinyl monomer] and [allyl (meth) acrylate / (meth) acrylic acid / Polymerizable vinyl monomer] copolymer is suitable because it has excellent balance among film strength, sensitivity, and developability.

Examples of commercially available products include ACRYBASE FF-187, FF-426 (manufactured by Fujikura Chemical Industry Co., Ltd.), ACRYLICURE RD-F8 (manufactured by Nippon Shokubai), and DAICEL OLEX CYCLOMER P (ACA) .

For the production of the binder resin, for example, a known radical polymerization method can be applied. The polymerization conditions such as the temperature and pressure at the time of producing the binder resin by the radical polymerization method, the kind and amount of the radical initiator, and the kind of the solvent can be easily set by those skilled in the art.

As the binder resin, it is also preferable to use a polymer containing a structural unit containing a graft chain and a structural unit containing an acid group (alkali-soluble group).

The definition of the structural unit containing the graft chain is the same as that of the structural unit containing the graft chain contained in the above-mentioned dispersant, and the preferable range is also the same.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable.

(Structural unit containing an acid group)

The structural unit containing an acid group preferably contains at least one structural unit selected from structural units derived from monomers represented by the following formulas (vii) to (ix).

(26)

In the formulas (vii) to (ix), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) An alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, etc.).

In the formulas (vii) to (ix), R ²¹ , R ²² and R ²³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or a methyl group More preferable. In the formula (vii), it is particularly preferable that R ²¹ and R ²³ are each a hydrogen atom.

X ₂ in the formula (vii) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

Y in the formula (viii) represents a methoxy group or a nitrogen atom.

L ₂ in formulas (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, and a substituted alkenylene group) (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ^{41 '} ), a substituted or unsubstituted arylene group -, wherein R ^{41 '} is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and combinations thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group and a heterocyclic group.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with one or more of other heterocyclic, aliphatic or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^42, where R ⁴² is an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L ₂ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₂ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by - (OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

In the formulas (vii) to (ix), Z ₂ is an acid group and is preferably a carboxylic acid group.

R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine or bromine), an alkyl group having 1 to 6 carbon atoms (for example, For example, a methyl group, an ethyl group, a propyl group, etc.), -Z ₂ , or L ₂ -Z ₂ . Here, L ₂ and Z ₂ are, and L ₂ and Z ₂ as agreed in the above, preferred examples are the same. R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

Wherein R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or a methyl group, L ₂ is a divalent linking group containing an alkylene group or an oxyalkylene structure, X ₂ is an oxygen An atom or an imino group, and Z &lt; ₂ &gt; is a carboxylic acid group.

As the monomer represented by the formula (vii), a compound wherein R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a meta-group is preferable.

As the monomer represented by the formula (ix), a compound wherein R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom or a methyl group, and Z ₂ is a carboxylic acid group is preferable.

The binder resin can be synthesized by the same method as the dispersing agent containing the structural unit containing the above graft chain, and its preferable acid value and weight average molecular weight are also the same.

The binder resin may contain one or more structural units containing an acid group.

The content of the structural unit containing an acid group is preferably 5 to 95% by mass with respect to the total mass of the binder resin, and is preferably 10 to 90% from the viewpoint of suppressing the damage of the image strength caused by the alkali development More preferable.

<Surfactant>

The curable composition preferably contains a surfactant. The surfactant contributes to the improvement of the coatability of the curable composition.

When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass based on the total mass of the curable composition.

The surfactant may be used alone or in combination of two or more. When two or more kinds of surfactants are used in combination, the total amount is preferably within the above range.

Examples of the surfactant include a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant.

For example, the liquid property (particularly, fluidity) of the curable composition is further improved by containing the fluorinated surfactant in the curable composition. That is, when a film is formed using a curable composition containing a fluorine-based surfactant, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, and coating property to the surface to be coated is improved . Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and most preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoints of the uniformity of the thickness of the coating film and / or the liquid-storing property (solubility), and the solubility in the curable composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101 and SC-101 (manufactured by Sumitomo 3M Co., Ltd.), F554 and F780 (manufactured by DIC Corporation), Fluorad FC430, (Manufactured by Asahi Glass Co., Ltd.), PF636, PF656 (manufactured by Asahi Kasei Corporation), SC-103, SC-104, SC-105, SC- , PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.

As the fluorine-based surfactant, a block polymer may be used. Specific examples thereof include the compounds described in Japanese Laid-Open Patent Publication No. 2011-089090. The compound (F-1) represented by the following formula may also be mentioned as a fluorochemical surfactant. In the compound (F-1), the structural units represented by (A) and (B) in the formula are 62 mol% and 38 mol%, respectively. Among the structural units represented by the formula (B), a, b, and c satisfy the relationship of a + c = 14 and b = 17, respectively. The weight average molecular weight of the following compounds is, for example, 15, 311.

(27)

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), poly Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Colloxystearate and sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 manufactured by BASF) Lubrizol Corporation) and the like. Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may also be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name, EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005 and W017 (Yusho Co., Ltd.) and the like.

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

<Silane coupling agent>

The silane coupling agent is a compound containing a hydrolyzable group and a functional group other than the hydrolyzable group in the molecule. The hydrolyzable group such as an alkoxy group is bonded to a silicon atom.

The hydrolyzable group means a substituent which is directly bonded to a silicon atom and capable of generating a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the carbon number thereof is preferably 6 or less, more preferably 4 or less. Particularly, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

When a cured film is formed on a substrate, it is preferable that the silane coupling agent does not contain a fluorine atom and a silicon atom (except for the silicon atom bonded to the hydrolyzable group) in order to improve the adhesion between the substrate and the cured film , A fluorine atom, a silicon atom (except for the silicon atom bonded to the hydrolyzable group), an alkylene group substituted with a silicon atom, a straight chain alkyl group having a carbon number of 8 or more, and a branched alkyl group having a carbon number of 3 or more.

The silane coupling agent preferably contains a group represented by the following formula (Z). * Indicates the binding position.

(Z) * -Si- (R _Z1 ) ₃

In the formula (Z), R _Z1 represents a hydrolyzable group and its definition is the same as described above.

The silane coupling agent preferably contains at least one curable functional group selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetane group. The curable functional group may be directly bonded to a silicon atom or may be bonded to a silicon atom through a linking group.

In addition, examples of the favorable mode of the curable functional group contained in the silane coupling agent include a radical polymerizable group.

The molecular weight of the silane coupling agent is not particularly limited and is preferably from 100 to 1,000, more preferably from 270 to 270, and still more preferably from 270 to 1,000, from the viewpoint of handling.

One example of the preferred embodiment of the silane coupling agent is the silane coupling agent X represented by the formula (W).

(W) ???????? R _Z2 -Lz-Si- (R _Z1 ) ₃ ?????

R _z1 represents a hydrolyzable group, and the definitions are the same as above.

R _z2 represents a curable functional group, the definitions are the same as above, and the preferable range is as described above.

Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -, or a combination thereof. Among these, a carbon number of 2 to 10 halogen atoms, at least one selected from the group consisting of an arylene group that may be substituted with a halogen atom to an alkylene group that may be substituted, and having 6 to 12 species to the, or those groups -NR ¹² -, A group formed by a combination of at least one kind of group selected from the group consisting of -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, and SO ₂ - , An alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms, -CO ² -, -O-, -CO-, -CONR ¹² -, or a group formed by a combination of these groups. Here, R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N -? - aminoethyl-? -Aminopropyl-methyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N- (Trade name: KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N-p-aminoethyl- gamma -aminopropyl-triethoxysilane aminopropyltriethoxysilane (trade name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-903), 3-aminopropyltrimethoxysilane (Trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), and glycidoxy octyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-4803) .

Other suitable examples of the silane coupling agent include a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and a hydrolyzable group bonded to a silicon atom.

The silane coupling agent Y may have at least one silicon atom in the molecule, and the silicon atom may be bonded to the following atoms or substituents. They may be the same atom, substitution or different. The substituent is preferably a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an amino group which may be substituted with an alkyl group and / or an aryl group, An alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents may be substituted with at least one substituent selected from the group consisting of a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group which may be substituted with an alkyl group and / An amido group, an urea group, an ammonium group, an alkylammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, or a salt thereof.

At least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.

The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y preferably has at least one nitrogen atom in the molecule and the nitrogen atom is present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom contains at least one organic group as a substituent . The structure of the amino group may be either in the form of a partial structure of a nitrogen-containing heterocycle or in the form of a substituted amino group such as aniline.

Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and combinations thereof. These substituents may further have a substituent and examples of the substituent which can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, a sulfonamido group, An amide group, an urea group, an alkylenoxy group ammonium group, an alkylammonium group, a carboxylic acid group or a salt thereof, and a sulfo group.

The nitrogen atom is preferably bonded to the curable functional group through an arbitrary organic linking group. Preferable examples of the organic linking group include the nitrogen atom and the substituent which can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is the same as described above, and the preferable range thereof is also the same as described above.

The silane coupling agent Y may have at least one curable functional group in one molecule, but may contain two or more curable functional groups. From the viewpoint of sensitivity and stability, the curable functional group is preferably contained in the molecule in an amount of 2 to 20, more preferably 4 to 15, and still more preferably 6 to 10.

The molecular weight of the silane coupling agent X and the silane coupling agent Y is not particularly limited, but the above range (more preferably 270 or more) may be mentioned.

The content of the silane coupling agent in the curable composition is preferably 0.1 to 10 mass%, more preferably 0.5 to 8 mass%, and further preferably 1.0 to 6 mass%, based on the total solid content in the curable composition.

The curable composition may contain one kind of silane coupling agent alone or two or more kinds of silane coupling agents. When the curable composition contains two or more silane coupling agents, the total amount may be within the above range.

<Ultraviolet absorber>

The curable composition may contain an ultraviolet absorber. As a result, the shape of the pattern of the cured film can be made more excellent (finer).

As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used. As specific examples thereof, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of Japanese Laid-Open Patent Publication No. 2012-068418 may be used, and these contents may be used in the specification.

In addition, a diethylamino-phenylsulfone-based ultraviolet absorber (trade name, UV-503, manufactured by Daito Kagaku Co., Ltd.) is suitably used.

Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of Japanese Laid-Open Patent Publication No. 2012-032556.

The content of the ultraviolet absorber is preferably from 0.001 to 15 mass%, more preferably from 0.01 to 10 mass%, and even more preferably from 0.1 to 5 mass%, based on the total solid content of the curable composition.

[Process for producing a curable composition]

The process for producing the curable composition includes the following mixing and dispersing process. It is preferable to include a purging step and / or a filtration step. Hereinafter, preferred embodiments of each step will be described in detail.

[Mixing and Dispersing Process]

The mixing and dispersing step is a step of mixing the above components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet mill, and a wet disperser) to obtain a curable composition. In the mixing and dispersing step, each component constituting the curable composition may be blended in a batch, or each component may be mixed in order after the components are dissolved or dispersed in an organic solvent. The order of addition and the working conditions at the time of compounding are not particularly limited. The mixing and dispersing step may include a step of producing a dispersion.

(A step of producing a dispersion liquid)

The step of preparing the dispersion is a step of mixing a colorant, a dispersant, and a solvent, and dispersing the colorant by the above-described method to prepare a dispersion. The curable composition can be prepared by mixing other components into the dispersion.

In the process of producing the dispersion, mechanical forces used for dispersing the pigment include compression, compression, impact, shearing, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high-speed impeller, a sand grinder, a float mixer, a high-pressure wet atomization and an ultrasonic dispersion. Also published in the publication of the actual comprehensive collection of dispersion techniques and industrial applications, focusing on suspension (high / liquid dispersion), published by the Management Development Center, published in "Dispersion Technology, Joho Kiko Publishing Co., Ltd., July 15, 2005" and "Suspension , October 10, 1978 " can be suitably used.

In the process of producing the dispersion, the pigment may be refined by a salt milling process. For example, the materials described in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Laid-Open Patent Publication No. 2012-046629 can be used as the material, apparatus and processing conditions used in the salt milling process.

The method for producing the curable composition preferably includes a step of obtaining the colorant by a thermal plasma method. The step of obtaining the colorant is carried out before mixing the above components. A specific manufacturing process of the coloring agent by the thermal plasma method is as described above.

<Political Process>

The coloring agent may be subjected to the following step before it is used in the mixing and dispersing step or the step of producing the dispersion liquid.

The term &quot; stationary process &quot; refers to a process in which the coloring agent obtained by the thermal plasma method is heated for a predetermined time (preferably 12 to 72 hours, more preferably 12 to 48 hours, Hour, more preferably 12 to 24 hours). At this time, it is more preferable that the moisture content in the sealed container is controlled.

At this time, the oxygen (O ₂ ) concentration and the water content in the closed vessel are preferably 100 ppm or less, more preferably 10 ppm or less, and further preferably 1 ppm or less.

The oxygen (O ₂ ) concentration and water content in the closed vessel can be adjusted by adjusting the oxygen concentration and the water content in the inert gas to be fed into the closed vessel. As the inert gas, nitrogen gas and argon gas are preferably used, and among them, nitrogen gas is more preferably used.

When the above step is performed, the surface of the colorant and the grain boundaries are stabilized. Thereby, occurrence of pinholes in the cured film obtained by curing the curable composition can be suppressed.

The above step may be replaced with the step H described in the production method of the colorant, and it is preferable to substitute the step H in that the curable composition has a better effect of the present invention.

<Filtration step>

The filtration step is a step of filtering the curable composition prepared by the above mixing and dispersion step with a filter. In the filtration process, it is possible to remove foreign matter from the curable composition and / or to reduce defects.

The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin (high density, containing ultrahigh molecular weight) such as polyethylene and polypropylene (PP) . Among these materials, polypropylene (containing high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably about 0.1 to 7.0 mu m, preferably about 0.2 to 2.5 mu m, more preferably about 0.2 to 1.5 mu m, and even more preferably about 0.3 to 0.7 mu m. By setting this range, fine foreign matters such as impurities and aggregates contained in the pigment can be reliably removed while suppressing clogging of the pigment.

When using a filter, other filters may be combined. At this time, the filtering by the first filter may be performed once, or may be performed twice or more. When filtering is performed two or more times in combination with other filters, it is preferable that the hole diameters of the second and subsequent times are equal to or larger than the hole diameters of the first filtering. The first filter having different pore diameters may be combined within the above range. The hole diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

The second filter may be formed of the same material as the first filter. The pore diameter of the second filter is preferably about 0.2 to 10.0 mu m, preferably about 0.2 to 7.0 mu m, and more preferably about 0.3 to 6.0 mu m.

[Coating film (light-shielding film)]

The cured film is obtained by curing the curable composition. The curing film includes a coloring agent. The cured film is suitably used as a light-shielding film, and more specifically, it is suitably used for shielding a portion around the light-receiving portion of the image sensor.

Hereinafter, a case where the cured film is used as a light shielding film around the light receiving portion of the image sensor will be described as an example.

The thickness of the light-shielding film is not particularly limited, but is preferably from 0.2 to 50 μm, more preferably from 0.3 to 10 μm, more preferably from 0.3 to 10 μm, in terms of the film thickness after drying, And more preferably not more than 5 mu m. Since the curable composition has a high optical density per unit volume (high light shielding property), it is also possible to reduce the thickness of the curable composition using a conventional black pigment.

The size of the light shielding film (the length of one side of the light shielding film provided around the sensor light receiving portion) is preferably 0.001 mm or more and 10 mm or less, more preferably 0.05 mm or more and 7 mm or less, mm or more and 3.5 mm or less is more preferable.

[Process for producing a cured film]

Next, a method for manufacturing a cured film (light-shielding film) will be described.

Hereinafter, the manufacturing method will be described in detail for each step.

The production method of the cured film includes the following steps of forming a curable composition layer and an exposure step. The cured film manufacturing method preferably further includes a developing step.

Curable composition layer forming step: A step of forming a curable composition layer on a support.

Exposure step: A step of exposing the curable composition layer.

Developing process: A step of developing the curable composition layer after exposure to form a patterned cured film (light shielding film).

Specifically, the curable composition is applied to the substrate directly or through another layer to form a curable composition layer (a curable composition layer formation process), and exposed through a predetermined mask pattern, (Exposure step) and developing with a developing solution (developing step), the cured film can be produced.

Hereinafter, each step will be described.

&Lt; Curable composition layer forming step &

The curable composition layer forming step is a step of forming a curable composition layer on a support (hereinafter also referred to as " substrate "). Among them, it is preferable to include an application step of applying a curable composition on a support to form a layer of a curable composition, and it is preferable that an application step of directly applying a curable composition on a support and forming a layer of a curable composition on a support It is more preferable to include them.

As the substrate, for example, an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, a transparent conductive film adhered thereto, a photoelectric conversion element substrate (E.g., a silicon substrate), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal-Oxide Semiconductor) substrate, and the like.

On these substrates, if necessary, an undercoat layer may be provided for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate.

As a method of applying the curable composition on a substrate, various coating methods such as slit coating, ink jetting, spin coating, casting, roll coating, and screen printing can be applied.

When a color filter containing a black matrix for a solid-state imaging device is manufactured, the coating film thickness of the curable composition is preferably 0.35 μm or more and 1.5 μm or less, more preferably 0.40 μm or more and 1.0 μm or less, from the viewpoint of resolution.

The curable composition applied on the substrate is usually dried at a temperature of 70 ° C or more and 110 ° C or less for about 2 minutes to 4 minutes or less. As a result, a curable composition layer can be formed.

<Exposure Step>

The exposure step is a step of exposing the layer of the curable composition (coating film) formed in the step of forming a curable composition layer through a mask, and curing only the part of the coated film that is irradiated with light.

The exposure is preferably performed by irradiation with an actinic ray or radiation, and ultraviolet rays such as g line, h line and i line are preferable, and a high pressure mercury lamp is more preferable. Exposure dose is not particularly limited, 200mJ / cm ² or more is preferable, and more preferably ^{200 ~ 1,500mJ / cm 2, 200} ~ 1,000mJ / cm 2 is more preferable, and 200 ~ 500mJ / cm ² is particularly preferred . When the exposure dose is within the above range, the cured film production method has better stability and productivity.

From the viewpoint of improvement in resolution, in forming a light-shielding film for a solid-state imaging element, exposure with an i-line stepper is preferable.

<Development Process>

The developing step is a step of developing the exposed curable composition layer. By the developing process, a patterned cured film can be obtained.

The method for producing the cured film preferably includes a developing step and a cleaning step described below. In the development step, an alkali development treatment (development step) is performed to elute the unirradiated portion in the exposure step into an aqueous alkali solution. As a result, only the photo-cured portion (coated film portion irradiated with light) remains.

When a light-shielding color filter containing a black matrix for a solid-state imaging element is manufactured as the developer, an organic alkali developing solution which does not cause damages to the underlying circuit or the like is preferable. The developing temperature is usually 20 to 30 占 폚, and the developing time is preferably 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. Examples of the inorganic developing solution include alkaline aqueous solutions obtained by dissolving sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate or sodium metasilicate at a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass% have. Examples of the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8- 5.4.0] -7-undecene in an amount of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on the total amount of the alkaline aqueous solution. To the alkaline aqueous solution, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and / or a surfactant may be added. As the developing method, for example, a puddle developing method, a shower developing method, or the like can be used.

<Cleaning step>

The cleaning step is a step of cleaning (rinsing) the developed curable composition layer with pure water or the like. The cleaning method is not particularly limited, and a known cleaning method can be used.

The method of manufacturing the cured film may include a post-baking step of heating the cured film and / or a curing step of exposing the cured film to the whole surface after the development step.

A color filter containing a cured film (black matrix) is suitable for solid-state image pickup devices such as CCD image sensors and / or CMOS image sensors. Especially, it is suitable for CCD image sensor and / or CMOS image sensor of high resolution exceeding 1 million pixels. That is, the color filter containing the cured film is suitable for a solid-state image pickup device. The color filter may include a structure in which a cured film for forming pixels of each color is embedded in a space defined by, for example, a lattice shape by the partition wall.

The cured film (black matrix) is disposed, for example, between a light-receiving portion of each pixel constituting a CCD image sensor and / or a CMOS image sensor, and a microlens for condensing.

[Solid-state image pickup device]

The solid-state imaging element contains the cured film (black matrix). It is preferable that the solid-state image pickup device contains a color filter containing a black matrix and, if necessary, a pattern-shaped coating film composed of pixels of different colors (three colors or four colors).

The solid-state image pickup device is not particularly limited as long as it contains the above-mentioned black matrix and functions as a solid-state image pickup device. For example, the solid-state image pickup device constitutes a light-receiving area of a solid-state image pickup device (CCD image sensor, CMOS image sensor, A solid-state image pickup device containing a plurality of photodiodes, a light receiving element made of polysilicon or the like, and a black matrix on the surface opposite to the light receiving element formation surface of the substrate.

The color filter may have a structure in which a cured film for forming pixels of each color is embedded in a space defined by, for example, a lattice shape by the partition. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the solid-state image pickup device having such a structure include the solid-state image pickup devices disclosed in Japanese Unexamined Patent Application Publication No. 2227478 and Japanese Unexamined Patent Application Publication No. 2014-179577.

[Image display device]

The cured film can be suitably used for an image display apparatus (for example, a liquid crystal display apparatus and an organic electroluminescence display apparatus).

The definition of the image display apparatus and the details of each image display apparatus are described in detail, for example, in "Electronic Display Device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 Issued)" and "Display Device (Ibukisumi Architect, Issued by Tohoshinho Co., Ltd.). The liquid crystal display device is described in, for example, " Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The cured film is suitable, for example, for a liquid crystal display device of the type described in the " Next Generation Liquid Crystal Display Technology ".

As an embodiment of the liquid crystal display device containing the cured film, for example, a color filter, a liquid crystal layer and a liquid crystal driving means (a simple matrix driving method and an active matrix driving method) are provided between a pair of substrates, And a liquid crystal display device containing at least the above. The liquid crystal display device includes a color filter containing a plurality of pixel groups and each pixel constituting the pixel group being separated from each other by the cured film (black matrix).

Another aspect of the liquid crystal display device includes at least a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of substrates, at least one of which is light transmissive, and the liquid crystal driving means includes an active element Transistor), and also contains a color filter containing the cured film (black matrix) between each active element.

The color filter containing the cured film is suitable for a color TFT (Thin Film Transistor) type liquid crystal display. The color TFT type liquid crystal display device is described in, for example, " Color TFT liquid crystal display (published by Kyoritsu Shootpan Co., Ltd., 1996) ". Also, the color filter may be a transverse electric field driving system such as IPS (In Plane Switching) or the like; Pixel division method such as MVA (Multi-domain Vertical Alignment); (Twisted Nematic), TN (Twisted Nematic), VA (Vertical Alignment), on-chip spacer (OCS), fringe field switching (FFS), and R-OCB Reflective Optically Compensated Bend).

The color filter is suitable for a liquid crystal display device of a color-filter on array (COA) method which is bright and fixed. In the COA type liquid crystal display device, the required characteristics for the color filter may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the usual required characteristics. The COA type liquid crystal display device containing the color filter has better resolution or better durability. Further, in order to satisfy the required property of low dielectric constant, a resin film may be further contained on the color filter layer.

These image display methods are described in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (published by Toray Research Center Research Division, 2001). In the above, EL stands for Electroluminescence, PDP stands for Plasma Display Panel, and LCD stands for Liquid Crystal Display.

The liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle assurance film in addition to the color filter. The color filter can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "Market of Liquid Crystal Display Materials and Chemicals (1994) issued by Shimaguchi Co., Ltd. (CMC Co., Ltd.)" and "2003 Liquid Crystal Related Market Phenomenon and Future Prospects (Published by Fuji Chimera Soken Co., Ltd., 2003).

For the backlight, please refer to the SID meeting Digest 1380 (2005) (A. Konnoet. Al), and / or Monthly Display December 2005, pages 18-24 (Yoshihiro Shimaya), 25-30 pages (Yagi Takaaki) .

The curing film may be a portable device such as a personal computer, a tablet, a mobile phone, a smart phone, and a digital camera; Office automation (OA) devices such as printer multi-function devices and scanners; Industrial devices such as surveillance cameras, bar code readers, and self-certification using automated teller machines (ATMs), high-speed cameras and face image authentication; Vehicle camera equipment; Medical camera devices such as an endoscope, a capsule endoscope, and a catheter; Optical filters and modules used for space sensors such as biosensors, biosensors, military reconnaissance cameras, three-dimensional map cameras, weather and marine observation cameras, land resource exploration cameras, and space exploration cameras for space astronomical and deep space targets Shielding layer, and furthermore, an antireflection member and an antireflection layer.

The cured film can be used for a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). The cured film is suitable for a member that provides a light shielding function or an antireflection function in addition to an optical filter and an optical film used in a micro LED and a micro OLED.

Examples of the micro LED and the micro OLED include those described in JP-A-2015-500562 and JP-A-2014-533890.

The cured film is suitable as an optical and optical film used in a quantum dot display. Further, the cured film is suitable as a member for imparting a shielding function and an antireflection function.

Examples of quantum dot displays are disclosed in U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 And the like.

Example

Hereinafter, the present invention will be described in more detail based on examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not construed to be limited by the following embodiments.

〔coloring agent〕

Each colorant was prepared by the following method.

&Lt; Titanium nitride-containing particles (TiN-1) >

First, Ti particles (TC-200, manufactured by DoHo Co., Ltd.) were subjected to plasma treatment in an Ar gas to obtain Ti nanoparticles. The Ti nanoparticles after the plasma treatment were left under an Ar gas atmosphere for 24 hours under the condition of an O ₂ concentration of 50 ppm or less at 30 캜. Then, O ₂ concentration was 30 ℃, 24 sigan value according to the introduction of O ₂ gas in the Ar atmosphere so that the 100ppm state (pre-treatment of the Ti particles).

Thereafter, the obtained Ti nanoparticles were classified using a TOSP separator manufactured by Hosokawa Micron under the condition that the yield was 10% to obtain Ti powder. The primary particle size of the obtained powder was found to be 120 nm by an average arithmetic average of 100 particles obtained by TEM observation.

Titanium nitride-containing particles TiN-1 were produced by using a device similar to the apparatus for producing black composite fine particles described in FIG. 1 of International Publication No. 2010/147098.

Specifically, in the black composite fine particle production apparatus, a high-frequency voltage of about 4 MHz and about 80 kVA was applied to the high frequency oscillation coil of the plasma torch, and argon gas of 50 L / min and nitrogen of 50 L / min as the plasma gas A mixed gas was supplied to generate an argon-nitrogen thermal plasma salt in the plasma torch. And a carrier gas of 10 L / min was supplied from a spray gas supply source of the material supply device.

Fe powder (JIP270M, manufactured by JFE Steel) and Si powder (Silicon powder SI006031) were mixed with the Ti particles thus obtained so that the mass ratio of Ti / Fe / Si = balance / 0.05.05.05. This mixture was supplied into a thermal plasma salt in a plasma torch together with argon gas as a carrier gas, and was evaporated in a thermal plasma salt to be highly dispersed in a gaseous state.

Nitrogen was used as the gas to be supplied into the chamber by the gas supply device. At this time, the flow rate in the chamber was 5 m / sec, and the supply amount was 1,000 L / min. The pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value).

Thus, titanium nitride-containing particles TiN-1 were obtained.

The content of titanium (Ti) atoms, iron (Fe) atoms and silicon (Si) atoms in the obtained titanium nitride-containing particles TiN-1 was measured by ICP emission spectroscopy. For ICP emission spectrometry, an ICP emission spectrochemical analyzer " SPS3000 " (trade name) manufactured by Seiko Instruments Inc. was used.

The content of nitrogen atoms was measured using an oxygen / nitrogen analyzer " EMGA-620W / C " (trade name) manufactured by Horiba Seisakusho Co., Ltd. and calculated by an inert gas melting-thermal conductivity method. As a result, the mass ratio of each atom contained in the titanium nitride-containing particles TiN was Ti / N / Fe / Si = 57/34 / 0.0030 / 0.0020.

The X-ray diffraction of the titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name "RU-200R" manufactured by Rigaku Denki Co., Ltd.) in which a powder sample was placed in a standard sample holder made of aluminum. The measurement conditions are as follows: the X-ray source is a CuK? Ray; the output is 50 kV / 200 mA; the slit system is 1 ° -1 ° -0.15 mm -0.45 mm; the measurement step (2θ) is 0.02 °; did.

Then, the diffraction angle of a peak originating from the TiN (200) plane observed near the diffraction angle 2? (42.6 °) was measured. Further, the crystallite size constituting the particles was obtained by using Scherrer's equation from the half width of the peak derived from the (200) plane. As a result, the diffraction angle of the peak was 42.62 占 and the crystallite size was 10 nm. In addition, no X-ray diffraction peak due to TiO ₂ was observed at all.

&Lt; Titanium nitride-containing particles TiN-2 >

Fe powder and Si powder were mixed so that the respective mass ratios of Ti / Fe / Si = remainder / 0.5 / 1 were obtained using "578347" manufactured by Sigma-Aldrich Co. instead of "TC- Titanium nitride-containing particles TiN-2 were obtained in the same manner as TiN-1, except for mixing.

The diffraction angle of the peak measured by X-ray diffraction was 42.81 占 and the crystallite size was 12 nm.

&Lt; Titanium nitride-containing particles TiN-3 >

Titanium nitride-containing particles TiN-3 were obtained in the same manner as in the case of TiN-1 except that the Fe powder and the Si powder were mixed so that the respective mass ratios were Ti / Fe / Si = remainder / 1/2.

The diffraction angle of the peak measured by X-ray diffraction was 43.1 DEG and the crystallite size was 12 nm.

<Production of Titanium Black A-1>

With a mean particle size of 15nm titanium oxide MT-150A (trade name, day car (Ltd.)) to 100g, BET (Brunauer, Emmett, Teller) specific surface area of silica particles of 300m ² / g AEROSIL300 (R) 300/30 (EVO Nick Ltd.) and 100 g of Disperbyk 190 (trade name, manufactured by Big Chemie) were weighed and added to 71 g of ion exchange water to obtain a mixture. Thereafter, using a MAZERSTAR KK-400W manufactured by KURABO, the mixture was treated at an idling speed of 1,360 rpm and a rotating speed of 1,047 rpm for 30 minutes to obtain a uniform mixture aqueous solution. The mixture aqueous solution was filled in a quartz container and heated to 920 占 폚 in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Kogyo Co., Ltd.). Subsequently, the inside of the small rotary kiln was replaced with nitrogen, and ammonia gas was flown at 100 mL / min for 5 hours at the same temperature, thereby performing nitridation reduction treatment. The recovered powder was pulverized with a mortar to obtain a titanium black having a specific surface area of 73 m &lt; ² &gt; / g in powder form including titanium atoms (titanium black particles and dispersed particles containing Si atoms) , &Quot; Titanium Black A-1 &quot;).

<Production of Niobium Nitride Containing Particles (NbN) Containing Fe Atoms>

A niobium nitride-containing particle containing Fe atoms was prepared by the following method.

First, Mitsuwa Kagakuyaku Hinzanai Oxide (powder) <100-325 mesh> was prepared as a raw material (hereinafter also referred to as "metal raw material powder").

Next, the above metal raw material powder was subjected to plasma treatment in an Ar gas to obtain Nb nanoparticles. The conditions of the plasma treatment were the following plasma treatment (1).

(Plasma treatment (1))

Plasma treatment (1) was carried out by the following method. (1) was carried out by using a device similar to the above-mentioned apparatus for producing black composite fine particles under the following conditions.

· High-frequency voltage applied to high-frequency oscillation coil: frequency about 4 MHz, voltage about 80 kVA

Plasma gas: argon gas (supply amount: 100 L / min)

Carrier gas: argon gas (supply amount 10 L / min)

Atmosphere in the chamber: argon gas (feed rate: 1,000 L / min, flow rate in the chamber: 5 m / sec)

· Atmosphere in the cyclone: argon gas, pressure of 50 kPa

· Material feed rate from chamber to cyclone: 10 m / s (average value)

Next, an Fe powder (JIP270M, manufactured by JFE Steel) was prepared and subjected to plasma treatment under the conditions of the plasma treatment (1) to obtain Fe nanoparticles.

Next, the obtained Nb nanoparticles and Fe nanoparticles were mixed to obtain a raw metal powder. This raw material metal powder was subjected to plasma treatment in a nitrogen gas to obtain niobium nitride-containing particles. The conditions of the plasma treatment were the following plasma treatment (2).

(Plasma treatment (2))

Plasma treatment (2) was carried out by the following method. Further, the apparatus used was the same as the plasma processing (1).

· High-frequency voltage applied to high-frequency oscillation coil: frequency about 4 MHz, voltage about 80 kVA

Plasma gas: argon gas and nitrogen gas (supplied at 50 L / min each)

Carrier gas: Nitrogen gas (supply amount 10 L / min)

Atmosphere in the chamber: nitrogen gas (feed rate: 1,000 L / min, flow rate in the chamber: 5 m / sec)

· Atmosphere in cyclone: Nitrogen gas, internal pressure 50 kPa

· Material feed rate from chamber to cyclone: 10 m / s (average value)

After the completion of the plasma treatment (2), nitrogen gas at 20 캜 was introduced under the condition that the relative humidity was 95% when the atmosphere was in the atmosphere, using Ar gas, by a classification type humidity supplying device SRH manufactured by Nihon Shintech Co., did. Thereafter, the obtained particles were classified under the condition of a yield of 10% using a Tosp separator made by Hosokawa Micron to obtain niobium nitride-containing particles (NbN). Further, nitrogen gas was supplied to the separator.

The obtained niobium nitride-containing particles were found to have a content of iron (Fe) atoms of 50 mass ppm by ICP emission spectrometry.

<Production of vanadium nitride-containing particles (VN) containing Fe atoms>

Except that the metal vanadium powder VHO made by Daikko Kogyo Co., Ltd. was used instead of Mitsuwagakagaku-ku Hinzanai Ondum (powder) < 100-325mesh > in the production of the niobium nitride- (VN) containing vanadium nitride was prepared. The content of iron (Fe) atoms in the obtained vanadium nitride-containing particles was measured by ICP emission spectroscopy and found to be 50 mass ppm.

[Polyfunctional thiol compound]

As the polyfunctional thiol compound, the following SH-4, SH-3 and SH-2 were used.

· SH-4 (corresponding to pentaerythritol tetra (3-mercaptopropionate), tetra-functional thiol compound)

(28)

· SH-3 (equivalent to trimethylolpropanol (3-mercaptopropionate), trifunctional thiol compound)

[Chemical Formula 29]

· SH-2 (equivalent to 1,4-butanediol bis (thioglycolate), bifunctional thiol compound)

(30)

[Dispersant]

As the dispersant, a dispersant A having the following structure was used. The numerical values given in each structural unit are intended to indicate the mass% of each structural unit with respect to the total structural unit.

· Dispersant A

(31)

[Binder Resin]

As the binder resin, the following resin A was used. The numerical values given in each structural unit are intended to represent the mole% of each structural unit with respect to the total structural unit. In the formulas of the resin A, the respective abbreviations indicate the following.

BzMA: benzyl methacrylate

MMA: methyl methacrylate

· Resin A

(32)

[Polymerizable compound]

Polymerizable compound M1: dipentaerythritol hexaacrylate (trade name: " KAYARAD ", manufactured by Nippon Kayaku Co., Ltd.,

(33)

[Photopolymerization initiator]

OXE-01: Irgacure OXE01 (trade name, manufactured by BASF Japan)

(34)

OXE-02: Irgacure OXE02 (trade name, manufactured by BASF Japan)

(35)

PI-3: A photopolymerization initiator having the following structure

(36)

NCI-831 (trade name, manufactured by ADEKA)

(37)

IRG-379: IRGACURE 379 (trade name, manufactured by BASF Japan)

(38)

[Polymerization inhibitor]

Ih-1: 4-methoxyphenol

Ih-2: 2,6-Di-tert-butyl-4-methylphenol

Ih-3: 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical

〔Surfactants〕

F-1: The compound represented by the following formula (weight average molecular weight (Mw) = 15,311)

In the following formulas, the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. Among the structural units represented by the formula (B), a, b, and c satisfy the relationship of a + c = 14 and b = 17, respectively.

[Chemical Formula 39]

[Organic solvents]

PGMEA: propylene glycol monomethyl ether acetate

· Cyclopentanone

· Acetic acid butyl

[Preparation of colorant dispersion]

First, the colorant, the dispersant, and the organic solvent were mixed by a stirrer (EUROSTAR manufactured by IKA Corporation) for 15 minutes to obtain a mixed solution of the above components. Next, the resulting mixed solution was subjected to dispersion treatment using NPM-Pilot manufactured by Shinmaru Enterprise Co., Ltd. under the following conditions to obtain a colorant dispersion.

<Dispersion Condition>

· Bead diameter: φ0.05mm, (Zirconia beads, YTZ made by Nikka Corporation)

· Beads filling rate: 65 vol%

· Mill speed: 10m / sec

Separator speed: 13 m / s

· Mixed liquid amount to be dispersed: 15 kg

· Circulating flow (pump supply): 90kg / hour

· Treatment temperature: 19 ~ 21 ℃

· Cooling water: water

· Processing time: About 22 hours

[Preparation of curable composition]

Next, the colorant dispersion, the polyfunctional thiol compound, the binder resin, the polymerizable compound, the polymerization initiator, the polymerization inhibitor, and the surfactant were mixed and stirred, The respective curable compositions of the Examples and Comparative Examples were obtained. The content of each component in Table 1-1, Table 1-2, and Table 2 is all% by mass.

The final solid content of each of the curable compositions was adjusted with an organic solvent so as to have the solid content concentrations shown in Tables 1-1, 1-2 and 2. The organic solvent was used in combination so that the mass ratio in each curing composition was PGMEA / butyl acetate / cyclohexanone = 27/18/27.

[evaluation]

The following evaluation tests were carried out on each of the curable compositions of Examples and Comparative Examples. The results are summarized in Table 1-1 and Table 1-2.

[OD value]

On each glass plate (Eagle XG, manufactured by Corning) having a thickness of 0.7 mm and a square of 10 cm, a coating film was formed by spin coating using each of the curable compositions. At this time, the number of revolutions was adjusted so as to obtain a cured film having a film thickness of 1.5 탆. A film forming, to 100 ℃ on a hot plate, and dried by heat treatment for 2 minutes, exposed in a exposure dose of 500mJ / cm ^2, to obtain cured films. The OD value of the glass substrate containing the obtained cured film was measured by a spectrophotometer U-4100 (manufactured by Hitachi High Technologies). The larger the OD value, the better the light shielding property of the cured film. The results are summarized in Table 1-1, Table 1-2 and Table 2.

The OD values shown in Table 1-1, Table 1-2, and Table 2 are the minimum values at wavelengths of 400 to 800 nm. That is, the cured film (film thickness: 1.5 m) of each example has an OD value equal to or more than the OD value shown in Tables 1-1, 1-2, and Table 2 over the entire wavelength range of 400 to 800 nm.

[Pattern shape]

Using the respective curable compositions on the Si substrate, the number of revolutions was adjusted so as to obtain a cured film having a film thickness of 1.5 mu m, and a coating film was formed by spin coating. The formed coating film was dried on a hot plate by heat treatment at 100 DEG C for 2 minutes to obtain a cured film. With respect to the Si substrate containing the obtained cured film, the substrate having the coated film after the pre-baking was exposed to light through the photomask having a 200 mu m long x 20 mu m wide line pattern formed thereon using an i-line stepper (FPA3000i5 + , The coating film was exposed. The coated film after exposure was subjected to a puddle development for 30 seconds by Coater Developer ACT8 manufactured by Tokyo Electron using tetramethylammonium hydroxide as a developer. After development, shower rinse treatment was performed for 20 seconds by pure water. The coated film after development was post-baked (temperature: 220 캜, time: 300 seconds). The pattern shape of the coated film after post-baking was measured by a scanning SEM (Scanning Electron Microscope). Specifically, the film thickness of the end portion of the line pattern and the film thickness of the central portion were measured, and the ratio (film thickness of the end portion of the pattern / film thickness of the central portion) was calculated and evaluated according to the following criteria. The results are summarized in Table 1-1, Table 1-2 and Table 2. In addition, evaluation "2" or more is a practical range.

7: The ratio is more than 0.98 and not more than 1.00, and the difference in film thickness between the central portion and the end portion of the pattern can not be seen by the observation by SEM.

6: The ratio is more than 0.96 but not more than 0.98, and a slight difference is seen in the film thickness of the pattern central portion and the end portion.

· 5: The ratio is more than 0.94 and not more than 0.96, and a difference is seen in the film thicknesses at the central portion and the end portion of the pattern.

· 4: A level of more than 0.92 but not more than 0.94.

· 3: The level is more than 0.90 but not more than 0.92, and the thickness of the end portion is thin and deformed but practically no problem.

2: The ratio is more than 0.80 but not more than 0.90, and the thickness of the end portion is thin, but the practical level is possible.

· 1: The ratio is not more than 0.80, the thickness of the end portion is thin, and not allowed.

[Stability over time]

Each of the curable compositions after the preparation was sealed in a 100 cc Bloom bottle and stored in a thermostatic chamber at 45 캜 for 7 days. Thereafter, the pattern shape was evaluated in the same manner as described above. The results are shown in Table 2.

[Table 1-1]

[Table 1-2]

[Table 2]

From the results shown in Tables 1-1 and 1-2, it was found that the curable composition containing the colorant, the photopolymerization initiator, the polymerizable compound and the polyfunctional thiol compound, of the cured film obtained by curing the curable composition, The cured film obtained by curing the curable composition of each example having an optical density per film thickness of 1.5 占 퐉 of 4.0 or more had an excellent pattern shape. On the other hand, the curable composition of Comparative Example had no desired effect.

The curable composition of Example 48, in which the content of the colorant was 55% by mass or more based on the total solid content of the curable composition, was higher than that of the curable composition of Example 49 in which the content of the dispersant was about the same and the content of the colorant was 53% The pattern shape of the resulting cured product was more excellent.

The curable compositions of Examples 1, 2 and 3, in which the content of the polyfunctional thiol compound was 1 to 5.5% by mass with respect to the content of the colorant, were compared with those of the curable composition of Example 4, The shape of the water pattern was better.

The curable composition of Example 45 containing two or more phenol compounds as a polymerization inhibitor was cured at a lower exposure dose as compared with the curable composition of Example 36 and the pattern shape of the cured product was excellent.

The curable composition of Example 46 containing a phenol-based compound and a hindered amine-based compound as a polymerization inhibitor was cured at a lower exposure dose as compared with the curable composition of Example 36, and the pattern shape of the cured product was excellent.

The curable composition of Example 5 in which the polyfunctional thiol compound was trifunctional had a better pattern shape of the cured product than the curable composition of Example 9. [

The curable composition of Example 1, in which the polyfunctional thiol compound was tetrafunctional, had a better pattern shape of the cured product than the curable compositions of Examples 9 and 5.

The curable composition of Example 34 in which the photopolymerization initiator was an oxime compound had a better pattern shape of the cured product than the curable composition of Example 25.

The curable compositions of Examples 13 and 48, in which the content of the photopolymerization initiator was more than 1% by mass and less than 10% by mass based on the total solid content of the curable composition, were compared with the curable compositions of Examples 50 and 51, The shape was better.

The curable compositions of Examples 13 and 48, in which the content of the polymerizable compound was more than 3.5% by mass and less than 20% by mass based on the total solid content of the curable composition, were compared with the curable compositions of Examples 50 and 51, The pattern shape was better.

The curable compositions of Examples 2 and 48, in which the content of the dispersant was 17% by mass or more, were more excellent in the pattern shape of the cured product than the curable compositions of Examples 13 and 54.

A curable composition was prepared in the same manner as in Example 1, except that the surfactant F-1 was not used, and evaluation was conducted using the same. As a result of the evaluation, it was found that the same results as in Example 1 were obtained.

[Preparation of Carbon Black Dispersion (CB Dispersion) and Evaluation of Curable Composition]

In the preparation of the above colorant dispersion, the coloring agent was dispersed in carbon black (trade name "Color Black S170", manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m ² / g, carbon black produced by the gas black method) A carbon black dispersion (CB dispersion) was obtained by the same method.

In the preparation of the curable composition of Example 1, a colorant dispersion liquid containing titanium nitride-containing particles TiN-1 was prepared in the same manner as in Example 1, except that the colorant dispersion was prepared in the same manner as in Example 1, except that the colorant dispersion was prepared by adding 58% by mass of titanium nitride- The total content of the titanium nitride-containing particles TiN-1 in the curable composition: carbon black in the curable composition = 45: 13 (mass ratio), the titanium nitride-containing particles TiN-1 in the curable composition and the carbon black was 58 mass% %) Was used in place of the curable composition, and the curable composition was evaluated in the same manner. As a result of the evaluation, it was found that the same light-shielding properties and pattern shapes as in Example 1 were obtained.

[Preparation of a chromatic pigment dispersion (PY dispersion) and evaluation of a curing composition]

A chromatic pigment dispersion (PY dispersion (a pigment dispersion) was prepared in the same manner as in the preparation of the above colorant dispersion except that the coloring agent was Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name: 6150 Pigment Yellow 5GN) ).

In the preparation of the curable composition of Example 1, a colorant dispersion liquid containing titanium nitride-containing particles TiN-1 was prepared in the same manner as in Example 1, except that the colorant dispersion was prepared in the same manner as in Example 1, except that the colorant dispersion was prepared by adding 58% by mass of titanium nitride- PY dispersion (titanium nitride-containing particles TiN-1 in the curable composition: Pigment Yellow 150 in the curable composition = 45: 13 (mass ratio), the total content of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the curable composition Is 58% by mass), a curable composition was prepared in the same manner as above, and evaluation was conducted using the same. As a result of the evaluation, it was found that the same light-shielding properties and pattern shapes as in Example 1 were obtained, and a darker black film was obtained.

[Preparation of a chromatic pigment dispersion (PR dispersion)] [

A chromatic pigment dispersion (PR dispersion) was obtained in the same manner as in the preparation of the above colorant dispersion except that C. I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals) was used as the colorant.

[Preparation of a chromatic pigment dispersion (PB dispersion)] [

A chromatic pigment dispersion (PB dispersion) was obtained in the same manner as in the preparation of the above colorant dispersion except that C. I. Pigment Blue 15: 6 (manufactured by DIC Corporation) was used as the colorant.

[Preparation of a chromatic pigment dispersion (PV dispersion)] [

A chromatic pigment dispersion (PV dispersion) was obtained in the same manner as in the preparation of the above colorant dispersion except that C. I. Pigment Violet 23 (manufactured by Clariant) was used as the colorant.

The titanium nitride-containing particles TiN-1, PY, PR, PB, and TiN-1 were prepared in the same manner as in the preparation of the curable composition of Example 1 except that the pigment dispersion containing the titanium nitride- 1: PY: PR: PB: PV = 70: 17: 37) and the PV dispersion (ratio of titanium nitride-containing particles TiN-1, PY, PR, PB and PV in the curable composition; TiN- : 36: 10 (mass ratio), the total content of titanium nitride-containing particles TiN-1, PY, PR, PB and PV in the curable composition was 58 mass%) was used to prepare a curable composition. And evaluated. As a result of the evaluation, it was found that the same light-shielding property and the same pattern shape as in Example 1 were obtained, and a film excellent in light-shielding property in the infrared region was obtained.

In the preparation of the curable composition of Example 1, the titanyl nitride-containing particle TiN-1 and the following compound SQ-1 were used instead of the colorant dispersion in which the titanium nitride-containing particles TiN-1 were added so as to contain 58% (Titanium nitride-containing particles TiN-1 and compound SQ-23 in the curable composition: titanium nitride-containing particles TiN-1: compound SQ-23 = 50: 8 (mass ratio) TiN-1, and SQ-23 was 58 mass%) was used as the curing composition. As a result of the evaluation, it was found that the same light-shielding property and the same pattern shape as in Example 1 were obtained, and a film excellent in light-shielding property in the infrared region was obtained.

In the preparation of the curable composition of Example 1, the titanyl nitride-containing particles TiN-1 and the following compound A-52 shown below were used instead of the colorant dispersion in which the titanyl nitride-containing particles TiN-1 were added so as to contain 58% Titanium nitride-containing particles TiN-1: Compound A-52 = 50: 8 (mass ratio), titanium nitride-containing particles TiN-1 in the curable composition, TiN- 1, and the total content of the compound A-52 was 58 mass%) was used in place of the curing composition. As a result of the evaluation, it was found that the same light-shielding property and the same pattern shape as in Example 1 were obtained, and a film excellent in light-shielding property in the infrared region was obtained.

Compound SQ-23

(40)

Compound A-52

(41)

101 support
102 Curable composition layer
103 Photomask
201 curing membrane
301 Curing film after post-baking
401 Curable composition layer
402 mask shading part
501 curing membrane
601 Post-baked curing membrane

Claims (26)

As a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound,
The optical density per film thickness of 1.5 占 퐉 in the visible light region of the cured film obtained by curing the curable composition is 4.0 or more. The method according to claim 1,
Wherein the content of the coloring agent is 55% by mass or more based on the total solid content of the curable composition. The method according to claim 1 or 2,
Wherein the content of the polyfunctional thiol compound is 1 to 5.5% by mass with respect to the content of the colorant. The method according to any one of claims 1 to 3,
A curing composition further comprising a polymerization inhibitor. The method of claim 4,
Wherein the content of the polymerization inhibitor is 0.1 to 1.5% by mass with respect to the content of the polyfunctional thiol compound. The method according to claim 4 or 5,
Wherein the polymerization inhibitor contains a phenolic compound. The method according to any one of claims 4 to 6,
Wherein the polymerization inhibitor contains two or more phenolic compounds. The method according to any one of claims 4 to 7,
Wherein the polymerization inhibitor comprises a hindered amine compound. The method according to any one of claims 1 to 8,
Wherein the coloring agent is an inorganic pigment. The method of claim 9,
Wherein the inorganic pigment contains at least one member selected from the group consisting of a metallic pigment containing titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin, and a metal pigment containing silver and tin Curable composition. The method according to any one of claims 1 to 10,
Wherein the polyfunctional thiol compound is a compound having two or more groups represented by formula (1).
[Chemical Formula 1]

In the formula (1), L ¹ represents a single bond or -CO-, and L ² represents a single bond or a divalent linking group. The method according to any one of claims 1 to 11,
Wherein the polyfunctional thiol compound is trifunctional or higher. The method according to any one of claims 1 to 12,
Wherein the polyfunctional thiol compound is at least one selected from the group consisting of pentaerythritol tetra (3-mercaptopropionate), and trimethylol propanol (3-mercaptopropionate) . The method according to any one of claims 1 to 13,
Wherein the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass based on the total solid content of the curable composition. The method according to any one of claims 1 to 14,
Wherein the content of the polymerizable compound is more than 3.5 mass% and less than 20 mass% with respect to the total solid content of the curable composition. The method according to any one of claims 1 to 15,
Wherein the content of the dispersing agent is 17 mass% or more based on the total solid content of the curable composition. The method according to any one of claims 1 to 16,
Wherein the photopolymerization initiator is an oxime compound. A cured film obtained by curing the curable composition according to any one of claims 1 to 17. A color filter comprising the cured film according to claim 18. A light-shielding film containing the cured film according to claim 18. A solid-state imaging device comprising the cured film according to claim 18. An image display device comprising the cured film according to claim 18. A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 17,
And exposing the curable composition layer to light. 24. The method of claim 23,
Wherein an exposure amount of the curable composition layer in the exposure step is 200 mJ / cm ² or more. The method of claim 23 or 24,
Wherein the step of forming the curable composition layer comprises a step of directly applying the curable composition on the support and forming the layer of the curable composition on the support. 26. The method according to any one of claims 23 to 25,
A developing step of developing the exposed layer of the curable composition,
And a cleaning step of cleaning the developed layer of the curable composition.

Images