JP5184993B2 - Black curable composition, light-shielding color filter for solid-state image sensor, method for producing the same, and solid-state image sensor - Google Patents

Description

  The present invention relates to a black curable composition, a light-shielding color filter for a solid-state image sensor, a manufacturing method thereof, and a solid-state image sensor.

A color filter used in a liquid crystal display device is provided with a light-shielding color filter called a black matrix for the purpose of shielding light between colored pixels and improving contrast. A solid-state image sensor is also provided with a light-shielding color filter for the purpose of preventing noise and improving image quality.
A photosensitive resin composition containing a black color material such as carbon black or titanium black is known as a composition for forming a black matrix for a liquid crystal display device or a light-shielding color filter for a solid-state imaging device. (For example, refer to Patent Documents 1 to 5).

The black matrix for liquid crystal display devices is mainly required to have a light shielding property in the visible region, while the light shielding color filter for the solid-state imaging device has a light shielding property in the infrared region in addition to the light shielding property in the visible region. It is necessary to prepare.
That is, as a light-shielding color filter for a solid-state imaging device, it is necessary to shield light having a wavelength in the infrared region of 800 to 1300 nm as well as light shielding property in the visible region in order to prevent noise generation. When a light-shielding color filter for a solid-state image sensor is formed using a photosensitive resin composition using a black pigment such as carbon black, which has been used in a black matrix of a conventional liquid crystal display device, etc., the light shielding in the infrared region In order to satisfy the requirement of light shielding in the infrared region, it was necessary to increase the carbon content or to thicken the black layer of the light shielding color filter.

  When carbon black was used for curing by exposure to ultraviolet rays or the like, the transmittance in the wavelength region of 300 to 500 nm was extremely low, curing was difficult, and a product satisfying the above requirements could not be obtained. Titanium black has a higher light shielding property in the infrared region than carbon black, and has a transmittance of 300 to 500 nm higher than that of carbon black, but the transmittance is insufficient, resulting in insufficient curing and sensitivity. Lower.

Further, a light-shielding color filter for a solid-state image sensor is required to achieve both improvement of light-shielding property and thinning. In order to achieve both, it is necessary to increase the content of the black color material. Increasing the content of titanium black in order to obtain high light-shielding properties decreases the transmittance of exposure light, so that curing proceeds on the light-irradiated surface of the light-shielding color filter, but curing does not proceed easily in the vicinity of the substrate, If the exposure is increased to prevent this problem, the productivity will be inferior, the size will be larger than the desired pattern, or the taper will not be rectangular. As a result, a difficult problem has arisen in designing a fine pattern.
Japanese Patent Laid-Open No. 10-246955 JP-A-9-54431 Japanese Patent Laid-Open No. 10-46042 JP 2006-36750 A JP 2007-115921 A

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, the present invention has a light-shielding property in a wide range from the ultraviolet region to the infrared region, has good substrate adhesion, high sensitivity, and can form a high-definition pattern. It aims at providing the black curable composition useful for formation of a color filter.
Further, another object of the present invention is to use the black curable composition of the present invention so that it is fine and has a solid color pattern that achieves light shielding properties in a wide range from the ultraviolet region to the infrared region. An object of the present invention is to provide a light-shielding color filter for an image pickup device and a solid-state image pickup device including the same, in which noise generation is prevented and image quality is improved.

一般式（３）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。ｎは１〜５の整数である。
＜２＞ 前記（Ｂ）アルカリ可溶性樹脂の重量平均分子量／数平均分子量が、１．１〜３．０の範囲である＜１＞に記載の黒色硬化性組成物。 Specific means for solving the above problems are as follows.
<1> (A) Titanium black, (B) Alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000, (C) solvent, (D) oxime represented by the following general formula (3) A black curable composition comprising a photopolymerization initiator and (E) a compound containing an ethylenically unsaturated double bond.

In general formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.
<2> The black curable composition according to <1>, wherein the weight average molecular weight / number average molecular weight of the (B) alkali-soluble resin is in a range of 1.1 to 3.0.

<3> The black curable composition according to <1> or <2>, wherein the acid value of the (B) alkali-soluble resin is in the range of 50 to 200 mgKOH / g.
<4> The black curable composition according to any one of <1> to <3>, wherein the residual monomer content in the (B) alkali-soluble resin is 10% by mass or less.

< 5 > A light-shielding color filter for a solid-state imaging device, comprising the black curable composition according to any one of <1> to < 4 >.
< 6 > An antireflection film for a solid-state imaging device, comprising the black curable composition according to any one of <1> to < 4 >.

< 7 > A step of applying the black curable composition according to any one of <1> to < 4 > on a support, a step of exposing through a mask, and a step of developing to form a pattern. A method for producing a light-shielding color filter for a solid-state imaging device.
< 8 > A solid-state imaging device comprising the light-shielding color filter for a solid-state imaging device according to < 5 >.

According to the present invention, it has a light shielding property in a wide range from the ultraviolet region to the infrared region, has a good substrate adhesion, a high sensitivity, and can form a high-definition pattern. A black curable composition useful for forming a color filter can be provided.
Further, by using the black curable composition of the present invention, the light-shielding property for a solid-state imaging device having a fine color pattern that achieves light-shielding properties in a wide range from the ultraviolet region to the infrared region. It is possible to provide a color filter and a solid-state imaging device including the color filter, in which noise generation is prevented and image quality is improved.

Hereinafter, the best mode for carrying out the invention will be described in detail.
The present invention includes (A) titanium black, (B) an alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000, (C) a solvent, (D) an oxime represented by the general formula (3) It is achieved by a black curable composition comprising a system photopolymerization initiator and (E) a compound containing an ethylenically unsaturated double bond.
In addition, in the description of a group (atomic group) in this specification, the description which does not describe substitution and non-substitution means that what has a substituent is included with what does not have a substituent. For example, the expression “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The acrylic group and the methacryl group are collectively referred to as a (meth) acryl group.

In the present invention, the “light-shielding color filter” means (A) titanium black, (B) an alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000, (C) a solvent, (D) a general formula (3 ) An oxime-based photopolymerization initiator represented by (II), and (E) a black curable composition containing at least a compound containing an ethylenically unsaturated double bond. Say. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a black or gray color mixed with a chromatic color.
The “light-shielding color filter” includes (A) titanium black, (B) an alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000, (C) a solvent, and (D) a general formula (3). The black curable composition containing at least the oxime-based photopolymerization initiator represented by (E) and the compound containing an ethylenically unsaturated double bond is obtained by exposure and development. In other words, it may be a film or a light shielding filter.

<(A) Titanium black>
The (A) titanium black of the present invention is black particles having a titanium atom. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water repellent material as disclosed in JP-A-2007-302836. .

In addition, the titanium black of the present application is a composite oxide such as Cu, Fe, Mn, V, and Ni, and a black pigment such as cobalt oxide, iron oxide, carbon black, and aniline black for the purpose of adjusting dispersibility and colorability. One or a combination of two or more types may be included. In this case, titanium black particles occupy 50% by mass or more of the pigment.
In addition, for the purpose of controlling the light-shielding property of a desired wavelength, existing colorants such as red, blue, green, yellow, cyan, magenta, violet, orange, etc., or dyes, or carbon black, iron oxide It is also possible to add other black pigments such as manganese oxide and graphite.

The pigment used in combination is preferably in the range of 2 to 50 parts by mass of the combined pigment, more preferably in the range of 2 to 30 parts by mass of the combined pigment with respect to 100 parts by mass of the sum of the black pigment and the combined pigment. Most preferably, the combined pigment is in the range of 2 to 10 parts by mass. When the black pigment is within this range, the light shielding property is high and preferable.
Further, in the black pigment, the content of titanium black is in the range of 30 to 100 parts by mass, preferably in the range of 50 to 100 parts by mass with respect to 100 parts by mass of the black pigment. More preferably, it is the range of 75-100 mass parts. When titanium black is within this range, a wide range of wavelengths from the visible region to the infrared region can be shielded.

  Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., and Tilac D manufactured by Mitsubishi Materials Corporation.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

The average primary particle size of the titanium black particles is not particularly limited, but is preferably from 3 to 300 nm, more preferably from 10 to 150 nm, from the viewpoints of dispersibility and light shielding properties.
The specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent agent has a predetermined performance, and thus the value measured by the BET method is usually 5 to 150 m. ² / g approximately, it is preferably Among them, 20 to 100 m ² / g approximately.

In the present invention, titanium black is preferably a titanium black dispersion composition before it is made into a black curable composition. The titanium black dispersion composition can be obtained by dispersing a black pigment such as carbon black in addition to the above-described titanium black particles, or the above-described combination pigment with a dispersant and a solvent.
As the dispersant, a dispersant described later is preferably used. Further, it may be added at the time of pigment processing to be used as a pigment coating type dispersant, or may be added as a dispersant when a pigment such as titanium black is dispersed by a dispersing machine such as a bead mill.

  The preparation mode of the dispersion composition of the present invention is not particularly limited. For example, the pigment, the dispersant, and the solvent are mixed with a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. It can be obtained by carrying out fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.
<Dispersant>
Examples of the dispersant that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant is adsorbed on the surface of titanium black and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the titanium black surface can be cited as preferred structures.
On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modifying the titanium black surface.

  Specific examples of the dispersant that can be used in the present invention include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 ”manufactured by EFKA. (Polyurethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) ), 6750 (azo pigments) Conductor) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ” “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Kasei Corporation, manufactured by Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (Stearylamine Acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000 , 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

The addition amount of the dispersant in the present invention is preferably added so as to be 3 to 100% by mass, more preferably 5 to 100% by mass, based on all pigments including titanium black. 50% by mass is particularly preferred. When the amount of the dispersant is within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimal addition amount of the dispersant is appropriately adjusted depending on the combination of the size of titanium black, the type of pigment used, the size, the type of solvent, and the like.
If the dispersant is less than 5% by mass, it may be difficult to sufficiently modify the surface properties of titanium black. On the other hand, if it exceeds 100% by mass, the amount of polymer dispersed and blended with titanium black This is because there is a possibility that the properties of titanium black that are originally required, such as light shielding properties and coloring properties, may be impaired.

  As the solvent species that can be used in the dispersion composition of the present invention, the same solvents as those that can be used in the black curable composition described later can be used. The amount of the solvent used in the dispersion composition can be appropriately adjusted depending on the dispersion method.

<(B) Alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000>
The alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000 that can be used in the present invention is a linear organic polymer, and is a molecule (preferably an acrylic copolymer, a styrene copolymer). A molecule selected from an alkali-soluble resin having at least one group that promotes alkali solubility (for example, a carboxyl group, a phosphate group, a sulfonate group, a hydroxyl group, etc.) in a molecule having a copolymer as a main chain. Can do.

  More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid, as described in Japanese Unexamined Patent Publication Nos. 59-53836 and 59-71048. Acrylic copolymers such as acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having carboxylic acids in the side chains, and polymers having hydroxyl groups with acid anhydrides added. Can be mentioned.

The alkali-soluble resin of the present invention has a weight average molecular weight in the range of 20,000 to 100,000. Thereby, the substrate adhesion is remarkably improved.
The cause of this is unknown, but is presumed as follows. That is, the alkali-soluble resin is considered to be adsorbed to the substrate at the alkali-soluble part (acid group). However, as described above, since the black curable composition containing titanium black is insufficiently cured in the vicinity of the substrate, the alkali-soluble resin having a molecular weight of less than 20,000 is used for the light-shielding color filter layer in the vicinity of the substrate surface. The entanglement is small, and the substrate and the light-shielding color filter layer cannot be bonded. Therefore, the substrate adhesion is extremely deteriorated. However, the alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000 has a long polymer chain even if the curing progress in the vicinity of the substrate is insufficient. It is considered that the substrate and the light-shielding film can be bonded together. Further, when the molecular weight is large, the polymer chain has many alkali-soluble groups and can be adsorbed at multiple points with the substrate. For this reason, it is thought that board | substrate adhesiveness improves further.

  The weight average molecular weight of the alkali-soluble resin of the present invention is measured as a polystyrene equivalent value by GPC (gel filtration chromatography) method. The gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. It is preferable to use 2 to 6 columns connected together. Examples of the solvent used include ether solvents such as tetrahydrofuran and amide solvents such as N-methylpyrrolidinone, but ether solvents such as tetrahydrofuran are preferred. The measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently. The measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C.

More specifically, the weight average molecular weight of the present invention is measured under the following conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI detector)
Precolumn: TSKGUARDCOLUMN MP (XL) 6 mm x 40 mm (manufactured by Tosoh Corporation)
Sample side column: Directly connected to the following 4 columns (all manufactured by Tosoh Corporation)
TSK-GEL Multipore-HXL-M 7.8mm x 300mm
Reference side column: Same as sample side column Temperature chamber temperature: 40 ° C
Moving bed: Tetrahydrofuran Sample-side moving bed flow rate: 1.0 mL / min Reference-side moving bed flow rate: 0.3 mL / min Sample concentration: 0.1% by mass
Sample injection volume: 100 μL
Data collection time: 16 minutes to 46 minutes after sample injection Sampling pitch: 300 msec

  The weight average molecular weight of the alkali-soluble resin of the present invention is preferably in the range of 20,000 to 100,000, and most preferably in the range of 25,000 to 50,000. By being in this range, in addition to substrate adhesion, stability over time is good.

  The weight average molecular weight / number average molecular weight (polydispersity) of the alkali-soluble resin of the present invention is preferably in the range of 1.1 to 3.0, more preferably in the range of 1.3 to 2.0. preferable. By being in this range, low molecular components (oligomers) are reduced, and the substrate adhesion is further improved. The weight average molecular weight / number average molecular weight can be measured by the GPC method described above.

  The specific constituent unit of the alkali-soluble resin of the present invention is a co-polymer containing one or more carboxylic acid group-containing monomers represented by the general formula (α) and one or more monomers represented by the general formula (β). It is preferably a coalescence.

In general formula (α), R ^1α represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a halogen atom. R ^2α represents — (COO) m— (R ^3α ) n—CO ₂ H. R ^3α represents a divalent linking group. m and n represent 0 or 1.

In general formula (β), R ^1β represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a halogen atom. R ^2β represents —CO ₂ R ^3β , an aryl group, a heterocyclic group, a cyano group, or a carbamoyl group. R ^3β represents a substituted or unsubstituted alkyl group, cycloalkyl group, or aryl group.

The alkyl group in R ^{l [alpha]} of the general formula (alpha), preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like. The substituent which R ^1α may have is not particularly limited as long as it is a known substituent, but is preferably a halogen atom, a hydroxyl group or an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, such as methoxy, ethoxy, Propoxy, etc.), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyl Oxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like, and particularly preferably a halogen atom and a hydroxyl group.

R ^1α is most preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

In the general formula (α), R ^2α represents — (COO) m— (R ^3α ) n—CO ₂ H. R ^3α represents a divalent linking group. As the divalent linking group, an alkylene group (an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is most preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, An isopropylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, etc.), a cycloalkylene group (a cycloalkylene group having 3 to 30 carbon atoms is preferred, and carbon A cycloalkylene group having a number of 5 to 20 is most preferred, and examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group. Ethynylene group, propynylene, etc. ), An arylene group (an arylene group having 6 to 30 carbon atoms is preferred, and an arylene group having 6 to 20 carbon atoms is most preferred. Examples of the arylene group include a phenylene group, a methylphenylene group, a dimethylphenylene group, an ethylphenylene group, Alkylphenylene groups such as diethylphenylene group; cycloalkylphenylene groups such as cyclopentylphenylene group and cyclohexylphenylene group; hydroxydiphenylene group, fluorodiphenylene group, chlorodiphenylene group, bromodiphenylene group, iododiphenylene group, acetyldi Diphenylene group such as phenylene group; alkylnaphthalene group such as methylnaphthalene group, dimethylnaphthalene group, ethylnaphthalene group, diethylnaphthalene group; cyclopentylnaphthalene group, cyclohexylnaphthalene group What cycloalkyl naphthalene group; diphenyl group, a naphthalene group, fluorophenylene group, chloro phenylene group, bromophenylene group, iodo phenylene group, an acetyl phenylene group, hydroxy phenylene group, etc. anthracenylene group), or -R ^4.alpha. -OC (O) R ^5α- (R ^4α and R ^5α are each an alkylene group having 1 to 10 carbon atoms or an arylene group, and R ^4α and R ^5α may be the same or different).
R ^3α is most preferably an ethylene group, a propylene group, a cycloalkylene group, or a phenylene group.

  m and n represent 0 or 1. In particular, m and n are preferably 0, or m and n are preferably 1.

R ^1β in the general formula (β) represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a halogen atom. The preferable range of R ^{1β is the same as} the preferable range of R ^1α in the general formula (α).

R ^2β in the general formula (β) represents —CO ₂ R ^3β or an aryl group. R ^3β represents a substituted or unsubstituted alkyl group, a cycloalkyl group, or an aryl group. The alkyl group for R ^3β is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.

Examples of the substituent that the alkyl group in R ^3β may have include a halogen atom, a hydroxyl group, and an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, and naphthyl. , M-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic group heterocyclic group (preferably 5-7 membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed ring More preferably, the heterocyclic group is selected from a carbon atom, a nitrogen atom and a sulfur atom, and has at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom. And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thio Nyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t - butoxy, n- octyloxy, 2-methoxyethoxy), polyalkyleneoxy group (preferably, a substituted or unsubstituted polyalkyleneoxy group having 1 to 30 carbon atoms, for example, -O- _(CH 2 CH ₂ - O-) nZ (. Z is hydrogen atom, group represents an alkyl group having 1 to 5 carbon atoms, n represents represented by showing) an integer of _{1~10, -O- (CH (CH 3} ) CH 2 - O-) nZ (. Z represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, groups and n is represented by) represents an integer of _{1~10, -O- (CH 2 CH (} CH 3) - O-) nZ ( Is hydrogen atom, an alkyl group having 1 to 5 carbon atoms, n represents the group represented by an integer from 1 to 10.) Is exemplified.

The cycloalkyl group for R ^3β is preferably a cycloalkyl group having 3 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. Examples of the cycloalkyl group include cyclohexyl, cyclopentyl, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and the like. Substituents which may have a cycloalkyl group at the R ^{3 [beta]} is the same as the substituent that may be possessed by the alkyl group in R ^{3 [beta].}

The aryl group in R ^3β is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, and the like. The substituent that the aryl group in R ^3β may have is the same as the substituent that the alkyl group in R ^3β may have.

The aryl group for R ^2β is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, and the like. The substituent that the aryl group in R ^3β may have is the same as the substituent that the alkyl group in R ^3β may have.

The heterocyclic group for R ^2β is preferably a C 1-30 heterocyclic group, and more preferably a C 1-20 heterocyclic group. Examples of the heterocyclic group include imidazole, pyrazole, pyrrolidone, pyridine and the like. Substituent that may be possessed by the heterocyclic group group in R ^{3 [beta]} is the same as the substituent that may be possessed by the alkyl group in R ^{3 [beta].}

The carbamoyl group in R ^2β is preferably an aryl group having 1 to 30 carbon atoms, and more preferably an aryl group having 1 to 20 carbon atoms. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

  The specific alkali-soluble resin is particularly preferably a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith. Other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylate, benzyl (meth) acrylate, aryl (meth) acrylate, styrene, vinyltoluene, N-vinylpyrrolidone, N-vinylpyridine, N-vinylimidazole, N, N-dimethylacrylamide and acrylonitrile are particularly preferred. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with the substituent.

The alkali-soluble resin preferably has an acid value in the range of 50 to 200 mgKOH / g, preferably 50 to 150 mgKOH / g, and more preferably 70 to 120 mgKOH / g. When the acid value exceeds 200 mgKOH / g, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, less than 50 mgKOH / g, the solubility in alkali is so small that it takes too much time for development, which is not preferable. In particular, it is preferably 50 to 200 mg KOH / g from the viewpoint of developability and dispersibility.
In order to make the acid value of alkali-soluble resin into the range specified above, it can be easily performed by appropriately adjusting the copolymerization ratio of each monomer. Moreover, the range of the weight average molecular weight can be easily achieved by using an appropriate amount of a chain transfer agent according to the polymerization method in the copolymerization of the monomers.

  The alkali-soluble resin is preferably produced by radical polymerization. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic resin by radical polymerization can be easily set by those skilled in the art. Is possible.

  As the initiator used for radical polymerization, a commercially available initiator can be used. For example, an azo initiator (for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (methyl 2-methylpropionate), 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], etc.), peroxides (for example, benzoyl peroxide, peracetic acid, hydrogen peroxide, ammonium persulfate, etc.) and the like. However, an azo initiator is most preferable. Although reaction temperature changes with initiators, 40-120 degreeC is preferable from a viewpoint of manufacture aptitude.

  In radical polymerization, a solvent can be used without any particular limitation, but hydrocarbon solvents (eg, n-hexane, n-heptane, n-decane, petroleum ether, etc.), aromatic solvents (eg, benzene, toluene) , Xylene, mesitylene, etc.), ester solvents (eg, ethyl acetate, butyl acetate, ethyl lactate, 2-acetoxy-1-methoxypropane, etc.), alcohol solvents (eg, methanol, ethanol, n-propanol, isopropanol, n- Butanol, n-octanol, 1-methoxy-2-propanol, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, isobutyl methyl ketone, etc.), ether solvents (eg, diethyl ether, dibutyl ether, tetrahydrofuran) 1 4-dioxane, etc.), amide solvents (eg, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidinone, etc.), sulfur-containing solvents (eg, dimethyl sulfoxide, sulfolane, etc.), nitriles System solvents (for example, acetonitrile, propionitrile, etc.) and water are preferable, and ester solvents, alcohol solvents, and ketone solvents are particularly preferable. These solvents may be used alone or in combination. The amount of the solvent used is preferably 1 to 10 times by mass, most preferably 2 to 5 times by mass with respect to the monomer.

  The alkali-soluble resin preferably has a residual monomer content in the resin of 10% by mass or less, more preferably 5% by mass or less, and most preferably 2% by mass or less. Thereby, storage stability improves. Examples of the method for reducing the residual monomer content include (1) purification by reprecipitation and (2) additional addition of a radical polymerization initiator, and purification by reprecipitation is particularly effective and effective for removing residual monomers. When reprecipitation is performed, the solvent used is not particularly limited as long as it does not dissolve the polymer, but water, alcohol solvents and hydrocarbon solvents are preferable. The solvent used for reprecipitation is preferably used in an amount of 1 to 20 times by mass, more preferably 2 to 10 times by mass with respect to the polymerization solution. When a radical polymerization initiator is additionally added, 0.01 to 10 parts by mass is preferable with respect to 100 parts by mass of the resin, and 0.05 to 5 parts by mass is most preferable.

In particular, the alkali-soluble resin of the present invention is preferably produced by a dropping polymerization method. Thereby, it can adjust to a suitable weight average molecular weight and molecular weight distribution, and board | substrate adhesiveness improves. Furthermore, there is little risk of runaway polymerization during production, and stable production is possible.
The dropping time in the dropping polymerization method is preferably 1 to 24 hours, and most preferably 2 to 12 hours. If the time is shorter than this time, it is difficult to control the molecular weight, and if it is longer, the productivity is lowered.

  The addition amount when adding the alkali-soluble resin to the black curable composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. . When the amount of the alkali-soluble resin is less than 5% by mass, the film strength is lowered. When the amount is more than 90% by mass, the acid content increases, so that it becomes difficult to control the solubility and the pigment is relatively reduced. Therefore, sufficient image density cannot be obtained. Moreover, it is preferable at the point which becomes easy to obtain the coating film of sufficient thickness. In particular, a good coating can be obtained with a high yield for slit coating suitable for coating on a wide substrate having a large area.

In order to improve the crosslinking efficiency of the black curable composition in the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin having no polymerizable group, Polymers containing an aryl group, a (meth) acryl group, an aryloxyalkyl group or the like in the side chain are useful.
The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting.
Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as alkali-soluble groups such as COOH groups and OH groups and carbon-carbon unsaturated bonds are included.

(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin, (2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule,
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

(C) Solvent The black curable composition of the present invention has at least one (C) solvent. (C) As a solvent, the liquid selected from the organic solvent shown below is mentioned, The solubility of each component contained in a dispersion liquid, the applicability | paintability at the time of applying to a curable composition, etc. are considered. Although these are basically not particularly limited as long as these desired physical properties are satisfied, it is preferably selected in consideration of safety.
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol monomethyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, pro Glycol propyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; and aromatic hydrocarbons, e.g., toluene, xylene and the like; are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

  As content of the (C) solvent in the black curable composition of this invention, 2-90 mass% is preferable, 2-80 mass% is more preferable, 5-70 mass% is the most preferable.

By adding to the pigment dispersion of the present invention, (D) an oxime photopolymerization initiator represented by the general formula (3) and (E) a compound containing an ethylenically unsaturated double bond, A black curable composition having excellent image properties, color characteristics, coating properties, and developability can be provided.

<(D) Photopolymerization initiator>
The black curable composition of the present invention contains an oxime-based photopolymerization initiator represented by the general formula (3) (hereinafter simply referred to as “photopolymerization initiator” as appropriate) .
The photopolymerization initiator in the present invention is a compound that is decomposed by light and starts and accelerates polymerization of a compound containing an ethylenically unsaturated double bond described later (E), and has an absorption in a wavelength region of 300 to 500 nm. It is preferable. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include mbenzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate, and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

As the biimidazole compound, for example, a hexaarylbiimidazole compound (rophine dimer compound) is preferable.
Examples of the hexaarylbiimidazole compound include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, JP-B-6-29285, U.S. Pat. No. 3,479,185, and the like. Various compounds described in each specification such as 4,311,783 and 4,622,286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) vididazole, 2, 2'-bis (o , O′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5 Examples include '-tetraphenylbiimidazole.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. The organic borate described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, or organic boron oxosulfonium complex, JP-A-6-175554 No. 6, JP-A-6-175553 Organoboron iodonium complexes described in JP-A-9-188710, organoboron phosphonium complexes described in JP-A-9-348710, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068 and JP-T 2004-534797 Compounds and the like.
The photopolymerization initiator in the present invention, the sensitivity, an oxime-based photopolymerization initiator represented by the following formula in terms of through time stability, coloring at the time of post-heating (3).

In the general formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.
X in the general formula (3) is preferably an alkyl group having 1 to 10 carbon atoms or a halogen atom, and most preferably an alkyl group having 1 to 5 carbon atoms. R is preferably an acyl group having 1 to 20 carbon atoms, and most preferably an acyl group having 1 to 5 carbon atoms. A is preferably an alkylene group having 1 to 10 carbon atoms, and most preferably an alkylene group having 1 to 5 carbon atoms. Ar is preferably a phenyl group or a halogen atom-containing aryl group, and most preferably a halogen atom-containing aryl group. n is preferably 1 to 3, and most preferably 1.

  Specific examples of the oxime compound include the following compounds, and the compound of the general formula (3) is preferable. Moreover, it is not limited to the compound illustrated below.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

In particular, when the black curable composition of the present invention is used for producing a color filter of a solid-state imaging device, it is necessary to form fine pixels with a sharp shape. It is important that the unexposed areas are developed without residue. From this point of view, an oxime compound represented by the general formula (3). In particular, when forming fine pixels in a solid-state image sensor, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen contained in the photopolymerization initiator. It is necessary to keep the amount low. Considering these points, it can be said that the use of the oxime compound represented by the general formula (3) as a photopolymerization initiator ( D ) is most preferable for forming a finely colored pattern such as a solid-state imaging device.

  The content of the (D) photopolymerization initiator contained in the black curable composition of the present invention is preferably 0.1 to 50% by mass, more preferably based on the total solid content of the curable composition. It is 0.5-30 mass%, Most preferably, it is 1-20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

<(E) Compound containing ethylenically unsaturated double bond>

  The compound containing an ethylenically unsaturated double bond that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond other than the above-mentioned resin, and has terminal ethylene. Selected from compounds having at least one, preferably two or more, unsaturated unsaturated bonds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Furthermore, monomers containing acid groups can also be used, for example, (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipenta Erythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester It is done. In these, pentaerythritol triacrylate succinic acid monoester etc. are mentioned.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group in a compound represented by the following general formula to a polyisocyanate compound having two or more isocyanate groups. Etc.

Formula ^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH
(However, R ¹⁰ and R ¹¹ represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid-based compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combined use, addition amount and the like can be arbitrarily set according to the performance design of the black curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  In addition, the selection and use method of the addition polymerization compound is also an important factor for compatibility and dispersibility with other components (eg, resin, photopolymerization initiator, pigment) in the black curable composition. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei), UA-7200 (Shin Nakamura Chemical Co., Ltd.) Product).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

  The content of the compound (E) containing an ethylenically unsaturated double bond in the present invention is preferably 1% by mass to 90% by mass in the solid content of the black curable composition of the present invention. It is more preferably from 80% by mass to 80% by mass, and further preferably from 10% by mass to 70% by mass.

  In particular, when the black curable composition of the present invention is used for forming a coloring pattern of a color filter, the content of the compound (E) containing an ethylenically unsaturated double bond is 5% by mass to 50% in the above range. The mass is preferably 7% by mass, more preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

The black curable composition of this invention may further contain the arbitrary components explained in full detail below as needed.
Hereinafter, optional components that the black curable composition of the present invention may contain will be described.

[(F) Sensitizer]
The black curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, those sensitized by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer used in the black curable composition of the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  More preferable examples of the sensitizer in the black curable composition of the present invention include compounds represented by the following general formulas (e-1) to (e-4).

(In formula (e-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents the basicity of the dye in combination with adjacent A ¹ and the adjacent carbon atom. Represents a nonmetallic atomic group forming a nucleus, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of a dye. W may represent an oxygen atom or a sulfur atom.)

(In Formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ² —, where L ² represents —O— or —S—. In addition, W is synonymous with that shown in Formula (e-1).)

(In the formula (e-3), A ² represents a sulfur atom or NR ⁵⁹ , L ³ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

(In Formula (e-4), A ³ and A ⁴ each independently represent —S— or —NR ⁶² , R ⁶² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁴ and L ⁵ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent group. And can be bonded to each other to form an aliphatic or aromatic ring.)

The content of the sensitizer in the black curable composition of the present invention is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. 0.5-15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Moreover, as a preferable sensitizer which can be contained in the black curable composition of the present invention, in addition to the above sensitizer, a compound represented by the following general formula (II), and a general formula (III) described later are used. And at least one selected from the following compounds.
These may be used individually by 1 type, and may use 2 or more types together.

In general formula (II), R ¹¹ and R ¹² each independently represents a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. Represent. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹¹ may be the same or different. When n ′ is 2 or more, a plurality of R ¹² may be the same or different. In the general formula (II), the isomer by the double bond is not limited to either.

The compound represented by the general formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^{−. 1} or more is more preferable, and ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group.

In general formula (III), A represents an aromatic ring or a hetero ring which may have a substituent, X ² represents an oxygen atom, a sulfur atom, or —N (R ²³ ) —, and Y represents an oxygen atom. , sulfur atom, or -N ^{(R 23)} - represents a. R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ²¹ , R ²² , and R ²³ are bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (III), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ²¹ , R ²² and R ²³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by formula (III), Y is preferably an oxygen atom or —N (R ²³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ²³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, Y is most preferably —N (R ²³ ) —.

  Hereinafter, although the preferable specific example of a compound represented by general formula (III) is shown, this invention is not limited to this. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

[(G) Co-sensitizer]
The black curable composition of the present invention preferably further contains (G) a co-sensitizer.
In the present invention, the co-sensitizer further improves the sensitivity of (D) the photopolymerization initiator and (F) the sensitizer to active radiation, or contains (E) an ethylenically unsaturated double bond due to oxygen. It has an action such as suppressing polymerization inhibition of the compound.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1 to 30 mass with respect to the mass of the total solid content of the black curable composition of the present invention, from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. % Is preferable, a range of 1 to 25% by mass is more preferable, and a range of 0.5 to 20% by mass is further preferable.

<Other polymers>
The black curable composition of the present invention has other polymer materials [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid from the viewpoint of improving dispersion stability and developing property control. Ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine A dispersant such as can be further added. Such other polymer materials can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

  In addition to the above-mentioned dispersant, methacrylic acid / benzyl methacrylate, preferably, methacrylic acid / benzyl methacrylate having an acid value of 20 to 150 mgKOH can be used.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the black curable composition. Is desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the total solid content of the black curable composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5 mass% to about 10 mass% of the total solid content of the black curable composition.

<Other additives>
Furthermore, in the present invention, in order to improve the physical properties of the cured film, a known additive such as an inorganic filler, a plasticizer, or a substrate adhesive that can improve the substrate adhesion may be added.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

When the black curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as “substrate adhesion agent”). May be added.
As the substrate adhesion agent, known materials can be used, but it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Li isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The content of the substrate adhesive is from 0.1% by mass to 30% with respect to the total solid content of the black curable composition of the present invention, from the viewpoint of leaving no residue in the unexposed part of the curable composition. It is preferably at most mass%, more preferably at least 0.5 mass% and at most 20 mass%, particularly preferably at least 1 mass% and at most 10 mass%.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of this invention has the pattern which uses the black curable composition of this invention on a support body, It is characterized by the above-mentioned.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention comprises a step of applying the black curable composition of the present invention on a support to form a curable composition layer (hereinafter referred to as “curable composition layer forming step” as appropriate). Abbreviated), a step of exposing the curable composition layer through a mask (hereinafter abbreviated as “exposure step” where appropriate), and developing the curable composition layer after exposure to develop a colored pattern. (Hereinafter, abbreviated as “development process” where appropriate).

Specifically, the black curable composition of the present invention is applied directly or via another layer onto a support (substrate) to form a curable composition layer (curable composition layer forming step). ), Exposing through a predetermined mask pattern, curing only the light-irradiated coating film part (exposure process), and developing with a developer (development process) to form a pattern film composed of pixels of each color Thus, the color filter of the present invention can be manufactured.
Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

[Curable composition layer forming step]
In the curable composition layer forming step, the black curable composition of the present invention is applied on the support to form a curable composition layer.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, a solid-state imaging device, etc. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the black curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .

The coating thickness of the black curable composition is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and still more preferably 0.2 μm to 3 μm in terms of the thickness after drying.
Moreover, when manufacturing the color filter for solid-state image sensors, as a coating film thickness of a black curable composition, 0.35 micrometer-1.5 micrometers in the thickness after drying are preferable from a viewpoint of resolution and developability. 0.40 μm to 1.0 μm is more preferable.

  The black curable composition coated on the support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a black curable composition layer.

[Exposure process]
In the exposure step, the black curable composition layer formed in the black curable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably from ^{5mJ / cm 2 ~1500mJ / cm 2} , more preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  As the alkali used in the developer, for example, an inorganic developer such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metaoxalate or the like can be used, but preferably an organic developer. Specifically, for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, An alkaline aqueous solution obtained by diluting an organic alkaline compound such as 0] -7-undecene with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In addition, in the manufacturing method of the color filter of this invention, after performing the black curable composition layer formation process mentioned above, an exposure process, and the image development process, the formed colored pattern is heated and / or exposed as needed. It may include a curing step for curing.

  By repeating the black curable composition layer forming step, the exposure step, and the developing step (and the curing step if necessary) described above for the desired number of hues, a color filter having a desired hue is produced.

Since the color filter of the present invention uses the black curable composition of the present invention, the formed pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. It is possible to form a high-resolution pattern that is excellent in sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or CMOS that exceeds 1 million pixels. That is, the color filter of the present invention is preferably applied to a solid-state image sensor.
The light-shielding color filter of the present invention can be used, for example, as a light-shielding color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing or around the light receiving portion.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. Unless otherwise specified, “part” is based on mass.

(Synthesis Example 1) Synthesis of Resin 1 For dropwise addition of 18 g of methacrylic acid, 80 g of benzyl methacrylate, 1.0 g of 2,2′-azobis (methyl 2-methylpropionate), and 100 g of 1-methoxy-2-propanol The monomer solution was added dropwise to 100 g of 1-methoxy-2-propanol heated to 80 ° C. in a nitrogen atmosphere over 6 hours. Thereafter, 1.0 g of 2,2′-azobis (methyl 2-methylpropionate) was added, heated to 90 ° C., and heated for 2 hours. 1-methoxy-2-propanol was added to this solution to make a 30% by mass solution.

(Synthesis Examples 2-9) Synthesis of Resins 2-9 Using the monomers and initiators listed in Table 1, the same synthesis as in Synthesis Example 1 was performed except that the monomer solution for dropping was adjusted. Obtained. The initiator A in Table 1 is 2,2′-azobis (methyl 2-methylpropionate), and the initiator B is 2,2′-azobis (isobutyronitrile). Moreover, the structure of the compound X is the following structure.

(Synthesis Example 10) Synthesis of Resin 10 For dropwise addition of 20 g of methacrylic acid, 80 g of benzyl methacrylate, 1.0 g of 2,2′-azobis (methyl 2-methylpropionate), and 100 g of 1-methoxy-2-propanol The monomer solution was added dropwise to 100 g of 1-methoxy-2-propanol heated to 80 ° C. in a nitrogen atmosphere over 6 hours, and further heated for 2 hours. After the dropwise addition, the obtained solution was added dropwise to a mixed solvent of 200 mL of methanol and 800 mL of water. The obtained solid was collected by filtration and dried to give a 30% by mass solution of 1-methoxy-2-propanol.

(Synthesis Example 11) Synthesis of Resin 11 For dropwise addition of 20 g of methacrylic acid, 80 g of benzyl methacrylate, 1.0 g of 2,2′-azobis (methyl 2-methylpropionate), and 100 g of 1-methoxy-2-propanol The monomer solution was added dropwise to 100 g of 1-methoxy-2-propanol heated to 80 ° C. in a nitrogen atmosphere over 6 hours, and further heated for 2 hours. To this solution, 1-methoxy-2-propanol was added to make a 30% by mass solution.

(Synthesis Example 12) Synthesis of Resin 12 A solution in which 20 g of methacrylic acid, 80 g of benzyl methacrylate, and 100 g of 1-methoxy-2-propanol were mixed was heated to 80 ° C. in a nitrogen atmosphere. Next, 1.0 g of 2,2′-azobis (methyl 2-methylpropionate) was added and heated for 2 hours. Next, 0.05 g of 2,2′-azobis (methyl 2-methylpropionate) was added and heated for 2 hours. Further, 0.05 g of 2,2′-azobis (methyl 2-methylpropionate) was added, heated to 90 ° C. and heated for 2 hours. To this solution, 1-methoxy-2-propanol was added to make a 30% by mass solution.

(Synthesis Example 13) Synthesis of Resin 13 A monomer for dropping in which 20 g of methacrylic acid, 80 g of benzyl methacrylate, 5.0 g of 2,2′-azobis (methyl 2-methylpropionate), and 100 g of 1-methoxy-2-propanol were mixed. The solution was added dropwise to 100 g of 1-methoxy-2-propanol heated to 80 ° C. in a nitrogen atmosphere over 6 hours. Thereafter, 1.0 g of 2,2′-azobis (methyl 2-methylpropionate) was added, heated to 90 ° C., and heated for 2 hours. 1-methoxy-2-propanol was added to this solution to make a 30% by mass solution.

Table 1 shows the weight average molecular weight, polydispersity, acid value, and residual monomer amount of Resins 1-13. The amount of residual monomer was determined by high performance liquid chromatography (measuring device: Waters 2695 manufactured by Waters, column: Shim-pack CLC-ODS (6.0 mm × 15 cm, manufactured by Shimadzu Corporation), eluent: tetrahydrofuran / water (phosphoric acid 0.1 vol%, Quantification was carried out using 0.1 vol% of triethylamine) = 65/35).
In Table 1, the numbers in parentheses in the columns of monomer 1, monomer 2, monomer 3, and initiator represent parts by mass of each material used.

( Reference Example 1)
(Preparation of dispersion)
Titanium Black 13M-T (Gemco Co., Ltd.) 45 parts, Solsperse 36000
10 parts (manufactured by Abyssia) and 10 parts of resin (1) were mixed and subjected to high viscosity dispersion treatment with two rolls. The viscosity at this time is designated as viscosity A.
Next, 10 parts of the resin (1) and 200 parts of propylene glycol monomethyl ether acetate were added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment with a disperser (trade name: Dispermat GETZMANN) for 5 hours using 0.3 mm zirconia beads to prepare a dispersion (L-1). The viscosity at this time is designated as viscosity B.

(Preparation of black curable composition)
A black curable composition (M-1) was prepared according to the following.
Resin (1) 1.6 parts Dipentaerythritol hexaacrylate 2.3 parts Ethoxylated pentaerythritol tetraacrylate 0.8 parts Dispersion (L-1) 30 parts Propylene glycol monomethyl ether acetate 10 parts Ethyl -3-Ethoxypropionate 8 parts / initiator: listed in Table 2 0.8 parts

(Production and evaluation of light-shielding color filter for solid-state image sensor)
Using the above black curable composition M-1, the spin coating speed was adjusted so that the film thickness after pre-baking was 1.0 μm, and the film was uniformly coated on a silicon wafer, and the surface temperature was 120 ° C. Then, a heat treatment (prebaking) with a hot plate was performed for 120 seconds to obtain a silicon wafer substrate having a coating film of 1.0 μm.
Next, using an i-line stepper, FPA-3000iS + (manufactured by Canon Inc.), an exposure dose in the range of 100 to 5000 mJ / cm ² is set to 100 mJ / cm ² through a 3.0 mm line and space pattern photomask. Irradiation was performed while changing in steps of cm ² .
After the irradiation, paddle development is performed for 60 seconds at 23 ° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), and then rinse is performed using pure water for 20 seconds in a spin shower. Washed with pure water. Thereafter, the attached water droplets were removed with high-pressure air, and the substrate was naturally dried to obtain a black image pattern (3.0 μm line-and-space pattern).

(Evaluation)
The following evaluation was performed using the black curable composition M-1 obtained as described above. The results are shown in Table 2.

-Evaluation of substrate adhesion-
100 patterns were observed with SEM, and the exposure amount at which pattern defects could not be observed was measured. It represents that board | substrate adhesiveness is so high that this exposure amount is small.
-Evaluation of stability over time-
The black curable composition was stored at 25 ° C., the viscosity at the time of preparing the black curable composition and the viscosity after 7 days from storage were measured, and the stability over time is shown in Table 2 as (viscosity after 7 days−initial viscosity). The difference was shown. The smaller the value, the better the stability over time.

(Examples 4 and 8, Reference Examples 2, 3, 5 to 7 , 9 to 16, Comparative Examples 1 and 2)
Substrate adhesion was evaluated in the same manner as in Reference Example 1 except that the resin (1) and initiator in Reference Example 1 were replaced with the resins and initiators listed in Table 2.
The initiators shown in Table 2 are
A: IRGACURE OXE02 (Ciba Specialty Chemicals)
B: IRGACURE 379 (Ciba Specialty Chemicals)
C: DAROCURE TPO (Ciba Specialty Chemicals)
D: The following compound E: The following compound is represented. The structures of A, B, C, D and E are shown below.

From Table 2, it can be seen that in Examples 4 and 8 using the black curable composition of the present invention, the minimum exposure amount is small, and there is no pattern defect even at a small exposure amount. On the other hand, Comparative Example 1 and Comparative Example 2 using a resin whose weight average molecular weight deviates from the scope of the present invention requires a large minimum exposure amount, and pattern loss tends to occur at a low exposure amount. I understand.
Moreover, the temporal stability of the comparative example has a large numerical value, and the temporal stability of the black curable composition is poor. On the other hand, it can be seen that the examples of the present invention are excellent in stability over time.

( Reference Example 17)
<Production of solid-state image sensor>
-Preparation of chromatic color curable composition-
In the black curable composition M-1 prepared in Reference Example 1, titanium black 13M-T [manufactured by Gemco Co., Ltd.], which is a black pigment, was replaced with the following chromatic pigment in the same manner as in Reference Example 1, A chromatic curable composition for red (R) C-1, a chromatic curable composition for green (G) C-2, and a chromatic curable composition for blue (B) C-3 were prepared.

Chromatic pigment for forming chromatic pixels for each color of RGB, pigment for red (R) C.I. I. Pigment Red 254
-Green (G) pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 [mass ratio] mixture and blue (B) pigment C.I. I. Pigment Blue 15: 6 and C.I. I. 30/70 [mass ratio] mixture with pigment violet 23

-Production of color filters for solid-state image sensors-
The light-shielding color filter for a solid-state imaging device prepared in Reference Example 1 is used as a black matrix, and the red (R) chromatic curable composition C-1 is used on the black matrix, as described in Example 1. A red (R) colored pattern was formed in the same manner as described above. Further, similarly, a chromatic color pattern of green (G) and blue (B) was sequentially formed to produce a color filter for a solid-state imaging device.

-Evaluation-
When the obtained color filter for a solid-state image sensor is incorporated in a solid-state image sensor, the solid-state image sensor has high light-shielding properties, high resolution, and excellent color separation properties. confirmed.

Claims (8)

(A) titanium black, (B) alkali-soluble resin having a weight average molecular weight in the range of 20,000 to 100,000, (C) solvent, (D) oxime-based photopolymerization represented by the following general formula (3) A black curable composition comprising an agent and (E) a compound containing an ethylenically unsaturated double bond.

In general formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.   2. The black curable composition according to claim 1, wherein the (B) alkali-soluble resin has a weight average molecular weight / number average molecular weight of 1.1 to 3.0.   The black curable composition according to claim 1 or 2, wherein the acid value of the (B) alkali-soluble resin is in the range of 50 to 200 mgKOH / g.   The black curable composition according to any one of claims 1 to 3, wherein the residual monomer content in the (B) alkali-soluble resin is 10% by mass or less. The light-shielding color filter for solid-state image sensors which uses the black curable composition of any one of Claims 1-4 . The antireflection film for solid-state image sensors which uses the black curable composition of any one of Claims 1-4 . Solid imaging which has the process of apply | coating the black curable composition of any one of Claim 1 to 4 on a support body, the process of exposing through a mask, and the process of developing and forming a pattern Manufacturing method of light-shielding color filter for element. The solid-state image sensor provided with the light-shielding color filter for solid-state image sensors of Claim 5 .