JP2002371204A - Modified carbon black, photosensitive black resin composition and black matrix resist composition for colored filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified carbon black excellent in dispersability, light insulation property, and photosensitivity by a simple operation, a photosensitive black resin composition suitable for a black matrix resist for a colored filter capable of forming a black matrix of high dispersion stability, resolution, photosensitivity, and low reflectivity, a black matrix resist using the photosensitive black resin composition, and a black matrix using the black matrix resist. SOLUTION: This modified carbon black excellent in dispersion stability and having a radical-polymerizable group and its dispersion solution are obtained by treating a carbon black with a compound having an ethylenic unsaturated group and an isocyanato group in a molecule, and the above-mentioned purpose is dissolved using the modified carbon black.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified carbon black which is suitable for forming a high-definition black matrix because of its excellent dispersibility, light-shielding properties and photosensitivity, and which can reduce the reflectance when formed into a black matrix. The present invention relates to a photosensitive black resin composition obtained using carbon black, a black matrix resist for a color filter obtained using the photosensitive black resin composition, and a black matrix formed using the black matrix resist.

[0002]

2. Description of the Related Art In a color filter used in a color liquid crystal display device or the like, a black matrix is formed for the purpose of blocking light between fine pixels colored at least two or more hues. Such a black matrix is usually formed of a metal thin film having a fine pattern on a glass substrate in many cases.
There are films of r, Ni, Al and the like, and a film formation method is generally a vapor deposition method, a sputtering method, or a vacuum film formation.

The black matrix is formed by photolithography of the above metal thin film. Specifically, a photoresist is applied to a metal thin film, dried, irradiated with ultraviolet rays through a photomask, a resist pattern is formed, and then etching and resist peeling are performed. However, the black matrix produced as described above has a problem that the production cost is high due to the complexity of the process. Furthermore, when a color filter using this metal thin film is mounted on a transmissive display,
Since the reflectivity of the surface of the metal thin film is high, there is a problem that when strong external light hits the filter, the reflected light is strong and the display quality is significantly deteriorated.

[0004] In order to solve the above problems of the metal thin film, a method of forming a black matrix by photolithography with a coloring material in which a pixel is formed by photopolymerization using a photopolymerizable compound having an ethylenically unsaturated bond has been proposed. It has been reported. In this case, carbon black or another organic pigment is used as the black coloring material to be internally added, but carbon black must be used to obtain sufficient light-shielding properties. For example, in JP-A-4-63870, carbon black and an organic pigment are dispersed in a photopolymerizable compound,
A method of forming a black matrix by using this has been proposed. However, this composition is difficult to obtain a uniform dispersion state of carbon black,
In addition, there is a problem in that photopolymerization is inhibited by radical scavenging of carbon black, and it is difficult to form a sufficient pixel.

In Japanese Patent Application Laid-Open No. 6-67421, for the purpose of suppressing polymerization inhibition due to radical scavenging of carbon black, grafting is performed with a polymer compound having reactivity with a functional group on the surface of carbon black. A method using carbon black as a black colorant is disclosed. However, in this method, the grafted carbon black itself has little or no photopolymerizability. Therefore, in order to obtain a resin composition for a black matrix having sufficient photopolymerization properties, a large amount of photosensitive resin is required for the grafted carbon black. It is necessary to incorporate a hydrophilic resin or graft a high molecular weight polymer, so there is an upper limit to the amount of carbon black in the grafted carbon black. It was difficult.

In Japanese Patent Application Laid-Open No. 9-3356, an unsaturated epoxy ester having an epoxy group and an ethylenically unsaturated group in one molecule is required for the surface of carbon black in order to obtain photosensitivity and light shielding properties in a thin film. A method of treating with a resin is proposed. However, in this method, the unsaturated epoxy ester resin treatment must be performed while heating to 140 ° C., and the production is troublesome.

[0007]

SUMMARY OF THE INVENTION The present invention provides a modified carbon black which is excellent in dispersibility, high light-shielding properties and photosensitivity by a simple operation at room temperature, and at the same time, provides a high dispersion by using the modified carbon black. Stability, resolution, light sensitivity,
And at the same time to provide a photosensitive black resin composition suitable for a black matrix resist of a color filter capable of forming a black matrix of low reflectance, a black matrix resist using the photosensitive black resin composition,
And a black matrix using the black matrix resist.

[0008]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that by treating carbon black with a compound having an ethylenically unsaturated group and an isocyanate group in one molecule, it has excellent dispersion stability, A modified carbon black having a polymerizable group can be obtained. Further, by combining the modified carbon black, a binder resin, an ethylenically unsaturated compound, and a photopolymerization initiator, dispersion stability, resolution, light It was possible to obtain a photosensitive black resin composition excellent in sensitivity. Furthermore, the black matrix resist composition using the photosensitive black resin composition of the present invention was able to form a black matrix having low reflectance. The present invention is as follows.

[1] A modified carbon black treated with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule.

[2] The modified carbon black according to [1], which is treated with 0.5 to 50 parts by mass of a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule per 100 parts by mass of carbon black. .

[3] The modified carbon black according to [1] or [2], wherein the compound having an isocyanate group and an ethylenically unsaturated bond in one molecule is 2-methacryloyloxyethyl isocyanate.

[4] A modified carbon black having a 2-methacryloyloxyethylcarbamoyl group.

[5] A method for producing a modified carbon black, which comprises treating with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule.

[6] A method for producing a modified carbon black, comprising treating with 0.5 to 50 parts by mass of a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule.

[7] A method for producing a modified carbon black, comprising treating carbon black with 2-methacryloyloxyethyl isocyanate.

[8] The method for producing a modified carbon black according to any one of [5] to [7], wherein the method is performed while pulverizing the carbon black.

[9] A photosensitive black resin composition comprising the modified carbon black (A) according to any one of [1] to [4].

[10] The photosensitive composition according to [9], comprising a binder resin (B), an ethylenically unsaturated compound (C), a photopolymerization initiator (D), and an organic solvent (E). Black resin composition.

[11] The photosensitive black resin composition according to [10], wherein the binder resin (B) is an acrylic copolymer having a carboxyl group.

[12] The photopolymerization initiator (D) is (a) a hexaarylbiimidazole compound, (b) a triazine compound, (c) an aminoacetophenone compound,
(10) The photopolymerization initiator according to [10] or [11], which is at least one photopolymerization initiator selected from a combination of a sensitizing dye and an organic boron salt-based compound represented by the general formula (1). Photosensitive black resin composition.

[0021]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an optionally substituted alkyl, aryl, aralkyl, alkenyl, alkynyl, silyl, heterocyclic group, or halogen atom Wherein Z ⁺ represents an arbitrary cation. [13] The photosensitive black resin according to any one of [10] to [12], which contains a polyfunctional thiol (F) as a chain transfer agent. Composition.

[14] The photosensitive black resin composition according to [14], wherein the ratio between the polyfunctional thiol (F) and the photopolymerization initiator (D) is from 10: 1 to 1:10.

[15] The photosensitive black resin composition according to any one of [10] to [12], wherein the content of each component other than the organic solvent (E) is as follows.

The modified carbon black (A) according to any one of [1] to [4], 25 to 60% by mass Binder resin (B) 10 to 40% by mass Ethylenically unsaturated compound (C) 5 to 40% by mass Photopolymerization initiation Agent (D) 3 to 25% by mass

[16] The photosensitive black resin composition according to [13] or [14], wherein the content of each component other than the organic solvent (E) is as follows: Modified carbon black (A) according to [1] to [4] 25 to 60% by mass Binder resin (B) 10 to 40% by mass Ethylenically unsaturated compound (C) 5 to 40% by mass Photopolymerization initiator (D ) 2 to 20% by mass Polyfunctional thiol (F) 2 to 20% by mass

[17] A black matrix resist composition for a color filter, comprising the photosensitive black resin composition according to any one of [9] to [16].

[18] A black matrix formed by using the black matrix resist composition for a color filter according to [17].

[19] A modified carbon black dispersion containing the modified carbon black according to any one of [1] to [4].

[20] The modified carbon black dispersion according to [19], which contains an organic solvent.

[21] The modified carbon black dispersion according to [20], further comprising a polymer dispersant.

[22] A method for producing a modified carbon black dispersion, which comprises treating a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule into carbon black in an organic solvent.

[23] The method for producing a modified carbon black dispersion according to [22], wherein the treatment is performed while dispersing.

[24] The modified carbon black dispersion according to [22] or [23], wherein the compound having an isocyanate group and an ethylenically unsaturated bond in one molecule is 2-methacryloyloxyethyl isocyanate. Liquid production method.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. "Parts" and "%" representing quantitative ratios in the following description
Is based on mass unless otherwise specified. (Definition of terms) In this specification, the term "(meth) acrylic acid" is used to mean both acrylic acid and methacrylic acid, and the term "(meth) acryloyl" is meaning to include both acryloyl and methacryloyl. Used for

The modified carbon black of the present invention, which is treated with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule, is prepared by suspending carbon black in an organic solvent having no active hydrogen and further adding The compound can be easily prepared by adding a compound having an isocyanate group and an ethylenically unsaturated bond to the molecule and dispersing the mixture with a disperser such as a paint conditioner or a bead mill. Preferably, to reduce the particle size of the carbon black, particularly in order to react in a state close to the primary particles,
It is desirable to use SUS beads or the like. By this treatment, a functional group having active hydrogen such as a hydroxyl group on the surface of carbon black and an isocyanate group are added, and it can be estimated that a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule is bonded to the surface of the carbon black particles. .

The temperature for treating carbon black is 0 ° C.
Any temperature up to the boiling point of the solvent may be used,
0 ° C to 60 ° C, more preferably 20 ° C to 30 ° C
(Room temperature in the usual sense).

The treatment time varies depending on the use of the catalyst described below, but may be 0.5 hours or more, preferably 1 hour.
The time is from 8 hours to 8 hours, more preferably from 2 hours to 5 hours.

In carrying out this treatment, an appropriate dispersing agent may be added so that aggregation of the carbon black particles is suppressed and a compound having an isocyanate group and an ethylenically unsaturated bond can be uniformly added to the surface of the carbon black particles. good. Further, a urethane bond forming catalyst for promoting the reaction between the isocyanate group and the hydroxyl group may be added so that the treatment can be completed in a short time.

As the carbon black used as a raw material of the modified carbon black of the present invention, commercially available carbon blacks can be arbitrarily used. Here, carbon black is
It is a black or grayish black powder produced by incomplete combustion or thermal decomposition of organic matter, and its main component is carbon.
The microscopic state of the carbon black surface varies depending on the production method. Examples of the production method include a channel method, a furnace method, a thermal method, a lamp black method, an acetylene method, and the like. But it can be used without any problems.

The average particle diameter of carbon black is preferably in the range of 5 to 200 nm in consideration of dispersibility and resolution. If it is less than 5 nm, uniform dispersion becomes difficult, and if it exceeds 200 nm, the resolution decreases. Preferably it is in the range of 10 to 100 nm.

Specific examples of commercially available carbon black include, for example, Printex 95, manufactured by Degussa Corporation.
Printex90, Printex85, Print
ex75, Printex55, Printex45,
Printex40, Printex30, Print
ex3, PrintexA, PrintexG, Spe
CialBlack550, SpecialBlack
350, SpecialBlack250, Speci
alBlack100, SpecialBlack4,
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA10
0, MA220, MA230, # 52, # 50, # 4
7, # 45, # 2700, # 2650, # 2200, #
1000, # 990, # 900, manufactured by Cabot: Mo
narch460, Monarch430, Monar
ch280, Monarch120, Monarch8
00, Monarch4630, REGAL99, RE
GAL99R, REGAL415, REGAL415
R, REGAL250, REGAL250R, REGA
L330, BLACK PEARLS480, manufactured by Colombian Carbon: RAVE11, RAVEN1
5, RAVEN30, RAVEN35, RAVEN4
0, RAVEN410, RAVEN420, RAVEN
450, RAVEN500, RAVEN780, RAV
EN850, RAVE890H, RAVE100
0, RAVEN 1020, RAVEN 1040 and the like.

Specific examples of the compound having an isocyanate group and an ethylenically unsaturated bond in one molecule used in the present invention include, for example, 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko; hereinafter also referred to as MOI). ), Methacrylic isocyanate,
Compounds obtained by reacting m-isopropenyl-α, α-dimethylbenzyl isocyanate, a hydroxyl group-containing (meth) acrylate and a diisocyanate compound at a molar ratio of 1: 1 can be exemplified.

Here, as the hydroxyl group-containing (meth) acrylate, for example, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 3-chloro-2-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) ) Acrylate, polypropylene glycol mono (meth) acrylate, caprolactone-modified hydroxyethyl (meth)
Examples include acrylates, mono (meth) acrylates of diols composed of condensates of phthalic anhydride and ethylene glycol, and mono (meth) acrylates of diols composed of condensates of phthalic anhydride and propylene glycol.

As the diisocyanate compound,
For example, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, ω,
ω'-diisocyanate dimethylcyclohexane, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate,
1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-
2,4′-diisocyanate, 1,5-naphthalenediisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate and the like, and low molecular weight diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and 1,3-butanediol, and the diisocyanate And an adduct body obtained by reacting an excess amount of the above.

When reacting a hydroxyl group-containing (meth) acrylate with a diisocyanate compound, a known urethane bond-forming catalyst may be added as a catalyst. Examples of such a catalyst include tertiary amines (eg, triethylamine, triethylamine, Ethylenediamine, triethylamine, 1,4
Known urethane bonds such as -diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, and organic tin compounds (eg, dibutyltin dilaurate, tin octylate, etc.). Forming catalysts.

However, in the present invention, as the compound having an isocyanate group and an ethylenically unsaturated bond in one molecule, the workability at the time of preparing the modified carbon black and the photosensitivity using the modified carbon black are described. 2-Methacryloyloxyethyl isocyanate (MOI) is particularly preferred from the viewpoints of stability and photosensitivity of the black resin composition.

The compounding ratio of the compound having an isocyanate group and an ethylenically unsaturated bond in one molecule to carbon black is 0.5 to 100 parts by mass of carbon black.
５０50 parts by mass. If the amount is less than 0.5 parts by mass, the dispersibility is reduced, and the reflectance and light sensitivity of the photosensitive black resin composition are reduced. If the amount exceeds 50 parts by mass, the amount that cannot be added to the carbon black surface increases, so that the stability of the photosensitive resin composition decreases. Preferably 1-4
0 parts by mass, more preferably 2 to 30 parts by mass.

The organic solvent which can be used for preparing the modified carbon black of the present invention is not required to have an active hydrogen capable of reacting with an isocyanate group. Examples of such an organic solvent include diisopropyl ether and ethyl. Ethers such as isobutyl ether and butyl ether, ethyl acetate, isopropyl acetate, butyl acetate (n,
sec, tert), amyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-
Esters such as ethyl methoxypropionate, propyl 3-methoxypropionate, and butyl 3-methoxypropionate, methyl ethyl ketone, isobutyl ketone, diisopropyl ketone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl isoamyl ketone, methyl isobutyl ketone , Ketones such as cyclohexanone, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate , Dipropylene glycol mo Ethyl ether acetate, and the like. These solvents are desirably used after being dehydrated.

Catalysts which can be used for preparing the modified carbon black of the present invention include, for example, tertiary amines (eg, triethylamine, triethylenediamine, triethylamine, 1,4-diazabicyclo [2.2.2] octane, Known catalysts for forming urethane bonds, such as 8-diazabicyclo [5.4.0] -7-undecene, etc.) and organic tin compounds (eg, dibutyltin dilaurate, tin octylate, etc.).

The dispersant which can be used when preparing the modified carbon black of the present invention has affinity for carbon black, and includes, for example, surfactants such as nonionic, cationic and anionic, and polymeric dispersants. Among them, a polymer dispersant is preferable, and a polymer dispersant having a basic functional group such as a nitrogen-containing heterocycle such as a tertiary amino group, pyridine, pyrimidine and pyrazine is particularly preferably used. .

The modified carbon black treated and adjusted by the method of the present invention is obtained as a dispersion, and the dispersion obtained here is composed of the binder resin (B), the ethylenically unsaturated compound (C), A polymerization initiator (D), a polyfunctional thiol (F) and the like can be blended and used as it is to form a photosensitive black resin composition.

The binder resin (B) used in the photosensitive black resin composition of the present invention is preferably a binder resin having a carboxyl group since solubility in an aqueous alkali solution (alkali developability) is required. An acrylic copolymer having a carboxyl group is particularly preferable because an excellent coating film having a resist film strength, heat resistance, substrate adhesion and the like can be obtained. Furthermore, 2 to 40% by mass of a carboxyl group-containing monomer (a) and an amide monomer (b)
An acrylic copolymer obtained by radical polymerization of 2 to 40% by mass and 20 to 96% by mass of a monomer (c) other than the above (a) and (b) has a balance between dispersion stability of carbon black and alkali developability. It is particularly preferable because it can be taken.

The following compounds are specifically exemplified as the monomer used as the raw material of the acrylic copolymer. Examples of the carboxyl group-containing monomer (a) include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid,
2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid,
Examples include (meth) acrylic acid dimer, maleic acid, crotonic acid, itaconic acid, fumaric acid, and the like. Examples of the amide monomer (b) include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N
-Diethyl (meth) acrylamide, N, N-di-n-
Butyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n
-Butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (1-methylbutyl) (meth) acrylamide, diacetone (meth) acrylamide, N- (meth) acryloylmorpholine , N-vinylpyrrolidone, N-vinylcaprolactam and the like.

The monomers other than (a) and (b) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. A) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, (meth) acrylonitrile, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorooctylethyl (meth) (Meth) acrylate monomers such as acrylate, styrene, α-methylstyrene, (o,
(m, p-) hydroxystyrene, vinyl acetate and the like.

Further, an epoxy group and an ethylene group in one molecule of glycidyl (meth) acrylate, allyl glycidyl ether, etc. are added to a part of the carboxyl group of the side chain of the acrylic copolymer obtained by copolymerizing the above monomer. Reacting the epoxy group of the compound having an unsaturated group, or reacting a part or all of the hydroxyl groups of the acrylic copolymer with 2-
1 such as methacryloyloxyethyl isocyanate
An acrylic copolymer having an ethylenically unsaturated group on the side chain obtained by reacting an isocyanate group of a compound having an isocyanate group and an ethylenically unsaturated group in the molecule can also be used without any problem.

The preferred molecular weight of the acrylic copolymer described above is determined by gel permeation chromatography (GP).
The weight average molecular weight in terms of polystyrene according to C) is 1,0.
In the range of 0.00 to 500,000, preferably 3,0
00 to 200,000. If it is less than 1,000, the film strength will be significantly reduced. On the other hand, when it exceeds 500,000, the alkali developability is significantly reduced.

However, when the photosensitivity is insufficient with the binder resin alone, an epoxy (meth) acrylate resin can be used in combination as the binder resin component in the photosensitive black resin composition of the present invention. The epoxy (meth) acrylate resin is a resin obtained by adding an unsaturated monocarboxylic acid to an epoxy group of the epoxy resin.

Examples of usable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
Novolak epoxy resin, (o, m, p-) cresol novolak epoxy resin, phenol novolak epoxy resin, naphthol-modified novolak epoxy resin, and halogenated phenol novolak epoxy resin. The preferred molecular weight of these epoxy resins is GPC
Weight average molecular weight in the range of 300 to 100,000. If the molecular weight is less than 300, the film strength decreases, and if the resin exceeds 100,000, gelation easily occurs at the time of the addition reaction of the unsaturated monocarboxylic acid, and the production may be difficult.

The unsaturated monocarboxylic acids used in the synthesis of the epoxy (meth) acrylate resin include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, Examples thereof include (meth) acryloyloxyethyl hexahydrophthalic acid, (meth) acrylic acid dimer, itaconic acid, crotonic acid, and cinnamic acid. Of these, acrylic acid is particularly preferred because of its high reactivity.

The addition reaction of the unsaturated monocarboxylic acid to the epoxy resin can be carried out by a known method, for example, at 50 to 150 ° C. in the presence of an esterification catalyst. As the esterification catalyst, for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used.

The addition amount of the unsaturated monocarboxylic acid is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, per equivalent of epoxy group of the epoxy resin. When the amount of the unsaturated monocarboxylic acid added deviates from the above range, the curing properties tend to be deteriorated.

Further, the epoxy (meth) acrylate resin is used to improve the alkali developability.
A polybasic acid anhydride can be added to the hydroxyl group of the acrylate resin to give a carboxyl group. Specific examples of polybasic acid anhydrides include, for example, maleic anhydride,
Examples include succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride and the like.
A known method can be used for the addition reaction of the polybasic acid anhydride, and it can be obtained by continuing the reaction under the same conditions as the addition reaction of the unsaturated monocarboxylic acid. The addition amount of the polybasic acid anhydride is such that the resin acid value is 10 to 150.
mgKOH / g.
140 mg KOH / g is particularly preferred. Acid value is 10mg
If it is less than KOH / g, alkali developability will be poor,
On the other hand, if it exceeds 150 mgKOH / g, the developing speed becomes too high, and the practicality is poor.

The ethylenically unsaturated compound (C) used in the photosensitive black resin composition of the present invention is a compound which is polymerized and cross-linked by a radical generated from a photopolymerization initiator upon irradiation with actinic rays. If the boiling point is low, the solvent volatilizes at the time of drying the solvent before exposure, the ratio of each component of the composition changes, and desired characteristics cannot be exhibited. Therefore, a compound having a boiling point of 150 ° C. or higher is preferable. Specific examples of such compounds include:
For example, 4-tert-butylcyclohexyl (meth)
Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, ethoxydiethylene glycol (meth) A) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N- Such as (meth) acryloylmorpholine, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl acid phosphate, N-vinylpyrrolidone, and N-vinylcaprolactam A compound having one ethylenic unsaturation in one molecule, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol di (meth) acrylate And the like having two or more ethylenically unsaturated groups in one molecule.

The photopolymerization initiator (D) in the photosensitive black resin composition of the present invention is a compound which is excited by an actinic ray to generate a radical and initiate polymerization of an ethylenically unsaturated bond. As the photopolymerization initiator used in the photosensitive black resin composition of the present invention, it is necessary to generate radicals under high light shielding, and therefore, those having high photosensitivity are used. Such photopolymerization initiators include (a) hexaarylbiimidazole compounds, (b) triazine compounds,
(C) an aminoacetophenone-based compound, (d) a combination of a sensitizing dye and an organic boron salt-based compound represented by the general formula (1), (e) a titanocene-based compound, and (f) an oxadiazole-based compound. Preferably, (a) hexaarylbiimidazole compounds, (b) triazine compounds, (c) aminoacetophenone compounds, (d)
It is a combination of a sensitizing dye and an organic boron salt-based compound represented by the general formula (1).

Specific examples of the hexaarylbiimidazole compound (a) include, for example, 2,2'-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o
-Bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) -1,2'-biimidazole, 2,2'-bis (o, p-dichlorophenyl)-
4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) -1,2′-biimidazole, 2,2′-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetra (m
-Methoxyphenyl) -1,2'-biimidazole,
2,2′-bis (o-methylphenyl) -4,4 ′,
5,5′-tetraphenyl-1,2′-biimidazole and the like.

When a hexaarylbiimidazole compound is used, benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethylamino) benzophenone, Benzophenone-based compounds such as 4,4'-bis (diethylamino) benzophenone,
2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone,
-A thioxanthone-based compound such as chlorothioxanthone may be added as a sensitizer.

Specific examples of the triazine compound (b) include, for example, 2,4,6-tris (trichloromethyl)
-S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-propionyl-4,6-
Bis (trichloromethyl) -s-triazine, 2-benzoyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (4-methoxyphenyl) -6-trichloromethyl-s
-Triazine, 2- (4-methoxyphenyl) -2,6
-Bis (trichloromethyl) -s-triazine, 2-
(4-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-chlorostyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-amino Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (3
-Chlorophenyl) -6-trichloromethyl-s-triazine, 2- (4-aminostyryl) -4,6-bis (dichloromethyl) -s-triazine and the like.

Specific examples of the aminoacetophenone-based compound (C) include, for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1 and the like.

In the photopolymerization initiator comprising the combination (d) of the sensitizing dye and the organic boron salt compound represented by the general formula (1), the quaternary organic boron salt compound is represented by the general formula (1).

[0070]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an optionally substituted alkyl, aryl, aralkyl, alkenyl, alkynyl, silyl, heterocyclic group, or halogen atom And Z ⁺ represents an arbitrary cation.) The quaternary organic boron salt-based compound alone can absorb ultraviolet rays and generate radicals, but can have high sensitivity by combining with a sensitizer. It can be a suitable photopolymerization initiator.

The quaternary organic boron salt compounds of the present invention
And an arbitrary cation (Z ⁺ ). An alkyl group, an aryl group, an aralkyl group as R ₁ , R ₂ , R ₃ and R ₄ in the general formula (1);
Examples include an alkenyl group, an alkynyl group, a silyl group, and a heterocyclic group, which may have a substituent. Specific examples of the substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-octyl, n-dodecyl, Cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, anisyl, biphenyl, naphthyl, benzyl, phenethyl, diphenylmethyl, methoxy, ethoxy,
n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, methylenedioxy group, ethylenedioxy group, phenoxy group,
Examples include a naphthoxy group, a benzyloxy group, a methylthio group, a phenylthio group, a 2-furyl group, a 2-thienyl group, a 2-pyridyl group, a fluoro group, and the like, but the present invention is not limited to these examples.

Specific examples of the quaternary organic boron anion in the general formula (1) include, for example, methyl triphenyl borate, n-butyl triphenyl borate, n-octyl triphenyl borate, n-dodecyl triphenyl borate, sec. -Butyl triphenyl borate, te
rt-butyl triphenyl borate, benzyl triphenyl borate, n-butyl tri (p-anisyl) borate, n-octyl tri (p-anisyl) borate, n-
Dodecyl tri (p-anisyl) borate, n-butyl tri (p-tolyl) borate, n-butyl tri (o-tolyl) borate, n-butyl tri (4-tert-butylphenyl) borate, n-butyl tri (4-fluoro-
2-methylphenyl) borate, n-butyltri (4-
Fluorophenyl) borate, n-butyltri (1-naphthyl) borate, ethyltri (1-naphthyl) borate, n-butyltri [1- (4-methylnaphthyl)] borate, methyltri [1- (4-methylnaphthyl)] borate , Triphenylsilyltriphenylborate, trimethylsilyltriphenylborate, tetra-n-butylborate, di-n-butyldiphenylborate, tetrabenzylborate, etc., wherein R ₁ is an alkyl group, R ₂ , R ₃ And a compound having a structure in which R ₄ is a naphthyl group has a good balance between stability and photoreactivity, and is suitable for the present invention.

Specific examples of Z ⁺ in the general formula (1) include, for example, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, tetraoctylammonium, N-methylquinolinium, N-ethylquino Lithium, N-methylpyridinium, N-ethylpyridinium, tetramethylphosphonium, tetra-n-butylphosphonium, trimethylsulfonium, triphenylsulfonium, trimethylsulfoxonium, diphenyliodonium, di (4-te
rt-butylphenyl) iodonium, lithium cation, sodium cation and the like. Anions and Z
Any combination of ⁺ and can be used in the present invention. However, the invention is not limited to these examples. Further, two or more quaternary boron salt compounds may be used in combination.

The sensitizer used in combination with the quaternary organic boron compound can be arbitrarily used as long as it can absorb light to decompose the quaternary organic boron salt compound. A compound selected from a series compound, a thioxanthone series compound, a quinone series compound and / or a cationic dye represented by the general formula (2) can be suitably used. ^{D + · A - (2)} - Specific examples of the (in the formula, D ⁺ represents a cation having a maximum absorption wavelength in the wavelength range of 300 to 500 nm, A represents an anion) benzophenone compounds, e.g. , Benzophenone, 4-methylbenzophene, 2,
4,6-trimethylbenzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, (2-acryloyloxyethyl) (4-benzoylbenzyl) dimethylammonium bromide, 4- (3 -Dimethylamino-2-hydroxypropoxy) -benzophenone methochloride monohydrate, (4-benzoylbenzyl) trimethylammonium chloride and the like.

Specific examples of the thioxanthone compounds include, for example, thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone,
(3-dimethylamino-2-hydroxypropoxy)-
3,4-dimethyl-9H-thioxanthen-9-one
Methochloride and the like.

Specific examples of the quinone-based compound include:
For example, 2-ethylanthraquinone, 9,10-phenanthrenequinone and the like can be mentioned.

D ⁺ in the cationic dye of the general formula (2) is a cation of a compound having a maximum absorption wavelength in a wavelength region of 300 to 500 nm. Here, preferred examples of D ⁺ include methine, polymethine, azamethine, and diazamethine compounds.
Table 1 shows the structure specifically, but the present invention is not limited to these examples.

[0078] A in the general formula (2) ^- can be obtained by, for example, Cl ^-, Br ^-, I ^- and a halogen anion, benzenesulfonic acid anion, p- toluenesulfonate anion, methanesulfonic acid anion, 1 Sulfonic acid anions such as -naphthalenesulfonic acid anion, tetraphenyl borate, tetraanisyl borate, n-butyl triphenyl borate, tetrabenzyl borate,
Borate anions such as tetrafluoroborate, ClO
_{^{4 -, PF 6 -, SbF}} 6 - equal BF ₄ ^- various anions and the like. However, the invention is not limited to these examples.

Each of these sensitizers may be used alone, or two or more of them may be used in an optional ratio as needed.

[0080]

[Table 1]

Examples of the titanocene compound (e) include JP-A-59-152396 and JP-A-61-15119.
7, JP-A-63-10602, JP-A-63-10602
JP-A-41484, JP-A-2-291, JP-A-3-12403, JP-A-3-20293,
JP-A-3-27393, JP-A-3-52050, JP-A-4-221958, JP-A-4-21
No. 975 can be used. Specifically, for example, dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-T
i-diphenyl, dicyclopentadienyl-Ti-bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl-Ti-bis (2,3,5,6-
Tetrafluorophenyl), dicyclopentadienyl-
Ti-bis (2,4,6-trifluorophenyl), dicyclopentadienyl-Ti-bis (2,6-difluorophenyl), dicyclopentadienyl-Ti-bis (2,4-difluorophenyl) , Bis (methylcyclopentadienyl) -Ti-bis (2,3,4,5,6-
Pentafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,3,5,6-tetrafluorophenyl), bis (methylcyclopentadienyl)
—Ti-bis (2,6-difluorophenyl) and the like.

Examples of the oxadiazole compound (f) include, for example, 2-phenyl-5 having a halomethyl group.
-Trichloromethyl-1,3,4, -oxadiazole, 2- (p-methylphenyl) -5-trichloromethyl-1,3,4, -oxadiazole, 2- (p-methoxyphenyl) -5 -Trichloromethyl-1,3,4
-Oxadiazole, 2-styryl-5-trichloromethyl-1,3,4, -oxadiazole, 2- (p-methoxystyryl) -5-trichloromethyl-1,3
4, -oxadiazole, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4, -oxadiazole and the like can be mentioned.

Further, in the photosensitive black resin composition of the present invention, a polyfunctional thiol as a chain transfer agent can be used as a part of the photopolymerization initiator system. Addition of the polyfunctional thiol suppresses polymerization inhibition by oxygen, and can cause a uniform photocuring reaction even under high light shielding.

As a preferable polyfunctional thiol to be added, any compound having two or more thiol groups may be used.
For example, hexanedithiol, decanedithiol, 1,
4-butanediol bispropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Triazine, 2- (N, N-dibutylamino) -4,6-
Dimercapto-s-triazine and the like. These polyfunctional thiols can be used alone or in combination of two or more.

A polyfunctional thiol, a hexaarylbiimidazole compound (a), a triazine compound (b),
The combination ratio of the aminoacetophenone-based compound (c) and / or the combination of the sensitizing dye and the organic boron salt-based compound (d), the titanocene-based compound (e), and the oxadiazole-based compound (f) is 10: 1 to 1: 10 is preferred. If the compounding ratio is out of this range, sufficient light sensitivity cannot be obtained. More preferably, it is 5: 1 to 1: 5.

Photopolymerization initiators other than those described above can be optionally added to the photosensitive black resin composition of the present invention. Examples of such a photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane. -1-one, 1-hydroxycyclohexyl phenyl ketone, 4
Acetophenone compounds such as -tert-butyl-trichloroacetophenone, benzoin compounds such as benzyldimethylketal, benzoinethylether and benzoinisopropylether; glyoxyester compounds such as methylphenylglyoxylate;
Acylphosphine oxide compounds such as -trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-
Dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4
Bisacylphosphine oxide compounds such as 6-trimethylbenzoyl) phenylphosphine oxide and the like can be mentioned.

Further, a hydrogen-donating compound can be added to the photosensitive black resin composition of the present invention. A hydrogen donor is an initiator excited by light, and a compound capable of donating hydrogen to a radical generated from the initiator, for example, triethanolamine, an aliphatic amine such as methyldiethanolamine, 2-dimethylaminoethylbenzoic acid,
Examples thereof include aromatic amines such as ethyl 4-dimethylaminobenzoate and isobutyl 4-dimethylaminobenzoate, and aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzoxazole. .

The preferred amounts of the components other than the organic solvent in the photosensitive black resin composition of the present invention are as follows. The content of the modified carbon black (A) is preferably 25 to 60% by mass, and more preferably 30 to 50% by mass. 2
If it is less than 5% by mass, a sufficient optical density cannot be obtained, and if it exceeds 60% by mass, the film strength decreases. The content of the binder resin (B) is preferably from 10 to 40% by mass, more preferably from 15 to 30% by mass. When the amount is less than 10% by mass, the film strength decreases, and when the amount exceeds 40% by mass, a sufficient optical density cannot be obtained. 5 to 40 ethylenically unsaturated compounds (C)
% By mass, more preferably 10 to 30% by mass. If the amount is less than 5 parts by mass, sufficient light sensitivity cannot be obtained, and if it exceeds 40 parts by mass, sufficient optical density cannot be obtained.
The photopolymerization initiator (D) is preferably from 3 to 25% by mass, more preferably from 5 to 20% by mass. If the amount is less than 3% by mass, sufficient photosensitivity cannot be obtained.

When the polyfunctional thiol (F) is further added, the content of the photopolymerization initiator (D) is preferably from 2 to 20% by mass, more preferably from 3 to 15% by mass. 2% by mass
If it is less than 20%, sufficient light sensitivity cannot be obtained. In that case, the preferable blending amount of the polyfunctional thiol (F) is 2 to 20% by mass, more preferably 3 to 15% by mass. 2% by mass
If it is less than 20%, the effect of the polyfunctional thiol will not be exhibited. The photosensitive black resin composition of the present invention usually contains carbon black (A), binder resin (B), ethylenically unsaturated compound (C), photopolymerization initiator (D), and / or polyfunctional thiol (F). Used in a state of being dissolved in the organic solvent (E).

The organic solvent is not particularly limited. Examples thereof include ethers such as diisopropyl ether, ethyl isobutyl ether and butyl ether, ethyl acetate, isopropyl acetate, butyl acetate (n, sec, tert),
Esters such as amyl acetate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, and butyl 3-methoxypropionate; methyl ethyl ketone , Isobutyl ketone, diisopropyl ketone, ethyl amyl ketone,
Ketones such as methyl butyl ketone, methyl hexyl ketone, methyl isoamyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate And glycols such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and dipropylene glycol monoethyl ether acetate.

The organic solvent is capable of dissolving or dispersing each component, and it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. More preferably from 120 to
It has a boiling point of 170 ° C. These solvents can be used alone or as a mixture. The photosensitive black resin composition of the present invention is desirably prepared using these solvents such that the solid content concentration is in the range of 5 to 50% by weight, preferably 10 to 30% by weight.

The photosensitive black resin composition of the present invention may be used in combination with other black or colored inorganic or organic pigments as a coloring material other than the above-mentioned modified carbon black. Examples of such pigments include inorganic black pigments such as titanium black and iron black; I. Pigment Yellow 20,2
4,86,93,109,110,117,125,1
37,138,147,148,153,154,16
6, C.I. I. Pigment Orange 36, 43, 51,
55, 59, 61, C.I. I. Pigment Red 9, 9
7, 122, 123, 149, 168, 177, 18
0,192,215,216,217,220,22
3,224,226,227,228,240, C.I.
I. Pigment Violet 19,23,29,30,
37, 40, 50, C.I. I. Pigment Blue 15,
15: 1, 15: 4, 22, 60, 64, C.I. I. Pigment Green 7, C.I. I. Pigment Brown 2
Organic pigments such as 3, 25, and 26 can be mentioned.

In the photosensitive black resin composition of the present invention, an adhesion improver, a leveling agent, a development improver,
An antioxidant, a thermal polymerization inhibitor and the like can be suitably added. Next, a method for producing the photosensitive black resin composition of the present invention will be described. In the present invention, the modified carbon black obtained by treating with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule has already been subjected to a dispersion treatment,
Since the carbon black particles are finely divided, they can be easily produced by mixing and stirring other components to dissolve them. Since fine dust is often mixed in the production process, it is desirable that the obtained photosensitive black resin composition is subjected to a filtration treatment with a filter or the like.

The photosensitive black resin composition of the present invention has an extremely high dispersion stability of a modified carbon black obtained by treating with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule, and has a high light sensitivity. By remarkably improving it, it can be used as a black UV-curable paint, but it can be particularly suitably used for a black matrix resist of a color filter.

The black matrix is obtained by applying a photosensitive black resin composition on a transparent substrate, drying the solvent in an oven or the like, exposing and developing to form a black matrix pattern, and then performing post-baking. Completed by

Here, the transparent substrate is not particularly limited. For example, inorganic glass such as quartz glass, borosilicate glass, lime soda glass having a silica-coated surface, polyester or polypropylene such as polyethylene terephthalate, etc. Films or sheets of thermosetting plastics such as polyolefins such as polyethylene, thermoplastics such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins and polyester resins are preferably used. Such a transparent substrate may be subjected in advance to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as a silane coupling agent or a urethane polymer, etc., in order to improve physical properties such as surface adhesiveness. .

[0097] In addition to the dip coating, the roll coater, the wire bar, the flow coater, the die coater, and the spray coating, a spin coating method such as a spinner is preferably used.

For drying the solvent, the solvent is dried by a drying device such as a hot plate, an IR oven, and a convection oven. Preferred drying conditions are 40 to 150 ° C., and the drying time is 10 seconds to 60 minutes. Alternatively, the solvent may be dried in a vacuum state.

In the exposure method, a photomask is placed on the sample, and image exposure is performed through the photomask. Light sources used for exposure include, for example, lamp light sources such as xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, and nitrogen lasers. Can be When only the wavelength of the specific irradiation light is used, an optical filter can be used.

The photosensitive black resin composition of the present invention has high sensitivity even at a high optical density, and can be cured by irradiation with light energy of 100 mJ / cm 2 or less. Here, the light irradiation energy amount is, for example, USHIO INC.
UV integrated light meter UIT-150 (light receiving unit UVD
-S365).

In the developing treatment, the resist is developed by a dip, shower, paddle method or the like using a developing solution. The developer is
There is no particular limitation on the solvent as long as it is a solvent capable of dissolving the unexposed resist film. For example, organic solvents such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, many organic solvents have environmental pollution, harm to the human body, and danger of fire. Therefore, it is preferable to use an alkali developing solution having no such danger. Examples of such an alkaline developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide, or diethanolamine, triethanolamine, and tetraalkylammonium hydroxide salts. And an aqueous solution containing an organic alkaline agent. If necessary, the alkali developer may contain a surfactant, a water-soluble organic solvent, a low-molecular compound having a hydroxyl group or a carboxyl group, or the like. In particular,
It is preferable to add a surfactant because many surfactants have an effect of improving developability, resolution, background contamination and the like.

Examples of the surfactant for the developer include:
Examples thereof include an anionic surfactant having a sodium naphthalene sulfonate group and a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a cationic surfactant having a tetraalkylammonium group.

The conditions of the developing method are not particularly limited, but are usually 10 to 50 ° C., preferably 15 to 45 ° C.
At a developing temperature of, by a method such as dip development, spray development, brush development, or ultrasonic development.

The post-baking is carried out using the same apparatus as for the solvent drying at a temperature of 150 to 300 ° C. for 1 to 120 minutes. The black matrix thus obtained has a thickness of 0.1 to 2 μm. , Preferably 0.1 to 1.5
μ, more preferably in the range of 0.1 to 1 μ. Further, in order to function as a black matrix, it is preferable that the optical density is 3 or more in the film thickness.

The black matrix pattern formed in this step has a gap of 20 to 200 μm between the black matrices.
An opening of about m is provided. In the subsequent step, R (red), G (green), and B (blue) pixels are formed in this space.

[0106]

EXAMPLES The present invention will be described below with reference to examples.
Of course, the present invention is not limited at all by these examples.

Example 1 Dibutyltin dilaurate
0.02 parts by mass, 100.0 parts by mass of propylene glycol monomethyl ether acetate (PMA) dehydrated with molecular sieves 3A, Special Bl
ack 4 (Degussa Carbon Black) 10.0 parts by mass and 2-methacryloyloxyethyl isocyanate (MOI) 1.0 part by mass are placed in a stainless steel can, and stainless beads having a diameter of 3 mm are further added. The mixture is shaken with a paint conditioner for 3 hours. Thus, a dispersion of the modified carbon black (A) was obtained. This was designated as Example 1.

(Example 2) In Example 1, the carbon black used was Special Black 250.
(Degussa) A dispersion of modified carbon black (A) was obtained in the same manner except that the amount was changed to 10.0 parts by mass and the MOI to 0.5 part by mass. This was designated as Example 2.

Example 3 In Example 1, the carbon black used was Special Black 250.
(Degussa) A dispersion of modified carbon black (A) was obtained in the same manner except that the amount was changed to 10.0 parts by mass and the MOI to 0.5 part by mass. This was designated as Example 3.

Comparative Example 1 Carbon black was treated in the same manner as in Example 1 except that the MOI was not used. This was designated as Comparative Example 1.

(Comparative Example 2) Carbon black was treated in the same manner as in Example 2 except that the MOI was not used. This was designated as Comparative Example 2.

Evaluation of Dispersibility The modified carbon blacks of Examples 1 to 3 and Comparative Examples 1 and 2
2 carbon black dispersion 1.5 cm in height,
0.5 g each was taken in a sample bottle having a height of 10 cm, 10 g of PMA was further added, and the mixture was thoroughly stirred. After that, it was left still, and the sedimentation state of the modified carbon black and carbon black after 5 hours was visually observed. The case where no sedimentation occurred was judged as good dispersibility, and the case where sedimentation occurred and the supernatant layer was formed was judged as poor dispersibility.

In Examples 1 to 3, no sedimentation occurred and the dispersibility was good. On the other hand, Comparative Examples 1 and 2 were poor in dispersibility due to the sedimentation of carbon black.

The above results show that the modified carbon black (A) treated with a compound having an isocyanate group and an ethylenically unsaturated group in one molecule has good dispersibility.

Synthesis of Acrylic Copolymer (Synthesis Example 1) In a four-necked flask equipped with a dropping funnel, a thermometer, a condenser, and a stirrer, 12.0 parts by mass of methacrylic acid (MA), methyl methacrylate ( MMA) 13.0 parts by mass, n-butyl methacrylate (BMA) 39 parts by mass, N-acryloylmorpholine (ACMO) 11.0 parts by mass, P
225.0 parts by mass of MA was charged and the inside of the four-necked flask was replaced with nitrogen for 1 hour. After further heating to 90 ° C. in an oil bath, MA 12.0 parts by mass, MMA 13.0 parts by mass, BMA 39.0 parts by mass g, ACMO 11.0 parts by mass, PMA 225.0 parts by mass, 2, A mixture of 3.2 parts by mass of 2'-azobisisobutyronitrile (AIBN) was added dropwise over 1 hour. 100 hours after polymerization for 3 hours
C. to 1.0 parts by weight of AIBN and 1 part of PMA
5.0 parts by mass of the mixed solution was added, polymerization was further performed for 1.5 hours, and the mixture was allowed to cool. The acrylic copolymer thus obtained was designated as AP-1. The solid concentration of AP-1 is 23.3.
%, The acid value was 94 mgKOH / g, and the weight average molecular weight in terms of polystyrene measured by GPC was 26,000.

(Synthesis Example 2) Dropping funnel, thermometer, cooling pipe,
In a four-necked flask equipped with a stirrer, 15.0 parts by mass of MA, 12.5 parts by mass of MMA, 38.0 parts by mass of BMA,
9.5 parts by mass of ACMO and 225.0 parts by mass of PMA were charged, and the inside of the four-necked flask was replaced with nitrogen for 1 hour. After further heating to 90 ° C. in an oil bath, MA 15.0 parts by mass, MMA 12.5 parts by mass, BMA 38.0 parts by mass g, ACMO 9.5 parts by mass, PMA 225.0 parts by mass, AIBN 3.2 A part by weight of the mixture was dropped over 1 hour. After polymerization for 3 hours, the mixture was heated to 100 ° C.
A mixed solution of 1.0 parts by mass of IBN and 15.0 parts by mass of PMA was added, polymerization was further performed for 1.5 hours, and then the mixture was allowed to cool. The acrylic copolymer thus obtained was named AP-2.
AP-2 has a solid content of 23.3% and an acid value of 117 mg.
The weight average molecular weight in terms of polystyrene measured by KOH / g and GPC was 25,000.

(Synthesis Example 3) Dropping funnel, thermometer, cooling pipe,
In a four-necked flask equipped with a stirrer, 12.0 parts by mass of MA, 12.0 parts by mass of MMA, 37.0 parts by mass of BMA, 14.0 parts by mass of N-vinylcaprolactam (VC), 225.0 parts by mass of PMA And the inside of the four-necked flask was replaced with nitrogen for 1 hour. 90 ℃ in oil bath
After heating to 12.0 parts by weight of MA, MMA 1
2.0 parts by mass, BMA 37.0 parts by mass, VC 14.0
Parts by mass, 225.0 parts by mass of PMA, AIBN 3.2
A part by weight of the mixture was dropped over 1 hour. After polymerization for 3 hours, the mixture was heated to 100 ° C., and a mixed solution of 1.0 parts by mass of AIBN and 15.0 parts by mass of PMA was added. The acrylic copolymer thus obtained was designated as AP-3. The solid content concentration of AP-3 was 23.0%, the acid value was 93 mgKOH / g, and the weight average molecular weight in terms of polystyrene measured by GPC was 22,2.
000.

Preparation of Black Resin Composition PMA dehydrated with dibutyltin dilaurate and molecular sieves 3A in the composition shown in Tables 2 to 5,
Floren DOPA-33 (Kyoeisha Chemical Co., Ltd. dispersant solid concentration 30%), Special Blac
k4 (Degussa Carbon Black) and MOI were placed in a stainless steel can, and after stirring well, stainless beads having a diameter of 3 mm were added, and the mixture was shaken with a paint conditioner for 3 hours to treat the carbon black. Then AP-1
And shaken for 1 hour with a paint conditioner. The black resin composition thus obtained was filtered with a filter having a pore diameter of 0.8 μm (for Kiriyama Filter Paper GFP) to remove dust and large particles of carbon black. This was designated as Black Resin Composition-1.

By the same method, black resin compositions-2 to 5 and comparative black resin compositions having the compositions shown in Tables 2 to 5 were prepared. Preparation of photosensitive black resin composition Black resin compositions-1 to 5, comparative black resin composition, photopolymerization initiator, ethylenically unsaturated compound, and organic solvent are shown in Tables 2 to 4.
And a photosensitive black resin composition. These evaluations were performed by the following methods.

Evaluation of photosensitivity The photosensitive black resin compositions of Examples 4 to 13 and Comparative Examples 3 and 4 shown in Tables 2 to 4 were applied to glass substrates (size 100 × 100).
mm) and dried at room temperature for 30 minutes.
Vacuum dried for minutes. The film thickness of the coating film is measured in advance with a film thickness meter (SURFCOM130A manufactured by Tokyo Seimitsu Co., Ltd.).
-251 A / B), and photocured by changing the exposure amount. The exposure amount is a UV integrated light meter (Ushio Electric Co., Ltd.)
It was measured using an IT-150 light receiving unit UVD-S365). Further, alkali development was performed with a 0.1% aqueous solution (25 ° C.) of developer 9033 (manufactured by Shipley Far East Co., Ltd.), which is an alkali developer containing potassium carbonate, for a predetermined time (development time was before exposure). The time was set to twice the time when the coating film was completely developed by alkali development). After the alkali development, the glass substrate was washed with water and dried by air spray, and the thickness of the remaining coating film was measured. Regarding the light sensitivity, the exposure amount at which the value (residual film sensitivity) calculated by the following formula became 95% or more was defined as the light sensitivity of the photosensitive black resin composition. The results are shown in Tables 2 to 5. Residual film sensitivity (%) = 100 × (film thickness after alkali development) /
(Film thickness before alkali development)

The results shown in Tables 2 to 5 show that the photosensitivity was significantly increased when the modified carbon black treated with a compound having an ethylenically unsaturated group and an isocyanate group in one molecule was used.

Evaluation of Physical Properties of Coating Film The photosensitive black resin compositions of Examples 4 to 13 and Comparative Examples 3 and 4 shown in Tables 2 to 5 were applied to a glass substrate (size 100 × 100).
mm) and dried at room temperature for 30 minutes.
Vacuum dried for minutes. After light-curing with an ultra-high pressure mercury lamp at an exposure amount twice that of the photosensitivity of each photosensitive black resin composition, 2
Post-baking was performed at 00 ° C. for 30 minutes, and the following evaluation was performed.

(OD value) A calibration curve was prepared by measuring the transmittance at 550 nm using a standard plate having a known OD (optical density) value. Next, the OD value was calculated by measuring the transmittance at 550 nm of the glass substrates coated with the photosensitive black resin compositions of the respective examples and comparative examples. The results are shown in Tables 2 to 5.

(Reflectance) Spectrophotometer (U manufactured by Shimadzu Corporation)
V-3100PC), the reflectance of the coating film of each photosensitive black resin composition at 550 nm was measured.

(Pencil scratch value) JIS K5400
The coating strength of each sample was evaluated by the method shown in “General Paint Test Method 8.4 Pencil Scratch Value”. The results are shown in Tables 2 to 5.

[0126]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

From the results shown in Tables 2 to 5, the photosensitive black resin composition using carbon black treated with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule has a high optical density. It was also confirmed that the resulting coating film had a characteristic of low reflectance.

[0128]

As described above, the modified carbon black of the present invention, which is treated with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule, is excellent in dispersibility and has an ethylenically unsaturated group. The photosensitive black resin composition using porous carbon black has characteristics that are excellent in light-shielding properties, photosensitivity, and dispersion stability. Therefore, the photosensitive black resin composition of the present invention can be suitably used for a black matrix for a color filter which requires high optical density, high definition, and low reflectance.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08F 265/02 C08F 265/02 4J026 292/00 292/00 4J037 C09C 1/48 C09C 1/48 C09D 17/00 C09D 17 / 00 G02B 5/00 G02B 5/00 B 5/20 101 5/20 101 G02F 1/1335 500 G02F 1/1335 500 G03F 7/004 505 G03F 7/004 505 (72) Inventor Katsumi Murofushi Kawasaki-shi, Kanagawa 5-1, Ogimachi, Kawasaki-ku Showa Denko KK Kawasaki Laboratory F-term (reference) 2H025 AA01 AA18 AB13 AD01 BC42 CA02 CA28 CA39 CA41 CB14 CB43 CC03 CC12 CC20 FA17 2H042 AA09 AA15 AA26 2H048 BA11 BA47 BA48 2H09Y FA02 FB04 FB13 FC10 FD04 LA17 LA30 4J011 NA17 NA25 PA03 PA69 PB06 PB08 PB15 PB22 PB25 PB40 PC02 PC05 QA03 QA12 QA17 QA22 QA23 QA24 RA03 SA05 SA78 SA85 SA88 UA01 WA10 4J026 AA43 DBABABAB30A37ACB CB19 CB21 CB24 CC11 CC16 CC29 DD11 DD19 DD23 DD24 EE02 EE28 EE29 EE43 FF05 FF15

Claims (24)

[Claims] 1. A modified carbon black treated with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule. 2. With respect to 100 parts by mass of carbon black,
2. A compound treated with 0.5 to 50 parts by mass of a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule.
The modified carbon black according to the above. 3. The modified carbon black according to claim 1, wherein the compound having an isocyanate group and an ethylenically unsaturated bond in one molecule is 2-methacryloyloxyethyl isocyanate. 4. A modified carbon black having a 2-methacryloyloxyethylcarbamoyl group. 5. A method for producing a modified carbon black, comprising treating with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule. 6. With respect to 100 parts by mass of carbon black,
A method for producing a modified carbon black, comprising treating with 0.5 to 50 parts by mass of a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule. 7. A method for producing a modified carbon black, comprising treating the carbon black with 2-methacryloyloxyethyl isocyanate. 8. The method for producing a modified carbon black according to claim 5, wherein the method is performed while pulverizing the carbon black. 9. A photosensitive black resin composition comprising the modified carbon black (A) according to claim 1. 10. The photosensitive black according to claim 9, comprising a binder resin (B), an ethylenically unsaturated compound (C), a photopolymerization initiator (D), and an organic solvent (E). Resin composition. 11. The photosensitive black resin composition according to claim 10, wherein the binder resin (B) is an acrylic copolymer having a carboxyl group. 12. A photopolymerization initiator (D) comprising (a) a hexaarylbiimidazole compound, (b) a triazine compound, (c) an aminoacetophenone compound, (d) a sensitizing dye, and a compound represented by the general formula (1): The photosensitive black resin composition according to claim 10, wherein the photosensitive black resin composition is one or more photopolymerization initiators selected from combinations of the organic boron salt-based compounds shown in (1). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ are each independently an optionally substituted alkyl, aryl, aralkyl, alkenyl, alkynyl, silyl, heterocyclic group, or halogen atom And Z ⁺ represents any cation) 13. The composition according to claim 10, which contains a polyfunctional thiol (F) as a chain transfer agent.
A photosensitive black resin composition according to any one of the above. 14. The photosensitive black resin composition according to claim 13, wherein the ratio of the polyfunctional thiol (F) to the photopolymerization initiator (D) is from 10: 1 to 1:10. 15. The photosensitive black resin composition according to claim 10, wherein the content of each component other than the organic solvent (E) is as follows. The modified carbon black (A) according to any one of claims 1 to 4, 25 to 60% by mass Binder resin (B) 10 to 40% by mass Ethylenically unsaturated compound (C) 5 to 40% by mass Photopolymerization initiator (D) 3 ~ 25% by mass 16. The photosensitive black resin composition according to claim 13, wherein the content of each component other than the organic solvent (E) is as follows. The modified carbon black (A) according to any one of claims 1 to 4, 25 to 60% by mass Binder resin (B) 10 to 40% by mass Ethylenically unsaturated compound (C) 5 to 40% by mass Photopolymerization initiator (D) 2 -20% by mass Polyfunctional thiol (F) 2-20% by mass 17. A black matrix resist composition for a color filter, comprising the photosensitive black resin composition according to claim 9. Description: 18. A black matrix formed using the black matrix resist composition for a color filter according to claim 17. 19. A modified carbon black dispersion containing the modified carbon black according to claim 1. Description: 20. The modified carbon black dispersion according to claim 19, comprising an organic solvent. 21. The modified carbon black dispersion according to claim 20, further comprising a polymer dispersant. 22. A method for producing a modified carbon black dispersion, comprising treating a carbon black with a compound having an isocyanate group and an ethylenically unsaturated bond in one molecule in an organic solvent. 23. The method for producing a modified carbon black dispersion according to claim 22, wherein the treatment is performed while dispersing. 24. The process for producing a modified carbon black dispersion according to claim 22, wherein the compound having an isocyanate group and an ethylenically unsaturated bond in one molecule is 2-methacryloyloxyethyl isocyanate. Method.