JPH0667421A - Black photopolymerizable composition, black hardened film of the composition, and production of color filter - Google Patents

Abstract

PURPOSE:To improve photosensitivity and dispersion stability and to easily produce a black matrix excellent-in light shielding property and resolution by using a polymer-grafted carbon black. CONSTITUTION:This compsn. consists of a photosensitive resin and polymer- grafted carbon black. This photosensitive resin consists of a photopolymn. initiator, photopolymerizable compd. having ethylenic unsatd. double bonds, and if necessary, other resin. The carbon black is grafted with a polymer compd. having reactive groups in the molecule. These reactive groups are preferably selected from aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group, isocyanate group, vinyl group, acryl group, methacryl group, silicon-base hydrolytic group, and amino group. The carbon black has preferably <=0.1mum average particle size and pH<=7.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention comprises a photopolymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator, and optionally a resin, and a polymer-grafted carbon black. To a black photopolymerizable composition, a light-shielding film using the same, and a method for producing a color filter.

[0002]

2. Description of the Related Art In a color filter used in a color liquid crystal display device or the like which is being converted from a CRT, a black matrix is formed for the purpose of blocking light between fine pixels colored in at least two kinds of hues. ing.
This black matrix is used not only for the purpose of improving the contrast of the displayed image, but also for the purpose of preventing malfunction of the transistor used in the TFT drive type liquid crystal display which has been actively researched and developed in recent years.

The black matrix as described above is usually formed of a metal thin film having a fine pattern on a glass substrate, and a concrete example thereof is a film of Cr, Ni, Al or the like. Generally, the vapor deposition method, the sputtering method, and the vacuum film formation are used.

The black matrix is formed by photolithography using the above metal thin film. In particular,
A photoresist is applied on the metal thin film, dried, and then irradiated with ultraviolet rays through a photomask to form a resist pattern, followed by etching and resist stripping.
However, since the black matrix manufactured as described above has a high manufacturing cost due to the complexity of the process, there is a problem that the cost of the color filter using the black matrix also increases.

When a color filter using this metal thin film is mounted on a transmissive display, the metal surface generally used as a metal thin film has a high reflectance, and when strong external light hits the filter, for example, Cr is used. The thin film has a problem that the reflected light is strong and the display quality is remarkably deteriorated. On the other hand, various methods have been studied in order to improve the problems of the black matrix using the metal thin film as described above. For example, Japanese Patent Application Laid-Open No. 2-239204 proposes a method of forming a black matrix using a light-shielding material such as carbon black dispersed in a polyimide resin. According to this method, a highly reliable black matrix can be obtained because the external light reflection is small and the heat resistance of the polyimide resin of the base material is high. However, this method is disclosed in JP-A-2-23920.
After the composition described in 4 is applied to a substrate and dried, a photoresist is further applied on the substrate, and the steps of patterning, etching, and resist stripping are performed, which simplifies the process and reduces the cost. In terms of aspects.

Various methods for forming a black matrix by dye-added photolithography in which a photopolymerizable compound having an ethylenically unsaturated double bond is used to form pixels by a photopolymerization initiator have also been reported.

In this case, as the black coloring material to be internally added,
Although a mixture of carbon black and other organic pigments is used, it is necessary to use carbon black in order to obtain a sufficient light-shielding property. JP-A-4-63870 proposes a method of forming a black matrix by dispersing carbon black and an organic pigment in a photopolymerizable compound. However, this composition must contain an organic pigment in order to have a transmittance of ultraviolet rays around 400 nm necessary for photocuring, and it was difficult to obtain sufficient light-shielding property at a low film thickness. Furthermore, since carbon black has a weaker affinity for other substances such as organic polymers and organic solvents than the cohesive force between particles, it is extremely difficult to obtain a uniform and stable dispersion state. In addition, JP-A-4-638
In the method described in 70, carbon black traps radicals generated from a photopolymerization initiator by ultraviolet rays, which hinders photopolymerization and makes it difficult to form sufficient pixels with an economical exposure amount. There were problems such as the pattern coming off.

[0008]

It has been desired to develop a black photopolymerizable composition which is excellent in photosensitivity, light-shielding property and dispersion stability and which can easily produce a high-definition black matrix.

[0009]

As a result of intensive studies to solve these problems, the present inventors have found that a specific resin composition solves the above problems, and It came to completion.

That is, the present invention comprises: (1) a photosensitive resin comprising a photopolymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator, and optionally other resins, and polymer grafting. Black photopolymerizable composition characterized by comprising a carbon black (2) The carbon black is an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group, an isocyanate group, a vinyl group, an acryl group, The black color described in the above item (1), which is grafted with a polymer compound having one or more kinds of reactive groups selected from a methacrylic group, a silicon-based hydrolyzable group and an amino group in the molecule. Photopolymerizable composition (3) Polymer compound containing acrylic acid and / or styrene and / or polyoxyethylene as a main component The black photopolymerizable composition according to the above (1) or (2), which is a product. (4) The above description (1) to (3), wherein a carbon black having an average particle size of 0.1 μm or less is used. (5) The black photopolymerizable composition according to the above (1) to (4), which uses a carbon black having a PH of 7 or less as the carbon black (5) (6) The above (1) to (5) Black cured film obtained using the black photopolymerizable composition of (7) A light-shielding film is formed by photolithography using the black photopolymerizable composition of the above (1) to (5). Method for forming light-shielding film (8) A method for producing a color filter, characterized in that a black matrix is produced using the black photopolymerizable composition according to the above (1) to (5).

The black photopolymerizable composition of the present invention will be described in detail.

In the present invention, a photosensitive resin is defined as a photopolymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator, and optionally other resins. The black photopolymerizable composition of the present invention is a composition containing carbon black, and since carbon black may absorb the ultraviolet rays necessary for photopolymerization, it is preferable to use a highly sensitive photopolymerizable compound,
For efficient photopolymerization, it is preferable to prepare the photosensitive resin composition so that the proportion of the photopolymerizable compound in the photosensitive resin is 60% by weight or more. Examples of the photopolymerizable compound having at least one ethylenically unsaturated double bond that can be used include the following compounds.

Monovalent compounds such as ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate. Or esters of acrylic acid or methacrylic acid of polyhydric alcohol; polyester (meth) obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid Acrylate; polyurethane (meth) acrylate obtained by reacting a compound having a polyol group with two isocyanate groups and then reacting with (meth) acrylic acid; Scan phenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, polycarboxylic acid polyglycidyl ester,
Epoxy (meth) obtained by reacting (meth) acrylic acid with an epoxy resin such as polyol polyglycidyl ether, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin Usual photopolymerizable resins such as acrylates may be mentioned.

Among these photopolymerizable compounds, compounds having an average molecular weight of 1000 or more have a very high photopolymerization rate, and it is particularly useful to incorporate these compounds in the photosensitive resin composition.

In the present invention, a photopolymerizable compound having both an acidic group such as a carboxyl group and an ethylenically unsaturated double bond is particularly preferably used. These compounds are extremely useful in increasing the content of the photopolymerizable compound having an ethylenically unsaturated double bond in the photosensitive resin, increasing the polymerization rate under atmospheric exposure and enabling aqueous development. .
Specific examples of such a photopolymerizable compound having an ethylenically unsaturated double bond and an acidic group such as a carboxyl group include:

Bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy Epoxy (meth) obtained by reacting an acid anhydride with a hydroxyl group obtained by reacting a (meth) acrylic acid with an epoxy group such as resin or dihydroxybenzene type epoxy resin
Acrylate-carboxylic acid adduct; hydroxyethyl at the maleic anhydride portion of the copolymer with monomers such as ethylene, propylene, isobutylene, styrene, vinylphenol, acrylic acid, acrylic acid ester and acrylamide, which are copolymerizable with maleic anhydride. A compound obtained by reacting an acrylate having an alcoholic hydroxyl group such as acrylate or an acrylate having an epoxy group such as glycidyl methacrylate with half-esterification; acrylic acid,
Examples thereof include a compound obtained by further reacting acrylic acid with a hydroxyl group of a copolymer of an acrylate and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate.

These compounds may be used alone or as a mixture, and are preferably used in such a proportion that the total weight thereof accounts for 60% or more in the photosensitive resin.

Other resins optionally used to form the photosensitive resin include film-forming polymeric binders. As the film-forming polymer binder, any organic polymer binder compatible with the photopolymerizable compound can be used, and examples thereof include polymethacrylic acid ester or its partial hydrolyzate and polyvinyl acetate. Or a hydrolyzate thereof, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylpyrrolidone, a copolymer of styrene and maleic anhydride or a half ester thereof, (meth) acrylic acid, ( A copolymer or the like having a glass transition point of 35 ° C. or higher selected from a group of copolymerizable monomers such as (meth) acrylic acid ester, acrylamide, and acrylonitrile is used. Among these, those having an acidic group such as a carboxyl group are advantageous in that they enable aqueous development which is more economical and safe than organic solvent development. The film-forming polymer binder as described above is preferably used in the photosensitive resin in an amount of 40% by weight or less.

An epoxy compound may be used as another resin, which is optionally used for forming a photosensitive resin, for the purpose of improving heat resistance. The epoxy compound is useful in improving heat resistance by thermally reacting with the compound having a carboxylic acid or the like and crosslinking.

Specific examples of such epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, polycarboxylic acid polyglycidyl esters, polyol polyglycidyl ethers, aliphatic or alicyclic epoxies. Resin, amine epoxy resin, triphenol methane type epoxy resin, dihydroxybenzene type epoxy resin and the like can be mentioned. These compounds are 30% by weight with respect to the photopolymerizable compound.
It is used in the following range, preferably in the range of 5 to 15%.

As the photopolymerization initiator used in the present invention, various photopolymerization initiators can be used alone or as a mixture, but in general, in a colored photopolymerizable resin in which a pigment is dispersed in a photopolymerizable resin, The ultraviolet rays necessary for the photopolymerization initiator to generate radicals are absorbed by the pigment, and the radicals cannot be generated sufficiently, so that the polymerization may be insufficient. Therefore, a highly sensitive compound or composition is required as a photopolymerization initiator for a photosensitive resin containing a pigment.

Specific examples of such a photopolymerization initiator include:
Benzyl, benzoin ether, benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, benzylmethylketal, dimethylaminomethylbenzoate, 2-n-butoxyethyl -4-Dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3'-dimethyl-4-methoxybenzophenone, methylobenzoyl formate, 2-methyl-1
-(4- (Methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-
On, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, 2,4-
Diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like can be mentioned. These photopolymerization initiators are used in the range of 0.5 to 30% by weight, preferably 2 to 15% by weight, based on the photopolymerizable compound, and these may be used alone or in combination of two or more. Can be done.

In the present invention, a hexaarylbisimidazole compound or a hydrogen donor may be used in combination as a photopolymerization initiator. As a specific example, US Pat.
557 or those disclosed in European Patent A24629 and the like can be used, but as particularly preferable in terms of stability and sensitivity, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5 is preferable. '-Tetraphenylbisimidazolyl, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetra- (p-methoxyphenyl) -bisimidazolyl and the like can be mentioned, and these are 0.5 to 30% by weight, preferably 2-1 to the photopolymerizable compound.
It is optionally used within the range of 5% by weight.

Further, as the hydrogen donor, an aromatic mercaptan compound, an aromatic amine compound or the like can be used. Among them, the aromatic mercaptan hydrogen donor has a mercapto group having 1 or more benzene or a heterocycle as a nucleus.
In this case, one or two mercapto groups may be substituted with alkyl, aralkyl or phenyl, or a dimer in the form of disulfide. Preferred examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and the like, and these may be added in an amount of 0.5 to 30% by weight, preferably 2 to 15% by weight, based on the photopolymerizable compound, if desired. used. As the aromatic amine-based hydrogen donor, a compound having 1 or 2 amino groups with benzene or a heterocycle as a mother nucleus is preferable. In this case, the amino group is substituted with an alkyl group or a substituted alkyl group. The monoamino compound may be further substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like. These are 0.5 to 30% by weight with respect to the photopolymerizable compound, preferably 2
Optionally used in the range of ~ 15% by weight.

Further, in producing a color filter using the black photopolymerizable composition of the present invention, in order to improve the coatability of the black photopolymerizable composition of the present invention to a substrate such as a glass plate, an organic material is used. You may dilute using a solvent. As the organic solvent, methyl cellosolve, ethyl cellosolve, propyl cellosolve, isopropyl cellosolve, alkyl cellosolves such as butyl cellosolve and acetates thereof, ethylene glycol, diethylene glycol,
Alkylene glycols such as propylene glycol and their alkyl ethers and alkyl ether acetates, cyclohexanone, diglyme, toluene, xylene and the like can be used, but are not limited thereto. These can be used alone or in combination of two or more, and the solid content with the resin pigment and the photopolymerization initiator is usually 5
It is prepared so as to contain 80% by weight.

A radical polymerization type resin containing ordinary carbon black as a black colorant is difficult to complete polymerization due to the polymerization inhibiting action of carbon black, and as a result, a radical polymerization type resist containing ordinary carbon black is used. Had insufficient adhesion of the pixel to the substrate, and had problems such as peeling of the pixel during development, resolution, and solvent elution of residual monomer from the cured film. This phenomenon was more remarkable as the particle size of carbon black was smaller. In the present invention, in order to solve the above problems, a specific polymer-grafted carbon black is used as a carbon black having a small particle size, which is black and is not easily affected by polymerization inhibition and has a large coloring power.

Regarding this polymer-grafted carbon black, the polymer compound used for grafting the surface of the carbon black must be one that has a reactive group that can easily react with the functional group present on the surface of the carbon black. I won't. Specific examples of this reactive group include an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, an isocyanate group, a vinyl group, a silicon-based hydrolyzable group, and an amino group. It is a polymer compound having one kind or two or more kinds therein. Particularly, in terms of reactivity with functional groups on the surface of carbon black, a polymer having one or more kinds selected from aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group and isocyanate group as a reactive group. A compound is preferable, more preferably an aziridine group,
It is a polymer compound having, as a reactive group, one or more selected from an oxazoline group and an N-hydroxyalkylamide group. When reacting carbon black and a polymer having reactivity with carbon black, substances other than the polymer, such as polymer components, monomers and organic solvents, may be present in the reaction system.

The polymer compound used for the grafting of carbon black in the present invention is appropriately selected according to the properties to be imparted to the polymer-grafted carbon black, such as hydrophilicity, lipophilicity or other affinity, and Acrylic acid and / or polyoxyethylene as the main component vinyl-based copolymer or vinyl-based monomer when imparting property, and styrene-based vinyl-based copolymer when imparting lipophilicity. Copolymers or vinyl monomers are preferably used. Specific examples of such polymer-grafted carbon black include carbon black graft polymer GLK-20 (trade name, manufactured by Nippon Shokubai, styrene-butyl acrylate copolymer graft), carbon black polymer CBW-60 (trade name, Grafted with styrene-polyoxylene-acrylic acid copolymer made by Nippon Shokubai)
Etc. Further, the carbon black in the present invention can be used as long as it has a quinone group and / or a carboxyl group and / or a hydroxyl group as a functional group on the surface thereof, and particularly when a carbon black having a pH of 7 or less is used, the above polymer is obtained. It is preferable because it can be efficiently grafted. In the grafting reaction, the particle size of the carbon black is arbitrary, but from the viewpoint of coloring power, the average particle size is 0.1 μm or less, preferably 0.04 μm.
The following carbon blacks are useful.

The polymer-grafted carbon black as described above may be used as a black colorant in combination with other organic pigments in some cases. Although the mixing ratio of the polymer-grafted carbon black and the organic pigment is arbitrary, the light-shielding property of the organic pigment is lower than that of carbon black, and therefore the light-shielding property of the cured film formed by using the black photopolymerizable composition is impaired. It is desirable to use an organic pigment within a certain range, and the total weight of the polymer-grafted carbon black and optionally other organic pigment is 10 with respect to the photosensitive resin.
~ 90 wt%, preferably 20-70 wt%.

The polymer-grafted carbon black as described above and other organic pigments may be dispersed together with a dispersant, if necessary, by a dispersing machine such as a sand mill or a triple roll mill.

The black photopolymerizable composition of the present invention comprises a photopolymerizable compound, a photopolymerization initiator, optionally other resin, polymer-grafted carbon black, optionally other organic pigment, optionally a dispersant and an organic solvent. Is obtained by mixing in the proportions as described above. Mixing is preferably carried out while processing with an ordinary mixer or disperser. The obtained black photopolymerizable composition of the present invention can be filtered for the purpose of removing coarse particles and foreign matters in the system. The filtration is, for example, 1 μm or less in pore size, more preferably 0.5 μm
It may be carried out under pressure by using the following membrane, surface, and depth type filter media.

The black photopolymerizable composition of the present invention is applied on a support such as glass, polycarbonate, silicon wafer, paper, plastic sheet, synthetic paper, etc. by a bar coater, spin coater, roll coater, spray coating, dipping, gravure printing. After coating with a coating method such as screen printing, the light-shielding film can be obtained by irradiating with ultraviolet rays of 20 to 300 mJ and curing. It is also possible to produce a black matrix in a color filter using the black photopolymerizable composition of the present invention. The black photopolymerizable composition of the present invention is applied to a substrate such as a glass plate by a spin coater or the like, and a solvent is dried to form a smooth coating film, and a desired pixel is formed on the coating film. In addition, the UV is usually 20 to 20 through a negative photomask.
Irradiate 300 mJ. At this time, it is preferable to use an apparatus such as a mask aligner so that parallel rays are uniformly irradiated on the entire coating film. . If necessary, this irradiated coating film may be heated for a short time to promote polymerization. Next, it is immersed in a developing solution or exposed to a shower to dissolve the uncured portion and develop. Then, the target pixel (black matrix) can be obtained by completely curing it by a high temperature post-baking process. The preferable film thickness of the black matrix is usually 0.2 to 5.0 μm.

When a black matrix in a color filter is manufactured using the black photopolymerizable composition of the present invention, a black matrix, a red, green and blue colored patterns are formed in this order on a glass substrate or the like. Either a method or a method of forming a colored pattern of each color of red, green and blue, and a black matrix in this order on a glass substrate or the like is possible.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The unit is parts by weight.

(Photosensitive Resin Preparation Example 1) The following compounds, styrene-maleic acid half ester acrylate 30 parts Phenol novolac epoxy acrylate 30 parts Dipentaerythritol hexaacrylate 10 parts Irgacure 369 (trade name, manufactured by Ciba Geigy, photopolymerization initiator) ) 2 parts Diethylthioxanthone 1 part Biimidazole 1 part 2-Mercaptobenzothiazole 1 part Ethyl cellosolve acetate 25 parts A composition was mixed to obtain a photosensitive resin.

(Photosensitive resin preparation example 2) KAYARAD R5198 (trade name, manufactured by Nippon Kayaku, trisphenol-based epoxy acrylate polybasic acid adduct) 27 parts KAYARAD R2243 (trade name, manufactured by Nippon Kayaku, bisphenol) A-based polyfunctional epoxy acrylate) 27 parts KAYARAD TMPTA (trade name, manufactured by Nippon Kayaku, trimethylolpropane triacrylate) 9 parts AK601 (trade name, manufactured by Nippon Kayaku, alicyclic epoxy monomer) 7 parts Irgacure 369 (product) 2 parts 1-chloro-4-propoxy-thioxanthone 1 part Biimidazole 1 part 2-Mercaptobenzoxazole 1 part Ethyl cellosolve acetate 25 parts A composition was mixed to obtain a photosensitive resin.

Reference Example 1 2- (1-aziridinyl)-
Ethyl methacrylate 1 part, styrene 20 parts, polyethylene glycol acrylate 15 parts, acrylic acid 14
And 50 parts of carbon black MA-600 (trade name, manufactured by Mitsubishi Kasei Co., Ltd., carbon black, average particle size 20 μm) were heated and stirred for polymerization in the presence of 1 part of benzoyl peroxide to obtain a polymer-grafted carbon black. .

Reference Example 2 1 part of isopropenyl oxazoline, 25 parts of styrene, 15 parts of nonylphenoxy polyethylene glycol acrylate, 9 parts of acrylic acid, and 50 parts of carbon black Special Black 350 (trade name, manufactured by Degussa, pH 3), A polymer-grafted carbon black was obtained in the same manner as in Reference Example 1.

(Reference Example 3) Polyethylene glycol glycidyl ether acrylate 5 parts, methyl styrene 25
Parts, methyl methacrylate 20 parts, carbon black Ra
ven1060 (trade name, Colombian carbon, p
H2.4) was added in the same manner as in Reference Example 1 to obtain a polymer-grafted carbon black.

Reference Example 4 N-hydroxyethylmethacrylamide 1 part, acrylamide 34 parts, N-vinylpyrrolidone 15 parts, carbon black Regal 400R
(Trade name, manufactured by Cabot, pH 4) was subjected to heat stirring polymerization in the presence of 0.5 part of ammonium persulfate to obtain a polymer-grafted carbon black.

Example 1 To 100 parts of the photosensitive resin obtained in Preparation Example 1 of photosensitive resin,
40 parts of the polymer-grafted carbon black obtained in Reference Example 1 was added and dispersed. This black photopolymerizable composition was manufactured by Corning No. A 7059 glass substrate was spin-coated to a dry film thickness of 1.5 μm, and the coated film was dried at 100 ° C. for 10 seconds. Next, the film was exposed to 100 μm with a super-high pressure mercury lamp through a dot-like and linear photomask with an interval of 10 μm.
After mJ exposure, develop with a 0.1% tetramethylammonium hydroxide aqueous solution shower for 30 seconds 1
A high resolution black matrix of 0 μm dots and stripes was obtained. The black photopolymerizable composition was dispersion stable even after 6 months from the preparation.

Examples 2 to 4 A black photopolymerizable composition was prepared in the same manner as in Example 1 except that the amounts of polymer-grafted carbon black and organic pigment shown in Table 1 and a photosensitive resin were used. Further, using the black photopolymerizable composition, a black matrix was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A black colorant was carbon black MA-600 (trade name,
A black photopolymerizable composition was prepared in the same manner as in Example 1 except that only 40 parts of Mitsubishi Kasei Co., Ltd.) was used, and after 1 month, the carbon black component was precipitated. Further, when a black matrix was produced immediately after the preparation in the same manner as in Example 1, the pixels came off during development. Further, even when a black matrix was prepared in the same manner with an exposure amount of 500 mJ, pixels were peeled off during development.

Comparative Example 2 Example 1 was repeated except that 40 parts of the organic pigment was used as the black colorant.
A black photopolymerizable composition was prepared in the same manner as in 1. to prepare a black matrix. However, although the resolution was high, the film strength was insufficient and the light-shielding property was extremely poor.

Table 1

[0046]

By using the polymer-grafted carbon black, a black photopolymerizable composition having excellent photosensitivity and dispersion stability can be obtained, and by using the black photopolymerizable composition, black having excellent light-shielding property and resolution can be obtained. The matrix can now be easily manufactured.

Claims (8)

[Claims] 1. At least one ethylenically unsaturated double bond.
Black photopolymerizable composition comprising a photosensitive resin comprising one or more photopolymerizable compounds, a photopolymerization initiator, and optionally other resins, and carbon black grafted with a polymer compound. Composition. 2. A polymer compound comprising an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group,
The black light according to claim 1, which is a polymer compound having in its molecule one or more reactive groups selected from an isocyanate group, a vinyl group, an acrylic group, a methacrylic group, a silicon-based hydrolyzable group, and an amino group. Polymerizable composition. 3. The black photopolymerizable composition according to claim 1, wherein the polymer compound is a copolymer containing acrylic acid and / or styrene and / or polyoxyethylene as a main component. 4. The carbon black has an average particle diameter of 0.1 μm.
The black photopolymerizable composition according to claim 1, which is the following carbon black. 5. The black photopolymerizable composition according to claim 1, wherein the carbon black is PH7 or less. 6. A black cured film obtained by using the black photopolymerizable composition according to claim 1. 7. A method of forming a light-shielding film, which comprises forming a light-shielding film by photolithography using the black photopolymerizable composition according to claim 1. 8. A method for producing a color filter, which comprises producing a black matrix using the black photopolymerizable composition according to any one of claims 1 to 5.