CN1573542A - Colored photoresist composition - Google Patents

Abstract

A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a pigment dispersant (E) and a solvent (F ), when the colored photosensitive resin composition is coated on a glass substrate to form a resin layer, the resin layer is pre-dried, exposed through a mask, developed, and post-dried, the resulting hardened The hardness of the resin layer is more than 3H to less than 9H in pencil hardness, and the photosensitive resin layer obtained after pre-drying and mask exposure is immersed in an alkaline aqueous solution at 25°C under stirring at 100rpm for 120 seconds, and then the non-exposed part of the photosensitive resin layer The transmittance (average value of 400 to 780 nm) of the dissolved portion is not less than 98% and not more than 100%.

Description

Colored photosensitive resin composition

technical field

The present invention relates to a colored photosensitive resin composition.

Background technique

A color filter used in a color liquid crystal display device, an imaging element, etc. is manufactured by forming colored layers corresponding to the three primary colors of red, green, and blue on a substrate patterned with a black matrix.

Colored layers (colored pixels) that are conventionally formed in a pattern are not sufficiently hard, and the colored layer may be damaged in post-processes such as alignment film rubbing treatment after color filter production, or the coloring layer may be interposed between two layers when assembling a liquid crystal panel. The pressure generated by the spacer material between the substrates tends to deform the colored layer, thereby locally changing the gap of the liquid crystal cell, which easily causes problems such as display defects.

The colored layer can be formed from a colored resin composition. As a colored resin composition, a colored photosensitive resin composition containing a colorant, a binder resin, a dispersant, a solvent, and ceramic particles is known (see JP-A-10-186126), but the composition After drying and exposure through the mask, the photosensitive resin layer of the non-exposed part is immersed in an aqueous alkali solution to dissolve the photosensitive resin layer, because ceramic particles are contained and residues occur, and the transmittance of the dissolved part (average of 400-780nm value) is lowered, and the image quality is not satisfactory.

invention disclosure

An object of the present invention is to provide a colored photosensitive resin composition that is excellent in developability and can form a cured resin layer with high surface hardness.

As a result of earnest research, the inventors of the present invention have found a colored photosensitive resin composition that is excellent in developability and can form a cured resin layer with high surface hardness.

That is, the present invention provides the following [1] to [11].

[1] A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a pigment dispersant (E) and Solvent (F), when the colored photosensitive resin composition is coated on a glass substrate to form a resin layer, the resin layer is pre-dried, exposed through a mask, developed, and post-dried, the resulting The hardness of the obtained hardened resin layer is pencil hardness above 3H to below 9H, and the photosensitive resin layer obtained after pre-drying and mask exposure is immersed in an alkaline aqueous solution at 25°C under stirring at 100rpm for 120 seconds. After the photosensitive resin layer The transmittance (average value of 400 to 780 nm) of the melted portion of the non-exposed portion is not less than 98% and not more than 100%.

[2] The colored photosensitive resin composition according to [1], wherein the binder resin (B) is a resin containing a structural unit derived from (meth)acrylic acid.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the content of structural units derived from (meth)acrylic acid in the total structural units constituting the binder resin (B) is 16 mol % or more to 40 mol% or less.

[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the binder resin (B) further contains a structural unit derived from benzyl (meth)acrylate.

[5] The colored photosensitive resin composition described in any one of [1] to [4], wherein the binder resin (B) is a resin further comprising a structural unit represented by formula (I):

In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.

[6] The colored photosensitive resin composition according to any one of [1] to [5], wherein the polystyrene-equivalent weight average molecular weight of the binder resin (B) is 5,000 to 35,000.

[7] The colored photosensitive resin composition described in any one of [1] to [6], wherein the pigment dispersant (E) is composed of polyester-based, polyethyleneimine-based, polyurethane-based, and acrylic-based at least one surfactant selected from the group.

[8] The colored photosensitive resin composition according to any one of [1] to [7], wherein the pigment dispersant (E) is an acrylic surfactant.

[9] A method for forming a colored pattern, comprising forming a resin layer composed of the colored photosensitive resin composition described in any one of [1] to [8] on a substrate, and exposing the resin layer through a mask. , development, and post-drying.

[10] The colored pattern forming method according to [9], wherein the temperature of the post-baking treatment is 180°C to 250°C.

[11] A color filter comprising a colored pattern formed by the method described in [9] or [10].

Embodiment of the invention

The colored photosensitive resin composition of the present invention contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a pigment dispersant (E) and a solvent ( F) the colored photosensitive resin composition, the colored photosensitive resin composition is coated on a glass substrate to form a resin layer, the resin layer is pre-dried, exposed through a mask, developed, and post-dried, after The hardness of the cured resin layer obtained after drying is more than 3H to less than 9H in pencil hardness, and the photosensitive resin layer obtained after pre-drying and mask exposure is immersed in an alkaline aqueous solution at 25°C under 100rpm stirring for 120 seconds. The transmittance (average value of 400 to 780 nm) of the portion of the photosensitive resin layer where the non-exposed portion is dissolved is 98% or more and 100% or less.

The hardness of the cured resin layer (coating film) must be pencil hardness of not less than 3H and not more than 9H, preferably not less than 4H and not more than 9H, more preferably not more than 5H and not more than 9H. The cured resin layer (coating film) is the part that becomes the pixel portion, but when the pencil hardness is 3H to 9H, the resin layer (coating film) is cured in steps such as the preparation of the liquid crystal alignment film after the pixel is formed. It is hard to be damaged, so it is better. Pencil hardness is measured according to the method of JIS K 5400.

It is preferable to apply the colored photosensitive resin composition on a glass substrate and perform the prebaking at 100° C. for about 3 minutes.

The photosensitive resin layer obtained after pre-drying and mask exposure was immersed in an aqueous alkali solution at 25° C. under stirring at 100 rpm. Here, the alkaline aqueous solution generally uses an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalenesulfonate in mass fractions, respectively.

When the non-exposed portion of the photosensitive resin layer is immersed in an aqueous alkali solution at 25° C. under stirring at 100 rpm, it is preferably dissolved within 120 seconds, more preferably within 1 second to within 100 seconds, and even more preferably between 1 second to 1 second. It dissolves within 80 seconds, more preferably within 1 second to 60 seconds. When the time required for dissolution is within the above-mentioned range, a decrease in the productivity of the color filter can be suppressed, which is preferable.

The non-exposed portion of the photosensitive resin layer must have a transmittance (the average value of the transmission wavelength in the range of 400nm to 780nm) of the part where the photosensitive resin layer dissolves after being immersed in an aqueous alkali solution at 25° C. under stirring at 100 rpm for 120 seconds. From 99% to 100%, preferably from 99% to 100%, more preferably from 99.5% to 100%. When the transmittance is at least 98% and at most 100%, it is preferable because the influence on the brightness of the colored layer is small.

The colorant (A) used in the present invention may be an organic colorant or an inorganic colorant. Organic colorants can be either organic pigments or organic dyes. Furthermore, the organic colorant may be either a synthetic colorant or a natural colorant. Inorganic colorants may be inorganic pigments such as metal oxides, metal complex salts, and inorganic salts of barium sulfate (extender pigments). Among these colorants, an organic colorant is preferably used, and an organic pigment is more preferably used.

As organic pigments and inorganic pigments, compounds classified as pigments in "Colour Index" (Colour Index, published by The Society of Dyers and Colourists) can be cited.

Specifically, C.I. Pigment Yellow-1, C.I. Pigment Yellow-3, C.I. Pigment Yellow-12, C.I. Pigment Yellow-13, C.I. Pigment Yellow-14, C.I. Pigment Yellow-15, C.I. Pigment Yellow-16, C.I. Pigment Yellow-17, C.I. Pigment Yellow-20, C.I. Pigment Yellow-24, C.I. Pigment Yellow-31, C.I. Pigment Yellow-53, C.I. Pigment Yellow-83, C.I. Pigment Yellow-86, C.I. Pigment Yellow-93, C.I. Pigment Yellow- 94. C.I. Pigment Yellow-109, C.I. Pigment Yellow-110, C.I. Pigment Yellow-117, C.I. Pigment Yellow-125, C.I. Pigment Yellow-128, C.I. Pigment Yellow-137, C.I. Pigment Yellow-138, C.I. Pigment Yellow-139, C.I. Pigment Yellow-147, C.I. Pigment Yellow-148, C.I. Pigment Yellow-150, C.I. Pigment Yellow-153, C.I. Pigment Yellow-154, C.I. Pigment Yellow-166, C.I. Pigment Yellow-173, C.I. Pigment Yellow-194, C.I. Pigment Yellow pigments such as Huang-214;

C.I. Pigment Orange-13, C.I. Pigment Orange-31, C.I. Pigment Orange-36, C.I. Pigment Orange-38, C.I. Pigment Orange-40, C.I. Pigment Orange-42, C.I. Pigment Orange-43, C.I. Pigment Orange-51, C.I. Pigment Orange-55, C.I. Pigment Orange-59, C.I. Pigment Orange-61, C.I. Pigment Orange-64, C.I. Pigment Orange-65, C.I. Pigment Orange-71, C.I. Pigment Orange-73 and other orange pigments;

C.I. Pigment Red-9, C.I. Pigment Red-97, C.I. Pigment Red-105, C.I. Pigment Red-122, C.I. Pigment Red-123, C.I. Pigment Red-144, C.I. Pigment Red-149, C.I. Pigment Red-166, C.I. Pigment Red-168, C.I. Pigment Red-176, C.I. Pigment Red-177, C.I. Pigment Red-180, C.I. Pigment Red-192, C.I. Pigment Red-209, C.I. Pigment Red-215, C.I. Pigment Red-216, C.I. Pigment Red- 224, C.I. Pigment Red-242, C.I. Pigment Red-254, C.I. Pigment Red-264, C.I. Pigment Red-265 and other red pigments;

C.I. Pigment Blue-15, C.I. Pigment Blue-15:3, C.I. Pigment Blue-15:4, C.I. Pigment Blue-15:6, C.I. Pigment Blue-60 and other blue pigments;

C.I. Pigment Violet-1, C.I. Pigment Violet-19, C.I. Pigment Violet-23, C.I. Pigment Violet-29, C.I. Pigment Violet-32, C.I. Pigment Violet-36, C.I. Pigment Violet-38 and other purple pigments;

C.I. Pigment Green-7, C.I. Pigment Green-36 and other green pigments;

C.I. Pigment Brown-23, C.I. Pigment Brown-25 and other brown pigments;

C.I. Pigment Black-1, C.I. Pigment Black-7 and other black pigments, etc.

Pigment Yellow-138, C.I. Pigment Yellow-139, C.I. Pigment Yellow-150, C.I. Pigment Red-177, C.I. Pigment Red-209, C.I. Pigment Red-254, C.I. Pigment Violet-23 , C.I. Pigment Blue-15:6 and at least one pigment selected from C.I. Pigment Green-36.

These organic pigments and inorganic pigments may be used alone or in combination of two or more.

For example, in order to form a red pixel, it is preferable to contain C.I. Pigment Red-254 and C.I. Pigment Yellow-139.

In order to form a green pixel, it is preferable to contain at least one selected from the group consisting of C.I. Pigment Yellow-150 and C.I. Pigment Yellow-138 and C.I. Pigment Green-36.

In order to form a blue pixel, it is preferable to contain C.I. Pigment Blue-15:6 and C.I. Pigment Violet-23.

The organic pigments in the above-mentioned pigments may also be subjected to rosin treatment, surface treatment using pigment derivatives introduced with acidic groups or basic groups, etc., grafting treatment on the surface of pigments with polymer compounds, etc., micronization with sulfuric acid, etc., if necessary. Micronization treatment such as method, washing treatment with organic solvent or water to remove impurities, removal treatment of ionic impurities by ion exchange method, etc. Furthermore, after preparation of a colored photosensitive resin composition, removal processing, such as an ion exchange method, can also be implemented, for example.

The content of the colorant (A) is usually not less than 25 parts by mass and not more than 60 parts by mass, preferably not less than 27 parts by mass and not more than 55 parts by mass, when the solid content in the colored photosensitive resin composition is 100 parts by mass , More preferably 30 mass parts or more - 50 mass parts or less. If the content of the colorant (A) is more than 25 parts by mass and less than 60 parts by mass, the color density is satisfactory when making a color filter, and a necessary amount of binder resin can be contained in the composition, so Since a pattern with sufficient mechanical strength can be formed, it is preferable.

Here, the solid content in a colored photosensitive resin composition means what remains after removing a solvent (F) from a colored photosensitive resin composition.

In the coloring photosensitive resin composition of this invention, when using a pigment as a coloring agent (A), it is preferable that the particle diameter is uniform. In order for the pigment to have a uniform particle size, a method of dispersing a surfactant as a pigment dispersant (E) and performing a dispersion treatment, etc. are mentioned.

Examples of the pigment dispersant (E) include surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyesters, acrylics, polyurethanes, and polyethyleneimines. , and these may be used alone or in combination of two or more.

Examples of polyoxyethylene alkyl ether-based surfactants include those having the following formula (14102 Chemical Commodities, page 1286 (Chemical Industry Daily, published on January 29, 2002)):

RO(CH ₂ CH ₂ O) _n H

In the formula, R represents a C _12-22 alkyl group, and n represents a number of 2-60.

Examples of polyoxyethylene alkyl ether-based surfactants include polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene oleyl ether. Ether, polyoxyethylene 2-ethylhexyl ether, etc.

Commercially available polyoxyethylene alkyl ether surfactants include BLAUNON-EL series, BLAUNON-CH series, BLAUNON-SR series, BLAUNON-EN series, BLAUNON-EH series, BLAUNON-DAL series, BLAUNON- DAI series, BLAUNON-DAH series, BLAUNON-OX series (all manufactured by Aoki Oil & Fat Co., Ltd.), etc., and equivalent products from other companies can also be used in the same way.

Examples of polyoxyethylene alkylphenyl ether surfactants include those with the following formula (14102 Chemical Commodities, page 1287 (Chemical Industry Daily, published on January 29, 2002));

In the formula, m represents an integer of 1 to 5, n represents a number of 2 to 60, R represents a C _{12 to 22} alkyl group or a substituted phenyl group, but when m is 2 to 5, R can be the same or different .

Examples of commercially available polyoxyethylene alkylphenyl ether surfactants include BLAUNON-NK series, BLAUNON-N series, BLAUNON-DP series, BLAUNON-DNP series, BLAUNON-DSP series, BLAUNON-TSP series, BLAUNON-PH series, BLAUNON-BA series, etc., equivalent products from other companies can also be used.

Polyester-based surfactants have a polyester structure. As a polyester surfactant, Disperbyk-161, the same brand 170 (made by BYK Chemie), PB821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

Polyethyleneimine-based surfactants have an ethyleneimine structure. Examples of polyethyleneimine-based surfactants include Sorsperse 24000 GR (manufactured by Seneca), and equivalents from other companies can also be used in the same manner.

Acrylic surfactants have an acrylic copolymer structure. Examples of the acrylic surfactants include Disperbyk-352, TOTO 354, TOTO 2000, TOTO 2001 (manufactured by BYK Chemie), and EFKA-Polymer 401 (manufactured by EFKA Chemicals). Equivalent products from other companies are also available. The same can be used.

Polyurethane-based surfactants have a polyurethane structure. Examples of polyurethane-based surfactants include EFKA-Polymer 452 and EFKA-47 (manufactured by EFKA Chemicals), and equivalent products from other companies can also be used in the same manner.

Furthermore, examples of surfactants other than the above include trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflo- (manufactured by Kyoei Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products Co., Ltd.), Megafax (manufactured by Dainippon Ink Chemical Co., Ltd. ), Flora-do (manufactured by Sumitomo Suri-Em Co., Ltd.), Asahiga-do, Sa-flon (manufactured by Asahi Glass Co., Ltd.).

As the pigment dispersant (E), it is preferable to use at least one surface-active agent selected from the group consisting of polyester-based surfactants, polyethyleneimine-based surfactants, polyurethane-based surfactants, and acrylic-based surfactants. Active agent, preferably acrylic surfactant.

The usage-amount of a pigment dispersant (E) is 1 mass part or less normally with respect to 1 mass part of a coloring agent (A), Preferably it is 0.05 mass part or more - 0.5 mass part or less. When the usage-amount of a pigment dispersant (E) is 1 mass part or less with respect to 1 mass part of a coloring agent (A), since it exists in the tendency for a uniform particle diameter pigment to be obtained, it is preferable.

The binder resin (B) used in the colored photosensitive resin composition of the present invention preferably contains a structural unit derived from (meth)acrylic acid. The binder resin (B) is more preferably an acrylic copolymer of a structural unit derived from (meth)acrylic acid and other monomers copolymerizable therewith.

Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid. The content of the structural unit derived from (meth)acrylic acid is preferably from 16 mol % to 40 mol % in total structural units constituting the binder resin (B). When the content of the (meth)acrylic acid unit is within the above range, the solubility of the non-pixel portion in the resin layer during image development is good, and residue tends to be less likely to remain in the non-pixel portion after image development, which is preferable.

Examples of other copolymerizable monomers include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated Ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, macromonomers with an acryloyl group or a methacryloyl group at the end of the polymer molecular chain, etc. .

Examples of the acrylic copolymer include methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/methacrylic acid Isonorbornyl acrylate copolymer, methacrylic acid/styrene/benzyl methacrylate/N-phenylmaleimide copolymer, and copolymers containing constituents represented by the following formula (I):

In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.

Among them, methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/isonorbornyl methacrylate copolymer are preferably used. substance, methacrylic acid/the constituents represented by the formula (I) (R ¹ is a methyl group, R ² is a hydrogen atom)/benzyl methacrylate copolymer and the constituents represented by the formula (I) (R ¹ is a methyl group, R ² is a hydrogen atom)/benzyl methacrylate copolymer.

A binder resin with constituents shown in formula (I), such as methacrylic acid/constituents represented by formula (I) (R ¹ is a methyl group, R ² is a hydrogen atom)/benzyl methacrylate copolymer The product can be obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and then reacting the obtained two-component polymer with a component represented by the following formula (II):

In formula (II), R ² represents a hydrogen atom.

The acid value of the binder resin (B) used for this invention is 50-150 normally, Preferably it is 60-135, More preferably, it is 70-135. When the acid value is 50 to 150, the solubility to the developing solution increases, the unexposed portion becomes easy to dissolve, and the sensitivity increases, and the pattern of the exposed portion remains during development, which tends to increase the residual film rate. , so it is better. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration with an aqueous potassium hydroxide solution.

Furthermore, the binder resin (B) has polystyrene conversion weight average molecular weight normally 5,000-35,000, Preferably it is 6,000-30,000, More preferably, it is 7,000-28,000. When the molecular weight is 5,000 to 35,000, the hardness of the cured resin layer (coating film) increases, the remaining film rate is also high, the solubility of the unexposed portion to the developing solution is good, and the resolution tends to be improved, so it is preferable.

The mass fraction of the binder resin (B) relative to the solid content of the colored photosensitive resin composition is usually at least 5% by mass and at most 50% by mass, preferably at least 10% by mass and at most 40% by mass. , More preferably, it is not less than 15% by mass and not more than 35% by mass. When the content of the binder resin is at least 5% by mass and at most 50% by mass, pattern formation is possible, and the resolution and residual film ratio tend to be improved, which is preferable.

The photopolymerizable compound (C) used in the present invention is a compound capable of initiating polymerization by active radicals generated from a photopolymerization initiator by irradiation with light. As a photopolymerizable compound (C), the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned, for example. This compound may be a monofunctional photopolymerizable compound or a bifunctional or trifunctional or higher polyfunctional photopolymerizable compound.

Examples of monofunctional photopolymerizable compounds include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy acrylate Ethyl ester, N-vinylpyrrolidone, etc.

Examples of bifunctional photopolymerizable compounds include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, and ethylene glycol dimethacrylate. ester, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, and the like.

Examples of trifunctional or higher polyfunctional photopolymerizable compounds include tri(hydroxymethyl)propane triacrylate, tri(hydroxymethyl)propane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. , pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc.

These photopolymerizable compounds may be used alone or in combination of two or more. The content of the photopolymerizable compound (C) is usually not less than 16% by mass and not more than 31% by mass, preferably not less than 18% by mass, in terms of mass fraction relative to the solid content of the colored photosensitive resin composition. - 30% by mass or less, more preferably 19% by mass or more and 29% by mass or less. When the content of the photopolymerizable compound (C) is 16% by mass or more to 31% by mass or less, hardening occurs sufficiently and the residual film rate increases, which is preferable.

Examples of the photopolymerization initiator (D) used in the present invention include acetophenone-based compounds, triazine-based compounds, biimidazole-based compounds, and oxime compounds, and mixtures of two or more of these compounds.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2 -Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal , 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- Oligomers of 1-[4-(1-methylvinyl)phenyl]propan-1-one, etc. Among these, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one is preferably used. Furthermore, multiple types of acetophenone-based and other photopolymerization initiators can also be used in combination.

Examples of other photopolymerization initiators include active radical generators and acid generators capable of generating active radicals by irradiation with light.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-( 3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

Examples of biimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4 , 4',5,5'-tetrakis(p-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(p-bromophenyl) ) biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(o, p-dichlorophenyl)biimidazole, 2,2'-bis(o-bromo Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenyl Biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o,o'- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole Imidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, etc.

O-acyl oxime compounds can be mentioned as oxime compounds, and specific examples thereof include 1-(4-benzenesulfonylaminophenyl)butan-1,2-dione 2-oxime-O-benzoate, 1-(4-Benzenesulfonylaminophenyl)oct-1,2-dione 2-oxime-O-benzoate, 1-(4-benzenesulfonylaminophenyl)oct-1-one oxime-O- Acetate, 1-(4-benzenesulfonylaminophenyl)butan-1-one oxime-O-acetate, etc.

Examples of active radical generators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin butyl ether.

Examples of benzophenone-based compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfite, 3, 3',4,4'-Tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and the like.

Examples of thioxanthone-based compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone, etc.

Examples of the triazine-based compound include the same ones as those described above.

Examples of active radical generators other than those mentioned above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5 , 5′-tetraphenyl-1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, benzene Methyl glyoxylate, titanocene compounds, etc.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate Sulphonium, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, hexafluoroantimony onium salts such as diphenyliodonium acid, nitrobenzyl tosylate, benzoin tosylate, etc.

Furthermore, among the above-mentioned compounds that are active radical generators, there are compounds that generate radicals and simultaneously generate acids. For example, triazine-based photopolymerization initiators can also be used as acid generators.

The content of the photopolymerization initiator (D) is usually not less than 0.1 parts by mass and not more than 30 parts by mass based on 100 parts by mass of the total amount of the binder resin (B) and the photopolymerizable compound (C). Preferably, it is 1 mass part or more - 25 mass parts or less. If the content of the photopolymerization initiator is more than 0.1 parts by mass and less than 30 parts by mass, the sensitivity is improved, the exposure time is shortened, and the productivity is improved, and there is a tendency not to cause poor resolution due to excessive sensitivity. good.

As the photopolymerization initiator (D), it is preferable to use 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamine 1-(4-morpholinophenyl)butan-1-one, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine.

In the present invention, a photopolymerization initiation adjuvant can also be used. The photopolymerization initiation adjuvant is preferably used in combination with a photopolymerization initiator, and is a compound for promoting polymerization of a photopolymerizable compound that is polymerized by the photopolymerization initiator. As a photopolymerization start adjuvant, an amine compound, an alkoxy anthracene compound, a thioxanthone compound, etc. are mentioned.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate, Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-di( Dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferably used.

Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl - 9,10-diethoxyanthracene, etc.

Examples of the thioxanthone-based compound include the same ones as those described above.

A photopolymerization start adjuvant may be used individually or in combination of multiple types. Furthermore, what is marketed as a photopolymerization start adjuvant can also be used, and as a commercially available photopolymerization start adjuvant, a brand name "EAB-F" (made by Hodogaya Chemical Industry Co., Ltd.) etc. are mentioned, for example.

Examples of the combination of the photopolymerization initiator and the photopolymerization initiation aid in the colored photosensitive resin composition of the present invention include diethoxyacetophenone/4,4'-bis(diethylamino)benzophenone, 2-Methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one/4,4′-bis(diethylamino)benzophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one/4,4′-bis(diethylamino)benzophenone, benzyl dimethylacetacetal/4,4′-bis(diethylamino) Benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one/4,4'-bis(diethylamino)benzophenone , 1-hydroxycyclohexyl phenyl ketone/4,4'-di(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl ] Propan-1-one oligomer/4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) Butan-1-one/4,4'-bis(diethylamino)benzophenone, etc. Among these, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one/4,4'-bis(diethylamino)benzophenone is preferably used.

When using these photopolymerization start adjuvants, the usage-amount is 10 mol or less normally with respect to 1 mol of photopolymerization initiators, Preferably it is 0.01 mol or more - 5 mol or less.

Examples of the solvent (F) used in the present invention include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Examples of ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, Diethylene glycol dipropyl ether, Diethylene glycol dibutyl ether, Propylene glycol monomethyl acetate Ether ester, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol acetate Methyl ether ester, methoxybutyl acetate, methoxypentyl acetate, anisole, phenetole, methyl anisole, etc.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.

Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.

Examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and the like.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, methoxy butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2 - Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, acetate 3 - Methoxybutyl, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone and the like.

As amides, N,N-dimethylformamide, N,N-dimethylacetamide, etc. are mentioned, for example.

As another solvent, N-methylpyrrolidone, dimethylsulfoxide, etc. are mentioned, for example.

The above solvents may be used alone or in combination of two or more. The content in the colored photosensitive resin composition is usually not less than 70% by mass and not more than 95% by mass, preferably not less than 75% by mass and not more than 90% by mass, in terms of mass fraction. When the content of the solvent (F) is within the above range, the flatness at the time of coating is good, and the display characteristics are good when forming a color filter, which is preferable.

The solvent (F) preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate. In the case of using at least one solvent selected from the group consisting of propylene glycol monomethyl ether and 3-ethoxy ethyl propionate together with other solvents, the mixing ratio, in terms of mass fraction, relative to the total In terms of the amount of solvent used, at least one selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate is usually preferably from 50 to 100% by mass, more preferably from 60 to 100% by mass. %. At least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate has flatness if the mass fraction is 50 to 100% by mass relative to the total solvents Tendency to be good, and therefore better.

In the colored photosensitive resin composition used in this invention, you may contain an epoxy compound. Examples of the epoxy compound include epoxy compounds capable of crosslinking the binder resin in the post-baking treatment (heat treatment) of the colored pattern after development. Furthermore, an epoxy compound which can be polymerized independently by heating may also be used. Since the epoxy compound hardens the colored pattern by either crosslinking the binder resin or polymerizing itself, sublimation from the colored pattern is hardly generated in the post-baking, so it is preferably used.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak resin Aromatic epoxy resins such as type epoxy resins;

Alicyclic epoxy resin, polycyclic epoxy resin, glycidyl ester resin, glycidyl amine resin, epoxidized oil and other epoxy resins;

Brominated derivatives of said epoxy resins;

Epoxides of aliphatic compounds, epoxides of cycloaliphatic compounds, epoxides of aromatic compounds, epoxides of butadiene (co)polymers, epoxides of isoprene (co)polymers compound, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc.

The content of the epoxy compound in the colored photosensitive resin composition is usually 15% or less, preferably 0.5% or more to 12% or less, in terms of mass fraction relative to the solid content of the colored photosensitive resin composition , more preferably at least 1% to at most 10%. When the content of the epoxy compound is at most 15% by mass, hardening can sufficiently occur and the residual film rate can be increased, which is preferable.

The colored photosensitive resin composition of the present invention may contain surfactants, fillers, polymer compounds other than binder resins, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulation agents, organic acids, etc. , organic amine compounds, hardeners and other additives.

As the surfactant, at least one selected from the group consisting of silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms can be used.

Examples of silicone-based surfactants include surfactants having a siloxane bond. Specifically, Toray Silicone DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, polyether modified silicone oil SH8400 (trade name, manufactured by Toraysilicone Co.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Toshiba Silicone Co., Ltd.), etc.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, examples include Florina-to (trade name) FC430, TO FC431 (manufactured by Sumitomo Suri-Em Co., Ltd.), Megaface (trade name) F142D, TO F171, TO F172, TO F173, TO F177, TO F183, TO R30 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Eftop (trade name) EF310, same as EF303, same as EF351, same as EF352 (manufactured by Shin Akita Chemical Co., Ltd.), Sa-Fron (trade name) S381, same as S382, same as SC101, same as SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Research Institute of Fine Chemicals (Co., Ltd.), BM-1000, BM-1100 (both trade names, manufactured by BM Chemie Co., Ltd.), etc.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (trade name) R08, DON BL20, DON F475, DON F477, DON F443 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and the like are exemplified.

These surfactants may be used alone or in combination of two or more.

These surfactants can be used in an amount of at most 0.6 parts by mass, preferably at least 0.001 parts by mass to 0.5 parts by mass with respect to 100 parts by mass of the colored photosensitive resin composition excluding the surfactant. Since flatness tends to become favorable that the content of surfactant is 0.6 mass part or less, it is preferable.

Examples of fillers include fine particles of glass and alumina.

Examples of polymer compounds other than the binder resin include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl )-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxymethyl Silane, 3-Chloropropylmethyldimethoxysilane, 3-Chloropropyltrimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Mercaptopropyltrimethoxy Methyl silane, etc.

Examples of antioxidants include 4,4'-thiobis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Examples of ultraviolet absorbers include benzotriazoles such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-hydroxy-4-octyl Benzophenone series such as oxybenzophenone, benzoate series such as 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-(4,6-di Triazine series such as phenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, and the like.

As an anti-aggregation agent, sodium polyacrylate etc. are mentioned, for example.

Examples of organic acids include:

Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, diethylacetic acid, heptanoic acid, octanoic acid and other aliphatic monocarboxylic acids;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid , Dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid and other aliphatic dicarboxylic acids acids;

Aliphatic tricarboxylic acids such as propanetricarboxylic acid, aconitic acid, and camphortricarboxylic acid;

Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, 2,3-dimethylbenzoic acid, and linoleic acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid;

Aromatic polycarboxylic acids such as trimellitic acid, trimellitic acid, trimellitic acid, pyromellitic acid, etc.

Examples of organic amine compounds include:

N-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n- Monoalkylamines such as dodecylamine;

Cycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, etc.;

Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di Dialkylamines such as sec-butylamine, di-tert-butylamine, di-n-pentylamine, and di-n-hexylamine;

Alkyl-cycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;

Dicyclohexylamine and other dicycloalkylamines;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine , tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine, etc. Base amines;

Dialkyl-cycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;

Monoalkyldicycloalkylamines such as methyldicycloalkylamine, ethyldicycloalkylamine, tricyclohexylamine, etc.;

2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, etc. Monoalkanolamines;

Cycloalkanolamines such as 4-amino-1-cyclohexanol;

Diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine and other dialkanolamines;

Bicycloalkanolamines such as bis(4-cyclohexanol)amine;

Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, and tri-n-hexanolamine;

Tricycloalkanolamines such as tris(4-cyclohexanol)amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino -1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol and other aminoalkanediols kind;

Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;

1-aminocyclopentanonemethanol, 4-aminocyclopentanonemethanol and other cycloalkanonemethanols containing amino groups;

1-Aminocyclohexanone Methanol, 4-Aminocyclohexanone Methanol, 4-Dimethylaminocyclopentane Methanol, 4-Diethylaminocyclopentane Methanol, 4-Dimethylaminocyclohexane Methanol, 4 - Naphthenic alcohols containing amino groups such as diethylaminocyclohexanemethanol;

β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid and other aminocarboxylic acids;

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-tert-butylaniline, N, N- Aromatic amines such as dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;

Aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, and p-diethylaminobenzyl alcohol;

Aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;

Aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, etc.

Examples of the curing agent include compounds capable of crosslinking the binder resin by reacting with carboxyl groups in the binder resin by heating. Furthermore, a compound which itself polymerizes and hardens a colored pattern can also be mentioned. As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example.

Examples of epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolak resins, Epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, polycyclic epoxy resins, glycidyl ester type resins, glycidyl amine type resins, epoxy resins such as epoxidized oils, or these epoxy resins Brominated derivatives of resins, aliphatic, cycloaliphatic or aromatic epoxides other than epoxy resins and their brominated derivatives, epoxides of butadiene (co)polymers, isoprene (co) ) polymer epoxy, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc.

Examples of the oxetane compound include dioxetane carbonate, dioxetane xylylene, dioxetane adipate, dioxetane terephthalate, Dioxetanyl cyclohexanedicarboxylate, etc.

When the colored photosensitive resin composition of the present invention contains an epoxy compound or an oxetane compound as a curing agent, it may also contain an oxygen group capable of making the epoxy group of the epoxy compound or the A compound formed by ring-opening polymerization of a heterocyclobutane skeleton. As said compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator etc. are mentioned, for example.

Examples of polycarboxylic acids include

Phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid and other aromatic polycarboxylic acids;

Succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid and other aliphatic polycarboxylic acids;

Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1, Alicyclic polycarboxylic acids such as 2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of polyvalent carboxylic acid anhydrides include

Aromatic polycarboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride;

Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarboxylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride and other aliphatic polycarboxylic acid anhydrides ;

Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclic Alicyclic anhydrides such as pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, Haimic anhydride, 4-norbornene-1,2-dicarboxylic anhydride, etc. Polycarboxylic acid anhydrides;

Ester group-containing carboxylic acid anhydrides such as ethylene glycol trimellitic anhydride, glycerin trimellitic anhydride, and the like.

As the polyvalent carboxylic acid anhydrides, those commercially available as epoxy resin hardeners can also be used. Examples of the epoxy resin hardener include “Adekaha-Dona-EH-700” (manufactured by Asahi Denka Kogyo Co., Ltd.), “Rikasid HH” (manufactured by Shinnippon Chemical Co., Ltd.), and “MH- 700" (manufactured by Nippon Chemical Co., Ltd.), etc.

As the acid generator, there may be mentioned the same ones as above.

These curing agents may be used alone or in combination of two or more.

As a method of forming a color filter using the colored photosensitive resin composition of the present invention, other colored photosensitive resin combinations in which the colored photosensitive resin composition of the present invention is applied to a substrate or a solid formed on the substrate are mentioned. On the object layer (hereinafter referred to as the substrate, etc.), pre-dry the coated resin layer to remove volatile components such as solvents, expose the resin layer from which volatile components have been removed through a photomask, and then develop with a developing solution such as an aqueous alkali solution. Like, post-drying to form a hardened resin layer, taking the above step as a step, repeating this step with a colored photosensitive resin composition containing other colors, and finally forming a color filter with three colors of red, green and blue (RGB). Optical methods, etc.

Examples of the substrate include flat-surfaced substrates such as glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, aramid substrates, polyamideimide substrates, polyimide substrates, Al substrates, and GaAs substrates. . Pretreatments such as chemical treatment using chemicals such as silane coupling agents, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum vapor deposition treatment can also be performed on these substrates. Furthermore, a TFT (Thin Film Transistor), a CCD (Charge Coupled Device), or the like may be formed on the surface of the substrate.

In order to coat the colored photosensitive resin composition on the substrate, for example, the colored photosensitive resin composition of the present invention may be applied by spin coating, casting, roll coating, slot and spin coating, What is necessary is just to coat on a board|substrate etc. by a common coating method, such as a slot coating method, and to volatilize a volatile component, such as a solvent, by heating (pre-baking). In this manner, a resin layer composed of the solid content of the colored photosensitive resin composition can be formed on a substrate or the like.

Then, the resin layer composed of the solid content of the colored photosensitive resin composition is exposed to light. Exposure may be performed by a method of irradiating light through a photomask, or the like. Examples of the light to be used include ultraviolet rays generally called g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). Although light is irradiated through a photomask, the photomask here is, for example, a light-shielding layer provided on the surface of a glass plate to shield light. The part of the glass plate that is not provided with a light-shielding layer is a light-transmitting part that can transmit light, so that the colored photosensitive resin composition layer is exposed according to the pattern of this light-transmitting part pattern, and the unirradiated area and the irradiated area that does not irradiate light are produced. irradiated area of the light. The amount of light irradiation in the irradiated area can be determined according to the weight average molecular weight of the binder resin, the monomer ratio, the content, the type or content of the photopolymerizable compound, the type or content of the photopolymerization initiator, and the content of the photopolymerization initiation adjuvant. Appropriate selection such as type and content.

Developed after exposure. For image development, for example, it is only necessary to bring the exposed resin layer into contact with a developing solution. Specifically, it is only necessary to immerse the substrate with the resin layer formed on the surface in the developing solution.

Examples of the developer include aqueous solutions of basic compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. By developing, the non-irradiated area which was not irradiated with light in the resin layer was removed. On the other hand, the light-irradiated area remained as it was, forming a pattern.

After developing, it is usually washed with water and dried to obtain the target pattern. Furthermore, after image development and drying, post-drying may be performed in a drying furnace or the like to form a cured resin layer. By post-drying, the mechanical strength of the pattern is improved. When using what further contains a hardening|curing agent as a colored photosensitive resin composition, a colored pattern can harden|cure further, and can improve the mechanical strength further. The post-drying temperature is usually above 180°C to below 250°C, preferably above 200°C to below 230°C. If the post-baking temperature is within the above-mentioned range, curing will proceed sufficiently, which is preferable. In addition, the post-drying time is usually 5 to 40 minutes, preferably 10 to 36 minutes, more preferably 15 to 30 minutes. If the post-baking time is within the above-mentioned range, curing will proceed sufficiently, which is preferable.

In this way, the target colored pattern is formed, but the color of the coloring agent contained in the colored photosensitive resin composition is replaced, and the same as above is performed, and the resin layer is formed on the substrate again, after exposing the resin layer, developing, and then performing After drying, the coloring pattern can be further formed. By changing the color of the colorant contained in the colored photosensitive resin composition and repeating the above operation, a colored pattern can be further formed, and a desired color filter can be manufactured.

Then, on the obtained color filter, an ITO film vapor deposition process was performed. The color filters obtained in this way contain the above-mentioned colored patterns, and by using each of the color filters, it becomes possible to manufacture a suitable liquid crystal display device.

The colored photosensitive resin composition of the present invention has excellent developability due to its good residue level, can form a cured resin layer with high surface hardness, and the cured resin layer is also excellent in solvent resistance, and can be formed into a tapered cross-sectional shape. A cured resin layer having a rectangular shape and no roughness on the surface can be preferably used to form a coloring pattern used in a color liquid crystal display device or an imaging element, and a color filter using the pattern.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is of course not limited to these examples.

Example 1

[Preparation of Colored Photosensitive Resin Composition 1]

(A) C.I. Pigment Blue 15:6 (1.967 parts by mass)

(A) C.I. Pigment Violet 23 (0.030 parts by mass)

(E) Polyester-based dispersant (0.599 parts by mass)

(B) Copolymer of methacrylic acid and benzyl methacrylate [the compositional ratio of methacrylic acid unit and benzyl methacrylate unit is 3:7 by mass ratio (molar ratio), weight average molecular weight (Mw) 25,000〕(1.764 parts by mass)

(C) Dipentaerythritol hexaacrylate ("KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.) (1.176 parts by mass),

(D) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (0.353 parts by mass),

(D2) 4,4'-bis(diethylamino)benzophenone ("EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.)) (0.118 parts by mass),

Epoxy compound [o-cresol novolac type epoxy resin, "Sumiepokishi ESCN-195XL-80" (manufactured by Sumitomo Chemical Industries, Ltd.)] (0.294 parts by mass) and

(F) Propylene glycol acetate-methyl ether ester (23.700 parts by mass) was mixed to obtain colored photosensitive resin composition 1 .

〔Formation of colored layer〕

The colored photosensitive resin composition 1 obtained above was coated on the surface of a glass substrate (manufactured by Corning Co., Ltd., "#1737") by the spin coating method, and then the volatile components were volatilized at 100° C. for 3 minutes to form a colored photosensitive resin composition. Resin composition layer 1A. After cooling, the entire surface of this colored photosensitive resin composition layer was irradiated with i-rays [wavelength 365 nm] without passing through a photomask. The light source of the i-line is an ultra-high pressure mercury lamp, and the irradiated light amount is 150mJ/cm ² . Then, develop by immersing in a developing solution at 25° C. (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate by mass fraction, respectively) for 120 seconds, and wash with pure water. A blue colored layer formed on the entire surface of the glass substrate was obtained. The coated substrate was dried at 220° C. for 20 minutes to form a colored photosensitive resin composition layer 1B. Moreover, after layer 1A was cooled, this colored photosensitive resin composition layer was irradiated with i-ray [wavelength 365 nm] through a photomask for exposure. The light source of the i-line adopts ultra-high pressure mercury lamp, which is irradiated in the way of parallel light. The amount of irradiated light was 150 mJ/cm ² . As the photomask, photomasks for forming linear color pixels with a line width of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm were used. Then, put the exposed glass substrate [the colored photosensitive resin composition layer is formed on the surface] at 25°C in a developing solution (by mass fraction, containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalenesulfonate respectively). % aqueous solution) for 120 seconds for image development, washed with pure water, and heated at 220° C. for 20 minutes to form a blue pixel 1C.

〔evaluate〕

Layer 1A was developed by immersing in a stirred 25°C developing solution (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate respectively by mass fraction) for 120 seconds and washed with pure water. After that, no lumps were observed in the developing solution, and the coating layer was dissolved. When the particle size distribution of the developer in which the coating layer is dissolved is measured by the light scattering method using a Microtrac particle size measuring device [UPA150, 9230UPA (manufactured by LEED & NORTHRUP)], the maximum particle size is 1.0 μm or less. Furthermore, the transmittance (average value of 400nm to 780nm) of the glass portion after the coating film layer is dissolved is 98% or more.

Then, according to the test method described in JIS K 5400, on a pencil hardness testing machine, the maximum hardness that does not damage the coating film when the pencil "Mitsubishi Hiuni" is loaded with a load of 9.8N is obtained as a measured value. As a result of measuring the pencil strength of the 1B layer of the coating film formed earlier by the above method, the pencil strength was 4H.

Furthermore, in the formed blue pixel 1C, the cross-sectional shape was a conical shape, the surface was not rough, and the performance of the colored photosensitive resin composition 1 was favorable.

Example 2

[Preparation of Colored Photosensitive Resin Composition 2]

Except having used the polyethyleneimine type dispersant instead of the polyester type dispersant used in Example 1, it mixed similarly to Example 1, and obtained the colored photosensitive resin composition 2.

〔evaluate〕

Except that the colored photosensitive resin composition 2 obtained above is used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation is the same as in Example 1, and the 2A layer is immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, as a result of measuring the pencil strength of the 2B layer in the same manner as in Example 1, the pencil strength was 4H. In the formed blue pixel 2C, the cross-sectional shape is forward-tapered, there is no roughness on the surface, and the performance of the colored photosensitive resin composition 2 is good.

Example 3

[Preparation of Colored Photosensitive Resin Composition 3]

Except that the polyester-based dispersant used in Example 1 was replaced with a polyurethane-based dispersant, it was mixed in the same manner as in Example 1 to obtain a colored photosensitive resin composition 3 .

〔evaluate〕

Except that the colored photosensitive resin composition 3 obtained above was used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation was the same as in Example 1, and the 3A layer was immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, as a result of measuring the pencil strength of the 3B layer in the same manner as in Example 1, the pencil strength was 4H. In addition, in the formed blue pixel 3C, its cross-sectional shape is forward-tapered, and there is no roughness on the surface, and the performance of the colored photosensitive resin composition 3 is good.

Comparative example 1

[Preparation of Colored Photosensitive Resin Composition 4]

[The composition ratio of methacrylic acid unit and benzyl methacrylate unit is calculated as 3: 7 by mass ratio (molar ratio) of the copolymer of methacrylic acid and benzyl methacrylate, and the weight average molecular weight (Mw) is 36,000] (1.764 parts by mass) in place of the binder resin (B) used in Example 1, and mixed in the same manner as in Example 1 to obtain colored photosensitive resin composition 4 .

〔evaluate〕

Except that the colored photosensitive resin composition 4 obtained above was used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation was the same as in Example 1, and the 4A layer was immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass portion after the coating film layer is dissolved is 95% to 98%.

Then, as a result of measuring the pencil strength of the 4B layer in the same manner as in Example 1, the pencil strength was 5H. In addition, in the obtained blue pixel 4C, although the cross-sectional shape was a forward taper shape, fringing was observed, and the performance of the colored photosensitive resin composition 4 was poor.

Comparative example 2

[Preparation of Colored Photosensitive Resin Composition 5]

In addition to the copolymer of methacrylic acid and benzyl methacrylate [the composition ratio of methacrylic acid unit and benzyl methacrylate unit is 3: 7 by mass ratio (molar ratio), and the weight average molecular weight (Mw) is 4,800 ] Except that the binder resin (B) used in Example 1 was replaced, it mixed like Example 1, and the colored photosensitive resin composition 5 was obtained.

〔evaluate〕

Except that the colored photosensitive resin composition 5 obtained above was used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation was the same as in Example 1, and the 5A layer was immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, as a result of measuring the pencil strength of the 5B layer in the same manner as in Example 1, the pencil strength was 1H. In addition, the cross-sectional shape of the formed blue pixel 5C is conical, but the surface roughness can be seen. Furthermore, the residual film rate was also low, and the performance of the colored photosensitive resin composition 5 was poor.

Example 4

[Preparation of Colored Photosensitive Resin Composition 6]

In addition to replacing the polyester-based dispersant used in Example 1 with an acrylic dispersant, the binder resin (B) is replaced by a copolymer of methacrylic acid and benzyl methacrylate [methacrylic acid unit and benzyl methacrylate The composition ratio of the ester unit is 35:65 according to the mass ratio (molar ratio), and the weight-average molecular weight (Mw) is 10,000], and no epoxy compound is added, mixed as in Example 1 to obtain a colored photosensitive resin composition 6.

〔evaluate〕

Except that the colored photosensitive resin composition 6 obtained above was used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation was the same as in Example 1, and the 6A layer was immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, as a result of measuring the pencil strength of the 6B layer in the same manner as in Example 1, the pencil strength was 9H. In addition, in the formed blue pixel 6C, the cross-sectional shape is forward-tapered, the surface is not rough, and the performance of the colored photosensitive resin composition 6 is good.

Example 5

[Preparation of Colored Photosensitive Resin Composition 7]

In addition to using methacrylic acid, benzyl methacrylate and formula (I) [in formula (I), R ¹ represents a methyl group, R ² represents a hydrogen atom] The copolymer [methacrylic acid unit and methacrylic acid unit] The composition ratio of the benzyl ester unit to the component represented by the formula (I) is 25:60:15 in terms of mass ratio (molar ratio), and the weight average molecular weight (Mw) in terms of polystyrene is 9,000] instead of Example 4. The binder resin (B) was mixed in the same manner as in Example 1 except that no epoxy compound was added to obtain a colored photosensitive resin composition 7.

〔evaluate〕

Except that the colored photosensitive resin composition 7 obtained above was used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation was the same as in Example 1, and the 7A layer was immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, when the pencil strength of the 7B layer was measured in the same manner as in Example 1, the pencil strength was 9H. Furthermore, in the formed blue pixel 7C, the cross-sectional shape is forward-tapered, the surface is not rough, and the performance of the colored photosensitive resin composition 7 is good.

Example 6

[Preparation of Colored Photosensitive Resin Composition 8]

Except that the binder resin (B) of embodiment 4 is changed into the binder resin (B) used in embodiment 5, and no epoxy compound is added, the same mixing as in example 1 is obtained to obtain colored photosensitive resin composition 8 .

〔evaluate〕

Except that the colored photosensitive resin composition 8 obtained above was used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation was the same as in Example 1, and the 8A layer was immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, as in Example 1, when the pencil strength of the 8B layer was measured, the pencil strength was 9H. In addition, in the formed blue pixel 8C, its cross-sectional shape is forward-tapered, there is no roughness on the surface, and the performance of the colored photosensitive resin composition 8 is good.

Example 7

[Preparation of Colored Photosensitive Resin Composition 9]

Except the copolymer [methacrylic acid unit, benzyl methacrylate unit and the composition ratio of styrene unit with methacrylic acid, benzyl methacrylate and styrene unit are 30: 60 by substance mass ratio (molar ratio): 10. The polystyrene-equivalent weight average molecular weight (Mw) is 16,000] except that the binder resin (B) in Example 1 was replaced, and mixed in the same manner as in Example 1 to obtain a colored photosensitive resin composition 9 .

〔evaluate〕

Except that the colored photosensitive resin composition 9 obtained above was used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation was the same as in Example 1, and the 9A layer was immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, when the pencil strength of the 9B layer was measured in the same manner as in Example 1, the pencil strength was 6H. Furthermore, in the formed blue pixel 9C, the cross-sectional shape is forward-tapered, the surface is not rough, and the performance of the colored photosensitive resin composition 9 is good.

Example 8

[Preparation of Colored Photosensitive Resin Composition 10]

[The composition ratio of methacrylic acid unit, benzyl methacrylate unit and isonorbornyl methacrylate unit is based on the mass ratio of The (molar ratio) is 30:60:10, and the polystyrene-equivalent weight average molecular weight (Mw) is 16,000] except that the binder resin (B) in Example 1 is replaced, and mixed in the same manner as in Example 1 to obtain a colored photosensitive Resin composition 10.

〔evaluate〕

Except that the colored photosensitive resin composition 10 obtained above is used instead of the colored photosensitive resin composition 1 obtained in Example 1, the operation is the same as in Example 1, and the layer 10A is immersed in the developing solution at 25°C under stirring for 120 seconds. After developing and washing with pure water, no lumps were observed in the developing solution, and the coating layer was dissolved. When measuring the particle size distribution of the coating layer components dissolved in the developer, the maximum particle size is 1.0 μm or less. In addition, the transmittance (average value of 400nm to 780nm) of the glass part after the coating film layer was dissolved was 98% or more.

Then, when the pencil strength of the 10B layer was measured in the same manner as in Example 1, the pencil strength was 7H. Furthermore, in the formed blue pixel 10C, the cross-sectional shape is forward-tapered, the surface is not rough, and the performance of the colored photosensitive resin composition 10 is good.

Claims (11)

1. photosensitive composition, comprise colorant (A), resin glue (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D), pigment dispersing agent (E) and solvent (F), described photosensitive composition is coated with on glass substrate and forms resin bed, make described resin bed prebake, through mask exposure, video picture, when dry the back, the hardness of the resulting hard resin-layer in back oven dry back be pencil hardness 3H above～below the 9H, and prebake, in 25 ℃ of aqueous alkalis of photo-sensitive resin through obtaining behind the mask exposure under 100rpm stirs the transmissivity (mean value of 400～780nm) of dipping part of the non-exposure of photo-sensitive resin portion dissolving after 120 seconds more than 98%～below 100%.

2. the photosensitive composition of claim 1 record, wherein, resin glue (B) is the resin that comprises the structural unit of deriving from (methyl) acrylic acid.

3. the photosensitive compositions of claim 1 or 2 records, wherein, the amount of the structural unit of in the general construction unit that constitutes resin glue (B), deriving from (methyl) acrylic acid more than the 16mol%～below the 40mol%.

4. the photosensitive composition of any one record in the claim 1～3, wherein, resin glue (B) further comprises the structural unit of deriving from (methyl) benzyl acrylate.

5. the photosensitive composition of any one record in the claim 1～4, wherein, resin glue (B) is the resin that further comprises structural unit shown in the formula (I):

R in the formula (I) ¹And R ²Represent hydrogen atom or methyl independently of one another.

6. the photosensitive composition of any one record in the claim 1～5, wherein, the polystyrene conversion weight-average molecular weight of resin glue (B) more than 5,000～below 35,000.

7. the photosensitive composition of any one record in the claim 1～6, wherein, pigment dispersing agent (E) is at least a surfactant of selecting a group that forms from polyester system, polyethyleneimine system, polyurethane series and acrylic acid series.

8. the photosensitive composition of any one record in the claim 1～7, wherein, pigment dispersing agent (E) is the acrylic acid series surfactant.

9. the formation method of colored pattern is characterized in that forming the resin bed of being made up of the photosensitive composition of any one record in the claim 1～8 on substrate, make this resin bed behind mask exposure, video picture, dry the back then.

10. the colored pattern method of formationing of claim 9 record, wherein, the temperature of back oven dry processing is more than 180 ℃～below 250 ℃.

11. chromatic filter comprises the colored pattern with the method formation of claim 9 or 10 records.