JP2010054912A - Color photosensitive resin composition - Google Patents

Abstract

【選択図】なしA colored photosensitive resin composition having good heat resistance and solvent resistance is provided.
A binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a blue colorant (D), a solvent (E) and a color containing a compound represented by formula (I). Photosensitive resin composition.

[Selection figure] None

Description

  The present invention relates to a colored photosensitive resin composition and the like.

The pixel of the color filter used in the display device is formed using a colored photosensitive resin composition.
In the formation of each pixel, in detail, using a coating device on a substrate, a coloring photosensitivity including any one of the three colors R (red), G (green), and B (blue). After applying the resin composition, removing volatile components by means of heating, etc., and then exposing through a mask, then developing the unexposed part in the case of negative type, and developing the exposed part in the case of positive type, such as an alkaline aqueous solution A pattern is formed by developing and removing with a liquid, and the obtained pattern is subjected to heat treatment (hereinafter also referred to as post-baking) to form a pixel. Then, the same operation is performed using the remaining two colored photosensitive resin compositions of the three RGB colors, and a color pattern is formed by the same operation, and finally the color filter having the three RGB colors Form.
For example, Patent Document 1 discloses a colored photosensitive resin composition containing a blue pigment, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and an o-cresol novolac type epoxy resin.

JP 2003-131374 A

  In the conventional colored photosensitive resin composition described above, heat resistance and solvent resistance may not always be sufficient.

  The present invention includes a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a blue colorant (D), a solvent (E), and a color containing a compound represented by formula (I). It is a photosensitive resin composition.

[In Formula (I), X, Y and Z each independently represent a single bond, a group represented by Formula (I-1) or a group represented by Formula (I-2).

R ^{1 to} R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^{4 to} R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. ]

  Moreover, this invention is the said colored photosensitive resin composition whose content of the compound represented by a formula (I) is 0.1-20 mass% with respect to solid content of a colored photosensitive resin composition. .

  The present invention also provides the colored photosensitive resin composition, wherein the photopolymerization initiator (C) is at least one compound selected from the group consisting of triazine compounds, acetophenone compounds, biimidazole compounds, and oxime compounds. It is.

  Moreover, this invention is a color filter formed using the said colored photosensitive resin composition.

  Moreover, this invention is a display apparatus containing the said color filter.

  The colored photosensitive resin composition of the present invention has good heat resistance and solvent resistance.

  The colored photosensitive resin composition of the present invention comprises a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a blue colorant (D), a solvent (E), and a formula (I). Contains the represented compound. The colored photosensitive resin composition may further contain other additives (F) as necessary.

  The binder resin (A) has alkali solubility, and at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride described above. It is preferably a copolymer of at least one compound selected from the group consisting of products and a monomer copolymerizable with the compound.

  Examples of at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid and the like. These may be used alone or in combination of two or more. Here, the description of (meth) acrylic acid in this specification represents at least one selected from the group consisting of acrylic acid and methacrylic acid.

Monomers that can be copolymerized with at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meta) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate , Adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate, dicyclope Thenyl (meth) acrylate and ester containing an alicyclic group of unsaturated carboxylic acids such as dicyclopentenyloxyethyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Unsaturated carboxylic acid oxetane esters such as oxetane (meth) acrylate;
Monosaturated carboxylic esters of glycols such as oligoethylene glycol monoalkyl (meth) acrylates;
Aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
N-substituted maleimide compounds such as N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide and the like can be mentioned, preferably methyl (meth) acrylate, benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclo Examples include decyloxyethyl (meth) acrylate, styrene, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide. These monomers may be used alone or in combination of two or more.

Among them, as a copolymer preferably used, the following (A1), (A2), and (A4) are copolymerized to obtain a copolymer 1, and the obtained copolymer 1 and (A3) are copolymerized. A copolymer 2 is obtained by reacting at a site derived from (A4) of the polymer 1, and the obtained copolymer 2 and (A5) are further combined with (A4) and (A3) of the copolymer 1. Examples thereof include a copolymer obtained by reacting with a site generated by the reaction.
(A1); a compound (A2) having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and an unsaturated bond; a copolymerizable with (A1) and (A4) Saturated compound (A3); Carboxylic acid having unsaturated bond (A4); Compound having unsaturated bond and epoxy group (A5); Acid anhydride provided that (A1) to (A5) are not identical to each other Absent.

  As the compound (A1) having at least one skeleton selected from the group consisting of an unsaturated bond, a tricyclodecane skeleton and a dicyclopentadiene skeleton, and an unsaturated bond, specifically, dicyclopentanyl (meta ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in combination of two or more.

Specific examples of the unsaturated compound (A2) copolymerizable with (A1) and (A4) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) ) Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as acrylates and aminoethyl (meth) acrylates;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meta) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate Ester compounds containing an alicyclic group of an unsaturated carboxylic acid such as
Monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;
Ester compounds containing an aromatic ring of unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, α-phenylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
Examples thereof include N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide. These can be used alone or in combination of two or more.

  Specific examples of the carboxylic acid (A3) having an unsaturated bond include (meth) acrylic acid. (Meth) acrylic acid can be used alone or in combination of two or more. In addition to these (meth) acrylic acids, other carboxylic acids having an unsaturated group can be used in combination. Specific examples of other carboxylic acids having an unsaturated group include at least one unsaturated group selected from carboxylic acids having other unsaturated groups such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Carboxylic acid is mentioned. Moreover, the carboxylic acid which has an unsaturated group containing a hydroxyl group and a carboxyl group like (alpha)-(hydroxymethyl) acrylic acid can also be used together.

  As the compound (A4) having an unsaturated bond and an epoxy group, glycidyl (meth) acrylate, (meth) acrylic acid-β-methylglycidyl, (meth) acrylic acid-β-ethylglycidyl, (meth) acrylic acid -Β-propylglycidyl, α-ethylacrylic acid-β-methylglycidyl, (meth) acrylic acid-3-methyl-3,4-epoxybutyl, (meth) acrylic acid-3-ethyl-3,4-epoxybutyl , (Meth) acrylic acid-4-methyl-4,5-epoxypentyl, (meth) acrylic acid-5-methyl-5,6-epoxyhexyl, glycidyl vinyl ether, etc., preferably glycidyl (meth) acrylate Is mentioned.

  The acid anhydride (A5) is a compound having one acid anhydride group, specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, etc., preferably tetrahydrophthalic anhydride.

  The binder resin (A) used in the present invention is a resin having alkali solubility, and is preferably obtained by copolymerizing (A1), (A2) and (A4) to obtain a copolymer 1. The copolymer 1 is obtained by reacting the copolymer 1 with (A3) to obtain a copolymer 2, and further reacting the obtained copolymer 2 with (A5).

  First, in order to obtain the copolymer 1, (A1), (A2), and (A4) are copolymerized. This copolymerization is performed under normal conditions.

  The polymerization method may be carried out by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent and raising the temperature while stirring, or raising the temperature of the monomer to which the radical polymerization initiator has been added, It may be dropped into the stirred solvent. Further, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

The solvent used is not particularly limited as long as it is inert to radical polymerization, and usually used organic solvents can be used.
Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate; propylene Glycol monoalkyl ether acetates; Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, and butyl carbitol; Triethylene glycol dialkyl ethers Class: Propylene glycol dialkyl ether Diether ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more.

  The usage-amount of a solvent is 30-1000 weight part with respect to 100 weight part of copolymers, Preferably it is 50-800 weight part. Within this range, it is preferable because the molecular weight can be easily controlled.

  The radical polymerization initiator used is not particularly limited as long as it can initiate radical polymerization, and generally used organic peroxide catalysts and azo compounds can be used. Peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and azo compounds.

Specific examples include, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxy-2- Ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (tert- Butylperoxy) hexyl 3,3-isopropyl hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-tert-butyl) (Cyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (tert-butylperoxy) 3,3,5 -Trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) 3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide and the like.
It is preferable to select a radical polymerization initiator having an appropriate half-life according to the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part normally with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The ratio of the constituent components derived from the respective monomers is preferably in the following range in terms of a mole fraction with respect to the total number of moles of the constituent components constituting the copolymer 1.

Structural units derived from (A1); 2 to 40 mol%
Structural units derived from (A2); 2 to 95 mol%
Structural units derived from (A4); 3 to 65 mol%

Moreover, it is more preferable in the ratio of the said structural component being the following ranges.

Structural units derived from (A1); 5-35 mol%
Structural units derived from (A2); 5 to 80 mol%
Structural units derived from (A4); 15-60 mol%

  When the composition ratio is within the above range, the balance between flexibility and heat resistance is good, and a preferable trunk polymer is obtained.

  Next, (A3) is added to the copolymer 1 to impart light / thermosetting properties to the binder resin (A).

  Reaction of the copolymer 1 and (A3) can be performed on the conditions as described in Unexamined-Japanese-Patent No. 2001-89533, for example. Specifically, the solution of the copolymer 1 was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube (a solution obtained by copolymerizing the above (A1), (A2) and (A4)) May be used as is.), And stirred in an air atmosphere and heated to 120 ° C. (A3), trisdimethylaminomethylphenol and hydroquinone were added into the aged product, and the reaction was continued at 120 ° C. for 6 hours. When the solid content acid value was 0.8, the reaction was terminated and light / thermosetting was performed. A copolymer 1 imparted with properties is obtained.

The amount of (A3) added is 5 to 100 mol%, preferably 5 to 100 mol%, based on the epoxy group (derived from the A4 component) in the resin obtained by copolymerizing (A1), (A2) and (A4). 10 to 95 mol%.
It is preferable that the composition ratio of (A4) is in the above range because sufficient photocurability and thermosetting can be obtained and the reliability is excellent.

  Next, the copolymer 2 and (A5) are reacted to produce a binder resin (A) imparted with alkali solubility.

  The reaction between the copolymer 2 and (A5) can be performed, for example, under the conditions described in JP-A-2001-89533. Specifically, binder resin (A) capable of alkali development is obtained by adding (A5) and triethylamine to copolymer 2 and reacting at 120 ° C. for 3.5 hours.

  The addition amount of (A5) is 5 to 100 mol%, preferably 10 to 95 mol%, based on the number of moles of the alcoholic hydroxyl group of copolymer 2 (derived from component A3).

  The weight average molecular weight in terms of polystyrene of the binder resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 30,000. When the weight average molecular weight of the binder resin (A) is in the above range, the coating property is good, the film is not easily reduced during development, and the non-pixel portion is liable to be removed during development. ,preferable.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. The molecular weight distribution in the above range is preferable because the developability is excellent.

  Content of binder resin (A) used for the colored photosensitive resin composition of this invention is a mass fraction with respect to solid content of a colored photosensitive resin composition, Preferably it is 5-90 mass%, More preferably It is 10-70 mass%. When the content of the binder resin (A) is in the above range, the solubility in the developer is sufficient, development residue is hardly generated on the substrate of the non-pixel portion, and the pixel portion of the exposed portion is not developed during development. It is preferable because film loss is unlikely to occur and the non-pixel portion tends to be easily removed. Solid content means the total amount of the component remove | excluding the solvent from the coloring photosensitive resin composition.

  The binder resin (A) has a (meth) acryl group on the side chain of a binder resin such as a resin obtained by reacting a binder resin having a carboxyl group with a compound containing an epoxy group and a (meth) acryl group. It is also possible to use a binder resin into which is introduced.

Examples of the photopolymerizable compound (B) contained in the colored photosensitive resin composition of the present invention include monofunctional monomers, bifunctional monomers, and polyfunctional monomers.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Examples thereof include bis (acryloyloxyethyl) ether and 3-methylpentanediol di (meth) acrylate.
Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like.
Of these, bifunctional or higher functional bifunctional monomers and polyfunctional monomers are preferably used.
As these commercial products, for example, Aronix M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M -1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-8560, M-9050 (manufactured by Toa Gosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA- 20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.) ))).
Content of a photopolymerizable compound (B) is a mass fraction with respect to the sum total of the binder resin (A) and photopolymerizable compound (B) in a coloring photosensitive resin composition, Preferably it is 1-70 mass%. More preferably, it is 5-60 mass%. When the content of the photopolymerizable compound (B) is in the above range, the strength, smoothness, and reliability of the pixel portion tend to be favorable, which is preferable.

  As the photopolymerization initiator (C) contained in the colored photosensitive resin composition of the present invention, acetophenone-based, biimidazole-based, oxime-based, and triazine-based compounds are preferably used.

  Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]. 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methylbenzyl) -2-dimethylamino -1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-moly Holinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholino Phenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2-Methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propan-1-one oligomer and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Enyl) biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), imidazole in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group Compounds (see, for example, JP-A-7-10913) and the like, and preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2 , 2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

  Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, a compound represented by formula (a), a compound represented by formula (b), and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl) Thenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Moreover, as long as the effects of the present invention are not impaired, a photopolymerization initiator or the like usually used in this field can be used in combination. Examples of the photopolymerization initiator include benzoin compounds and benzophenones. Compounds, thioxanthone compounds, anthracene compounds, and the like.
More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done.

  In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate A photopolymerization initiator such as a titanocene compound can be used.

Moreover, what is described in Japanese translations of PCT publication No. 2002-544205 gazette can be used as a photoinitiator which has the group which can raise | generate chain transfer.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the thing of following formula (2)-(7) is mentioned, for example.

  The photopolymerization initiator having a group capable of causing chain transfer can be used as the constituent component (A2) of the copolymer 1. And binder resin (A) obtained using (A2) can be used together with the binder resin of this invention.

Moreover, you may combine a photoinitiator adjuvant (C-1) with a photoinitiator. As the photopolymerization initiation assistant, an amine compound and the following carboxylic acid compound are preferable, and as the amine compound, an aromatic amine compound is more preferable.
Specific examples of the photopolymerization initiation aid (C-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine;
Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, Aromatic amine compounds such as 4,4′-bis (dimethylamino) benzophenone (common name; Michler's ketone), 4,4′-bis (diethylamino) benzophenone;
Phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, Aromatic heteroacetic acids such as naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid can be mentioned.

Content of a photoinitiator (C) is a mass fraction with respect to the sum total of binder resin (A) and a photopolymerizable compound (B), Preferably it is 0.1-40 mass%, More preferably, it is 1-. 30% by mass.
Moreover, when using photoinitiator adjuvant (C-1), the content is 0.1-50 mass% preferably based on said standard, More preferably, it is 0.1-40 mass%.
When the content of the photopolymerization initiator (C) is in the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the colored photosensitive resin composition, The smoothness on the surface of the pixel tends to be good, which is preferable. In addition to the above, when the amount of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity of the obtained colored photosensitive resin composition is further increased, and the above colored photosensitive resin composition is used. This is preferable because the productivity of the pattern substrate to be formed tends to be improved.

  The blue colorant (D) contained in the colored photosensitive resin composition of the present invention may be an organic pigment, an inorganic pigment, a dye, or a mixture of a pigment and a dye. But you can. Of these, organic pigments are preferably used because of their excellent heat resistance and color developability. In addition, the blue colorant of the present invention only needs to exhibit a blue color after mixing, and means that it can be used as a blue pixel of a color filter. For example, in Example 1 of Patent Document 1, there is a description of a blue colorant containing a pigment exhibiting a violet color. When the colorant of blue and other hue is contained, the colorants may be mixed in advance, or the colorant having blue and other hue may be mixed at the end, and the order of mixing may be any But it is possible.

Specific examples of organic pigments and inorganic pigments include compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specifically, for example, C.I. I. And blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, and the like. Among them, C.I. I. Pigment Blue 15: 6 is preferably contained.
Examples of purple pigments include C.I. I. Pigment Violet 19 and 23 may be contained.

Examples of the dye include compounds classified as acid dyes, direct dyes, basic dyes, disperse dyes, and oil-soluble dyes in the Color Index (published by The Society of Dyers and Colorists). For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Or the derivative | guide_body of these dyes is mentioned.
These blue colorants (D) may be used alone or in combination of two or more.

  Among the above pigments, organic pigments are optionally treated with rosin, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment onto the pigment surface with a polymer compound, sulfuric acid fine particles, etc. A pulverization process such as an atomization method, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method for ionic impurities, or the like may be performed.

When a pigment is used for the blue colorant (D), the particle size is preferably uniform. The blue pigment can be dispersed by adding a pigment dispersant to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.
Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. These may be used alone or in combination of two or more.
When the pigment dispersant is used, the amount used is preferably 1 part by mass or less, more preferably 0.05 to 0.5 part by mass, per 1 part by mass of the blue pigment. It is preferable that the amount of the pigment dispersant used is in the above range because a pigment in a uniform dispersion state tends to be obtained.

Content of a blue coloring agent (D) is a mass fraction with respect to the solid part in a coloring photosensitive resin composition, Preferably it is 10 mass%-60 mass%, More preferably, it is 15-50 mass%. is there.
When the content of the blue colorant (D) is in the above range, the color density when used as a color filter is sufficient, and a necessary amount of binder resin can be contained in the composition. Is preferable because a sufficient pattern can be formed.

The colored photosensitive resin composition of the present invention contains a solvent (E). As said solvent (E), the various organic solvent currently used in the field | area of a colored photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone.
Among the above solvents, organic solvents having a boiling point of 100 to 200 ° C. are preferable among the above solvents from the viewpoints of coating properties and drying properties, and more preferable are alkylene glycol alkyl ether acetates, ketones, 3 -Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate, particularly preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and 3-methoxypropion Examples include methyl acid.
These solvents (E) can be used alone or in admixture of two or more.
Content of the solvent (E) in the colored photosensitive resin composition of this invention is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 60-90 mass%, More preferably, it is 70-85 mass%. is there. When the content of the solvent (E) is in the above range, it is applied by a coating device such as a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater), and an ink jet. There exists a tendency for an applicability | paintability to become favorable and is preferable.

  The colored photosensitive resin composition of the present invention contains a compound represented by the formula (I). By containing the compound represented by the formula (I), heat resistance and solvent resistance are improved.

[In Formula (I), X, Y and Z each independently represent a single bond, a group represented by Formula (I-1) or a group represented by Formula (I-2).

R ¹ to R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms.
R ^{4 to} R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. ]

  X, Y and Z are preferably a single bond or a group represented by the formula (I-2).

R ^{1 to} R ³ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

As R < ⁴ > -R < ¹⁷ >, Preferably a hydrogen atom and a C1-C6 alkyl group are mentioned.

As the compound represented by the formula (I), preferably at least two of X, Y and Z are a single bond, R ^{1 to} R ³ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^A compound in which ^{4 to} R ¹⁷ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably two of X, Y and Z are single bonds, and the remaining one is a compound represented by the formula (I-2) In which R ^{1 to} R ³ are hydrogen atoms and R ^{4 to} R ¹⁷ are hydrogen atoms.

The compound represented by the formula (I) can be obtained as, for example, Techmore (registered trademark) VG3101L (manufactured by Mitsui Chemicals, Inc.) represented by the following formula (Ib), 2- [4- (2 , 3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (in formula (I), R ¹ to R ¹⁷ represents a hydrogen atom, X and Y represent a single bond, and Z represents formula (I-2).

  Content of the compound represented by Formula (I) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 0.1-20 mass%, More preferably, it is 0.2-15 mass. %. When the content of the compound represented by the formula (I) is in the above range, the chemical resistance of the pixel portion and the coating film formed using the colored photosensitive resin composition tends to be good, Furthermore, heat resistance is good and preferable.

In the colored photosensitive resin composition of the present invention, a filler, a polymer compound other than the binder resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, a flocculant, and a chain transfer agent are included as necessary. Such additives (F) can also be used in combination.
Examples of the filler include glass, silica, and alumina.
Examples of the polymer compound other than the binder resin include curable resins such as maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
As the surfactant, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Or a combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink & Chemicals, Inc.) ), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Inc.) ) And the like.
Specific examples of the adhesion promoter 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) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
Specific examples of the antioxidant include 2,2′-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the flocculant include sodium polyacrylate.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

For example, the colored photosensitive resin composition can be applied onto a substrate as described below, and photocured and developed to form a pattern. First, this composition is apply | coated on base materials, such as a layer which consists of solid content of the board | substrates, such as glass, or the colored photosensitive resin composition formed previously. The application is performed using a known apparatus such as a spin coater, a slit coater, a slit and spin coater, a curtain flow coater, or a bar coater to form a colored photosensitive resin composition layer.
The colored photosensitive resin composition layer formed by coating is pre-baked to remove volatile components such as a solvent, thereby forming a smooth coating film. The thickness of the coating film at this time is usually about 1 to 6 μm. The coating film thus obtained is irradiated with ultraviolet rays (patterning exposure) through a mask for forming a target pattern. At this time, the entire exposed portion is irradiated with uniform parallel rays. In addition, it is preferable to use an apparatus such as a mask aligner or a stepper so that the positions of the mask and the substrate are accurately aligned.
Thereafter, the exposed coating film is brought into contact with an alkaline aqueous solution to dissolve the non-exposed portion and developed, whereby the intended pattern shape is obtained. The developing method may be any of a liquid filling method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development. After the development, it is washed with water, and further post-baked at 150 to 230 ° C. for 10 to 60 minutes, if necessary. The curing reaction further proceeds by post-baking, and reliability when used as a display device can be imparted.

The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.
Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The density | concentration of the alkaline compound in an alkali developing solution is a mass fraction with respect to the whole solution, Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
Specific examples of anionic surfactants include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.
Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is a mass fraction with respect to the total solution developer, preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.8. 1 to 5% by mass.

  A colored pixel pattern can be formed on the substrate or the color filter substrate through the operations such as application of the photosensitive resin solution, drying, patterning exposure to the resulting dried coating film, and development. Each of the above steps can be repeated using a colored photosensitive resin composition having a different hue to obtain a color filter.

Next, in order to manufacture the display device, the following method is exemplified.
For example, a liquid crystal display device can be manufactured by laminating ITO, an alignment film, a rubbing process substrate and a TFT substrate on a color filter obtained as described above via a spacer and injecting liquid crystal.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, numerical values are expressed on a mass basis unless otherwise specified.

Synthesis example 1
The structural unit of the binder resin Aa used in Example 1 and Comparative Example 1 is shown in Formula (X).

Explanation of Structural Unit a: Corresponding to the structural unit derived from (A1) in the copolymer 1.
b: Corresponding to the structural unit derived from (A2) in copolymer 1.
c: Corresponds to the structural unit derived from reacting (A3) with the structural unit derived from (A4) in copolymer 1.
d: Corresponding to a structural unit derived by reacting (A5) with a site derived from (A3) in copolymer 2.

Table 1 shows the molar ratios of the structural units a to d in the resin Aa, R in c and d, the polystyrene-equivalent weight average molecular weight (M _w ) and molecular weight distribution (M _w / M _n ) of the obtained resin Aa.

  About the measurement of polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder resin, it carried out on condition of the following using GPC method.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG4000HXL (trade name) + TSK-GELG2000HXL (trade name) (series connection)
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Injection volume: 50 μL
Detector; RI
Measurement sample concentration: 0.6 mass% (solvent: THF)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (all trade names) (manufactured by Tosoh Corporation)
The ratio of polystyrene-equivalent weight average molecular weight and number average molecular weight obtained by the above measurement method was defined as molecular weight distribution (Mw / Mn).

Example 1
[Preparation of colored photosensitive resin composition 1]
20 parts of resin Aa obtained above (in terms of solid content), 29.1 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropan-1-one (Irgacure 369 (trade name); manufactured by Ciba Specialty Chemicals) 4.4 parts, 4,4 '-(N, N-diethylamino) -benzophenone (EAB-F (trade name); Hodogaya) Chemical Industry Co., Ltd.) 1.5 parts and Techmore VG-3101L (trade name) (Mitsui Chemicals, Inc .; (2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- 3.6 parts of [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane)) with propylene glycol Bruno was dissolved in 30.2 parts of methyl ether acetate and 11.2 parts of 3-ethoxyethyl propionate. In advance, C.I. I. Pigment Blue 15: 6 and 5.5 parts C.I. I. A dispersion obtained by dispersing 0.1 part of Pigment Violet 23 and 2.8 parts of Ajisper PB821 (dispersant manufactured by Ajinomoto Co., Inc.) in 23.6 parts of propylene glycol monomethyl ether acetate was added to the colored photosensitive resin composition 1. Got. The composition is shown in Table 2.

[Formation of blue cured resin film]
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the colored photosensitive resin composition 1 was applied using a spin coater, and after application, the glass substrate was allowed to stand on a hot plate and prebaked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a stripe pattern with a line width of 50 μm) was set to 100 μm, and an ultrahigh pressure mercury lamp (USH-250D; (Electric Co., Ltd.) was used and irradiated with light at an exposure amount of 100 mJ / cm ² (based on 365 nm) in an air atmosphere. Thereafter, the substrate coated with the colored photosensitive resin composition was immersed in a developer at 23 ° C. (an aqueous solution containing 0.12% by mass of a nonionic surfactant and 0.05% by mass of potassium hydroxide) for 80 seconds. After developing, washing with water, and post-baking at 220 ° C. for 30 minutes, a blue pixel was obtained. The evaluation results are shown in Table 3.

  The red pixel and the green pixel can be created by the method described in JP-A-11-44955, and a color filter can be obtained using these blue pixel, red pixel, and green pixel.

[Heat-resistant]
The color difference before and after putting the obtained blue cured resin film into an oven at 230 ° C. for 2 hours was measured. The color difference was measured by measuring the front and rear L *, a * and b * using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS), and squared the difference between the front and rear L *, a * and b *. Obtained from the square root of the sum. Table 3 shows the measurement results. When the color difference is small, the heat resistance is good. In particular, when the color difference ΔE * ab is 3 or less, the change is particularly small and good.

[Solvent resistance (NMP resistance)]
NMP resistance: The obtained blue cured resin film was immersed in N-methylpyrrolidone (30 ° C. × 30 minutes), L *, a *, and b * before and after immersion were measured, and the color difference before and after immersion was as described above. The same calculation was performed. The results are shown in Table 3. When the color difference is small, the solvent resistance is good.

Comparative Example 1
With the composition shown in Table 2, a colored photosensitive resin composition 2 was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 3.

* 1; Epoxy equivalent 210 g / eq
* 2: o-cresol novolac type epoxy resin Epoxy equivalent 195 g / eq

  In the colored photosensitive resin composition of Example 1 containing the compound represented by the formula (I) of the present invention, it can be seen that the heat resistance and the solvent resistance (NMP resistance) are excellent at the same time. It can be seen that the colored photosensitive resin composition of Comparative Example 1 which does not contain the represented compound is inferior in heat resistance.

  The colored photosensitive resin composition of the present invention has good heat resistance and solvent resistance.

Claims (5)

Colored photosensitive resin composition containing binder resin (A), photopolymerizable compound (B), photopolymerization initiator (C), blue colorant (D), solvent (E) and a compound represented by formula (I) object.

[In Formula (I), X, Y and Z each independently represent a single bond, a group represented by Formula (I-1) or a group represented by Formula (I-2).

R ^{1 to} R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^{4 to} R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. ]   The colored photosensitive resin composition according to claim 1, wherein the content of the compound represented by the formula (I) is 0.1 to 20% by mass with respect to the solid content of the colored photosensitive resin composition.   The colored photosensitive resin composition according to claim 1 or 2, wherein the photopolymerization initiator (C) is at least one compound selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, and an oxime compound. object.   A color filter formed using the colored photosensitive resin composition according to claim 1.   A display device comprising the color filter according to claim 4.