JP6420634B2 - Resist composition, color resist composition, and color filter using the composition - Google Patents

Description

  The present invention is suitably used for the production of transparent resist compositions used for flat panel displays and touch panels, liquid crystal display elements for liquid crystal displays, and color filters used for display elements such as plasma displays, electroluminescence panels, and video cameras. The present invention relates to a color resist composition and a color filter using the color resist composition.

  Many resist compositions containing an alkali-developable resin composition, a photopolymerization initiator, and an organic solvent have been studied. Since this resist can be polymerized and cured by irradiating with ultraviolet rays or electron beams, basic components such as photo-curable inks, photosensitive printing plates, printed wiring plates, various photoresists, color liquid crystal display devices, and image sensors. It is widely used in the manufacture of color filters. In recent years, with the progress of miniaturization and high functionality of electronic devices, it is desired to form fine patterns with high accuracy.

  The pattern is formed by development with an alkaline developer. However, when the pattern becomes fine, there is a problem that a defect due to resist floating or peeling that remains at the time of development occurs.

  The main role of the solvent in the resist composition is to provide fluidity so that the resist can be applied. In order to solve various problems at the time of manufacturing various filters constituting the display or storing the resist, The organic solvent of the composition is being studied.

For example, Patent Document 1 discloses a technique for preventing solidification of a colored composition at the tip of a coating liquid discharge port in a die coating method by controlling solubility parameters of a resin and a solvent. Patent Document 1 discloses the use of a diethylene glycol solvent or a propylene glycol ester solvent as a usable solvent. As one of these solvents, propylene glycol monomethyl ether acetate (PGMEA) is exemplified.
Patent Document 2 discloses that a dipropylene glycol dimethyl ether solvent is used for forming a colored layer in which a dry matter of a radiation-sensitive composition for forming a colored layer generated in a slit nozzle portion is highly re-dissolvable and no bump holes are generated. It is disclosed to provide a radiation sensitive composition. Patent Document 2 exemplifies propylene glycol monomethyl ether acetate (PGMEA) as a usable solvent. Patent Document 3 discloses a photosensitive resin composition for a color filter that uses a solvent containing an alkyl group-containing aromatic solvent and has excellent storage stability. Patent Document 3 exemplifies propylene glycol monomethyl ether acetate (PGMEA) as a usable solvent.

  Since most of the organic solvent in the resist composition is removed from the coating film by drying or the like after coating, it is usually unlikely to contribute to solving problems during development. It did not solve the defect caused by the resist float and peeling.

  On the other hand, propylene glycol monomethyl ether acetate (PGMEA) and dialkylamide are well known as organic solvents contained in the resist composition, and are disclosed in many patent documents. For example, Patent Document 4 includes these examples as the organic solvent to be used. However, there is no disclosure that the combination of propylene glycol monomethyl ether acetate (PGMEA) and dialkylamide has a special effect.

JP 2005-234477 A JP 2006-349981 A JP 2007-3789 A JP 2007-226161 A

  The problem to be solved by the present invention is to suppress defects due to resist floating and peeling that occur during resist development with an alkaline developer.

The present inventors have found that in a resist containing an alkali-developable resin composition, an organic solvent having a specific composition improves adhesion at the time of resist development and suppresses floating and peeling. .
That is, the present invention relates to a resist composition containing (A) an alkali-developable resin composition, (B) a photopolymerization initiator and (C) an organic solvent, wherein (C) the organic solvent is propylene glycol monomethyl ether acetate. The present invention provides a resist composition containing (PGMEA) and a dibasic acid ester as essential components.
The present invention also provides a color resist composition obtained by adding a color material (D) to the resist composition.
Further, the present invention is characterized in that a colored layer and / or a light shielding layer (black matrix) is provided on a substrate, and at least one of the colored layer and the light shielding layer is a cured product of the color resist composition. A color filter for a liquid crystal display element is provided.

  The resist composition of the present invention can suppress defects due to resist floating and peeling that occur during resist development with an alkaline developer. Furthermore, the surface roughness of the light shielding layer or the colored layer produced using the color resist composition of the present invention can be reduced, and the occurrence of display unevenness in the color filter can be prevented.

Hereinafter, the resist composition of the present invention, the color resist composition, and the color filter using the composition will be described in detail based on preferred embodiments.
The resist composition of the present invention contains (A) an alkali-developable resin composition, (B) a photopolymerization initiator, and (C) an organic solvent.
The (C) organic solvent contains propylene glycol monomethyl ether acetate (PGMEA) and a dibasic acid ester as essential components. Hereinafter, the components (A) to (C) will be described.

First, the (A) alkali developable resin composition according to the present invention will be described.
(A) The alkali-developable resin composition enables negative patterning by development by changing the solubility in an alkaline developer before and after polymerization. Examples of the alkali-developable resin include those having a main component of a radically polymerizable resin having an ethylenically unsaturated bond or the like, or a cationically polymerizable resin such as an epoxy resin. Moreover, as an alkali developable group, what has acidic groups, such as a carboxylic acid group and a sulfonic acid group, is preferable.
Further, (A) the alkali-developable resin composition may contain a low-molecular monomer or oligomer component in order to adjust developability and physical properties after curing.
As the alkali-developable resin composition of the present invention, those having an ethylenically unsaturated bond and an acidic group are preferable because of excellent patternability and developability.

  (A) As an alkali developable resin which is a main component of the alkali developable resin composition, a preferred one is a resin precursor having a structure in which a polyfunctional epoxy compound (a1) and an unsaturated monobasic acid (a2) are reacted. Examples include (X) having a skeleton obtained by reacting the acidic group-introducing compound (a3), which may be subjected to crosslinking or modification as necessary.

  As the polyfunctional epoxy compound (a1), a polyglycidyl ether of a polyvalent hydroxy compound or an alkylene oxide adduct thereof, a polyglycidyl ester of a polybasic acid, a cyclohexene ring or a cyclopentene ring-containing compound is epoxidized with an oxidizing agent. Can be used, and specific examples thereof include the following compounds.

  That is, bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol S type epoxy resin, Alkylidene bisphenol polyglycidyl ether type epoxy resin such as bisphenol Z type epoxy resin; hydrogenated bisphenol type diglycidyl ether obtained by hydrogenating the above alkylidene bisphenol polyglycidyl ether type epoxy resin; ethylene glycol diglycidyl ether, 1,3- Propylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol di Glycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1 , 1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane, glycerin tri Glycidyl ethers of aliphatic polyhydric alcohols such as ricidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether; two or more polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ethers of polyether polyols obtained by adding an alkylene oxide of the following: phenol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolak type epoxy compounds A novolac-type epoxy compound such as 3,4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3, 4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) Adipate, methylenebis (3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Alicyclic epoxy compounds such as 1,2-epoxy-2-epoxyethylcyclohexane; glycidyl esters of dibasic acids such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diamino Glycidylamines such as diphenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dicyclopentadiene Dioxide compounds such as dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like.

Commercially available compounds can also be used as the polyfunctional epoxy compound (a1), for example, BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), Adeka Resin EP -4000, Adeka Resin EP-4003S, Adeka Resin EP-4080, Adeka Resin EP-4085, Adeka Resin EP-4088, Adeka Resin EP-4100, Adeka Resin EP-4900, Adeka Resin ED-505, Adeka Resin ED-506, Adeka Resin KRM-2110, Adeka Resin K -2199, Adeka Resin KRM-2720 (manufactured by ADEKA), R-508, R-5
31, R-710 (Mitsui Chemicals), Epicoat 190P, Epicoat 191P, Epicoat 604, Epicoat 801, Epicoat 828, Epicoat 871, Epicoat 872, Epicoat 1031, Epicoat RXE15, Epicoat YX-4000, Epicoat YDE-205, Epicoat YDE-305 (made by Japan Epoxy Resin Co., Ltd.), Sumiepoxy ELM-120, Sumiepoxy ELM-434 (made by Sumitomo Chemical Co., Ltd.), Denacol EM-150, Denacol EX-201, Denacol EX-211, Denacol EX-212, Denacol EX- 313, Denacol EX-314, Denacol EX-322, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX- 14, Denacol EX-711, Denacol EX-721, Denacol EX-731, Denacol EX-811, Denacol EX-821, Denacol EX-850, Denacol EX-851, Denacol EX-911 (manufactured by Nagase ChemteX Corporation), Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 80MF, Epolite 100MF, Epolite 1500NP, Epolite 1600, Epolite 3002, Epolite 4000, Epolite FR-1500, Epolite M-1230 EHDG-L (manufactured by Kyoeisha Chemical Co., Ltd.), SB-20 (manufactured by Okamura Oil Co., Ltd.), Epicron 720 (manufactured by Dainippon Ink & Chemicals, Inc.), UVR-610 , UVR-6105, UVR-6110, UVR-6200, UVR-6228 (manufactured by Union Carbide), Celoxide 2000, Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 3000, Cyclomer A200, Cyclo Mer M100, cyclomer M101, epolide GT-301, epolide GT-302, epolide 401, epolide 403, epolide HD300, EHPE-3150, ETHB, epoblend (manufactured by Daicel Chemical Industries), PY-306, 0163, DY-022 (Ciba Specialty Chemicals), Santo Tote ST0000, Epototo YD-011, Epototo YD-115, Epototo YD-127 Epototo YD-134, Epototo YD-172, Epototo YD-6020, Epototo YD-716, Epototo YD-7011R, Epototo YD-901, Epototo YDPN-638, Epototo YH-300, Neototo PG-202, Neototo PG-207 (Manufactured by Toto Kasei Co., Ltd.), Bremer G (manufactured by Nippon Oil & Fats Co., Ltd.) and the like.

  Among the polyfunctional epoxy compounds (a1), polyfunctional epoxy compounds represented by the following general formula (1) are preferable.

（式中、Ｘ¹は下記式（イ）、（ロ）若しくは（ハ）で表される置換基を表し、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、ｍは０〜１０の整数である。）

(In the formula, X ¹ represents a substituent represented by the following formula (A), (B) or (C), and R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, carbon, An alkyl group having 1 to 5 atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and m is an integer of 0 to 10).

（式中、Ｙ¹は、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基、炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｙ¹は、隣接するＹ¹同士で環を形成していてもよく、ｎは０〜４の整数を表す。）

(In the formula, Y ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms. A cyclic group or a halogen atom is represented, and the alkylene part in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and Y ¹ is adjacent to Y ^1. And may form a ring, and n represents an integer of 0 to 4.)

（式中、Ｙ²及びＺ²は、それぞれ独立して、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基、炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｚ²は、隣接するＺ²同士で環を形成していてもよく、ｐは０〜４の整数を表し、ｑは０〜８の整数を表し、ｒは０〜４の整数を表し、ｓは０〜４の整数を表し、ｒとｓの数の合計は２〜４の整数である。）

Wherein Y ² and Z ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Represents a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, ² may form a ring with adjacent Z ² , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, and s represents The integer of 0-4 is represented, and the sum total of the number of r and s is an integer of 2-4.)

In the general formula (1), the R ^1, R ^2, R ³ and an alkyl group having 1 to 5 carbon atoms represented by R ^4, methyl, ethyl, propyl, iso- propyl, butyl, sec- butyl Tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl and the like,
The R ^1, R ^2, R ³ and alkoxy group having 1 to 8 carbon atoms represented by R ^4, methyloxy, ethyloxy, iso- propyloxy, propyloxy, butyloxy, pentyloxy, iso- pentyloxy, Hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, etc.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include vinyl, allyl, butenyl, propenyl,
Examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ include fluorine, chlorine, bromine and iodine. In addition, all the halogen atoms in this specification are the same as this.

In (i) which is X ¹ in the general formula (1), the alkyl group having 1 to 20 carbon atoms represented by Y ¹ is exemplified by the above R ¹ , R ² , R ³ and R ⁴ . Hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, Tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Cyclononyl, Kurodeshiru and the like,
Examples of the aryl group having 6 to 30 carbon atoms represented by Y ¹ include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, and 4-vinylphenyl. 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) Phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di- t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4 Di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-triphenyl Fluorophenyl, perfluorophenyl and the like,
Examples of the arylalkyl group having 7 to 30 carbon atoms represented by Y ¹ include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl, and the like.
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by Y ¹ include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl , Furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2 -Piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl and the like.

In (c) which is X ¹ in the general formula (1), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 7 carbon atoms represented by Y ² and Z ² Examples of the -30 arylalkyl group and the heterocyclic group having 2 to 20 carbon atoms include those exemplified in (i) which is X ¹ in the general formula (1).

  Examples of the unsaturated monobasic acid (a2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, and hydroxypropyl acrylate. -Malate, dicyclopentadiene, maleate, or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups. Among these, acrylic acid, Methacrylic acid is preferred.

  As said acidic group introduction | transduction compound (a3), a polybasic acid compound is preferable and a polybasic acid anhydride is more preferable. Examples of the polybasic acid anhydride include succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, 2,2′-3,3′-benzophenone tetracarboxylic acid anhydride, 3 , 3′-4,4′-benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride, hexahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl -3-cyclohexene-1,2-dicarboxylic anhydride, tri Examples include alkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl hymic anhydride, etc. Among these, biphenyltetracarboxylic dianhydride, pyromellitic anhydride from the viewpoint of alkali developability. A diacid anhydride such as a product, or a combination of the diacid anhydride and a monoacid anhydride such as succinic anhydride is preferable.

  (A) Modification | denaturation or bridge | crosslinking given to an alkali developable resin composition is performed as needed for adjustment of an acid value, introduction | transduction of the further ethylenically unsaturated bond group, and adjustment of molecular weight. The acid value can be adjusted by using a monoepoxy compound or a polyfunctional epoxy compound, and (meth) acrylic acid esters such as (meth) acrylic acid glycidyl ether for introducing an ethylenically unsaturated bond. The molecular weight can be adjusted using a cross-linked or polyfunctional epoxy compound, and the cross-linking can be performed using a polybasic acid compound exemplified above.

  The low molecular weight monomer or oligomer component for adjusting developability and physical properties after curing contained in the alkali developable resin composition (A) preferably has an ethylenically unsaturated bond. Acrylate compounds are preferred. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate , Zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, Ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, dipenta Risuritoru, polyhydroxy one or more polyvalent (meth) acrylate compound to the hydroxyl group of (meth) acrylic acid is bound by esterification reaction of compounds such as tricyclodecane dimethylol, and the like.

  In the resist composition of the present invention, the content of the (A) alkali-developable resin composition is the total mass of the total solid content excluding the solvent (including (C) organic solvent, other organic solvents, etc.) from the resist composition. 5 to 60 mass%, particularly 10 to 50 mass% is preferable.

Next, (B) the photopolymerization initiator according to the present invention will be described.
As the photopolymerization initiator (B), conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl- 1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butylbenzene Nzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6- Examples include bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, a compound represented by the following general formula (2), and among these, sensitivity and From the viewpoint of heat resistance, a compound represented by the general formula (2) is preferable.

（式中、Ｒ²¹及びＲ²²は、それぞれ独立に、水素原子、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ²³及びＲ²⁴は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ²⁵、ＯＲ²⁶、ＳＲ²⁷、ＮＲ²⁸Ｒ²⁹、ＣＯＲ³⁰、ＳＯＲ³¹、ＳＯ₂Ｒ³²又はＣＯＮＲ³³Ｒ³⁴を表し、Ｒ²³及びＲ²⁴は、互いに結合して環を形成していてもよく、
Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｘ²は、酸素原子、硫黄原子、セレン原子、ＣＲ³⁵Ｒ³⁶、ＣＯ、ＮＲ³⁷又はＰＲ³⁸を表し、
Ｘ³は、単結合又はＣＯを表し、
Ｒ³⁵、Ｒ³⁶、Ｒ³⁷及びＲ³⁸は、それぞれ独立して、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、該アルキル基又はアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環基で置換されていてもよく、−Ｏ−で中断されていてもよく、
Ｒ³⁵、Ｒ³⁶、Ｒ³⁷及びＲ³⁸は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよく、
ａは、０〜４の整数を表し、
ｂは、０〜５の整数を表す。）

(In the formula, R ²¹ and R ²² are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ²³ and R ²⁴ are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ²⁵ , OR ²⁶ , SR ²⁷ , NR ²⁸ R ²⁹ , COR ³⁰ , SOR ³¹ , SO ₂ R ³² or CONR ³³ R ³⁴ , R ²³ and R ²⁴ may be bonded to each other to form a ring;
R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently an alkyl group having 1 to 20 carbon atoms, 6 to 6 carbon atoms A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ³⁵ R ³⁶ , CO, NR ³⁷ or PR ³⁸ ;
X ³ represents a single bond or CO,
R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms. The methylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group or heterocyclic group, and may be interrupted with -O-,
R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )

In the above general formula (2), R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms and an arylalkyl group having 7 to 30 carbon atoms, represented by R ³⁷ and R ³⁸ , R ²¹ , R ²² , R ²⁵ , R Examples of the heterocyclic group having 2 to 20 carbon atoms represented by ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , and R ³⁴ include those in the general formula (1). is X ¹ those exemplified in the description of (i) can be mentioned.
Examples of the heterocyclic group that may be substituted with the alkyl group or arylalkyl group represented by R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are X ¹ in the above general formula (1). Examples thereof are the same as the heterocyclic groups exemplified in the above.
The ring which R ²³ and R ²⁴ may be bonded to each other is the same as the ring which may be formed by adjacent Y ¹ in (a) which is X ¹ in the general formula (1). A ring is mentioned.

Among the compounds represented by the general formula (2), compounds represented by the following general formula (2 ′) are preferable, and among them, those in which R ²⁴ is a nitro group or COR ³⁰ are more preferable, and R ²⁴ and It is particularly preferable that the position of X ^{3 is at} the position of the following general formula (2 ″).

（式中、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ³⁷、Ｘ³、ａ及びｂは、上記一般式（２）と同じである。）

(In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ , R ³⁷ , X ³ , a and b are the same as those in the general formula (2).)

（式中、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ³⁷、Ｘ³、及びａは、上記一般式（２）と同じである。）

(In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ , R ³⁷ , X ³ , and a are the same as those in the general formula (2).)

  In the resist composition of the present invention, the content of the (B) photopolymerization initiator occupies the total mass of the total solid content excluding the solvent (including (C) an organic solvent and other organic solvents) from the resist composition. The ratio is preferably 0.5 to 30% by mass, particularly 1 to 20% by mass.

Next, (C) the organic solvent according to the present invention will be described.
The organic solvent (C) according to the present invention contains propylene glycol monomethyl ether acetate (PGMEA) and a dibasic acid ester as essential components, and has adhesion to the resist composition of the present invention. It has an effect of improving and suppressing peeling and floating during development.

Examples of the dibasic acid ester include dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate, dimethyl glutarate, diethyl glutarate, dimethyl malonate, diethyl malonate, and combinations thereof.
Among these, succinic anhydride, dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate, dimethyl glutarate, diethyl glutarate or a combination thereof is preferable from the viewpoint of coating unevenness.

  As for the composition ratio of the essential component in the (C) organic solvent which concerns on this invention, 1-10 mass parts is preferable with respect to 100 mass parts of PGMEA, and 2-8 mass parts is more preferable. If the dibasic acid ester is less than 1 part by mass, the effect of improving the resist adhesion may not be obtained, and if it is more than 50 parts by mass, the resist coating property may be deteriorated.

  The total ratio of the essential components PGMEA and dibasic acid ester in the entire organic solvent (C) according to the present invention is preferably 25 to 100% by mass, more preferably 40 to 100% by mass.

  The (C) organic solvent according to the present invention may contain one or more other organic solvents in addition to the above essential components.

  Other organic solvents contained in the resist composition of the present invention include, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; ethyl ether, dioxane , Tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n acetate -Ester solvents such as butyl, γ-butyrolactone, propylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol Ether monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Cellsolve solvents such as ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate and -methoxybutyl acetate; methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, 1,3 -Alcohol solvents such as butanediol; benzene, toluene, BTX solvents such as xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil ( Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc .; Halogenated aliphatic hydrocarbon solvents, such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; Halogenated aromatic hydrocarbons, such as chlorobenzene System solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone and the like.

  Also, among the other organic solvents described above, by using an appropriate amount of a boiling point of 160 ° C. or higher and 215 ° C. or lower (except dimethyl succinate), the solvent after the resist coating is dried and removed. Since the unevenness of the generated film thickness is reduced, it is preferably used. Among organic solvents having a boiling point of 160 ° C. or higher and 215 ° C. or lower, 1,3-butanediol, diisobutyl ketone, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, γ-butyrolactone, and N-methylpyrrolidone are: In addition to the effect of reducing the unevenness of the film thickness, the effect of improving the resist adhesion at the time of development, which is the effect of the present invention, is enhanced, so that it is preferably used. The preferable content of the organic solvent having a boiling point of 160 ° C. or higher and 215 ° C. or higher is 0.1 to 30% by mass, and more preferably 1 to 20% by mass with respect to the entire organic solvent (C).

In the resist composition of the present invention, (C) several organic solvents having different boiling points but different boiling points are used. Specifically, propylene glycol monomethyl ether acetate (PGMEA), 3-methoxybutyl acetate, 3 -A combination of organic solvents selected from ethyl ethoxypropionate, dimethyl succinate, and diethyl succinate is preferable because the organic solvent gradually volatilizes so that the coating property is improved.

  In the resist composition of the present invention, the content of the organic solvent (C) is preferably 50 to 99% by mass, particularly 70 to 95% by mass in the resist composition.

  A color material (D) can be further added to the resist composition of the present invention to form a color resist composition. Examples of the color material (D) used in the color resist composition include pigments and dyes. Which is added is not particularly limited, and either one of a pigment and a dye may be used, or both may be used in combination.

As the pigment used as the color material (D) in the color resist composition of the present invention, any of the known pigments used in the production of conventional color filters can be used. Below, the specific example of an organic pigment is shown with a curry index (CI) number. In the list below, “x” represents C.I. I. It is an integer that can be arbitrarily selected from the numbers.
・ Pigment Blue:
<C. I> 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: x, 56, 60, 61, 62 · Pigment Green:
<C. I> 1,1: x, 2,2: x, 4,7,10,36
・ Pigment Orange
<C. I> 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64
・ Pigment Red
<C. I> 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: x, 83, 88, 90, 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226
・ Pigment Violet:
<C. I> 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 23, 27, 32, 42
・ Pigment Yellow
<C. I> 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,156,175

  Further, as black pigments, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, diamond black LI, diamond black LH, diamond black N339, diamond Rack SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Curve Inc. Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBl ack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, Pr, 140%, Excluded.

  Other pigments include miloli blue, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate, silica, alumina, cobalt, manganese, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, Inorganic pigments such as phosphate ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridiane, emerald green, and cobalt green can also be used. These pigments can be used alone or in combination.

  The dyes that can be used as the colorant (D) include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes. Examples thereof include dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and these may be used alone or in combination.

  In the color resist composition of the present invention, the content of the color material (D) occupies the total mass of the total solids excluding the solvent (including (C) organic solvent, other organic solvents, etc.) from the color resist composition. The proportion is preferably 0.5 to 80% by mass, particularly preferably 5 to 70% by mass.

  In addition to the above essential components, a pigment dispersant, a chain transfer agent, a surfactant and the like can be used in combination with the resist composition and the color resist composition of the present invention.

  The pigment dispersant is used to prevent aggregation of the pigment when a pigment is used as the color material (D) of the color resist of the present invention. In particular, (D) when used as a black resist for forming a black matrix whose color material is carbon black, it is used to disperse a large amount of carbon black in order to obtain a necessary color density. Usually, when preparing a black resist, (D) carbon black which is a coloring material, a dispersant and an organic solvent are mixed in the form of a carbon black paste.

  As the carbon black pigment dispersant, a polymer dispersant is preferably used. Examples of the polymer dispersant include polyesters having a basic functional group, polyethers, acrylics, and polyurethanes. Examples of the basic functional group include primary, secondary, tertiary amino groups, azo groups, pyridine, pyrimidine, Examples thereof include nitrogen-containing groups such as pyrazine, and the basic functional group is preferably present at the resin terminal. The molecular weight is preferably in the range of 1000 to 100,000 in terms of weight average in terms of polystyrene. When the molecular weight is less than 1000, the dispersion stability is lowered, and when it exceeds 100,000, developability and resolution may be lowered.

  Specific examples of the polymeric dispersant satisfying such conditions include Disperbyk160, Disperbyk161, Disperbyk162, Disperbyk163, Disperbyk164, Disperbyk166, Dispersbyk166, and SOLPERSE20000, SOLPERSE20000 manufactured by Zeneca, SOLPERSE20000, SOLPERSE20000, and SOLPERSE20000 manufactured by GENECA. .

  Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercaptov Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  In the resist composition and the color resist composition of the present invention, the properties of the cured product can be improved by further using a thermoplastic organic polymer. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  In addition, the resist composition and the color resist composition of the present invention include, as necessary, thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; plasticizers; adhesion promoters; fillers. Conventional additives such as an antifoaming agent, a dispersant, a leveling agent, a silane coupling agent, and a flame retardant can be added.

  In the resist composition and color resist composition of the present invention, the content of optional components other than the essential components described above is a solvent (including (C) organic solvent, other organic solvents, etc.) from the resist composition and color resist composition. 0.1-10 mass% is preferable in the ratio which occupies for the total mass of the total solid except for.

  The resist composition and the color resist composition of the present invention are a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color display liquid crystal display panel such as a color television, a PC monitor, a portable information terminal, or a digital camera. Color filter, color filter for CCD image sensor, touch panel, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, resin for stereolithography, gel coat, photo for electronics Processes for manufacturing resists, electroplating resists, etching resists, both liquid and dry films, solder resists, insulating films, color filters for various display applications, or plasma display panels, electroluminescent display devices, and LCD manufacturing processes Resist, electricity and electrons for forming structures in Composition, solder resist, magnetic recording material, micro mechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coating, stencil for screen printing, stereolithography Materials for manufacturing three-dimensional objects, holographic recording materials, image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, printing It can be used for various applications such as photoresist materials for wiring boards, photoresist materials for UV and visible laser direct image systems, photoresist materials used for dielectric layer formation in the sequential lamination of printed circuit boards, or protective films. There is no particular limitation on its use.

  Next, the color filter of the present invention will be described below.

  The color filter of the present invention comprises a colored layer and / or a light shielding layer on a substrate, and at least one of the colored layer and the light shielding layer is a cured product of the color resist composition of the present invention.

Hereinafter, a process for producing an example of the color filter of the present invention in which a colored layer and / or a light shielding layer is formed on a substrate using the color resist composition according to the embodiment of the present invention will be described.
First, the color resist composition of the present invention, prepared as a black resist using (A) a black pigment such as carbon black as a color material, is uniformly applied on a substrate by spray coating, spin coating, roll coating, or the like. And dry. The layer formed in this step is called a “color resist composition layer”. As the substrate on which the color resist composition layer is formed, a transparent substrate is preferable, and specifically, a resin substrate such as a glass plate, polycarbonate, polymethyl methacrylate, polyethylene phthalate is preferably used. Moreover, what performed the planarization process to the side which forms a color resist composition layer as needed can also be used.

  Next, the formed color resist composition layer is patterned by a photolithography method. That is, the color resist composition layer is exposed by irradiating active energy rays such as ultraviolet rays and electron beams through a photomask having a predetermined pattern, and then developed using a developer such as an organic solvent or an alkaline aqueous solution.

  In the exposure step, the portion of the color resist composition layer irradiated with the active energy rays is polymerized and cured. When the color resist composition layer contains a photosensitive resin, the resin is also crosslinked and cured. In order to improve the exposure sensitivity, after forming a color resist composition layer, a solution of a water-soluble or alkaline water-soluble resin (for example, polyvinyl alcohol, water-soluble acrylic resin, etc.) is applied and dried, thereby allowing oxygen. Exposure may be carried out after forming a film that controls polymerization inhibition due to.

  In the development step, the portion not irradiated with the active energy ray is washed away with the developer. As the developer, an alkali developer such as an aqueous solution such as sodium carbonate or caustic soda, or an organic alkali solution such as dimethylbenzylamine or triethanolamine can be used. Moreover, you may add an antifoamer and surfactant to a developing solution as needed. Thereafter, the light-shielding layer is formed by immersing in the developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. By repeating the same operation for the red (R), green (G), and blue (B) colored layers, a color filter in which the light shielding layer is a cured product of the color resist composition of the present invention can be produced. Furthermore, in order to accelerate | stimulate superposition | polymerization of a color resist composition, it can also heat as needed. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  In this step, only the light shielding layer may be a cured product of the color resist composition of the present invention, and the light shielding layer and the colored layer may be a cured product of the color resist composition of the present invention. The color filter may be provided with a colored layer of yellow, magenta, cyan, or four or more colors instead of the RGB three-color type. The order of patterning the color resists for each color is not limited.

Hereinafter, a process for manufacturing another example of the color filter of the present invention will be described.
First, on a substrate having a light shielding layer formed of a light shielding film such as chromium or a light shielding black resin, a green resist is used by using, for example, a green pigment as a color material by spray coating, spin coating, roll coating, or the like. The color resist composition of the present invention prepared as above is uniformly applied and dried to form a color resist composition layer. Thereafter, a green colored layer is formed in the same manner. By repeating the same operation for the red and blue colored layers, a color filter in which the colored layer is a cured product of the color resist composition of the present invention can be produced. In this step, a substrate provided with a light shielding layer in advance was used. However, the light shielding layer may be provided as necessary, and only one colored layer may be a cured product of the color resist composition of the present invention. Two or more layers may be a cured product of the color resist composition of the present invention.

  In addition, the color filter of the present invention improves the level difference caused by the overlapping of the colored layer and the light shielding layer, and forms a color filter with good flatness, and impurities from the colored layer and the light shielding layer flow into the liquid crystal layer. In order to avoid this, a transparent resin film and a photosensitive transparent resin film may be provided as a protective layer on the colored layer and / or the light shielding layer. An inorganic film (ITO (indium tin oxide), ZnO, or the like may be provided as a transparent conductive film.

  FIG. 1 shows an example of the configuration of the color filter of the present invention. In FIG. 1, a lattice-patterned light shielding layer 2 and a colored layer 3 are formed on a transparent substrate 1, and a protective layer that is a surface flattening transparent layer is provided on the light shielding layer 2 and the colored layer 3. . Further, a transparent conductive film is formed on the protective layer, but is omitted in FIG.

  The color filter of the present invention described above is formed using the color resist composition according to the embodiment of the present invention, and receives the effect of the color resist composition according to the embodiment of the present invention, and is developed. It is possible to solve defects caused by floating or peeling off of the color resist. Furthermore, the surface roughness of the formed light shielding layer and colored layer is small, and a color filter having a good surface state can be obtained. Further, since the surface roughness of the light shielding layer and the colored layer is small, it is possible to prevent the occurrence of display unevenness due to the color filter when the panel is formed.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Production Example 1] Production of alkali-developable resin composition 1 30.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 7.52 g of acrylic acid, 2,6-di -T-butyl-p-cresol 0.080 g, tetrabutylammonium chloride 0.183 g and PGMEA 11.0 g were charged and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. After cooling to room temperature, 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 12.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 0.080 g of 2,6-di-t-butyl-p-cresol and 0.600 g of PGMEA were added. After stirring at 90 ° C. for 90 minutes and at 120 ° C. for 5 hours, 24.0 g of PGMEA was added to obtain an alkali-developable resin composition 1 as a PGMEA solution.

[Production Example 2] Production of alkali-developable resin composition 2 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, 0.585 g of tetrabutylammonium chloride and 65.9 g of PGMEA were charged and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. The mixture was cooled to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Furthermore, 9,9-bis (4-glycidyloxyphenyl) fluorene 30.0 g, 2,6-di-t-butyl-p-cresol 0.269 g, and PGMEA 1.50 g were added, and 90 minutes at 90 ° C. After stirring at 120 ° C. for 4 hours, 93.4 g of PGMEA was added to obtain an alkali-developable resin composition 2 as a PGMEA solution.

[Production Example 3] Production of alkali-developable resin composition 3 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane 89.9 g, acrylic acid 23.5 g, 2,6- Di-tert-butyl-p-cresol 0.457 g, benzyltriethylammonium chloride 0.534 g and PGMEA 75.6 g were charged and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione and 1.0 g of triethylamine, and stirred at 92 ° C. for 17 hours. The mixture was cooled to room temperature, 25.6 g of succinic anhydride, 1.39 g of tetra-n-butylammonium bromide and 40.42 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, 46.7 g of PGMEA was added to obtain an alkali-developable resin composition 3 as a PGMEA solution.

[Examples 1 to 4 and Comparative Examples 1 to 4] Preparation of resist compositions
According to the composition of [Table 1], the resist composition No. 1-No. 4 and comparative resist composition no. 1-No. 4 was obtained. In addition, a number represents a mass part.

[Examples 5 to 13 and Comparative Examples 5 to 9] Preparation of Color Resist Composition According to the formulation of [Table 2] and [Table 3], the color resist composition No. 5-No. 13 and comparative color resist composition No. 5-No. 9 was obtained. In addition, a number represents a mass part.

A-1 Alkali developable resin composition 1
A-2 Alkali developable resin composition 2
A-3 Alkali developable resin composition 3
B-1 NCI-831 (made by ADEKA)
B-2 NCI-930 (made by ADEKA)
B-3 OXE-01 (manufactured by BASF)
C-1 PGMEA
C-2 Dimethyl succinate (boiling point 200 ° C)
C-3 Diethyl succinate (boiling point 218 ° C)
C-4 DBE (Sankyo Chemical Co., Ltd. dibasic acid ester, boiling point 196-225 ° C.)
C-5 Dimethyl adipate (boiling point 109-110 ° C)
C-6 Dimethyl glutarate (boiling point 96 to 103 ° C.)
C-7 3-methoxybutyl acetate (boiling point 172 ° C.)
C-8 ethyl 3-ethoxypropionate (boiling point 170 ° C.)
C-9 cyclohexanone D-1 MA100 (carbon black; manufactured by Mitsubishi Chemical Corporation)
E-1 Kayalad DPHA (dipentaerythritol hexaacrylate; manufactured by Nippon Kayaku Co., Ltd.)
E-2 SE-TX-5010 (alkoxysilane coupling agent; manufactured by ADEKA)
E-3 KBM-403 (alkoxysilane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.)

Resist composition Nos. Prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were used. 1-No. 4 and comparative resist composition no. 1-No. The following evaluation was performed on 4. The results are shown in [Table 1].
(transparency)
The resist composition was spin-coated on the substrate to a thickness of 2 μm and dried. After prebaking at 110 ° C. for 2 minutes, exposure was performed at 100 mJ / cm ² using a high-pressure mercury lamp, and post-baking was performed at 230 ° C. for 20 minutes. Regarding the obtained clear film, a film having a transmittance of 95% or more at 400 nm was evaluated as “◯” and a film having a transmittance of less than 95% was evaluated as “X”.
(Adhesion)
The clear film obtained above was allowed to stand for 5 hours under the conditions of 120 ° C., 2 atm, and relative humidity of 100%. A hundred mass test was performed according to the method of JIS K5600-5-6. The case where the clear layer was not peeled off at all was marked as ◯, and the case where the clear layer was peeled off was marked as x.
(Volume resistivity)
The resist composition was spin-coated on a chromium substrate to a thickness of 2 μm and dried. After prebaking at 110 ° C. for 2 minutes, exposure was performed at 100 mJ / cm ² using a high-pressure mercury lamp, and post-baking was performed at 230 ° C. for 30 minutes. About the obtained clear film | membrane, it left still for 100 hours within a 85 degreeC85% high temperature and humidity apparatus, and measured the volume resistivity.
(Vacuum drying unevenness)
The resist composition was spin-coated on the substrate to a film thickness of 2 μm and allowed to stand for 1 minute. Drying was performed under reduced pressure at 50 Pa using a vacuum drier. A clear film surface having no unevenness was marked with ◯, and a clear film with unevenness being marked with ×.
(sensitivity)
The resist composition was spin-coated on the substrate to a thickness of 2 μm and dried. After pre-baking at 110 ° C. for 2 minutes, exposure was performed using a high-pressure mercury lamp. What hardened | cured at 30 mJ / cm < ² > was set to A, and what was not hardened unless it was 100 mJ / cm < ² > or more was set to B.

The color resist composition No. adjusted in Examples 5 to 16 and Comparative Examples 5 to 7 were used. 1-No. 16 and comparative color resist composition No. 1-No. For No. 7, the color resist composition was spin-coated (500 rpm) for 7 seconds on a glass substrate and dried. After prebaking at 70 ° C. for 15 minutes, the coating unevenness was visually evaluated. A sample having no color unevenness and having particularly high jetness was evaluated as ◎, a sample having no color unevenness and having a high jetness was rated as ◯, a color unevenness, low jetness, and gray was evaluated as ×. In addition, the surface of the film after pre-baking was palpated and evaluated as ◯ for non-sticky and x for sticky. These results are shown in [Table 2] and [Table 3].
From the results of [Table 2] and [Table 3], the comparative color resist composition No. 1-No. In No. 3, slight coating unevenness was observed and jetness was low. The surface of the film after pre-baking was sticky (tack). In contrast, the color resist composition No. 1-No. No coating unevenness was observed in No. 9, and the jetness was high. Further, the surface of the film after pre-baking was not sticky (tack).

The color resist composition No. adjusted in Examples 5 to 15 and Comparative Examples 5 to 7 were used. 1-No. 9 and comparative color resist composition no. 1-No. For No. 3, the adhesion was evaluated as follows.
The color resist composition was spin-coated (500 rpm) for 7 seconds on a glass substrate and dried. After pre-baking at 70 ° C. for 15 minutes, using an ultra-high pressure mercury lamp as a light source and exposing at an exposure amount of 40 mJ / cm ² , the developer was added to a 2.5 mass% sodium carbonate solution at 26 ° C. for 40 seconds. Immersion development was carried out for the development time, washed thoroughly with water, and post-baked at 230 ° C. for 60 minutes to obtain a solid sample. The adhesion of the solid sample was evaluated for each color resist composition. In addition, the thing with the line width of 6 micrometers or less of the photomask opening part remaining was set as (circle), and the thing which does not remain was set as x. The results are shown in the above [Table 2] and [Table 3].

From the above, the resist composition of the present invention is excellent in sensitivity and transparency and has a high volume resistivity. Further, it is clear that the resist composition and the color resist composition of the present invention have no coating film unevenness and high adhesion.

Claims (8)

In a resist composition containing (A) an alkali-developable resin composition, (B) a photopolymerization initiator, and (C) an organic solvent, the (C) organic solvent comprises propylene glycol monomethyl ether acetate (PGMEA), two An organic solvent selected from 1,3-butanediol, diisobutyl ketone, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, γ-butyrolactone, and N-methylpyrrolidone. resist composition containing.   The resist composition according to claim 1, wherein the composition of the organic solvent (C) is 1 to 10 parts by mass of dibasic acid ester with respect to 100 parts by mass of PGMEA.   The resist composition according to claim 1 or 2, wherein the dibasic acid ester is selected from dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate, dimethyl glutarate, and diethyl glutarate. The content of an organic solvent selected from 1,3-butanediol, diisobutyl ketone, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, γ-butyrolactone, N-methylpyrrolidone in the organic solvent (C) C) It is 0.1-30 mass% with respect to the whole organic solvent, The resist composition of any one of Claims 1-3 . The resist composition according to claim 1 , wherein the (A) alkali-developable resin composition has an ethylenically unsaturated bond. The color resist composition which added the color material (D) to the resist composition of any one of Claims 1-5 . The color resist composition according to claim 6, wherein the color material (D) is carbon black. A liquid crystal display device comprising a colored layer and / or a light shielding layer on a substrate, wherein at least one of the colored layer and the light shielding layer is a cured product of the color resist composition according to claim 6 or 7. Color filter.