JP2008122750A - Photosensitive resist composition for color filter, and the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resist composition for color filters which avoids occurrence of residue of pigment on a substrate in development and excels in both of adhesiveness in development and adhesiveness after post-bake. <P>SOLUTION: The photosensitive resist composition for color filters comprises a pigment (A), an acrylic polymer (B), a monomer (C), a photopolymerization initiator (D), a compound (E) having a siloxane structure and a solvent (F), wherein the compound (E) having the siloxane structure is a compound (E1) obtained by reacting a diamine with a (meth)acrylate having a glycidyl group or a compound (E2) obtained by reacting a diamine with a (meth)acrylate having a glycidyl group and a silane compound having a glycidyl group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive color resist composition for a color filter having good adhesion to a substrate, and a color filter for a liquid crystal display device.

  Currently, a pigment dispersion method using a resin composition in which a pigment is dispersed is mainly used as a method for producing a color filter used in a liquid crystal display device or the like. Examples of the pigment dispersion method include a photosensitive acrylic method and a non-photosensitive polyimide method. The production of the color filter by the photosensitive acrylic method uses a color resist having an acrylic polymer, an acrylic polyfunctional monomer or oligomer, a photopolymerization initiator, a solvent and a pigment as constituent components. First, the color resist is applied on a substrate. After drying, the pattern exposure, pattern development, and post-bake cycles are repeated for the required number of colors to obtain a colored coating pattern.

In this photosensitive acrylic method, the adhesion between the substrate and the color resist after development or post-baking after exposure and development is particularly important. If the adhesion between the substrate and the substrate during development is poor, pattern peeling occurs and When the adhesion with the substrate after baking is poor, peeling occurs in the reliability test of the liquid crystal display device, and the yield decreases in any case. Several photosensitive color resist compositions for color filters with improved adhesion to the substrate have been disclosed. Patent Documents 1 and 2 disclose compositions using a silane coupling agent, and Patent Document 3 discloses R ¹ _n Si (OR ² ) _4-n (where R ¹ is a vinyl group or an acyl group). , An allyl group, an allyloxy group, an allyloxyalkyl group, an alkylamino group, an amino group, a glycidyl group, and a glycidoxyalkyl group, and R ² is an organic group selected from hydrogen and an alkyl group , N represents an integer of 1 to 3), or a hydrolyzate of the organoalkoxysilane and / or a composition containing the hydrolysis condensate is described. Yes. Patent Document 4 describes a composition containing an imidazolesilane compound.

However, at present, the adhesiveness at the time of development and the adhesiveness after post-baking have not reached satisfactory levels. In particular, in the case of a composition using a silane coupling agent, an increase in the amount added improves the adhesion during development, but also improves the adhesion at the non-exposed area, so that the pigment remains on the substrate. There was a problem that occurred.
JP-A-10-133370 Japanese Patent Laid-Open No. 10-282325 JP 2000-028816 A JP 2004-280057 A

  The present invention was devised in view of the circumstances as described above, and the object of the present invention is that no pigment residue remains on the substrate during development, and adhesion during development and adhesion after post-baking. It is to provide a photosensitive resist composition for a color filter that is excellent in both properties, to improve the reliability of the color filter and the liquid crystal display device, to improve the yield, and to reduce the manufacturing cost.

In order to solve the above problems, the present invention has the following configuration.
(1) Color filter photosensitivity containing at least a pigment (A), an acrylic polymer (B), a monomer (C), a photopolymerization initiator (D), a compound (E) having a siloxane structure, and a solvent (F). Compound (E1) obtained by reacting a diamine represented by the following general formula (1) with a (meth) acrylate having a glycidyl group, or Photosensitive for color filters, which is a compound (E2) obtained by reacting a diamine represented by the following general formula (1), a (meth) acrylate having a glycidyl group and a silane compound having a glycidyl group Resist composition.

(In the formula, R ¹ represents an alkyl group having 10 or less carbon atoms, R ² represents an alkylene group having 10 or less carbon atoms, and n represents an integer of 1 to 10).
(2) The color filter photosensitivity according to (1), wherein the compound (E1) is a compound obtained by reacting 1 mol of a diamine with 4 mol of a (meth) acrylate having a glycidyl group. Resist composition.
(3) The compound (E2) is a compound obtained by reacting 1 mol of diamine, 3 mol of (meth) acrylate having a glycidyl group and 1 mol of a silane compound having a glycidyl group (1) The photosensitive resist composition for color filters as described in 1).
(4) The photosensitive resist composition for a color filter according to any one of (1) to (3), wherein the acrylic polymer (B) has a carboxyl group.
(5) The photosensitive resist composition for a color filter according to any one of (1) to (4), wherein the acrylic polymer (B) has an ethylenically unsaturated group in a side chain.
(6) The photosensitive resist composition for a color filter according to any one of (1) to (5), wherein the pigment (A) is titanium black and / or carbon black.
(7) A color filter using the photosensitive resist composition for a color filter according to any one of (1) to (6).

  When the photosensitive resist composition for color filter according to the present invention is used, no pigment residue is generated on the substrate during development, and both the adhesion during development and the adhesion after post-baking are excellent. Can be manufactured, the reliability of the liquid crystal display device is high, the yield is improved, and the manufacturing cost can be greatly reduced.

Hereinafter, the components of the present invention will be described.
In the present invention, an organic pigment or an inorganic pigment is used as the pigment (A).
Examples of such pigments include compounds classified as pigments in Color Index CI (published by The Society of Dyers and Colorists). As a specific example, as a red pigment, Color Index No. Pigment Red (hereinafter abbreviated as PR) 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 254, and the like, and Color Index No. Pigment Green (hereinafter abbreviated as PG) 7, 36, and the like, as a blue pigment, Color Index No. Pigment Blue (hereinafter abbreviated as PB) 15: 3, 15: 4, 15: 6, 21, 22, 60, 64, and the like, and Color Index No. Pigment Yellow (hereinafter abbreviated as PY) 20, 24, 86, 93, 109, 110, 117, 129, 138, 139, 150, 153, and the like, and Color Index No. Pigment Violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 37, 40, 50, and the like are Color Index No. Pigment Orange (hereinafter abbreviated as PO) 36, 43, 51, 55, 59, 61 and the like are Color Index No. Pigment black 7 or the like, carbon black, titanium black, metal oxide, or the like can be used. These pigments may be used alone or in combination of two or more. In addition, pigment derivatives such as sulfonic acids of pigments obtained by sulfonated organic pigments, specifically sulfonic acids of copper phthalocyanine, sulfonic acids of diketopyrrolopyrrole (PR254), sulfonic acids of quinophthalone (PY138), etc. When added in an amount of 0.5 to 10% by mass, preferably 2 to 7% by mass, there is an effect of stabilizing the dispersion of the pigment, which is preferable. Furthermore, it is preferable to use a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, or a polyallylamine polymer dispersant in combination at the time of dispersion because of the effect of stabilizing the dispersion. Since these polymer dispersants do not have photosensitivity, there is a concern that the photosensitivity of the target color resist may be deteriorated if added in a large amount. Therefore, an appropriate addition amount considering dispersion stability and photosensitivity is required. Is desirable. In particular, when the polyethyleneimine polymer dispersant or polyallylamine polymer dispersant is added to the pigment in an amount of 5 to 50 (mass%), more preferably 7 to 40 (mass%), the photosensitive performance is not deteriorated. Furthermore, there is an effect of highly stabilizing dispersion, which is even more preferable. These polymer dispersants include “Solspers (registered trademark)” 24000 (or 24000SC, 32500, 33500) manufactured by Abyssia Co., Ltd., “EFKA (registered trademark)” 4047 (or 4046) manufactured by Efka, and Ajinomoto Fine Techno. It is commercially available under trade names such as “Azisper (registered trademark)” PB821 (or PB822 etc.) manufactured by KK

  The composition of the present invention is particularly effective when a green pixel or a resin black matrix (hereinafter referred to as resin BM) having a high pigment ratio in the coating film is formed. As the pigment for the resin BM, a mixture of a red pigment and a blue and / or violet pigment, titanium black, and carbon black are preferable. In particular, when the resin BM is formed, a resin having excellent photosensitivity such as sensitivity during exposure can be obtained. Among titanium blacks, those having a high titanium nitride content are more preferable because high optical density (OD) can be obtained with the same film thickness. In addition, when titanium black and carbon black are mixed in a mass ratio of 50 ± 10% by mass, the transmitted color of the coating film is not bluish (titanium black color) or yellow (carbon black color) and close to neutral (neutral). Therefore, it is particularly suitable as a resin BM. Carbon black preferably has a primary particle diameter of 10 to 40 nm and its surface is oxidized with hypochlorous acid, nitric acid, hydrogen peroxide, or the like. In particular, those having an acid value of 1 to 30 (mgKOH / g), more preferably 5 to 25 (mgKOH / g) are preferable in terms of adhesion and solubility during development.

  In the present invention, the acrylic polymer (B) is an essential component, but an acrylic polymer having a carboxyl group is preferably used as the acrylic polymer (B). As the acrylic polymer having a carboxyl group, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and the like.

  These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, methacryl Isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and the like can be mentioned. Not shall. In particular, it is a quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene, and has an average molecular weight Mw of 2,000 to 100,000, an acid value of 70 to 150 (mgKOH / The polymer g) is preferred from the viewpoint of solubility in an alkali developer. Outside this range, the dissolution rate in the alkaline developer is undesirably lowered or increased too much.

  Further, when an acrylic polymer having an ethylenically unsaturated group in the side chain is used, the sensitivity at the time of exposure and development is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable. Such an acrylic polymer can be subjected to an addition reaction of an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic (co) polymer having a carboxyl group.

  Specific examples of the acrylic polymer having an ethylenically unsaturated group in the side chain include a copolymer described in Japanese Patent No. 3120476, JP-A-8-262221, or a commercially available acrylic polymer. Examples thereof include curable resin “Cyclomer (registered trademark) P” (Daicel Chemical Industries, Ltd.), alkali-soluble cardo resin, and the like. In particular, an acrylic polymer having an ethylenically unsaturated group in the side chain and an average molecular weight (Mw) of 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier, and using a standard polystyrene calibration curve) The polymer having an acid value of 70 to 150 (mg KOH / g) is most preferable from the viewpoints of photosensitive characteristics, solubility in an ester solvent, and solubility in an alkali developer.

  In the present invention, as the monomer (C), a polyfunctional or monofunctional acrylic monomer or oligomer can be used. Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylate, anhydrous Phthalic acid propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, Japanese Patent No. 3621533 and Japanese Patent Application Laid-Open No. 8-278630 Or full propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol Nord A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [ 4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4′-bis [4- (3-acryloxy) -2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2) -Hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full Examples include orange acrylate and biscresol full orange methacrylate. These can be used alone or in combination.

  By selecting and combining these polyfunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, it is desirable to use a compound having 3 or more, more preferably 5 or more functional groups, and dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable. When using a pigment that absorbs ultraviolet rays effective for photocrosslinking, such as resin BM, in addition to dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, the molecule contains many aromatic rings. The combined use of (meth) acrylate having a fluorene ring having high water repellency is more preferable because the pattern can be controlled to a desired shape during development. When resin BM uses a mixture of 10 to 60 parts by weight of dipentaerythritol hexa (meth) acrylate and / or dipentaerythritol penta (meth) acrylate and 90 to 40 parts by weight of (meth) acrylate having a fluorene ring as a monomer Most preferred.

  The photosensitive color resist composition for a color filter of the present invention contains a photopolymerization initiator (D) as an essential component. The photopolymerization initiator (D) is not particularly limited, and is a benzophenone compound, acetophenone compound, oxanthone compound, imidazole compound, benzothiazole compound, benzoxazole compound, oxime ester compound, carbazole compound, triazine. Known compounds such as inorganic photopolymerization initiators such as phosphinic compounds, phosphorus compounds, and titanates can be used. For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, Ciba Specialty Chemical “Irgacure (registered trademark)” 369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Ciba Specialty Chemical Co., Ltd. CGI-113 2- [4-Methylbenzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl Anthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4 , 5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” OXE01 1,2-octanedione, 1- [4 -(Phenylthio) -2- (O-benzoyl) Oxime)], an etanone that is CGI-242 of Ciba Specialty Chemicals Co., Ltd., 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O- Acetyloxime), 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine, “Adeka (registered trademark) optomer” N which is a carbazole-based compound manufactured by Asahi Denka Kogyo Co., Ltd. -1818, N-1919 and the like. These photopolymerization initiators can be used in combination of two or more. In particular, N, N′-tetraethyl-4,4′-diaminobenzophenone and Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 369 or Ciba Specialty Chemical Co., Ltd. CGI-113 and Asahi Denka Kogyo Co., Ltd. “ADEKA (registered trademark) Optmer” N-1818, N-1919 or Ciba Specialty Chemical Co., Ltd. CGI-242 Use of three types of carbazole compounds in combination is preferable because a photosensitive resist composition for color filters having high sensitivity and good pattern shape can be obtained. Although there is no limitation in particular as the addition amount of a photoinitiator, Preferably it is 2-50 mass% with respect to a color resist total solid, More preferably, it is 10-50 mass%.

  In the photosensitive resist composition for a color filter of the present invention, the resin component (total of polymer, monomer or oligomer and polymer dispersant) and the colorant containing at least the pigment are usually 20% by mass to 95% of the resin component. It is used by mixing in the range of mass%, preferably 25 mass% to 80 mass%. If the amount of the resin component is too small, the adhesion of the colored film to the substrate becomes poor. Conversely, if the amount of the pigment is too small, the color density or the optical density per unit thickness (OD value / μm) in the case of the resin BM. It becomes low and becomes a problem.

  The solvent (F) of the photosensitive resist composition for color filters of this invention is demonstrated. As the solvent (F) used in the present invention, esters, aliphatic alcohols, ketones and the like can be used.

  Specific esters include benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), γ-butyrolactone (boiling point 204 ° C.), methyl benzoate (boiling point 200 ° C.), diethyl malonate (boiling point 199 ° C.), 2-ethylhexyl acetate (bp 199 ° C.), 2-butoxyethyl acetate (bp 192 ° C.), 3-methoxy-3-methyl-butyl acetate (bp 188 ° C.), diethyl oxalate (bp 185 ° C.), ethyl acetoacetate ( Boiling point 181 ° C.), cyclohexyl acetate (bp 174 ° C.), 3-methoxy-butyl acetate (bp 173 ° C.), methyl acetoacetate (bp 172 ° C.), ethyl-3-ethoxypropionate (boiling point 170 ° C.), 2- Ethyl butyl acetate (boiling point 162 ° C), isopentyl propio (Boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), pentyl acetate (boiling point 150 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C) ) And the like, but is not limited thereto.

  Among these solvents, acetate-type or propionate-type solvents include 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and 3-methoxy-butyl. Particularly preferred are acetate and propylene glycol monomethyl ether acetate.

  In addition to the above solvents, propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene glycol tertiary butyl ether (boiling point 153 ° C.), dipropylene glycol monomethyl ether (boiling point 188 ° C.) Aliphatic ethers such as propylene glycol derivatives such as, aliphatic esters other than those described above, for example, ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isopentyl acetate (boiling point 142 ° C.), or butanol ( Boiling point 118 ° C.), aliphatic alcohols such as 3-methyl-2-butanol (boiling point 112 ° C.), 3-methyl-3-methoxybutanol (boiling point 174 ° C.), ketones such as cyclopentanone and cyclohexanone, xylene ( Boiling point 14 ° C.), ethyl benzene (boiling point 136 ° C.), solvent naphtha (petroleum fraction: it is also possible to use a solvent such as boiling point 165 to 178 ° C.).

  Furthermore, since application by a die coating apparatus has become mainstream with the increase in the size of the substrate, it is preferable to use a mixed solvent of two or more components in order to achieve appropriate volatility and drying properties. When the boiling points of all the solvents constituting the mixed solvent are 150 ° C. or less, film thickness uniformity cannot be obtained, the film thickness of the coating end part is increased, and the pigment is applied to the base part for discharging the coating liquid from the slit. Aggregates are formed, causing many problems that streaks occur in the coating film. On the other hand, when the mixed solvent contains a large amount of solvent having a boiling point of 200 ° C. or higher, the surface of the coating film becomes sticky and sticking occurs. Therefore, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C. or higher and 200 ° C. is desirable. In particular, as one component of the solvent constituting the mixed solvent, an ester solvent selected from 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and 3-methoxy-butyl acetate Is preferably a mixed solvent containing 30 to 75% by mass.

  Furthermore, it is more preferable to select 3-methoxy-3-methyl-butyl acetate as a component of the mixed solvent because the viscosity of the color resist solution can be increased at the same solid content concentration as compared with other esters.

  In the color resist for color filter of the present invention, the compound (E1) having a siloxane structure reacts with a diamine having a siloxane structure represented by the general formula (1) and a (meth) acrylate having a glycidyl group (E1). ) Or a compound (E2) obtained by reacting a diamine having a siloxane structure, a (meth) acrylate having a glycidyl group, and a silane compound having a glycidyl group, a pigment residue is generated on the substrate particularly during development. In addition, both the adhesiveness during development and the adhesiveness after post-baking can be used as a photosensitive resist composition for a color filter which is excellent.

  In the present invention, a compound (E1) obtained by reacting a diamine having a siloxane structure with a (meth) acrylate having a glycidyl group, or a diamine having a siloxane structure, a (meth) acrylate having a glycidyl group, and a silane compound having a glycidyl group The reacted compound (E2) will be described. This compound is modified by reacting the amino group of diamine with a glycidyl group. As an adhesion improver, an ethylenically unsaturated group effectively acts on the photosensitive performance and the siloxane structure portion on the adhesion to the substrate.

  The diamine having a siloxane structure is represented by the following general formula (1).

(In the formula, R ¹ represents an alkyl group having 10 or less carbon atoms, R ² represents an alkylene group having 10 or less carbon atoms, and n represents an integer of 1 to 10).
Here, R ¹ represents an alkyl group having 10 or less carbon atoms, and an alkyl group having 6 or less carbon atoms such as methyl, ethyl, propyl, butyl, phenyl and vinyl is preferable. n represents an integer of 1 to 10. However, when n is large, repelling may occur when a coating film is formed. Therefore, preferable n is an integer of 1 to 3. R ² represents an alkylene group having 10 or less carbon atoms, and an alkylene group having 6 or less carbon atoms such as methylene, ethylene, propylene, and phenylene is preferable.

  As the compound (E1) obtained by reacting a diamine having a siloxane structure with a (meth) acrylate having a glycidyl group, 1,3-bis (3-aminopropyl) tetramethyldisiloxane is particularly preferable from the viewpoint of easy availability of raw materials. A compound obtained by reacting glycidyl (meth) acrylate is preferable, and a compound obtained by reacting 2 to 4 mol, particularly 4 mol of glycidyl methacrylate is most preferable.

  The compound (E2) obtained by reacting a diamine having a siloxane structure with a (meth) acrylate having a glycidyl group and a silane compound having a glycidyl group has a (meth) acrylate having a glycidyl group with respect to the diamine having a siloxane structure. And by changing the reaction molar ratio of the silane compound having a glycidyl group. Here, as the silane compound having a glycidyl group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane and the like are preferable because of easy availability of raw materials. A compound obtained by reacting 1 mol of the compound of the general formula (1) with 1 to 3 mol of glycidyl (meth) acrylate and 3 to 1 mol of 3-glycidoxypropyltrimethoxysilane, 1 mol of the compound of the general formula (1) A compound obtained by reacting 1 to 3 mol of glycidyl (meth) acrylate and 3 to 1 mol of 3-glycidoxypropyltriethoxysilane, 1 mol of the compound of the above general formula (1) and 1 to 3 mol of glycidyl (meth) acrylate And a compound obtained by reacting 3 to 1 mol of 3-glycidoxypropylmethyldimethoxysilane, 1 mol of the compound of the above general formula (1), 1 to 3 mol of glycidyl (meth) acrylate, and 3-glycidoxypropylmethyldiethoxy Examples include compounds obtained by reacting 3 to 1 mol of silane. In particular, a structure in which the ethylenically unsaturated group is bifunctional or higher, preferably a trifunctional structure is preferable in terms of photosensitive performance. Of these, a compound obtained by reacting 1 mol of 1,3-bis (3-aminopropyl) tetramethyldisiloxane with 3 mol of glycidyl methacrylate and 1 mol of 3-glycidoxypropyltrimethoxysilane is most preferable.

  Since the above-mentioned compound used in the present invention has an effect of improving adhesion in a small amount, it is not necessary to add a large amount, preferably 0.2 to 20% by mass, more preferably 0, based on the total solid content of the color resist. 0.5 to 5% by mass.

  A surfactant can also be added to the photosensitive resist composition for color filters used in the present invention for the purpose of coating properties, smoothness of the colored coating and Benard cell. The addition amount of the surfactant is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass of the pigment. If the amount added is too small, the coating properties, smoothness of the colored coating and Benard cell are not effective, and if too large, the physical properties of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, and silicones based on polydimethylsiloxane Surfactants, fluorosurfactants and the like can be mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used.

  The photosensitive resist composition for a color filter of the present invention has a solid content (a ratio of all components other than the solvent contained in the color resist to the color resist solution) of 5 to 30% by mass, more preferably 7 to 25% by mass. A range is desirable. When the viscosity is measured at 25 ° C., the molecular weight of the polymer and / or the type and amount of the solvent are adjusted so that the viscosity is in the range of 1 to 40 (mPa · s), preferably in the range of 2 to 20 (mPa · s). Thus, the coating film can be made more uniform, which is desirable.

  The example of the manufacturing method of the color filter by the die coating apparatus using the photosensitive resist composition for color filters of this invention is demonstrated. As the substrate, a transparent substrate such as soda glass, non-alkali glass, or quartz glass is usually used, but is not particularly limited thereto. Examples of the die coating apparatus include a single wafer coating apparatus disclosed in Japanese Patent No. 3139358 and Japanese Patent No. 3139359. With this apparatus, the color resist can be applied onto the substrate by discharging the photosensitive resist composition (coating solution) for the color filter of the present invention from the die and moving the substrate. In this case, since a large number of substrates are applied in a single sheet, when the apparatus is operated for a long time, agglomerates of pigments are formed in the base part for discharging the coating liquid from the slits, which may cause a coating defect and reduce the yield. In this case, by providing a step of wiping the base, which is a discharge port of the apparatus, with a solvent containing 40% by mass or more of the ester solvent having a boiling point of 150 ° C. or higher with respect to the total solvent, the coating defects are eliminated and the base is removed. The rate is improved. After the color resist is applied on the substrate as described above, the solvent is removed by air drying, reduced pressure drying, heat drying or the like to form a color resist coating film. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of normal temperature to 100 ° C., 5 seconds to 10 minutes, and a degree of vacuum of 500 to 10 (Pa), and more preferably a pressure of 150 to 50 (Pa). Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes.

  Subsequently, a mask is placed on the coating and irradiated with ultraviolet rays using an exposure apparatus. Next, development is performed with an alkaline developer. It is preferable to use an alkaline developer added with 0.1 to 5% of a surfactant such as a nonionic surfactant because a better pattern can be obtained. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine.

  The concentration of the alkaline substance is 0.01% by mass to 50% by mass. Preferably it is 0.02 mass% to 10 mass%, More preferably, it is 0.02 to 1 mass%. In the case where the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone may be appropriately added to the developer.

Among these developers, an aqueous developer of an alkaline aqueous solution is preferable from the viewpoint of working environment and waste developer treatment.
The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. After development, a washing process with pure water or the like is added.

  The resulting color resist coating film pattern is then subjected to heat treatment (post-baking) to become a colored filter patterned. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.

  A color filter for a liquid crystal display device can be prepared by forming a colored pattern successively and repeatedly using the photosensitive resist composition for black, red, green and blue color filters of the present invention by the above method. Here, the patterning order of each color resist is not limited.

  Further, after the manufacturing method of the present invention, a protective film and a transparent conductive film can be formed on the pixel.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Evaluation method and criteria)
1. Pigment residue The unexposed part of the substrate after development post-baking (the part where the pattern is not formed) is wiped by reciprocating twice using "Toraysee (registered trademark)" manufactured by Toray Industries, Ltd., which has been moistened with ethanol. The degree of was investigated. The evaluation criteria were as follows.
○: No coloring, Δ: Lightly colored, ×: Clearly colored Adhesiveness during development Using a resolution test mask, develop 1.7 times as long as the unexposed area dissolves, and the 10 micron resist pattern on the substrate does not peel off. The 10 micron resist pattern was peeled off, but the 20 micron resist pattern was not peeled, and the 20 micron resist pattern was peeled off.

3. Adhesiveness after post-baking After pasting post-baking, Nichiban Co., Ltd. cellotape (registered trademark) CT-18 on a resist pattern exposed for 2 hours under a water vapor atmosphere of 2 atm and 120 ° C., The adhesiveness was evaluated by peeling the cellophane at a high speed in the direction of 90 ° (cellotape peeling test). A resist pattern that has been exposed for 3 hours does not peel ○ A resist pattern that has been exposed for 3 hours peels, but a resist pattern that has been exposed for 1 hour does not peel Δ A resist that has been exposed for 1 hour What was peeled only by the pattern was set as x.

Reference example 1
Synthesis of acrylic polymer (P1, P2) having carboxyl group in side chain According to the method described in Example 1 of Japanese Patent No. 3120476, methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 45/15 Acrylic polymer (P1) powder having characteristics of average molecular weight (Mw) 30,000 and acid value 80 (mgKOH / g) was obtained by reprecipitation with purified water, filtration and drying. . Similarly, methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 40/30/40) was synthesized using 3-methyl-3-methoxybutanol as a solvent, and the concentration was 40% by mass and the average molecular weight ( A solution of an acrylic polymer (P2) having characteristics of Mw) 40,000 and an acid value of 150 (mgKOH / g) was obtained.

Reference example 2
Synthesis of acrylic polymer (P3) having carboxyl group and methacryl group in side chain According to the method described in Example 1 of Japanese Patent No. 3120476, methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 30/40 / 30) After synthesis, 40 parts by weight of glycidyl methacrylate is added, reprecipitated with purified water, filtered, and dried, whereby acrylic having characteristics of average molecular weight (Mw) 40,000 and acid value 110 (mgKOH / g). Polymer (P3) powder was obtained.

Reference example 3
Synthesis of compound (E1) having an ethylenically unsaturated group and having a siloxane structure 1,3-bis (3-aminopropyl) tetramethyldisiloxane 24.8 g (0.1 mol) and glycidyl methacrylate 56.9 g (0.4 mol) and 0.08 g of a polymerization inhibitor hydroquinone monomethyl ether were charged into a flask and reacted at 55 ° C. for 4 hours with stirring, and then 81.7 g of propylene glycol monomethyl ether acetate was added to a concentration of 50% by mass. The solution was further diluted and reacted at 55 ° C. for 2 hours to obtain a solution (E1-AP1) of an adhesion improver having a viscosity of 11.5 mPa · s at 25 ° C.

Reference example 4
Synthesis of Compound (E1) Having an Ethylenically Unsaturated Group and Having a Siloxane Structure In Reference Example 3, 1,3-bis (3-aminopropyl) tetra is similarly obtained except that the molar ratio of glycidyl methacrylate is changed. An adhesion improver (E1-AP2) obtained by reacting methyldisiloxane (0.1 mol) and glycidyl methacrylate (0.3 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0 0.1 mol) and glycidyl methacrylate (0.2 mol) were reacted to obtain an adhesion improver (E1-AP3).

Reference Example 5
Synthesis of compound (E2) having an ethylenically unsaturated group and a siloxane structure 1,3-bis (3-aminopropyl) tetramethyldisiloxane 24.8 g (0.1 mol) and glycidyl methacrylate 42.6 g (0.3 mol) and 0.08 g of a polymerization inhibitor hydroquinone monomethyl ether were charged into a flask and reacted at 55 ° C. for 3 hours with stirring, and then 27.8 g of 3-glycidoxypropyltriethoxysilane (0.1%). Mol) and 95 g of propylene glycol monomethyl ether acetate to a concentration of 50% by mass and further reacted at 55 ° C. for 2 hours to obtain a solution (E2-AP1) of an adhesion improver having a viscosity of 9.4 mPa · s at 25 ° C. It was.

Reference Example 6
Synthesis of compound (E2) having an ethylenically unsaturated group and having a siloxane structure 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.1 mol) and glycidyl in the same manner as in Reference Example 5. Adhesion improver (E2-AP2) reacted with methacrylate (0.2 mol) and then reacted with 3-glycidoxypropylmethyldiethoxysilane (0.1 mol), Shin-Etsu Chemical Co., Ltd. Amino group-modified silicone oil product name PAM-E (amine equivalent 130 g / mol) (0.2 mol) and glycidyl methacrylate (0.2 mol) were reacted with 3-glycidoxypropylmethyldimethoxy An adhesion improver (E2-AP3) obtained by reacting silane (0.2 mol) was obtained.

Example 1
Weigh 300 g of Titanium Black 13M-T (titanium nitride) manufactured by Mitsubishi Materials Corporation, 150 g of a 45% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P3), and 1050 g of propylene glycol tertiary butyl ether, and zirconia beads. Was dispersed at 2000 rpm for 4 hours to obtain a pigment dispersion (TB1) having a pigment concentration of 20% by mass. 533 g of this pigment dispersion (TB1), 32.6 g of a 50% by weight propylene glycol monomethyl ether acetate solution of bisphenoxyethanol full orange acrylate, and propylene glycol of dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer Monomethyl ether acetate 50 mass% solution 32.6 g, “Irgacure” 369 15.5 g as photopolymerization initiator, Asahi Denka Kogyo Co., Ltd. “ADEKA (registered trademark) Optmer” N-1919 4.3 g and N, N′- 1.6 g of tetraethyl-4,4′-diaminobenzophenone, 8.57 g of E2-AP1 (50% solution) as an adhesion improver (2% by mass of solid content), propylene glycol monomethyl ether acetate 10 of silicone surfactant quality A solution prepared by dissolving 5.36 g of a% solution in 439 g of 3-methyl-3-methoxy-butyl acetate and 16 g of propylene glycol monomethyl ether acetate was added and mixed to prepare a black color resist (solid content concentration 18% by mass). . The viscosity of this color resist was 4 mPa · s at 25 ° C. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness became 1 μm (after post-baking). The coating speed was 3 m / min. The coated substrate was dried under reduced pressure (100 Pa) and then heat-treated for 2 minutes on a 90 ° C. hot plate to prepare a color resist coating film. Subsequently, this coating film was exposed (200 mJ / cm ² ) through a resolution test mask, and “Emulgen (registered trademark)” A-60 (HLB 12. 8, polyoxyethylene derivative) (manufactured by Kao Co., Ltd.) is added with 0.2% of the total amount of the developing solution by an alkali developing solution and spray-developed 1.7 times as long as the unexposed portion is dissolved. A patterning substrate was obtained by washing with water. The obtained patterning substrate was held in a hot air oven at 230 ° C. for 30 minutes and post-baked to obtain a patterning substrate. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 1.

Examples 2-4
In Example 1, the addition amount of the adhesion improver E2-AP1 was 5% by mass to solids (Example 2), 0.5% by mass to solids (Example 3), 0.2% by mass to solids A patterning substrate was obtained in the same manner as in Example 1 except that it was changed to (Example 4). According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 1.

Example 5
A patterning substrate was obtained in the same manner as in Example 1 except that the adhesive improver E2-AP1 was changed to E1-AP1 in Example 1. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 1.

Comparative Examples 1-7
In Example 1, a patterning substrate was obtained in the same manner as in Example 1 except that the adhesion improver was changed to the one described in Table 1. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 1.

  From the comparison of Examples 1 to 5 and Comparative Examples 1 to 7, in the black color resist (titanium black) composition, without the adhesion improver and the silane compound, no pigment residue is generated on the substrate during development. In addition, it can be seen that none of the adhesiveness during development and the adhesiveness after post-baking are satisfactory. In addition, the adhesion improver used in the composition of the present invention has an addition amount of 0.2% by mass, and the adhesion at the time of development and the adhesion after post-baking are slightly insufficient, but compared with those without the adhesion improver. The effect is recognized. An addition amount of 0.5 to 5% by mass has a sufficient effect.

Example 6
Mitsubishi Materials Corp. titanium black 13M-T (titanium nitride) 133.4g, Daido Kasei Co., Ltd. acid-treated carbon black 9930CF 133.4g, Ajinomoto Fine Techno Co., Ltd. "Ajisper (registered trademark)" PB821 66.7 g of propylene glycol monomethyl ether acetate in a 20% by weight solution 155.6 g of a 45% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P3), and 466.7 g of propylene glycol tertiary butyl ether and propylene glycol monomethyl ether acetate 544.4 g was weighed and dispersed for 3 hours at 2000 rpm using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (TCB1) having a pigment concentration of 17.78% by mass. To 386 g of this pigment dispersion (TCB1), 7.97 g of a 45% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P3), 30.8 g of a 50% by weight solution of bisphenoxyethanol full orange acrylate in propylene glycol monomethyl ether acetate, 13.19 g of a propylene glycol monomethyl ether acetate 50 mass% solution of dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. DHPA) as a polyfunctional monomer, “Irgacure” 369 8.38 g as a photopolymerization initiator, Ciba Specialty 6.7 g of CGI-242 Chemical Co., Ltd. and 1.7 g of N, N′-tetraethyl-4,4′-diaminobenzophenone, 5.07 g of E1-AP1 (50% solution) as an adhesion improver (2% by mass) Solids) 3.17 g of a 10% by weight solution of a silicone surfactant in propylene glycol monomethyl ether acetate 350 g of 3-methyl-3-methoxy-butyl acetate, 36 g of propylene glycol monomethyl ether acetate and 92.4 g of 3-methyl-3-methoxybutanol The solution dissolved in was added and mixed to prepare a black color resist (solid content concentration 14% by mass). The color resist had a viscosity of 3 mPa · s at 25 ° C. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness became 1 μm (after post-baking). Thereafter, a patterned substrate was obtained in the same manner as in Example 1. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 2.

Examples 7-8
In Example 6, a patterned substrate was obtained in the same manner as in Example 6 except that the type of adhesion improver was changed as shown in Table 2. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 2.

Comparative Examples 8-11
In Example 6, a patterned substrate was obtained in the same manner as in Example 6 except that the adhesion improver was changed to that described in Table 2. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 2.

  From the comparison of Examples 6 to 8 and Comparative Examples 8 to 11, in the black color resist (titanium black and carbon black) composition, the silane compound does not generate a pigment residue on the substrate during development, and development It can be seen that there is nothing satisfying both the adhesiveness at the time and the adhesiveness after post-baking. In the composition of the present invention, the sensitivity of the adhesion improving agent E1-AP1 was the highest, and the order was E1-AP1> E1-AP2> E1-AP3.

Example 9
240 g of acid-treated carbon black 9930CF manufactured by Daido Kasei Co., Ltd., 120 g of a 20 mass% propylene glycol monomethyl ether acetate solution of “Solspers (registered trademark)” 24000 (manufactured by Abyssia Co., Ltd.) 3-methyl- 160 g of a 45% by mass solution of 3-methoxybutanol and 980 g of propylene glycol monomethyl ether acetate are weighed and dispersed at 2000 rpm for 3 hours using a mill type disperser filled with zirconia beads, and a pigment dispersion having a pigment concentration of 16% by mass (CB1) was obtained. To 424 g of this pigment dispersion (CB1), 18.97 g of a 45% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P3), 39.5 g of a 50% by weight propylene glycol monomethyl ether acetate solution of bisphenoxyethanol full orange acrylate, 16.9 g of a propylene glycol monomethyl ether acetate 50% by mass solution of dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and “Irgacure (registered trademark)” 369 11.27 g as a photopolymerization initiator, Ciba-Specialty Chemical Co., Ltd. CGI-242 6.02g and N, N'-tetraethyl-4,4'-diaminobenzophenone 2.25g, E1-AP1 (50% solution) 6.18g as an adhesion improver ( 2 (Mass% vs. solid content), 3.86 g of a 10% by mass propylene glycol monomethyl ether acetate solution of a silicone surfactant was dissolved in 367 g of 3-methyl-3-methoxy-butyl acetate and 79 g of 3-methyl-3-methoxybutanol. The solution was added and mixed to prepare a black color resist (solid content concentration 16% by mass). The color resist had a viscosity of 3 mPa · s at 25 ° C. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness became 1 μm (after post-baking). Thereafter, a patterned substrate was obtained in the same manner as in Example 1. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 3.
Examples 10-13, Comparative Examples 12-14
In Example 9, a patterned substrate was obtained in the same manner as in Example 9 except that the addition amount and type of the adhesion improver were changed as shown in Table 3. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 3.

  From the comparison of Examples 9 to 13 and Comparative Examples 12 to 14, in the black color resist (carbon black) composition, only the composition of the present invention has no pigment residue on the substrate during development, and Both the adhesion during development and the adhesion after post-baking are satisfactory. In the composition of the present invention, the sensitivity of the adhesion improving agent E2-AP1 was the highest, and the order was E2-AP1> E2-AP2≈E2-AP3.

Example 14
Pigment Red PR-254 (IRGAPHOR (registered trademark) RED BT-CF manufactured by Ciba Specialty Chemicals Co., Ltd.) 153.6 g, pigment derivative (sulfonic acid of the same pigment) 6.4 g, polymer dispersant “Solsperse (registered) Trademark) "24000 (manufactured by Abyssia Co., Ltd.) 30 mass% propylene glycol monomethyl ether acetate solution 160 g and acrylic polymer (P1) synthesized in Reference Example 1 3-methoxy-3-methyl-butyl acetate 20 mass% solution 60 g , And 620 g of 3-methoxy-3-methyl-butyl acetate, and dispersed for 2 hours at 1500 rpm using a mill type disperser filled with zirconia beads, and a pigment having a pigment concentration of 16% by mass and a solid content of 22% by mass A dispersion (R1) was obtained. To 398 g of this pigment dispersion (R1), 293 g of a 20% by weight 3-methoxy-3-methyl-butyl acetate solution of acrylic polymer (P3), dipentaerythritol hexaacrylate as a polyfunctional monomer (DHPA manufactured by Nippon Kayaku Co., Ltd.) Of propylene glycol monomethyl ether acetate in an amount of 85.4 g, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (“Irgacure®” 369) as a photopolymerization initiator: Ciba・ Specialty Chemicals Co., Ltd. (21.3 g), E1-AP1 (50% solution) 9 g (2% by mass to solid content) as an adhesion improver and silicone surfactant 0.2 g 3-methyl- 136 g of 3-methoxybutanol and 3-methoxy-3-methyl-butyl acetate Solution added dissolved in 8g and propylene glycol monomethyl ether acetate 129 g, mixing red color filter photosensitive resist composition (solid content 20 wt%) was prepared. The color resist had a viscosity of 12 mPa · s at 25 ° C. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness was 2 μm (after post-baking). The coating speed was 3 m / min. The coated substrate was dried under reduced pressure (100 pa) and then heat-treated for 2 minutes on a hot plate at 90 ° C. to prepare a color resist coating film. Subsequently, this coating film was exposed through a resolution test mask (200 mJ / cm 2), and in an 0.04% KOH aqueous solution, “Emulgen” A-60 (HLB12.8, polyoxyethylene derivative) as a nonionic surfactant. ) (Produced by Kao Co., Ltd.) with an alkali developer added at 0.2% with respect to the total amount of the developer by spray development 1.7 times as long as the unexposed portion is dissolved, and then washed with pure water. A patterned substrate was obtained. The obtained patterning substrate was held in a hot air oven at 210 ° C. for 30 minutes and post-baked to obtain a patterning substrate. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 4.

Example 15 and Comparative Example 15
In Example 14, the patterning board | substrate was obtained like Example 14 except having changed the addition amount and kind of the adhesive improvement agent as described in Table 4. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 4.

Example 16
Pigment Green PG36 (MONASTRAL (registered trademark) GREEN 6YCL manufactured by Avisia Co., Ltd.) 104 g, Pigment Yellow PY150 (E4GN-GT manufactured by Bayer Co., Ltd.) 56 g, polymer dispersant “Solspers (registered trademark)” 24000 (Abisya Co., Ltd.) )) 30% by weight propylene glycol monomethyl ether acetate solution) 160g, 60g of 3-methoxy-3-methyl-butyl acetate 20% by weight solution of acrylic polymer (P3) synthesized in Reference Example 2, and 3-methyl-3- 620 g of methoxy-butyl acetate was weighed and dispersed at 1500 rpm for 2 hours using a mill type disperser filled with zirconia beads to obtain a pigment dispersion (G1) having a pigment concentration of 16% by mass. To 384 g of this pigment dispersion (G1), 271 g of a 20% by weight 3-methoxy-3-methyl-butyl acetate solution of acrylic polymer (P3), dipentaerythritol hexaacrylate as a polyfunctional monomer (DHPA manufactured by Nippon Kayaku Co., Ltd.) ) Of propylene glycol monomethyl ether acetate (79 g), “Irgacure (registered trademark)” 369 29.6 g as a photopolymerization initiator, and E1-AP1 (50% solution) 8.9 g (as a solid) 2% by mass), a solution obtained by dissolving 0.22 g of a silicone surfactant in 132 g of 3-methyl-3-methoxybutanol, 32 g of 3-methyl-3-methoxy-butyl acetate and 129 g of propylene glycol monomethyl ether acetate, Mixed and green color resist (solid A concentration of 20% by mass was prepared. The color resist had a viscosity of 7 mPa · s at 25 ° C. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness was 2 μm (after post-baking). Thereafter, a patterned substrate was obtained in the same manner as in Example 4. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 5.
Examples 17-18, Comparative Examples 16-18
In Example 16, a patterned substrate was obtained in the same manner as in Example 16 except that the type of the adhesion improver was changed as described in Table 5. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 5.

Example 19
Pigment Blue 15: 6 (Dainippon Ink Chemical Co., Ltd. Fast Gen Blue EP-CFE) 116.4 g, Pigment derivative (sulfonic acid of the same pigment) 3.6 g, Polymer dispersant Ajinomoto Fine Techno Co., Ltd. 180 g of a 20% by mass propylene glycol monomethyl ether acetate solution of Ajisper “PB821”, 45 g of a 20% by mass 3-methyl-3-methoxybutanol solution of the acrylic polymer (P2) synthesized in Reference Example 1, and 655 g of 3-methoxy-butyl acetate Weighed and dispersed at 3200 rpm for 2 hours using a mill type disperser filled with zirconia beads to obtain a pigment dispersion (B1) having a pigment concentration of 12% by mass. 531 g of this pigment dispersion (B1), 239 g of a 20% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P2), and propylene of dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer 164 g of glycol monomethyl ether acetate 50% by weight solution, 27.4 g of “Irgacure (registered trademark)” OXE01 as a photopolymerization initiator, 11.63 g of E1-AP1 (50% solution) as an adhesion improver (2% by weight to solid content) ), A solution prepared by dissolving 0.29 g of a fluorosurfactant in 239 g of propylene glycol monomethyl ether acetate was added and mixed to prepare a blue color resist (solid content concentration 20 mass%). The viscosity of this color resist was 14 mPa · s at 25 ° C. The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness was 2 μm (after post-baking). Thereafter, a patterned substrate was obtained in the same manner as in Example 4. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 6.

Example 20 and Comparative Example 19
In Example 19, a patterning substrate was obtained in the same manner as in Example 19 except that the type of the adhesion improver was changed as described in Table 6. According to the evaluation method and evaluation criteria, this substrate was examined for pigment residue, adhesion during development, and adhesion after post-baking. The results are shown in Table 6.

  From comparison of Examples 14 to 20 and Comparative Examples 15 to 19, with respect to red and blue color resists, only the composition of the present invention has no pigment residue on the substrate during development, and adhesion during development. And post-baking adhesion.

  Although the mechanism of this action is not clear, since the adhesion improver used in the composition of the present invention has a plurality of photoreactive groups, ultraviolet rays effective for photocrosslinking such as black and green color resists are pigmented. Even if it absorbs, it is considered that photocrosslinking occurs more effectively than in the case where the photoreactive group is monofunctional as in a normal silane compound. In addition, the glycidyl group-containing silane compound is considered to have good adhesion at the time of development because the glycidyl group reacts with the carboxyl group in the resin due to heat during drying, but it is likely to cause a pigment residue on the substrate. .

Claims (7)

Photoresist composition for color filter containing at least pigment (A), acrylic polymer (B), monomer (C), photopolymerization initiator (D), compound (E) having a siloxane structure, and solvent (F) In the product, the compound (E) having the siloxane structure is obtained by reacting the diamine represented by the following general formula (1) with a (meth) acrylate having a glycidyl group, or the following general formula A photosensitive resist composition for a color filter, which is a compound (E2) obtained by reacting the diamine represented by (1), a (meth) acrylate having a glycidyl group, and a silane compound having a glycidyl group. .

(In the formula, R ¹ represents an alkyl group having 10 or less carbon atoms, R ² represents an alkylene group having 10 or less carbon atoms, and n represents an integer of 1 to 10). 2. The photosensitive resist composition for a color filter according to claim 1, wherein the compound (E1) is a compound obtained by reacting 1 mol of a diamine with 4 mol of a (meth) acrylate having a glycidyl group. . The compound (E2) is a compound obtained by reacting 1 mol of a diamine, 3 mol of a (meth) acrylate having a glycidyl group, and 1 mol of a silane compound having a glycidyl group. A photosensitive resist composition for color filters. The photosensitive resist composition for a color filter according to any one of claims 1 to 3, wherein the acrylic polymer (B) has a carboxyl group. The said acrylic polymer (B) has an ethylenically unsaturated group in a side chain, The photosensitive resist composition for color filters in any one of Claims 1-4 characterized by the above-mentioned. The photosensitive resist composition for a color filter according to any one of claims 1 to 5, wherein the pigment (A) is titanium black and / or carbon black. A color filter using the photosensitive resist composition for a color filter according to claim 1.