TW201829489A - Resin composition for color filter, method for producing same, and color filter - Google Patents

Abstract

The present invention relates to a resin composition for a color filter, the resin composition comprising: (A) a specific copolymer including a structural unit represented by formula (1) below; (B) a solvent including a solvent containing a hydroxy group having 3-10 carbon atoms; (C) a reactive diluent; (D) a photopolymerization initiator; and (E) a coloring agent. In formula (1), R1 represents a hydrogen atom or a methyl group, R2-R4 each independently represent a hydrogen atom, an alkyl group having 1-6 carbon atoms, or an alkoxy group having 1-6 carbon atoms, and n is an integer of 1-10. At least one among R2-R4 is an alkoxy group having 1-6 carbon atoms.

Description

Resin composition for color filter, method for producing the same, and color filter

The present invention relates to a resin composition for a color filter, a method for producing the same, and a color filter.

In recent years, from the viewpoint of saving resources or energy, photosensitive resin compositions which can be cured by active energy rays such as ultraviolet rays or electron beams are widely used in various fields such as plating, printing, coatings, and adhesives. Further, in the field of electronic materials such as printed circuit boards, a photosensitive resin composition which can be cured by active energy rays is also used for a solder resist or a color filter resist.

The color filter is generally a transparent substrate such as a glass substrate; red (R), green (G), and blue (B) pixels formed on the transparent substrate; a black matrix formed at the boundary of the pixels; It is composed of a protective film formed on a pixel and a black matrix. The color filter configured as described above is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. As a method of forming a pixel and a black matrix (hereinafter, a pixel and a black matrix are referred to as "coloring patterns"), various manufacturing methods are disclosed. As a method of forming the coloring pattern, for example, a photosensitive resin composition is used as a resist, and a pigment/dye containing a photolithography method for repeatedly applying, exposing, developing, and baking the photosensitive resin composition is used. Dispersion method. This pigment/dye dispersion method is excellent in durability such as light resistance and heat resistance, and can form a color pattern having few defects such as pinholes, and is now widely used.

In general, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment/dye dispersion method has the above advantages, but conversely, since the pattern of each pixel of the black matrix, R, G, and B is repeatedly formed, the alkali-soluble resin as a binder of the coating film is required to be high. Heat decomposition resistance and heat yellowing. As a new material satisfying this requirement, the present inventors have proposed an alicyclic monomer and an ethoxylated o-phenylphenol (meth) acrylate (i.e., 2-phenylphenoxyethyl (meth) acrylate. The ester represents a copolymer derived from an alkylene oxide structure and a (meth) acrylate having an aryl residue (for example, refer to the specific document 1).

Further, in general, in a liquid crystal display device, liquid crystal is sandwiched between a separately produced color filter substrate and a TFT (Thin-Film-Transistor) substrate, and these members are fabricated by lamination. When these members are bonded together, an alignment film such as a polyimide film may be provided on the color filter substrate in order to align the liquid crystal. At this time, the color filter layer is exposed to a highly polar solvent such as N-methylpyrrolidone (NMP) contained in the polyimide resin, so that solvent resistance (NMP resistance) is required on the color filter layer. ).

Recently, in order to further improve the brightness or the high resolution, the coloring material in the pixel becomes a dye and the concentration thereof is also high. However, for the solubility of the solvent, the dye is higher than the pigment, there is a problem that the dye is eluted in the solvent exposed in the process, and the chromaticity of the pixel changes. For a pixel containing many dyes, an improved solvent resistance is required. Sex. Further, in the step of exposing the color filter layer to a solvent such as NMP, the evaluation condition having a condition of 40 ° C or higher and the NMP resistance of the color filter is also performed at a high temperature (50 ° C or higher).

Here, for example, there has been proposed a method of improving solvent resistance by using a copolymer having an epoxy group or an oxetanyl group and a carboxyl group or a phenolic hydroxyl group (for example, refer to Patent Documents 2 and 3). Or, as a polymerization initiator, a method of improving solvent resistance by using a polymerization initiator having a oxadiazole structure or a triazine structure containing a trihalomethyl group in a molecule (for example, refer to Patent Document 4), but These solvent resistances are still insufficient. Further, in order to enhance the color reproduction characteristics of the color filter, it is necessary to blend a coloring agent having a large amount of the coloring agent, or to increase the film thickness, and the like, and these tend to cause problems such as a decrease in sensitivity and a decrease in developability. Further improvement in performance is required (for example, refer to Patent Document 5). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2012-22048 [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei. No. Hei. Bulletin [Patent Document 5] Japanese Patent Laid-Open Publication No. 2014-164021

[Problems to be solved by the invention]

The present invention has been made in view of the above-described problems, and it is an object of the invention to provide a resin composition for a color filter of a color pattern which is excellent in sensitivity and developability and excellent in solvent resistance. Further, it is an object of providing a color filter having a color pattern excellent in solvent resistance. [Method for solving the problem]

The present inventors have intensively studied in order to solve the above problems, and as a result, it has been found that a resin composition containing a specific copolymer, a specific solvent, a reactive diluent, a photopolymerization initiator, and a colorant can solve the above problems to achieve the present invention. .

That is, the present invention is represented by the following [1] to [5]. [1] A resin composition for a color filter, comprising: (A) comprising a constituent unit (a-1) derived from a polymerizable unsaturated compound having an acid group, and represented by the following formula (1) A copolymer of a constituent unit (a-2) and a constituent unit (a-3) derived from another polymerizable unsaturated compound, wherein the total constituent unit is 100 mol%, and 1 mol% is contained. 50 mol% of the constituent unit (a-2), a copolymer having a weight average molecular weight of 1,000 to 50,000 and a molecular weight distribution (Mw/Mn) of 1.5 to 3.0, and (B) a hydroxyl group-containing solvent having 3 to 10 carbon atoms. Solvent, (C) reactive diluent, (D) photopolymerization initiator, and (E) colorant;

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; n is an integer of 1 to 10, but at least one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms). [2] The resin composition for a color filter according to [1], wherein the acid group of the structural unit (a-1) is a carboxyl group, and the (A) copolymer contains 10 mol% to 50 mol%. The above constituent unit (a-1), and the acid value of the (A) copolymer is from 20 KOHmg/g to 300 KOHmg/g. [3] The resin composition for a color filter according to [1] or [2], wherein the content of the (A) copolymer is 5 mass when the total of the components of the solvent (B) is removed to 100 parts by mass. The content of the (C) reactive diluent is from 5 parts by mass to 85 parts by mass, and the content of the (D) photopolymerization initiator is from 0.1 part by mass to 30 parts by mass, the above (E) coloring. The content of the agent is from 5 parts by mass to 75 parts by mass. [4] A color filter characterized by having a color pattern formed of a resin composition for a color filter according to any one of [1] to [3]. [5] A method for producing a resin composition for a color filter, comprising a polymerizable unsaturated compound having an acid group (A-1) in the presence of (B) a solvent, (A-2) After copolymerizing a monomer mixture of the compound represented by the following formula (2) and (A-3) another polymerizable unsaturated compound, (C) a reactive diluent and (D) a photopolymerization initiator are added. And (E) a step of mixing and mixing the coloring agent, wherein when the total of the (A-1) compound, the (A-2) compound, and the (A-3) compound is 100 mol%, the monomer mixture is Containing 1 mol% to 50 mol% of the (A-2) compound, and (B) the solvent is a solvent containing a hydroxyl group having 3 to 10 carbon atoms.

(In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; n is an integer of 1 to 10, but at least one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms). [Effects of the Invention]

According to the present invention, it is possible to provide a resin composition for a color filter type color filter which is excellent in sensitivity and developability and excellent in solvent resistance. Further, according to the present invention, it is possible to provide a color filter having a color pattern of excellent solvent resistance.

The resin composition for a color filter of the present invention contains (A) a copolymer, (B) a solvent, (C) a reactive diluent, (D) a photopolymerization initiator, and (E) a colorant.

[(A) Copolymer] The (A) copolymer in the present invention contains a constituent unit (a-1) derived from a polymerizable unsaturated compound having an acid group, and the following formula (1):

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; n is an integer of 1 to 10, but at least one of R ² to R ⁴ is a constituent unit (a-2) represented by an alkoxy group having 1 to 6 carbon atoms), and is not polymerizable from others. The constituent unit of the saturated compound (a-3).

In the (A) copolymer of the present invention, when the total of the constituent unit (a-1), the constituent unit (a-2), and the constituent unit (a-3) is 100% by mol, the copolymer contains 1 mol%. 50% of the constituent units (a-2). When the content ratio of the constituent unit (a-2) is less than 1 mol% or exceeds 50 mol%, the desired solvent resistance cannot be obtained. The content ratio of the constituent unit (a-2) is preferably from 5 mol% to 40 mol%, more preferably from 10 mol% to 30 mol%. Further, the (A) copolymer of the present invention preferably comprises 10 mol% to 50 mol% of the constituent unit (a-1), more preferably 15 mol% to 45 mol%, and most preferably 20 Mole%~40% by mole. When the content ratio of the constituent unit (a-1) is within the above range, more developability can be obtained. Further, the (A) copolymer of the present invention preferably comprises from 1 mol% to 89 mol% of the constituent unit (a-3), more preferably from 15 mol% to 80 mol%, and most preferably contains 30. Mole%~70% by mole. When the content ratio of the constituent unit (a-3) is within the above range, more developability and solvent resistance are obtained.

Further, the weight average molecular weight (Mw) of the (A) copolymer is from 1,000 to 50,000, preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, in terms of polyethylene. When the weight average molecular weight (Mw) of the (A) copolymer is less than 1,000, the coloring pattern after development is defective. On the other hand, when the weight average molecular weight (Mw) of the (A) copolymer exceeds 50,000, the development time is too long, and practicality is lost. The value of the weight average molecular weight (Mw) of the (A) copolymer in the present invention is measured by a gel permeation chromatography (GPC) under the following conditions and calculated in terms of polyethylene. Column: Shodex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40 ° C Sample: (A) Tetrahydrofuran solution having a copolymer content of 0.2% by mass Developing solvent: tetrahydrofuran detector : Micro-refractometer (trade name: Shodex (registered trademark) RI-71S, manufactured by Showa Denko Co., Ltd.) Flow rate: 1 mL/min

The molecular weight distribution (Mw/Mn) of the (A) copolymer in the present invention is from 1.5 to 3.0, preferably from 1.5 to 2.8, more preferably from 1.5 to 2.6. (A) If the molecular weight distribution (Mw/Mn) of the copolymer is less than 1.5, the weight average molecular weight, the acid value, etc., the target value range, or the reaction conditions at the time of producing the (A) copolymer, etc., must be With the tip setting, it seems unrealistic from the balance between the time spent on the review and the effect obtained. On the other hand, when the molecular weight distribution (Mw/Mn) of the (A) copolymer exceeds 3.0, the developability is deviated. Mw/Mn was determined by the above-mentioned GPC measurement.

The acid value of the (A) copolymer in the present invention is not particularly limited, but is preferably 20 KOHmg/g to 300 KOHmg/g, more preferably 30 KOHmg/g to 200 KOHmg/g. When the acid value of the (A) copolymer is 20 KOHmg/g or more, more developability can be obtained. On the other hand, when the acid value of the (A) copolymer is 300 KOHmg/g or less, the exposed portion (photohardened portion) cannot be dissolved in the alkali developer. Further, the acid value of the (A) copolymer is based on JIS K6901 5.3, using a value measured by a mixed indicator of Bromothymol blue and phenol red, meaning that the neutralized (A) copolymer is 1 g. The number of mg of potassium hydroxide required for the acidic component contained.

When the (A) copolymer of the present invention has an unsaturated group, the unsaturated group equivalent is not particularly limited, and is preferably 100 g/mol to 4000 g/mol, more preferably 200 g/mol to 3000 g/ Mol. When the unsaturated group equivalent of the (A) copolymer is 100 g/mol or more, it is effective to improve heat decomposition resistance and heat yellowing resistance. On the other hand, when the unsaturated group equivalent of the (A) copolymer is 4000 g/mol or less, it is effective to further improve the sensitivity.

The alkylene group of the (A) copolymer in the invention is not particularly limited, and is preferably 400 g/mol to 4000 g/mol, more preferably 500 g/mol to 3000 g/mol. When the alkylene equivalent of the (A) copolymer is 400 g/mol or more, it is effective to further improve heat decomposition resistance and heat yellowing resistance. On the other hand, when the alkylene equivalent of the (A) copolymer is 4,000 g/mol or less, it is effective to further improve the solvent resistance. Further, the molecular weight of the (A) copolymer of the alkylene equivalent (A) copolymer divided by the average number of alkylene groups per molecule is calculated based on the amount of the compound (A-2) added as described later.

The above (A) copolymer is a polymerizable unsaturated compound having (A-1) acid group in the presence of a solvent containing (B) a hydroxyl group-containing solvent having 3 to 10 carbon atoms, (A-2) ) (2):

(In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; n is an integer of 1 to 10. However, at least one of R ² to R ⁴ is a compound represented by an alkoxy group having 1 to 6 carbon atoms) and (A-3) other polymerizable unsaturated compound. The monomer mixture is prepared in the art by a copolymerization method by a known radical polymerization method. For example, after dissolving the (A-1) compound, the (A-2) compound, and the (A-3) compound in the solvent (B) to prepare a solution, a polymerization initiator is added to the solution at 50 ° C to 130 ° C. Let it react for 1 hour to 20 hours. (A) The number of repetitions of the respective compounds in the copolymer or the order of bonding of the respective compounds is not particularly limited. Further, after the preparation of the copolymer which does not include any of the constituent unit (a-1), the constituent unit (a-2), and the constituent unit (a-3), the constituent unit which is insufficient is introduced through the denaturation reaction. A copolymer comprising a constituent unit (a-1), a constituent unit (a-2), and a constituent unit (a-3) can be prepared in the copolymer.

In general, the acid group of the polymerizable unsaturated compound having an (A-1) acid group is not particularly limited, and a carboxyl group, a phosphate group (-OP(=O)(OH) ₂ ), or a sulfonic acid group (-S (=) O) ₂ OH) is preferred. Among these, the acid group of the polymerizable unsaturated compound having an (A-1) acid group is particularly preferred from the viewpoint of reactivity.

The polymerizable unsaturated compound having an (A-1) acid group is not particularly limited as long as it has a monomer having an acid group and an ethylenically unsaturated group. Specific examples of the compound (A-1) are, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(methyl)acryloxyethyl succinic acid, 2-propene oxime Oxyethylphthalic acid, 2-(methyl)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl acid phosphate, and the like. Among these, (meth)acrylic acid is preferred from the viewpoint of easiness of obtaining and reactivity. In the present invention, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid. The same is true for "(meth) acrylate".

Specific examples of the compound represented by the above formula (2) (A-2) include 3-(meth)acryloxypropylmethyldimethoxydecane and 3-(methyl)propene oxime. Propyl ethyl dimethoxy decane, 3-(methyl) propylene methoxy propyl methyl diethoxy decane, 3-(methyl) propylene methoxy propyl ethyl diethoxy decane 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, and the like. Among these, 3-(meth)acryloxypropyltrimethoxydecane and 3-(meth)acryloxypropyltriethoxydecane are obtained from the viewpoint of ease of availability and reactivity. It is better.

(A-3) Other polymerizable unsaturated compound (A-1) component and polymerizable unsaturated compound other than (A-2) component, which does not have an acid group or a decyl group and can be combined with the compound (A-1) And (A-2) a compound and a copolymerized polymerizable unsaturated compound. Specific examples of the other polymerizable unsaturated compound (A-3) are exemplified by dienes such as butadiene; methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (A) Ethyl acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, benzyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) ) methylcyclohexyl acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexane dimethanol mono (meth) acrylate, (meth) acrylate rosin, (meth) acrylate Oxime ester, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (A) 1,1,1-trifluoroethyl acrylate, (methyl) Perfluoroethyl ester, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate ), 3-(N,N-dimethylamino)propyl (meth)acrylate, glycerol mono(meth)acrylate, butyl triol mono(meth)acrylate, pentanetriol mono (a) Acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isodecyl (meth)acrylate, adamantyl (meth)acrylate, naphthalene (methyl) Acrylate, 蒽(meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-(meth)acrylate Epoxycyclohexylmethyl ester, (3-ethyloxetane-3-yl)methyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, (meth)acrylic acid 2 -isocyanatopropyl ester, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanate (meth)acrylate Acidic-1,1-dimethylethyl ester, 4-isocyanatocyclohexyl (meth)acrylate, ethylene of the aforementioned isocyanate group And a compound of an isocyanate group, a compound having a blocked isocyanate group, a N,N-dimethylaminoethyl (meth)acrylate, or a (meth)acrylic acid N which is blocked by a block agent. , N-diethylaminoethyl ester, N-tert-butylaminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, hexamethylpiperidinyl (meth)acrylate And other (meth) acrylates; decyl (meth) acrylate, N, N-dimethyl decyl (meth) acrylate, N, N-diethyl decyl (meth) acrylate, (A) N,N-dipropyl decylamine, N,N-diisopropyl decyl (meth) acrylate, decyl decyl (meth) acrylate, N-isopropyl (meth) propylene oxime Amine, (meth)acrylic acid morpholine, diacetone (meth)acrylamide or the like (meth)acrylic acid decylamine; norbornene (bicyclo[2.2.1]hept-2-ene), 5- Methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]hept-3-ene , 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]hept-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]hept-3-ene , dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]non-8-ene, tricyclo[5.2.1.0 ^2,6 ]non-3-ene , tricyclo [4.4.0.1 ^2,5 ] eleven-3-ene, tricyclo[6.2.1.0 ^1,8 ] eleven-9-ene, tricyclo[6.2.1.0 ^1,8 ] eleven-4- Alkene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]hept-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^{1, 6} ]hept-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,12 ]hept-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]hept-3-ene, pentacyclic [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadeca-4-ene, pentacyclic [7.4.0.1 ^{2 ,5} .1 ^9,12 .0 ^8,13 ] pentadeca-3-ene, 5-northene-2,3-dicarboxylic anhydride, (meth)acrylic acid-nonanilide, (meth) acrylonitrile a vinyl compound such as nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl pyridine, vinyl acetate or vinyl toluene; α-, o-, of styrene and styrene M-, p-alkyl, nitro, cyano, decylamine derivatives; unsaturated ethyl citrate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc. a dicarboxylic acid diester; an unsaturated polybasic acid anhydride such as maleic anhydride, itaconic anhydride or citraconic anhydride. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid are available from the viewpoint of easy availability and reactivity. Dicyclopentyl ester, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, N,N-diethylamino (meth)acrylate Ethyl ester, N,N-dimethyldecylamine (meth)acrylate, morpholine (meth)acrylate, styrene, vinyltoluene and norbornene are preferred, methyl (meth)acrylate, (methyl) Benzyl acrylate, dicyclopentanyl (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, styrene and Vinyl toluene is preferred. These (A-3) compounds may be used alone or in combination of two or more. Among them, alkyl (meth)acrylate is preferred from the viewpoints of heat decomposition resistance and heat yellow resistance, methyl (meth)acrylate, benzyl (meth)acrylate, and dicyclopentyl (methyl). Acrylate is preferred. Further, from the viewpoint of improving solvent resistance, a polymerizable compound having a functional group reactive with an acid group is preferred, and specific examples thereof include a glycidyl group, an oxetanyl group, an isocyanate group, and the like. Or a polymerizable compound having a blocked isocyanate. Preferably, from the viewpoint of availability and reactivity, glycidyl (meth)acrylate, methyl (3-ethyloxet-3-yl)methacrylate, and the like can be exemplified.

The block agent used as the block of the above isocyanate group may, for example, be an internal amide group such as ε-caprolactam, δ-valeroinamide, γ-butylide or β-propionamide; Alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl sarbuta, butyl sirolimus, methyl carbitol, benzyl alcohol, phenyl siroliol, sugar alcohol, cyclohexanol, etc. a phenol, cresol, xylenol, ethyl phenol, o-isopropyl phenol, butyl phenol such as p-tert-butyl phenol, p-tert-octyl phenol, nonyl phenol, dimercapto Phenol, styrene phenol, hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol, etc.; dimethyl malonate, diethyl malonate, B a reactive methylene such as methyl acetate, ethyl acetate or ethyl acetonate; a thiol such as butyl mercaptan, thiophenol or tert-dodecyl mercaptan; diphenylamine, benzene Amines such as cyanidin, aniline, carbazole, etc.; amides such as acetanilide, acetamidine, acetamide, benzamide; guanidinium succinate, bismuth maleate Imidoids such as imines; imidazole, 2 - an imidazole system such as methylimidazole or 2-ethylimidazole; a urea system such as urea, thiourea or ethylene urea; an amine formate such as phenyl N-phenylaminocarbamate or 2-oxazolidinone; An imine system such as ethyleneimine or polyethyleneimine; a ketoxime system such as formaldehyde oxime, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime or cyclohexanone oxime a bisulfite system such as sodium hydrogen sulfite or potassium hydrogen sulfite.

The compound (A-1), the compound (A-2) and (() are exemplified by the same ratio of the constituent units (a-1) to (a-3) constituting the above-mentioned (A) copolymer. When the total of the compounds of A-3) is 100 mol%, the monomer mixture preferably contains 10 mol% to 50 mol% of the compound (A-1), more preferably 15 mol% to 45 mol%. %, preferably contains 20% by mole to 40% by mole. Similarly, when the total of the (A-1) compound, the (A-2) compound, and the (A-3) compound is 100 mol%, the monomer mixture contains 1 mol% to 50 mol% ( The compound of A-2) preferably contains from 5 mol% to 40 mol%, more preferably from 10 mol% to 30 mol%. Similarly, when the total of the (A-1) compound, the (A-2) compound, and the (A-3) compound is 100 mol%, the monomer mixture preferably contains 1 mol% to 89 mol%. The compound of (A-3), more preferably 15 mol% to 80 mol%, preferably contains 30 mol% to 70 mol%.

From the viewpoint of controlling the weight molecular weight and molecular weight distribution (Mw/Mn) of the (A) copolymer to a specific range while obtaining a color pattern having a desired solvent resistance, it is used in a copolymerization reaction (B) The solvent must contain a hydroxyl group-containing solvent having 3 to 10 carbon atoms. When the copolymerization reaction is carried out using a solvent containing no hydroxyl group-containing solvent having 3 to 10 carbon atoms, gelation occurs, and the weight molecular weight and molecular weight distribution (Mw/Mn) of the obtained copolymer are not within a specific range. Among them, a solvent having one hydroxyl group is preferred from the viewpoint of controlling the molecular weight distribution. Specific examples of the hydroxyl group-containing solvent having 3 to 10 carbon atoms are exemplified by monools such as propanol, butanol, pentanol, hexanol, octanol, decyl alcohol, tridecyl alcohol, dodecanol, and benzyl alcohol. , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol Mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, (Poly) polyolefin diol monoalkyl ethers such as dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-dibutyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. These solvents having a hydroxyl group number of 3 to 10 and having a hydroxyl group may be used singly or in combination of two or more. Further, the above alcohol may contain various isomers such as propylene glycol, and in addition to 1-propanol, various isomers such as 2-propanol are also included.

Other solvents may be included in the solvent (B) used in the copolymerization reaction. Examples of other solvent systems include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. a polyolefin diol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and the like; Ketones such as ketoethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid Ester, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl 3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate , n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, acetone An ester of methyl ester, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate or the like; an aromatic hydrocarbon such as toluene or xylene; A carboxylic acid amide such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide. Among these, from the viewpoint of reactivity, a (poly) polyolefin diol monoalkyl ether acetate-based solvent such as propylene glycol monomethyl ether acetate is preferred.

The solvent (B) used in the copolymerization reaction preferably has a content of a hydroxyl group-containing solvent having 3 to 10 carbon atoms, preferably 10% by mass to 100% by mass, and preferably 20% by mass to 100% by mass. When the content ratio of the hydroxyl group-containing solvent having 3 to 10 carbon atoms is within the above range, the weight molecular weight and molecular weight distribution (Mw/Mn) of the (A) copolymer can be more easily controlled within a specific range, and coloring can be performed. The solvent resistance of the pattern is further enhanced.

The amount of the solvent (B) used in the copolymerization reaction is not particularly limited, but the total amount of the compound (A-1), the compound (A-2) and the compound (A-3) is 100 parts by mass. In the case of 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass. By setting the amount of the solvent (B) to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and the coloring or gelation of the (A) copolymer can be prevented. In addition, the amount of the solvent (B) is set to 1000 parts by mass or less, and the molecular weight of the (A) copolymer is suppressed by the chain transfer action, and the viscosity of the (A) copolymer can be controlled to an appropriate range.

The polymerization initiator which can be used in the copolymerization reaction is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethyl). Divaleronitrile), 2,2'-azobis(isobutyrate) dimethyl ester, benzammonium peroxide, t-butylperoxy-2-ethylhexanoate, and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be used is not particularly limited, but when the total amount of the compound (A-1), the compound (A-2) and the compound (A-3) is 100 parts by mass, it is preferably 0.5 parts by mass to 20 parts by mass, more preferably 1.0 parts by mass to 10 parts by mass.

In the resin composition for a color filter of the present invention, the blending amount of the (A) copolymer is such that the total of the components of the solvent (B) in the resin composition for removing the color filter is 100 parts by mass. It is preferably 5 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 75 parts by mass, most preferably 20 parts by mass to 65 parts by mass. When the blending amount of the (A) copolymer is within the above range, the curability of the resin composition for a color filter is more suitable.

[(B) Solvent] The solvent (B) to which the resin composition for a color filter of the present invention is blended may be used as it is, or may be used as it is when the copolymer (A) is prepared (copolymerization). Further, the solvent (B) exemplified above is added. Further, when other components are added, it may be a solvent which coexists therein.

In the resin composition for a color filter of the present invention, the blending amount of the solvent (B) is 100 parts by mass of the total of the components of the solvent (B) in the resin composition for removing the color filter. It is preferably 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass, most preferably 100 parts by mass to 700 parts by mass. (B) When the blending amount of the solvent is within the above range, the viscosity of the resin composition for a color filter is more suitable.

[(C) Reactive Diluent] The (C) reactive diluent to be blended as the resin composition for a color filter of the present invention is not particularly limited, and includes an ethylenically unsaturated double bond, a vinyl group, Methyl) propylene oxime is preferred. Specific examples of the (C) reactive diluent include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, and diallyl phthalate. An aromatic vinyl monomer such as diallyl phenyl phosphate; a polycarboxylic acid monomer such as vinyl acetate or vinyl adipate; methyl (meth)acrylate or (meth)acrylic acid Ethyl ester, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane Tris (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cis (hydroxyethyl) isocyanurate tris (meth) acrylate, etc. Acrylic monomer; triallyl cyanurate or the like. Among these, polyfunctional (meth) acrylates are particularly preferred. These (C) reactive diluents may be used alone or in combination of two or more.

The blending amount of the (C) reactive diluent in the resin composition for a color filter of the present invention is such that the sum of the components of the solvent (B) in the resin composition for removing the color filter is set to 100 mass. In the case of a part, it is preferably 5 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 75 parts by mass, most preferably 20 parts by mass to 65 parts by mass. (C) When the blending amount of the reactive diluent is within the above range, the viscosity and photocurability of the resin composition for a color filter are more suitable.

[(D) Photopolymerization initiator] The (D) photopolymerization initiator to be blended as the resin composition for a color filter of the present invention is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, and benzoin. Benzoin and other alkyl ethers such as ethyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t Acetophenones such as -butyldioxy-1-methylethyl)acetophenone; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- An alkylphenone such as a ketone; an anthracene such as 2-methylindole, 2-pentylindole, 2-t-butylindole or 1-chloroindole; 2,4- Thioxanthone such as dimethylthioxanthone, 2,4-diisopropylthioxanthone or 2-chlorothioxanthone; acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. Ketals; diphenyl ketone, 4-(1-t-butyldioxy-1-methylethyl)diphenyl ketone, 3,3',4,4'-fluorene (t-butyl) Diphenyl ketones such as dioxycarbonyl)diphenyl ketone; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoquinone)], B Ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(0-acetamidine) Terpene esters; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one; 2-benzyl-2-dimethylamino-1 -(4-morpholinylphenyl)butanone-1; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene) a mercaptophosphine oxide such as a phenylphosphine oxide; and a xanthone. These (D) photopolymerization initiators may be used alone or in combination of two or more.

The blending amount of the (D) photopolymerization initiator in the resin composition for a color filter of the present invention is such that the sum of the components of the solvent (B) in the resin composition for removing the color filter is set to 100. In the case of parts by mass, it is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 0.5 part by mass to 20 parts by mass, most preferably from 1 part by mass to 15 parts by mass. (D) When the blending amount of the photopolymerization initiator is within the above range, the photocurability of the resin composition for a color filter is more suitable.

[(E) Colorant] As the (E) colorant to which the resin composition for a color filter of the present invention is blended, a well-known dye or pigment can be used. When a dye as the (E) coloring agent is used, when a pigment is used, a coloring pattern of high luminance is obtained, and good alkali developability is exhibited.

As the dye, an acidic group having a carboxyl group or the like is used from the viewpoints of the solubility in the solvent (B) solvent or the alkali developer, the interaction of other components in the resin composition for a color filter, heat resistance, and the like. An acid dye, a salt of a nitrogen compound with an acid dye, a sulfonamide of an acid dye, or the like is preferred. As an example of such a dye, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73 , 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216 Acid ION 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and such derivatives and the like. Among these, an acid dye of an azo type, a xanthene type, an anthraquinone type or an anthraquinone type is preferable. These dyes can be used alone or in combination of two or more kinds depending on the color of the pixel.

As examples of the pigment, CIPigment Yellow-1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, Yellow pigments of 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CIPigment Orange 13, 31, 36, 38, 40, 42, 43, 51, Orange pigments of 55, 59, 61, 64, 65, 71, 73; CIPigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215 Red pigments of 216, 224, 242, 254, 255, 264, 265, etc.; blue pigments of CIPigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; CIPigment Violet 1, 19, 23 , purple pigments such as 29, 32, 36, 38; green pigments such as CIpigment green 7, 36, 58; brown pigments such as CIPigment Brown 23, 25; CIPigment Black 1, 7, carbon black, titanium black, iron oxide, etc. Black pigments, etc. These pigments can be used alone or in combination of two or more kinds depending on the color of the pixel of interest. Dyes and pigments can be used in combination.

In the resin composition for a color filter of the present invention, the blending amount of the coloring agent (E) is 100 parts by mass when the total of the components of the solvent (B) in the resin composition for removing the color filter is 100 parts by mass. It is preferably 5 parts by mass to 75 parts by mass, more preferably 5 parts by mass to 65 parts by mass, most preferably 10 parts by mass to 55 parts by mass.

When a pigment is used as the (E) coloring agent, a known dispersing agent may be blended in the resin composition for a color filter from the viewpoint of improving the dispersibility of the pigment. As the dispersant, a polymer dispersant excellent in dispersion stability over time is preferably used. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene glycol diester dispersant. A water sorbitol aliphatic ester dispersant, an aliphatic denaturing ester dispersant, and the like. As such a polymer dispersant, a product such as EFKA (FK chemicals (EFKA)), Disperbyk (manufactured by BYK Chemie Co., Ltd.), Disparlon (manufactured by Nanben Chemical Co., Ltd.), and SOLSPERS (manufactured by Zeneca Co., Ltd.) can be used. Famous marketers. The blending amount of the dispersing agent in the composition for a color filter of the present invention is appropriately adjusted depending on the type of the pigment or the like.

In the resin composition for a color filter of the present invention, in addition to the above components, a well-known additive such as a known coupling agent, a leveling agent, or a thermal polymerization inhibitor may be blended in order to impart specific characteristics. The blending amount of the additives in the resin composition for a color filter is not particularly limited as long as it does not inhibit the effects of the present invention.

The resin composition for a color filter of the present invention can be prepared by mixing the above components using a well-known mixing device, or by preparing a composition comprising the (A) copolymer and the (B) solvent, that is, (B) in the presence of a solvent, after copolymerizing a monomer mixture of the compound (A-1), the compound (A-2) and the compound (A-3), by adding (C) a reactive diluent, (D) a photopolymerization initiator and (E) a colorant may be mixed or prepared. In the latter preparation method, (B) the solvent is added in addition after the copolymerization as needed.

Since the resin composition for a color filter of the present invention has alkali developability, development can be carried out by using an aqueous alkali solution. In particular, the resin composition for a color filter of the present invention is excellent in sensitivity and imageability, and has excellent color resistance as a solvent resistance. Therefore, the resin composition for a color filter of the present invention is suitably used as a resist, and is suitably used for producing a resist for use in a built-in color filter such as an organic EL display device, a liquid crystal display device, or a solid-state imaging device.

[Color Filter] Next, a color filter produced by using the resin composition for a color filter of the present invention will be described. The color filter of the present invention has a color pattern formed by the resin composition for a color filter described above. Hereinafter, the color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing a color filter according to an embodiment of the present invention. As shown in FIG. 1, the color filter of the present invention includes: a substrate 1; RGB pixels 2 formed on one side of the substrate 1 and a black matrix 3 formed at the boundary of the pixel 2; 2 and the protective film 4 on the black matrix 3.

The color filter of the present invention is formed by using the resin composition for a color filter described above except that the pixel 2 and the black matrix 3 (coloring pattern) are used. Further, the configuration of the color filter shown in Fig. 1 is an example, and the color filter of the present invention is not limited to this configuration.

Next, a method of producing the color filter of the present invention will be described. First, a color pattern is formed on the surface of one side of the substrate 1. Specifically, the pixel 2 and the black matrix 3 are sequentially formed on the surface of one side of the substrate 1. The substrate 1 is not particularly limited, and examples thereof include a glass substrate, a tantalum substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyimide substrate, a polyimide substrate, an aluminum substrate, and Printed wiring board, array board, etc.

The coloring pattern can be formed by photolithography. Specifically, the resin composition for a color filter is applied onto one surface of the substrate 1 to form a coating film, and then the coating film is exposed through a mask of a specific pattern to expose the exposed portion. Light hardening. Further, after the unexposed portion is developed with an aqueous alkali solution, a specific coloring pattern can be formed by baking. The coating method of the resin composition for a color filter is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, and a slit coating method can be used. Bufa and so on.

Further, after the coating film is formed by applying the resin composition for a color filter, the coating film can be heated by a heating method using a circulating oven, an infrared heater, a heating plate or the like, and (B) The solvent evaporates. The heating conditions are not particularly limited, and are appropriately set in accordance with the composition of the resin composition for a color filter. For example, the coating film may be heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.

The light source used for the exposure of the coating film composed of the resin composition for a color filter is not particularly limited, and for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp or the like can be used. Further, the amount of exposure is not particularly limited, and is appropriately set in accordance with the composition of the resin composition for a color filter.

The aqueous alkali solution used for development is not particularly limited, and for example, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or potassium hydroxide; ethylamine, diethylamine or dimethylethanolamine can be used. An aqueous solution of an amine compound; an aqueous solution of a fourth ammonium salt such as tetramethylammonium hydroxide; 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino group- N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino group -N-ethyl-N-β-methoxyethylaniline and an aqueous solution of a p-phenylenediamine compound such as a sulfate, a hydrochloride or a p-toluenesulfonate. Among these, an aqueous solution using a p-phenylenediamine compound is preferred. Further, in such an aqueous alkali solution, an antifoaming agent or a surfactant may be added as needed. Further, it is preferred to carry out water washing and drying after the development by the aqueous alkali solution. The baking conditions are not particularly limited, and the color filter used may be subjected to heat treatment with a composition of a resin composition. In general, it can be heated at a temperature of 130 to 250 ° C for 10 to 60 minutes.

By using the resin composition for a color filter, coating, exposure, development, and baking as described above are repeated, and a desired pixel 2 and a black matrix 3 (coloring pattern) can be sequentially formed. Further, in the present embodiment, a method of forming a coloring pattern by photocuring has been described, but the present invention is not limited thereto. Instead of the (D) photopolymerization initiator, a resin composition in which a curing accelerator and a known epoxy resin are blended may be used, and after coating by an inkjet method, heating may be performed to form a desired coloring. Graphic type.

Next, a protective film 4 is formed on the coloring pattern (pixel 2 and black matrix 3). The protective film 4 is not particularly limited, and is formed using a known material and a forming method.

The color filter produced in such a manner is made of a resin composition for a color filter which is excellent in sensitivity and developability and has excellent solvent resistance and is excellent in solvent resistance, so that it has solvent resistance. Sex is an excellent color pattern (Pixel 2 and Black Matrix 3).

[Image Display Element] The image display element of the present invention includes the above-described color filter. The image display element of the present invention is not particularly limited as long as it includes the above-described color filter, and examples thereof include a liquid crystal display element and an organic EL display element. Since the image display element of the present invention includes the above-described color filter, it can be displayed with high brightness. [Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, and the present invention is not limited to the following examples.

In the examples and comparative examples, the molecular weight of the fluorenyl equivalent system (A) copolymer was divided by the average number of decyl groups per molecule, and the calculated value was calculated based on the amount of the compound (A-2) added.

(A) A synthesis example of the copolymer is shown below.

[Synthesis Example 1] 700.0 g of propylene glycol monomethyl ether was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while stirring with nitrogen gas, and the temperature was raised to 88 °C. Next, in 46.2 g (0.54 mol) of methacrylic acid, 60.5 g (0.24 mol) of 3-methacryloxypropyltrimethoxydecane and 166.0 g (1.66 mol) of methyl methacrylate To the monomer mixture, 27.3 g of 2,2'-azobis(isobutyric acid) dimethyl ester (polymerization initiator) was added, and the obtained product was dropped from the dropping funnel into the flask. After completion of the dropwise addition, the mixture was stirred at 88 ° C for 5 hours to carry out a copolymerization reaction to obtain a sample 1 (weight average molecular weight: 7100, molecular weight distribution (Mw/Mn): 2.1, acid value: 99 KOH mg/g, decyl equivalent: 1230 g/mol).

[Synthesis Examples 2 to 6 and Comparative Synthesis Examples 1 to 5] In the same manner as in Synthesis Example 1, except that the materials of Tables 1 and 2 were used, the copolymerization reaction was carried out to obtain Samples 2 to 11. The weight average molecular weight, molecular weight distribution (Mw/Mn), acid value, and alkylidene equivalent of the obtained sample are shown in Tables 1 and 2. Further, the molar % of the compound (A-1) (~-3) used in the (A) copolymer was prepared and shown in Table 3.

[Comparative Synthesis Example 6] 5 parts by mass of 2,2-azobisisobutyronitrile and 3-methoxybutyl acetate were placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube. 250 parts by mass of the ester, further added 18 parts by mass of methacrylic acid, 25 parts by mass of tricyclo [5.2.1.02.6]decane-8-yl methacrylate, 5 parts by mass of styrene, 3-propenyloxypropyltrimethyl 20 parts by mass of oxydecane and 32 parts by mass of 3-ethyl-3-methylpropenyloxymethyloxetane, after being substituted with nitrogen, slowly stirred while raising the temperature of the solution to 80 ° C . After 1 hour, the mixed solution was gelatinized, and the sample could not be produced satisfactorily.

Using the obtained samples 1 to 11, a resin composition (dye type) for a color filter and a resin composition (pigment type) for a color filter were prepared by the following methods.

<Preparation of Resin Composition (Dye Type) for Color Filter> According to the blending component and the blending ratio shown in Table 4, a color filter using a dye (VALIFAST BLUE 2620) as the (E) colorant was prepared. Resin composition (color resist). Further, the blending amount of the (A) copolymer in Table 4 is a solvent which does not include the synthesis of the (A) copolymer, and the blending amount of the solvent (B) in Table 4 is a total of the synthetic (A) copolymer. The solvent used at the time is additionally blended with propylene glycol monomethyl ether.

<Preparation of resin composition for color filter (pigment type)> 10 parts by mass of CI pigment green 36 and 33.75 parts by mass of propylene glycol were placed in a stainless steel container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm. Monomethyl ether acetate and 6.25 parts by mass of a dispersant (trade name: Disperbyk-161 BYK Chemie‧ Japan Co., Ltd.) were prepared by dispersing them by a paint shaker for 3 hours to prepare a green pigment dispersion. According to the blending component and the blending ratio shown in Table 5, a resin composition (color resist) for a color filter using the green pigment dispersion was prepared as the (E) colorant. Further, the blending amount of the (A) copolymer in Table 5 is a solvent which does not include the synthesis of the (A) copolymer, and the blending amount of the solvent (B) in Table 5 is a total of the synthetic (A) copolymer. The solvent used at the time is additionally blended with propylene glycol monomethyl ether.

<Evaluation of color resisting agent> (1) Alkali developability The resin composition for a color filter prepared was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure became 2.5 μm. The coating film was formed on the glass substrate by heating at 90 ° C for 3 minutes to volatilize the solvent. Next, a mask of a specific pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed (the exposure amount was 150 mJ/cm ² ) through the mask, and the exposed portion was photocured. Then, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 ° C and a pressure of 0.3 MPa to dissolve the unexposed portion and develop it, and then confirmed by the residue and the developed form. The residue after alkali development was confirmed by observation using an electron microscope S-3400 manufactured by Hitachi High-Technologies Co., Ltd., using an electron microscope S-3400 manufactured by Hitachi High-Technologies Co., Ltd. The basis for this assessment is as follows. ○: No residue ×: Residues The evaluation results of the alkali developability described above are shown in Table 6.

(2) Solvent resistance The resin composition for the color filter prepared was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after baking became 2.5 μm, and then The film was heated at ° C for 3 minutes to volatilize the solvent to form a coating film on the glass substrate. Next, the coating film was exposed to light having a wavelength of 365 nm, and the exposed portion was photocured, and then placed in a desiccator at a baking temperature of 230 ° C for 30 minutes to prepare a cured coating film. To a 500 mL glass bottle with a lid, 200 mL of N-methyl-2-pyrrolidone was added and allowed to stand at 60 °C. After the test piece to which the hardened coating film described above was attached was immersed therein, it was allowed to stand at a specific temperature for 30 minutes. The color change (ΔE ^* ab) before and after the immersion of the N-methyl-2-pyrrolidone of the test piece was measured by a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). When the value of ΔE ^* ab before and after immersion is 4.5 or less, the solvent resistance of the cured film can be said to be good. The evaluation results of the above solvent resistance are shown in Table 6.

Further, in Examples 6 and 12 in the above Table 6, CPI (registered trademark)-100P (manufactured by San-Apro Co., Ltd., photoacid generator) was added as an additive. The amount of CPI (registered trademark)-100P added is 1 part by mass based on 100 parts by mass of the (A) copolymer.

From the results of Table 6, when using the dye as the (E) coloring agent, the color resists (Examples 1 to 6) of the (A) copolymer obtained in Synthesis Examples 1 to 6 were used to impart alkali developability and Solvent resistance is an excellent pattern. In contrast, the color resists (Comparative Examples 1 and 2) of the (A) copolymers of Comparative Synthesis Examples 1 and 2 (the solvent containing no hydroxyl group having 3 to 10 carbon atoms) were used, and the solvent resistance was insufficient. The alkali developability using the color resist (Comparative Example 1) of the copolymer of Comparative Example 1 (A) was also insufficient. Further, among the compounds of the compound (A-1) (a-3), the color resist of the (A) copolymer of Comparative Synthesis Example 3 was used in the case where the content of the compound (A-2) was 55 mol% (Comparative) The alkali developability of Example 3) was good, but the solvent resistance was insufficient. The color resist (Comparative Example 4) of the (A) copolymer of Comparative Synthesis Example 4 containing no compound (A-1) was used, and the solvent resistance was good, but the alkali developability was insufficient. The color developability (Comparative Example 5) of the copolymer of Comparative Example 5 (A) which does not contain the compound (A-2) was good, but the solvent resistance was not sufficient.

When a pigment as the (E) coloring agent was used, the color resist (Examples 7 to 12) of the copolymer of (A) of Synthesis Examples 1 to 6 was used to provide an alkali developability and solvent resistance. On the other hand, the color resists (Comparative Examples 6 and 7) of the (A) copolymers of Comparative Synthesis Examples 1 and 2 (the solvent containing no hydroxyl group having 3 to 10 carbon atoms) were used, and the solvent resistance was insufficient. The alkali developability using the color resist (Comparative Example 6) of the copolymer of Comparative Example 1 (A) was also insufficient. Further, among the compounds of the compound (A-1) (a-3), the color resist of the (A) copolymer of Comparative Synthesis Example 3 was used in the case where the content of the compound (A-2) was 55 mol% (Comparative) The alkali developability of Example 8) was good, and solvent resistance was inadequate. The color resist (Comparative Example 9) of the (A) copolymer of Comparative Synthesis Example 4 containing no compound (A-1) was used, and the solvent resistance was good, and the alkali developability was insufficient. The color developability (Comparative Example 10) of the (A) copolymer of Comparative Synthesis Example 5 containing no compound (A-2) was good, but the solvent resistance was insufficient. [Industrial availability]

In the present invention, it is possible to provide a resin composition for a color filter which is excellent in sensitivity and developability and which is excellent in solvent resistance. Further, the present invention provides a color filter having a color pattern of excellent solvent resistance. Further, since the color filter of the present invention has high brightness and high reliability, it is suitable as an organic EL display device, a liquid crystal display device, or a color filter built in a solid-state image element.

1‧‧‧Substrate

2‧‧‧ pixels

3‧‧‧Black matrix

4‧‧‧Protective film

Fig. 1 is a schematic cross-sectional view showing a color filter according to an embodiment of the present invention.

Claims (5)

A resin composition for a color filter, comprising: (A) a constituent unit (a-1) derived from a polymerizable unsaturated compound having an acid group, and a constituent unit represented by the following formula (1) ( A-2) and a copolymer of a constituent unit (a-3) derived from another polymerizable unsaturated compound, which is 1 mol% to 50 mol% when the total of the total constituent units is 100 mol%. % of the constituent unit (a-2), a copolymer having a weight average molecular weight of 1,000 to 50,000 and a molecular weight distribution (Mw/Mn) of 1.5 to 3.0, and (B) a solvent containing a hydroxyl group solvent having 3 to 10 carbon atoms, (C) a reactive diluent, (D) a photopolymerization initiator, and (E) a colorant; (In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; n is an integer of 1 to 10, but at least one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms). The resin composition for a color filter according to claim 1, wherein the acid group of the structural unit (a-1) is a carboxyl group, and the (A) copolymer is a structural unit containing 10 mol% to 50 mol%. (a-1), and the acid value of the above (A) copolymer is from 20 KOHmg/g to 300 KOHmg/g. The resin composition for a color filter according to claim 1 or 2, wherein the content of the (A) copolymer is from 5 parts by mass to 85 parts by mass, based on 100 parts by mass of the total of the components of the solvent (B). The content of the (C) reactive diluent is 5 parts by mass to 85 parts by mass, the content of the (D) photopolymerization initiator is 0.1 parts by mass to 30 parts by mass, and the content of the (E) coloring agent is 5 Parts by mass to 75 parts by mass. A color filter characterized by having a color pattern formed by the resin composition for a color filter according to any one of the above 1 to 3. A method for producing a resin composition for a color filter comprising a polymerizable unsaturated compound having an acid group (A-1) in the presence of a solvent (B), and (A-2) (2) After the copolymerization of the compound represented by the compound and (A-3) other polymerizable unsaturated compound, (C) reactive diluent, (D) photopolymerization initiator and (E) are added. a coloring agent and a mixing step, wherein when the total of the (A-1) compound, the (A-2) compound, and the (A-3) compound is 100 mol%, the monomer mixture contains 1 mol. % to 50% by mole of the compound (A-2), and (B) the solvent is a solvent containing a hydroxyl group having 3 to 10 carbon atoms. (In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; n is an integer of 1 to 10, but at least one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms).