KR20030026889A - Resin composition - Google Patents

Abstract

PURPOSE: A resin composition containing a polycarboxylic acid and cured products thereof are provided to obtain a photosensitive resin composition presenting a high resolution. CONSTITUTION: The resin composition comprises a reaction product of (a) an epoxy compound having at least two epoxy groups in the molecule and (b) a polybasic carboxylic acid. In particular, the epoxy compound (a) is represented by the formula 1: wherein each of R1 and R2 independently represents a hydrogen atom, an alkyl group or a halogen atom, X represents a single bond, ketone group, sulfonate group, methylene group or the like, R3 represents an alkylene group, R4 represents a hydrogen atom, an alkyl group or a glycidyl group, m is an integer of 0 to 5, and n is an integer of 0 to 10.

Description

Resin composition {RESIN COMPOSITION}

This invention relates to the resin composition containing polycarboxylic acid resin, and its hardened | cured material. In particular, it relates to the photosensitive resin composition used suitably for the coloring photosensitive resin composition for color filters, the protective film for color filters, the spacer for color filters, the interlayer insulation film for color filters, etc.

The colored photosensitive resin composition containing alkali-soluble resin, a pigment, and a photoinitiator is widely used for manufacture of the color filter which is an element which comprises a color liquid crystal display device, a color solid-state imaging device, etc. As a method of manufacturing a color filter using such colored photosensitive resin composition, the layer 1 which consists of colored photosensitive resin composition, for example is formed in the surface of the board | substrate 2 (FIG. 1 (a)), and this layer (1) The method of developing after irradiating and exposing the light ray 4 through the photomask 3 (FIG. 1 (b)) is known. In the colored photosensitive resin composition layer 1, the light non-irradiated area | region 11 to which the light ray 4 was not irradiated at the time of exposure is removed by image development, and the light irradiation area 12 to which the light ray was irradiated remains without being removed. A black matrix or pixel 5 is formed (Fig. 1 (c)). In order to improve the mechanical strength of the formed black matrix or pixel, heat treatment is usually performed after development. By repeating the above operation while changing the color of the pigment contained in the colored photosensitive resin composition, the black matrix 5BM and the pixels 5R, 5G and 5B of the colors corresponding to the three primary colors can be formed sequentially, The color filter 6 can be obtained (FIG. 2).

In such a manufacturing method, in order to form a finer black matrix or a finer, higher transmissive color pixel, it is preferable to use a pigment having a small particle diameter as a pigment contained in the colored photosensitive resin composition. Moreover, in order to form a thinner black matrix and color pixel, it is necessary to raise the density | concentration of the pigment contained in a coloring photosensitive resin composition.

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel resin composition containing a polycarboxylic acid resin and a cured product thereof, and to provide a high resolution even when a high concentration of a photosensitive resin composition, particularly a pigment having a small particle system, is used. It is providing the coloring photosensitive resin composition which can obtain.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to satisfy such a requirement, the present inventors have comprised the resin composition characterized by containing (a) the reactant of the epoxy compound which has at least 2 or more epoxy groups in a molecule | numerator, and (b) polybasic carboxylic acid, or It further contains a polycarboxylic acid resin obtained by reacting (a) a reactant of an epoxy compound having at least two or more epoxy groups in a molecule with (b) a polybasic carboxylic acid, and (c) a polybasic carboxylic acid or an anhydride thereof. The resin composition characterized by the above-mentioned has found that the said problem can be improved, and came to this invention.

The present invention provides a resin composition comprising (a) a reactant of an epoxy compound having at least two or more epoxy groups in a molecule with (b) a polybasic carboxylic acid (hereinafter sometimes referred to as [A1]). It is.

The present invention also provides a polycar obtained by reacting (a) a reactant of an epoxy compound having at least two or more epoxy groups in a molecule with (b) a polybasic carboxylic acid, and (c) a polybasic carboxylic acid or an anhydride thereof. The resin composition characterized by further containing an acid resin (it may be represented below [A2]).

This invention also provides the photosensitive resin composition containing the addition-polymerizable compound which has at least 1 [A1] and / or [A2], and [B] ethylenically unsaturated bond, a [C] photoinitiator, and a [D] solvent. .

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows the process of forming a pixel and a black matrix on a board | substrate using a coloring photosensitive resin composition.

2 is a schematic diagram partially showing an example of a color filter;

<Explanation of symbols for main parts of drawing>

1: coloring photosensitive resin composition layer

2: substrate

3: mask pattern

4: rays

5: pixel, black matrix

6: color filter

31: glass plate

32: light shielding layer

5R, 5G, 5B: Color Pixels

5BM: Black Matrix

Among the reactants of (a) an epoxy compound having at least two or more epoxy groups in the molecule and (b) a polybasic carboxylic acid, the epoxy compound represented by the following general formula (1) and (b) a polybasic carboxyl are preferably used in the present invention. Can be obtained as a mountain.

Moreover, it is obtained by reacting (a) the reactant of the epoxy compound which has an epoxy group with at least 2 or more in an molecule | numerator used by this invention, (b) polybasic carboxylic acid, and (c) polybasic carboxylic acid or its anhydride. Preferred among the polycarboxylic acid resins can be obtained by reacting an epoxy compound represented by the following formula (1) with (b) a polybasic carboxylic acid, and (c) a polybasic carboxylic acid or an anhydride thereof.

The epoxy compound of the following formula (1) can be obtained by a known method. For example, it can be obtained by reacting the corresponding diol component with an appropriate amount of epichlorohydrin.

[Formula 1]

Wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or a halogen atom, X represents a single bond or a divalent moiety represented by any one of the following Formulas I-1 to I-8, and R3 represents an alkylene group R4 represents a hydrogen atom, an alkyl group, or a glycidyl group. m represents the integer of 0-5, n represents the integer of 0-10. When n is plural, R1 may be same or different, R2 may be same or different, R3 may be same or different, and R4 may be same or different.

[Formulas I-1 to I-8]

In the epoxy compound (1), examples of the alkyl group in R1 and R2 include an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. Can be mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, for example.

As an alkylene group in R <3>, a C1-C10 alkylene group, such as a methylene group, ethylene group, trimethylene group, tetramethylene group, is mentioned, for example. The alkylene group may have a substituent. As a substituent, a C1-C10 alkyl group, a C1-C10 alkoxyl group, a C6-C15 aryl group, a C7-C15 aralkyl group, a C2-C10 group, for example may have a hydroxyl group, a halogen atom, and a hydroxyl group Alkenyl group, C2-C10 acyloxy group, etc. are mentioned.

Here, as a halogen atom, a chlorine atom, a bromine atom, etc. are mentioned, for example. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group and propyl group. Examples of the alkyl group in the case of being substituted with hydroxyl group include hydroxyethyl group and hydroxypropyl group.

As a C1-C10 alkoxyl group, a methoxy group, an ethoxy group, a propyloxy group, butoxy group etc. are mentioned, for example. As a C6-C15 aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example. Examples of the aralkyl group having 7 to 15 carbon atoms include benzyl group and phenylethyl group. As a C2-C10 alkenyl group, a vinyl group, an allyl group, etc. are mentioned, for example. As a C2-C10 acyloxy group, an acetyloxy group, a benzoyloxy group, etc. are mentioned, for example.

The diol component for inducing the epoxy compound is a bisphenol compound represented by the following general formula (III). Here, as a bisphenol compound, 4,4'-biphenol, 3,3'-biphenol etc. are mentioned specifically as a bisphenol compound whose X is a single bond, for example.

[Formula III]

In the formula, R1, R2 and X each represent the same meaning as above.

X is a bisphenol compound represented by the formula (I-1) including 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- Bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluoro Phenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, and the like.

X is a bisphenol compound represented by the formula (I-2), which includes bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4-hydroxy-3,5- Dichlorophenyl) ketone and the like.

X is a bisphenol compound represented by the formula (I-3), including bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5- Dichlorophenyl) sulfone and the like.

X is a bisphenol compound represented by the formula (I-4), which includes bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy Hydroxy-3,5-dichlorophenyl) hexafluoropropane etc. are mentioned.

X is a bisphenol compound represented by the formula (I-5), and includes bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane etc. are mentioned.

X is a bisphenol compound represented by the formula (I-6), wherein bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5- Dibromophenyl) methane, phenol novolac, cresol novolac and the like.

X is a bisphenol compound represented by the formula (I-7): 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) Propane and the like.

X is a bisphenol compound represented by the formula (I-8), which includes bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether and bis (4-hydroxy-3,5- Dichlorophenyl) ether, and the like.

These bisphenol compounds are used individually or in combination of 2 types or more, respectively.

In such an epoxy compound (1), X is preferably a divalent residue represented by the formula (I-1).

Among these epoxy compounds (1), R1, R2 and R4 are hydrogen atoms, m = 0, X is a divalent residue represented by the formula (I-1), R1 is a methyl group, R2 and R4 are hydrogen atoms , m = 0, X is a divalent residue represented by formula (I-1), R 1, R 2 and R 4 are hydrogen atoms, R 3 is an ethylene group, X is a divalent residue represented by formula (I-1) A compound wherein R1, R2 and R4 are hydrogen atoms, R3 is an alkylene group represented by -C (CH ₃ ) H-CH _2- , X is a divalent residue represented by the formula (I-1), and R1 is a methyl group And a compound in which R2 and R4 are hydrogen atoms, R3 is an ethylene group, and X is a divalent residue represented by the formula (I-1).

Next, (b) polybasic carboxylic acid reacted with the epoxy compound represented by General formula (1) is demonstrated. (b) As the polybasic carboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl endmethylene tetra Hydrophthalic acid, chloric acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonedicarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyldicarboxylic acid, biphenyl The compound which has 2 or more carboxyl groups, such as ether tetracarboxylic acid, is mentioned.

You may use these individually or in combination of 2 or more types, respectively. Preferred polybasic carboxylic acids are polybasic carboxylic acids having unsaturated double bonds, and examples thereof include compounds having two or more carboxyl groups such as maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, chloric acid and the like.

The reaction is carried out, for example, by a method of reacting the epoxy resin and the polybasic acid in a solvent or in a solvent (diluent).

Examples of the solvent include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, 3-methoxybutyl acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, It is preferable to use solvents, such as 2-heptanone, ethyl methyl ketone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol methyl ether acetate.

Moreover, in reaction of an epoxy compound and (b) polybasic carboxylic acid, in order to accelerate | stimulate reaction, it is preferable to use a catalyst. Examples of the catalyst include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, chromium octanoate, zirconium octanoate, etc. Can be. The amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction raw material mixture.

Moreover, in order to prevent the superposition | polymerization during reaction, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like. The amount used is preferably 0.01 to 1% by weight based on the reaction raw material mixture.

Reaction temperature becomes like this. Preferably it is 60-150 degreeC. In addition, the reaction time is preferably 5 to 60 hours.

The usage-amount ratio of an epoxy compound and a polybasic acid is about 5 mol-95 mol normally with respect to 100 mol of total amounts of an epoxy compound and polybasic acid, Preferably it is about 10-90 mol.

The reactant obtained by the reaction of the epoxy compound with the (b) polybasic carboxylic acid may be extracted from the reaction mixture obtained and used as the photosensitive resin composition of the present invention, or may be purified after extraction, and extracted from the reaction mixture. It may be used without changing the state contained in the reaction mixture.

Next, the polybasic carboxylic acid of (c) used for manufacture of the polycarboxylic acid resin in this invention, and its anhydride are demonstrated. The polybasic carboxylic acid of (c) also has the same thing as the polybasic carboxylic acid mentioned in said (b), These polybasic carboxylic acid or its acid anhydride can be used.

The polybasic carboxylic acids of (b) and (c) may be the same or different.

The polycarboxylic acid resin in the present invention is a reaction product of (a) an epoxy compound having at least two or more epoxy groups in a molecule with (b) a polybasic carboxylic acid, and (c) a polybasic carboxylic acid or an anhydride thereof. It can be obtained by reacting.

The reaction ratio of (a) and (b) and (c) is generally 5 mol of the reactant of (a) and (b) and the reactant of (a) and (b) per 100 moles of the total amount of (c). It is about -95 mol, Preferably it is about 10-90 mol.

The reaction is carried out by a method of reacting the reactant (hereinafter sometimes referred to as carboxylic acid-modified epoxy resin) and (c) of (a) and (b) in a solvent or in a solvent, for example.

Examples of the solvent include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, 3-methoxybutyl acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are used. These solvents are used individually or in combination of 2 or more types, respectively, and the use quantity is 0.5 weight part or more and 20 weight part or less normally with respect to 1 weight part of carboxylic acid modified epoxy resins.

In order to make a carboxylic acid modified epoxy resin and polybasic acid or its acid anhydride react, what is necessary is just to mix a solvent, a carboxylic acid modified epoxy resin, polybasic acid, or its acid anhydride, and reaction temperature is 20 degreeC or more and 200 degrees C or less normally.

The polycarboxylic acid resin may be extracted from the obtained reaction mixture to be used as the colored photosensitive resin composition of the present invention, or may be used after being extracted and purified. The polycarboxylic acid resin may be used as it is in the reaction mixture without being extracted from the reaction mixture. Also good.

Such polycarboxylic acid resin has the weight average molecular weight of polystyrene conversion normally 1000 or more and 50000 or less, Preferably it is 1500 or more and 20000 or less. Moreover, it is preferable that an acid value is 50 or more and 200 or less, More preferably, it is 70 or more and 170 or less.

The ratio of [A1] in the photosensitive resin composition of this invention containing [A1] is 1% or more and 80% or less normally in mass fraction with respect to solid content of the photosensitive resin composition, Preferably it is 3% or more and 60 % Or less

In the photosensitive resin composition of this invention containing [A2], [A2] polycarboxylic acid resin is used as a binder and the usage-amount is normally 10% or more by mass fraction with respect to solid content of a coloring photosensitive resin composition. 80% or less, Preferably they are 20% or more and 70% or less.

Next, the compound which can be addition-polymerized which has at least 1 [B] ethylenically unsaturated bond is demonstrated.

As an ethylenically unsaturated compound, the compound which has 1 or more, preferably 2 or more of polymerizable carbon-carbon unsaturated bonds at the terminal is mentioned, For example, ester of unsaturated carboxylic acid and aliphatic polyhydric alcohol, unsaturated carboxylic acid, and aliphatic Amide with polyhydric amine, etc. are mentioned. Each of these compounds may be a monomer or a prepolymer, i.e., a dimer, a trimer, or a tetramer or more of an oligomer. Moreover, a mixture may be sufficient.

Here, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc. are mentioned, for example.

As an example of the ester monomer of an aliphatic polyhydric alcohol compound and unsaturated carboxylic acid, As an acrylate ester, For example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3- butanediol diacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1,4- Cyclohexanediol acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate,LE, and the like carbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyl oxyethyl) isocyanurate, polyester acrylate oligomer.

As methacrylic acid ester, for example, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol di Methacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, Dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (meta Krilloxy ethoxy) phenyl] dimethyl methane etc. are mentioned.

As the itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol Tetraitaconate, and the like.

Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

As isocrotonic acid ester, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. are mentioned.

Examples of the maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramalate, and the like. The mixture of these ester monomers is also mentioned.

As an example of the amide monomer of an aliphatic polyhydric amine compound and unsaturated carboxylic acid, For example, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis-meth Krylamide, diethylene triamine trisacrylamide, xylene bis acrylamide, xylene bis methacrylamide, etc. are mentioned.

The ethylenically unsaturated compound may be a vinylurethane compound obtained by adding a vinyl monomer represented by the following formula (2) to a polyisocyanate compound having two or more isocyanate groups in a molecule (Japanese Patent Publication No. 48-41708). Moreover, urethane acrylates (Japanese Patent Laid-Open No. 51-37193), polyester acrylates (Japanese Patent Laid-Open No. 48-64183, Japanese Patent Laid-Open No. 49-43191, Japanese Patent Laid-Open Fire extinguishing No. 52-30490), a photocurable monomer (Japan Adhesion Society, Vol. 20, No. 7, pp. 300 to 308 (1984)), or the like.

[Formula 2]

In the above formula, R 10 and R 11 each independently represent a hydrogen atom or a methyl group.

When using such an ethylenically unsaturated compound, the usage-amount is normally 50% or less in mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 40% or less, and usually 5% or more, Preferably it is 10% or more. .

Next, the photopolymerization initiator [C] will be described.

As a photoinitiator, an acetophenone type photoinitiator, a benzoin type photoinitiator, a benzophenone type photoinitiator, a thioxanthone type photoinitiator, a triazine type photoinitiator, an oxadiazole type photoinitiator, etc. can be used.

As an acetophenone type photoinitiator, diethoxy acetophenone, 2-hydroxy-2- methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-2- methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- And oligomers of on.

As a benzoin type photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the benzophenone-based photopolymerization initiators include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butyl Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As a thioxanthone type photoinitiator, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- Propoxy thioxanthone etc. are mentioned.

Examples of the triazine-based photopolymerization initiator include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

Examples of the oxadiazole photopolymerization initiators include 5- (p-methoxyphenyl) -2-trichloromethyloxadiazole, 5- (p-butoxystyryl) -2-trichloromethyloxadiazole, and the like. have.

As the photopolymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxylate, bispentadienyltitanium-di (penta Titanocene compounds, such as fluorophenyl), etc. can also be used.

Preferred among these photopolymerization initiators are triazine photopolymerization initiators and oxadiazole photopolymerization initiators.

These photoinitiators are used individually or in combination of 2 types or more, respectively. In the case of the resin composition characterized by containing [A1], the usage-amount is normally 0.5% or more and 20% or less by mass fraction with respect to solid content of the photosensitive resin composition. Preferably they are 1% or more and 10% or less. Moreover, in the case of the resin composition characterized by containing [A2], the usage-amount is normally 3 weight part or more and 60 weight part or less per 100 weight part of this [A2]. If it is less than 3 weight part, there exists a tendency for a sensitivity to fall, Preferably it is 5 weight part or more. When it exceeds 60 weight part, there exists a tendency for the intensity | strength of a coloring photosensitive resin composition layer to fall, Preferably it is 40 weight part or less.

The photosensitive resin composition of this invention may contain the photoinitiator adjuvant. The photopolymerization initiation aid is used to promote the photopolymerization reaction.

Examples of the photopolymerization initiation aid include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate. , Benzoic acid 2-dimethylaminoethyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Ketone of Michler), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, etc. are mentioned.

These photoinitiators can be used individually or in combination of 2 types or more, respectively. When using such a photoinitiator, the usage-amount is normally 0.01 mol or more and 10 mol or less with respect to 1 mol of photoinitiators.

Next, the solvent [D] will be described.

Examples of the solvent used in the present invention include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3 Ethyl oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate Methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate , 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4- Esters such as methoxypentyl acetate and 4-methyl-4-methoxypentyl acetate; Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Ethers such as glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Aromatic hydrocarbons, such as toluene and xylene, etc. are mentioned.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, 3-methoxybutyl acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate and 3-methoxypropionic acid Methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, etc. are mentioned.

These solvents are used individually or in mixture of 2 or more types, respectively, The usage-amount is used so that solid content concentration of a coloring photosensitive resin composition may be in the range of 2 to 50% by mass fraction.

Next, when using this invention as a coloring photosensitive resin composition, the [E] pigment used is demonstrated.

The pigment used for this invention may be an inorganic pigment, or an organic pigment may be sufficient.

As an inorganic pigment, metal compounds, such as a metal oxide and a metal complex salt, are mentioned, for example. Examples of the metal include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony. The metal oxide and the metal complex salt may be oxides or complex salts of these metals alone, or two or more complex oxides or complex salts of these metals.

Examples of the organic pigments include compounds classified as Pigments by Color Index (published by The Society of Dyers and Colourists). Can be.

Examples of such organic pigments include CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, and CI Pigment. Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI pigment yellow 1 08, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119 CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pig Yellow organic pigments, such as pigment yellow 155, CI pigment yellow 156, CI pigment yellow 166, CI pigment yellow 168, CI pigment yellow 175,

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pig Orange organic pigments such as pigment orange 51, CI pigment orange 61, CI pigment orange 63, CI pigment orange 64, CI pigment orange 71, CI pigment orange 73,

CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38, etc. Violet organic pigments,

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, C. I. Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57 CI Pigment Red 57: 1, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigtail TR Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150 CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment CI 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216 CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, Red organic pigments, such as CI pigment red 255, CI pigment red 264, CI pigment red 265,

Blue organic pigments such as C. I. Pigment Blue 15, C. I. Pigment Blue 15: 3, C. I. Pigment Blue 15: 4, C. I. Pigment Blue 15: 6, C. Pigment Blue 60,

Green organic pigments, such as C. I. pigment green 7 and C. I. pigment green 36,

Brown organic pigments such as C. I. pigment brown 23, C. I. pigment brown 25,

C. I. Black organic pigments, such as pigment black 1 and pigment black 7, etc. are mentioned.

These organic pigments are used individually or in combination of 2 types or more, respectively, according to the color of the pixel made into the objective.

Among these organic pigments, preferred organic pigments include CI Pigment Yellow 117, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 150, CI, for example, in a yellow organic pigment. Pigment yellow 155, CI pigment yellow 185,

As a red organic pigment, C. I. pigment red 166, C. I. pigment red 178, C. I. pigment red 209, C. I. pigment red 242, C. I. pigment red 254, etc.,

Examples of the black organic pigments include CI Pigment Black 1 and Pigment Black 7, and more preferably CI Pigment Yellow 150, CI Pigment Red 254, CI Pigment Black 1, and Pigment. Black 7 etc.

Moreover, as a black pigment used by the coloring photosensitive resin composition used in order to manufacture a black matrix, For example, carbon black, graphite (Japanese Unexamined-Japanese-Patent No. 5-311109, Japanese Unexamined-Japanese-Patent No. 6-11613, etc.), Azo black pigments (Japanese Patent Laid-Open No. 2-216102) and the like can be used. Moreover, black organic pigments, such as said C. I. pigment black 1 and pigment black 7, etc. can be used.

In addition, these black pigments include carbon black coated with a resin as described in Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969, and Japanese Patent Application Laid-Open No. 2001-106938. It can also be used. Moreover, the black pigment coat | covered with the inorganic substance as described in Unexamined-Japanese-Patent No. 2001-115043 can also be used.

The average particle diameter of a pigment is 0.005 micrometer or more and 0.2 micrometer or less normally, Preferably they are 0.01 micrometer or more and 0.1 micrometer or less. The pigment of such a particle diameter can be obtained by atomizing by normal methods, such as the kneader method, a sulfuric acid method, and an alkali reduction dissolution method, for example. The surface of the pigment may be modified (Japanese Patent Laid-Open No. 8-259876, etc.).

The usage-amount of the pigment in the coloring photosensitive resin composition of this invention is 15% or more and 60% or less by mass fraction with respect to solid content of a coloring photosensitive resin composition normally, Preferably it is 25% or more. When it exceeds 60%, it may become difficult to form a black matrix and a pixel in a target pattern, Preferably it is 50% or less.

The photosensitive resin composition of this invention containing [A1] can use the same binder resin as what is used for a normal photosensitive resin composition as binder resin. In the photosensitive resin composition of this invention containing [A2], although polycarboxylic acid resin [A2] is used as a binder, even if it uses together the same binder resin as used for a normal photosensitive resin composition with [A2], good.

The binder resin imparts alkali solubility to the unexposed coating film, and may be various kinds used in this field. For example, the epoxy resin of Unexamined-Japanese-Patent No. 2878486, Unexamined-Japanese-Patent No. 9-325494, and Unexamined-Japanese-Patent No. 9-40745, and a reactant of unsaturated monocarboxylic acid and polybasic carboxylic anhydride are Unsaturated group containing polycarboxylic acid resin, (meth) acrylic-type resin, etc. can be used. Especially, it is preferable that binder resin is an alkali-soluble copolymer which has a carboxyl group.

As an alkali-soluble polymer which has a carboxyl group, especially the copolymer of a carboxyl group-containing monomer and another monomer which can be copolymerized to it is used preferably.

The carboxyl group-containing monomer may be an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as unsaturated monocarboxylic acid or unsaturated dicarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, α-cro Unsaturated monocarboxylic acids such as acrylic acid and cinnamic acid; Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Trivalent or higher unsaturated polyvalent carboxylic acid or its anhydrides; Succinate mono (2-acryloyloxyethyl), succinate mono (2-methacryloyloxyethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl) Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyhydric carboxylic acid; Mono (meth) acrylates of both terminal dicarboxy polymers, such as (omega) -carboxypolycaprolactone monoacrylate and (omega) -carboxypolycaprolactone monomethacrylate, etc. are mentioned. These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types.

The monomer copolymerizable with these carboxyl group-containing monomers is a compound which has a polymerizable unsaturated bond. Specifically, for example, styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy Styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as indene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy tree Ethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glucol methacrylate, isobornyl acrylate, isobornyl Methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, oxetane acrylate, oxetane methacrylate, unsaturated carboxylic acid esters and the like;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Monoacryloyl group or monomethacryloyl group at the terminal of polymer molecular chains, such as polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, and polysiloxane Macro monomers to have are mentioned.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types. In this copolymer, the carboxyl group-containing monomer is preferably used in a molar ratio in the copolymerization component in a range of 10 to 50%, more preferably 15 to 40%.

As a preferable specific example of the alkali-soluble copolymer which has such a carboxyl group, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxy Ethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macro monomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethylmethacryl Late macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macro monomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macro monomer copolymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / amber acid Mono (2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monoacid mono (2-acryloyloxyethyl) / styrene / allyl (meth ) Acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer, etc. are mentioned.

As a more preferable specific example, benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, methyl methacrylate / methacrylic acid copolymer, methyl methacrylate / methacrylic acid / styrene And copolymers.

The polystyrene reduced weight average molecular weight of these copolymer resins is preferably in the range of 3,000 to 400,000, and more preferably in the range of 5,000 to 100,000. Further, the acid value is preferably 30 to 250, more preferably in the range of 60 to 180.

In the photosensitive resin composition of this invention containing [A1], 10-70 weight% is preferable with respect to the total solid component of a composition, and, as for the usage-amount of binder resin, 20-60 weight% is more preferable.

In the photosensitive resin composition of this invention containing [A2], the weight ratio (binder resin / ethylenic) of the total amount of binder resin used together with [A2], and the addition-polymerizable compound which has at least 1 [B] ethylenically unsaturated bond. It is preferable that an unsaturated bond compound) is 1.5 or more and 5 or less. More preferable weight ratio is 2 or more and 4 or less.

In addition, a small amount of thermal polymerization inhibitor can be added in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during production or storage of the photosensitive composition. Suitable thermal polymerization inhibitors include haloquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl- 6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine 1st cerium salt, etc. are mentioned. The amount of the thermal polymerization inhibitor added is preferably about 0.01% by weight to about 5% by weight based on the weight of the whole composition.

If necessary, various additives such as fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like can be added to the composition of the present invention.

Specific examples of these additives include fillers such as glass and alumina; Polymer compounds other than binder polymers such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Surfactants such as nonionic, cationic and anionic systems; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane ; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And aggregation inhibitors such as sodium polyacrylate.

The composition of the present invention can be added with an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid with a molecular weight of 1,000 or less, or an organic amino compound with a molecular weight of 1,000 or less having at least one amino group in the molecule. Specific examples of the carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl zucchinic acid, tetramethyl amber acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoric acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemimeltic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melellophanic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atroic acid, cinnamonic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, kumaric acid and umbelic acid.

As the organic amino compound, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n- Nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, o-methylcyclohexylamine, m-methylcyclohexylamine, p-methylcyclohexylamine, o-ethylcyclohexyl Mono (cyclo) alkylamines such as amine, m-ethylcyclohexylamine and p-ethylcyclohexylamine; Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t Di (cyclo) alkylamines such as -butylamine, di-n-pentylamine, di-n-hexylamine, methyl cyclohexylamine, ethyl cyclohexylamine, dicyclohexylamine; Dimethyl ethylamine, methyl diethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, tri- n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, di Tri (cyclo) alkylamines such as ethyl cyclohexylamine, methyl dicyclohexylamine, ethyl dicyclohexylamine and tricyclohexylamine;

2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino Mono (cyclo) alkanolamines such as -1-cyclohexanol; Diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclohexanol Di (cyclo) alkanolamines such as amines; Triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4-cyclohexanol) Tri (cyclo) alkanolamines such as amines;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2- Cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3- Amino (cyclo) alkanediols such as propanediol and 2-diethylamino-1,3-propanediol; 1-aminocyclopentanmethanol, 4-aminocyclopentanmethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclo Amino group-containing cycloalkanethanols such as hexanemethanol and 4-diethylaminocyclohexanemethanol; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 And aminocarboxylic acids such as -aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the compound in which the amino group is directly bonded to the phenyl group, the compound in which the amino group is bonded to the phenyl group via a carbon chain, and the like, and examples of the compound in which the amino group is directly bonded to the phenyl group include aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, pt-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, Aromatic amines such as N, N-diethylaniline and p-methyl-N, N-dimethylaniline;

aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol; aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol; and aminobenzoic acids (derivatives) such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

In this invention, an organic carboxylic acid and an organic amino compound can be used individually or in mixture of 2 or more types. The usage-amount of the organic carboxylic acid and organic amino compound in this invention is 0.001-15 weight% of the whole composition normally, Preferably it is 0.01-10 weight% of the whole composition.

The resin composition of this invention is apply | coated to a board | substrate by application | coating methods, such as rotation coating, casting | coating application | coating, roll coating, etc., forming a radiation sensitive composition layer, exposing through a predetermined | prescribed mask pattern, and developing by developing solution. Form a colored pattern. As radiation used at this time, especially ultraviolet rays, such as g line | wire, h line | wire, i line | wire, are used preferably. The coating thickness is a film thickness after drying, which is usually 0.1 to 10 µm, preferably 0.2 to 5.0 µm, particularly preferably 0.2 to 3.0 µm.

As a board | substrate used when forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like as desired.

As the developing solution, any composition can be used as long as it dissolves the radiation sensitive composition of the present invention and does not dissolve the radiation irradiation section. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. As an organic solvent, the above-mentioned solvent used when preparing the resin composition of this invention is mentioned.

As alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole , Alkaline compounds such as piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene have a concentration of 0.01 to 10% by weight, preferably 0.01 to 1% by weight An alkaline aqueous solution dissolved so as to be used is used. An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer.

The developing conditions can apply various conditions. For example, as the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (adhesive) developing method, or the like can be applied. Generally developing temperature can be set in 10 degreeC-40 degreeC. The developing time is generally set to 10 seconds to 300 seconds. Moreover, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes with water after image development.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is of course not limited by these. In the examples,% and parts indicating content to the amount of use are based on mass unless otherwise specified.

Synthesis Example 1

69.4 g of bisphenol fluorenediglycidyl ether, 29.3 g of itaconic acid, 0.13 g of triethylbenzylammonium chloride, 0.27 g of tetraethylammonium bromide, 0.029 g of metoquinone, and propylene glycol monomethyl in a 300 ml flask with four inlets. 27 g of ether acetate was prepared and prepared as a homogeneous solution at 150 ° C. to 160 ° C. under heat and stirring, followed by reaction at 120 ° C. for 12 hours to obtain a clear pale yellow viscous liquid.

71.7 g of propylene glycol monomethyl ether acetate was further added to the obtained viscous liquid to adjust the solid content concentration to 50% by weight. This is called compound P1.

Synthesis Example 2

80 g of Compound P1 obtained in Synthesis Example 1, 12 g of tetrahydrophthalic anhydride, and 12 g of propylene glycol monomethyl ether acetate were prepared and reacted at 105 to 110 ° C. under heating and stirring for 15 hours to give a pale yellow transparent unsaturated group-containing carbohydrate. Acid compound solution Aa was obtained.

Synthesis Example 3

80 g of Compound P1 obtained in Synthesis Example 1, 13.1 g of phthalic anhydride, and 13.1 g of propylene glycol monomethyl ether acetate were prepared and reacted at 105 to 110 ° C. under heating and stirring for 15 hours to give a pale yellow transparent unsaturated group-containing carboxylic acid. Compound solution Ab was obtained.

Synthesis Example 4

69.4 g of bisphenol fluorenediglycidyl ether, 19.5 g of itaconic acid, 0.13 g of triethylbenzyl ammonium chloride, 0.27 g of tetraethylammonium bromide, 0.029 g of metoquinone, and propylene glycol monomethyl in a 300 ml flask with four inlets. 17 g of ether acetate was prepared and prepared as a homogeneous solution at 150 ° C. to 160 ° C. under heating and stirring, followed by reaction at 120 ° C. for 12 hours to obtain a clear pale yellow viscous liquid. 71.9 g of propylene glycol monomethyl ether acetate was further added to the obtained viscous liquid to adjust the solid content concentration to 50% by weight. This is called compound P2.

Synthesis Example 5

80 g of Compound P2 obtained in Synthesis Example 4, 12 g of tetrahydrophthalic anhydride, and 12 g of propylene glycol monomethyl ether acetate were prepared and reacted at 105 to 110 ° C. under heating and stirring for 15 hours to give a pale yellow transparent unsaturated group-containing carbohydrate. Acid compound solution B1 was obtained.

Synthesis Example 6

80 g of Compound P2 obtained in Synthesis Example 4, 13.1 g of phthalic anhydride, and 13.1 g of propylene glycol monomethyl ether acetate were prepared and reacted at 105 to 110 ° C. under heating and stirring for 15 hours to give a pale yellow transparent unsaturated group-containing carboxylic acid. Compound solution B2 was obtained.

Example 1

[Production of Colored Photosensitive Resin Composition]

① 52 parts by mass of a pigment [40 parts by mass of a black pigment (CI pigment black 7) and 12 parts by mass of a dispersant] ② a copolymer of a binder resin benzyl methacrylate with methacrylic acid [content of benzyl methacrylate unit] 77% by silver mole fraction, the content of methacrylic acid units is 23% by mole fraction, the weight average molecular weight is 15000] 32 parts by mass, ③ compound having an ethylenically unsaturated bond [dipentaerythritol hexaacrylate] 6 6 parts by mass of compound P1 synthesized in Synthesis Example 1, 5 parts by mass of photopolymerization initiator [2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine], 374 mass parts of solvents [propylene glycol monomethyl ether acetate] were mixed, and the coloring photosensitive resin composition (black) was obtained.

[Formation of Colored Photosensitive Resin Composition Layer]

The coloring photosensitive resin composition obtained above was apply | coated to the surface of a glass substrate (made by "# 7059" Corning Co., Ltd.) by the spin coat method, it heated at 100 degreeC for 3 minutes, and was dried, and the coloring photosensitive resin composition layer was formed on the board | substrate. The thickness of the coloring photosensitive resin composition layer after this drying was 1.2 micrometers.

[Formation of Colored Pattern (Evaluation of Resolution)]

The ultraviolet-ray was irradiated to the board | substrate with which the coloring photosensitive resin composition layer was formed above with the ultrahigh pressure mercury lamp (a irradiation amount is 400 mJ / cm <2>) through the photomask which has a 7 micrometers L / S (line and space) pattern, and was exposed. The colored photosensitive resin composition layer after exposure was immersed and developed until it was able to obtain a pattern with a developing solution (an aqueous solution containing potassium hydroxide at a mass fraction of 0.004% and containing a nonionic surfactant).

After development, the mixture was washed with water and heated at 230 ° C. for 20 minutes to form a black colored pattern (black matrix) on the substrate 2. When this black matrix was observed with the optical microscope, the 7 micrometers L / S pattern was formed with good reproducibility.

Example 2

In the same manner as in Example 1, except that Compound P2 obtained in Synthesis Example 4 was used instead of the binder resin used in Example 1, a 7 µm L / S pattern was similarly formed with good reproducibility.

Comparative Example 1

① 52 parts by mass of a pigment [40 parts by mass of a black pigment (CI pigment black 7) and 12 parts by mass of a dispersant] ② a copolymer of a binder resin benzyl methacrylate with methacrylic acid [content of benzyl methacrylate unit] 77% by silver mole fraction, the content of methacrylic acid units is 23% by mole fraction, the weight average molecular weight is 15000] 32 parts by mass, ③ compound having an ethylenically unsaturated bond [dipentaerythritol hexaacrylate] 12 4 parts by mass of photopolymerization initiator [4,2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine] and 374 parts by mass of solvent [propylene glycol monomethyl ether acetate] To obtain a colored photosensitive resin composition (black).

The black matrix was observed with an optical microscope in the same manner as in Example 1 except that the substrate on which the colored photosensitive resin composition layer was obtained was used instead of the substrate on which the resin composition layer was formed. Although the coloring pattern of the line width was formed, the coloring pattern below that was not formed with good reproducibility.

Example 3 [Preparation of Colored Photosensitive Resin Composition]

① 52 parts by mass of a pigment (a mixture of 40 parts by mass of black pigment (CI pigment black 7) and 12 parts by mass of a dispersant) ② 32 parts by mass of binder resin (resin solution Aa obtained in Synthesis Example 2) 11 parts by mass of a compound having an ethylenically unsaturated bond and capable of addition polymerization [dipentaerythritol hexaacrylate], a photopolymerization initiator [2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-tri 5.0 mass parts of azine and 374 mass parts of solvents [propylene glycol monomethyl ether acetate] were mixed, and the coloring photosensitive resin composition (black) was obtained.

The coloring photosensitive resin composition layer was formed by the method similar to Example 1 using the coloring photosensitive resin composition obtained above, the black coloring pattern (black matrix) was further formed, and the resolution evaluation was performed. As a result of observing the formed black matrix with an optical microscope, a 7 µm L / S pattern was formed with good reproducibility.

Example 4

In the same manner as in Example 3, except that the resin solution Ab obtained in Synthesis Example 3 was used instead of the binder resin used in Example 3, a 7 µm L / S pattern was similarly formed with good reproducibility.

Example 5

[Production of colored photosensitive resin composition and formation of colored photosensitive resin composition layer]

A colored photosensitive resin composition (black) was obtained in the same manner as in Example 1 except that the resin solution B1 obtained in Synthesis Example 5 was used instead of the binder resin used in Example 3, and the colored photosensitive resin composition layer (thickness 1.2 μm) was obtained. Formed.

[evaluation]

Instead of the board | substrate with which the coloring photosensitive resin composition layer obtained in Example 3 was formed, using the board | substrate with which the coloring photosensitive resin composition layer obtained above was formed, it contains a developing solution [0.04% of potassium hydroxide in mass fraction, and contains a nonionic surfactant. Aqueous solution] was immersed until the pattern could be obtained and developed. Similarly, a 7 µm L / S pattern was formed with good reproducibility.

Example 6

In the same manner as in Example 5 except that the resin solution B2 obtained in Synthesis Example 4 was used instead of the binder resin used in Example 5, a 7 µm L / S pattern was similarly formed with good reproducibility.

Comparative Example 2

Copolymer of benzyl methacrylate with methacrylic acid instead of the binder resin used in Example 5 [Content of benzyl methacrylate unit is 65% in mole fraction, content of methacrylic acid unit is 35% in mole fraction, weight average The molecular weight was adjusted in the same manner as in Example 5 except that the amount of dipentaerythritol hexaacrylate was 22 parts by mass using 21 parts by mass. A colored photosensitive resin composition (black) was obtained and the colored photosensitive resin composition layer (thickness 1.2 micrometers) was formed.

[evaluation]

The black matrix was observed in the same manner as in Example 5 except that the substrate in which the colored photosensitive resin composition layer was obtained was used instead of the substrate in which the colored photosensitive resin composition layer was obtained in Example 5 was used. Although the coloring pattern of this 50 micrometer and the line | wire width exceeding this was formed, the coloring pattern below it was not formed reproducibly.

The novel resin composition containing the polycarboxylic acid resin of this invention and its hardened | cured material are used suitably as a photosensitive resin composition, and especially the coloring photosensitive resin composition containing a pigment can obtain high resolution. It is preferable because high resolution can be obtained even when a pigment having a small particle system is used at a high concentration.

The photosensitive resin composition of this invention is used suitably especially for the coloring photosensitive resin composition for color filters, the protective film for color filters, the spacer for color filters, the interlayer insulation film for color filters, etc.

Claims (10)

A resin composition comprising (a) a reactant of an epoxy compound having at least two or more epoxy groups in a molecule with (b) a polybasic carboxylic acid. The resin composition according to claim 1, wherein (a) an epoxy compound having at least two epoxy groups in the molecule is represented by the following formula (1). Formula 1 Wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or a halogen atom, X represents a single bond or a divalent moiety represented by any one of the following formulas I-1 to I-8, and R 3 represents an alkylene group , R4 represents a hydrogen atom, an alkyl group or a glycidyl group. m represents the integer of 0-5, n represents the integer of 0-10. When n is plural, R1 may be same or different, R2 may be same or different, R3 may be same or different, and R4 may be same or different. Formulas I-1 to I-8 It further contains a polycarboxylic acid resin obtained by reacting (a) a reactant of an epoxy compound having at least two or more epoxy groups in a molecule with (b) a polybasic carboxylic acid, and (c) a polybasic carboxylic acid or an anhydride thereof. Resin composition characterized by the above-mentioned. The resin composition of Claim 3 in which the epoxy compound which has at least 2 or more epoxy groups in (a) molecule | numerator is represented by following General formula (1). Formula 1 Wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or a halogen atom, X represents a single bond or a divalent moiety represented by any one of the following formulas I-1 to I-8, and R 3 represents an alkylene group , R4 represents a hydrogen atom, an alkyl group or a glycidyl group. m represents the integer of 0-5, n represents the integer of 0-10. When n is plural, R1 may be same or different, R2 may be same or different, R3 may be same or different, and R4 may be same or different. Formulas I-1 to I-8 The resin composition according to any one of claims 1 to 4, wherein (b) the polybasic carboxylic acid is a polybasic carboxylic acid having an unsaturated double bond. The resin composition according to claim 5, wherein (b) the polybasic carboxylic acid having an unsaturated double bond is at least one member selected from the group consisting of maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid and chloric acid. [A1] (a) an epoxy compound having at least two epoxy groups in a molecule and (b) a reactant with a polybasic carboxylic acid and / or [A2] an epoxy compound having at least two epoxy groups in a molecule (a) b) an addition-polymerizable compound having at least one polycarboxylic acid resin and [B] ethylenically unsaturated bond obtained by reacting a reactant with a polybasic carboxylic acid and (c) a polybasic carboxylic acid or an anhydride thereof, (C) Photopolymerization initiator and the solvent (D) are contained, The photosensitive resin composition characterized by the above-mentioned. The photosensitive resin composition of Claim 7 which further contains the pigment (E). The photosensitive resin composition of Claim 8 whose [E] pigment is a black pigment which consists of carbon black. Hardened | cured material of the photosensitive resin composition of any one of Claims 7-9.