TW201537297A - Colored photosensitive resin composition and color filter manufactured by the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, more specifically, the present invention relates to a colored photosensitive resin composition which is a composition characterized by including a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, where the colorant includes green pigment of Green Pigment 7, (B) the alkali-soluble resin includes a first resin with epoxy and a second resin with an acid group that can react with the epoxy and has an acid value of 170~300mgKOH/g. Accordingly, the disclosed is capable of reproducing colors in a wider range, in the same time, presenting a higher contrast and brightness, and having excellent coloring performance, patterns formation, image development, developing capability, sensitivity and adhesion.

Description

Colored photosensitive resin composition and color filter made of the same

The present invention relates to a colored photosensitive resin composition and a color filter manufactured therefrom, and more particularly to a display showing high contrast and brightness, and coloring power, pattern formation, developability, sensitivity and A color-sensitive photosensitive resin composition having good adhesion and a color filter made of the composition.

Recently, the liquid crystal display device has attracted attention as a next-generation advanced display element having low power consumption and good portability and high added value.

In such a liquid crystal display device, the active matrix liquid crystal display device is excellent in resolution and animation rendering capability, and the active matrix liquid crystal display device is provided with a thin film transistor, which can be used for each pixel (pixel). Adjust the voltage on (on) / off (off) switching elements.

In general, a liquid crystal display device is an array substrate manufacturing step of forming a thin film transistor and a pixel electrode, and a color filter substrate manufacturing step of forming a color filter and a common electrode, respectively forming an array substrate and a color filter substrate. And completed by a liquid crystal cell step of interposing liquid crystal between the two substrates.

The color filter includes pixels composed of red (R), green (G), and blue (B) colors, and the light passing through the liquid crystal cell passes through the color filter and exhibits a desired hue.

However, recently, with the spread of liquid crystal display devices, their use has expanded to various displays or televisions, and further improvement in color reproducibility has been demanded. In order to respond to the demand, it is required to provide a color filter having a wide color gamut. Especially for TV use, it is required to expand the color gamut more than before.

Moreover, in addition to expanding the color reproduction range, it is also required to improve display quality by high brightness and high contrast. However, the color reproduction range and the transmittance, the color reproduction range, and the contrast ratio are trade-offs. If the color reproduction range is to be expanded, there is a problem that the transmittance and the contrast ratio are lowered.

In connection with this, Korean Patent Publication No. 2005-0014725 proposes a C.I Pigment Green 7 single pigment or a mixed pigment of C.I Pigment Green 7 and C.I Pigment Yellow 150 as a pigment of a green color filter.

However, C.I Pigment Green 7 single pigment does not sufficiently meet the required characteristics, and C.I Pigment Yellow 150 contains environmentally harmful substances and is limited in use. Advanced technical literature

[Patent Document 1] Korean Patent Publication No. 2005-0014725

Problem to be solved by the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a colored photosensitive resin composition which has a wide color reproduction range, exhibits high contrast and brightness, and has good coloring power, pattern formation property, developability, sensitivity and adhesion.

Further, another object of the present invention is to provide a color filter manufactured using a colored photosensitive resin composition, and an image display device comprising the same. Technical means of solving problems

A colored photosensitive resin composition comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent; (A) The colorant includes a green pigment of Pigment Green 7; the (B) alkali-soluble resin (A) contains: a first resin containing an epoxy group; and a second resin containing an epoxy group as described above The acid group of the reaction has an acid value of 170 to 300 mgKOH/g.

2. The colored photosensitive resin composition according to the above 1, wherein the colorant further comprises at least one yellow pigment of Pigment Yellow 129 and Pigment Yellow 139.

3. The color-sensitive photosensitive resin composition according to the above 2, wherein the mass ratio of the colorant to the green pigment to the yellow pigment is from 100:0 to 80:20.

4. The colored photosensitive resin composition according to the above 1, wherein the first resin comprises a resin having a compound having an unsaturated bond and a carboxyl group, and a resin copolymerized with at least one of the following Chemical Formulas 1 to 2;

[Chemical Formula 1]

(wherein R ₁ is hydrogen, or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group with or without a hetero atom; and R ₂ is a single bond, or a carbon number of 1 to 20 with or without a hetero atom; An alkylene group or a cycloalkylene group; the above R ₁ and the aforementioned R ₂ as an alkylene group or a cycloalkylene group may each be further substituted by a hydroxyl group)

[Chemical Formula 2]

(wherein R ₁ is hydrogen, or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group with or without a hetero atom; and R ₂ is a single bond, or a carbon number of 1 to 20 with or without a hetero atom; An alkylene group or a cycloalkylene group; the above R ₁ and the aforementioned R ₂ as an alkylene group or a cycloalkylene group may each be further substituted by a hydroxyl group).

5. The colored photosensitive resin composition according to the above 1, wherein the second resin is one molecule or more selected from the group consisting of a dodecane skeleton and a cyclopentadiene skeleton, and comprises A resin having an unsaturatedly bonded compound, a compound containing an aromatic vinyl group, and a compound containing an acid-acting group capable of ring-opening the epoxy group of the first resin.

6. The colored photosensitive resin composition according to the above 5, wherein the compound containing an acid acting group is at least 1 selected from the group consisting of an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid. Kind of compound.

7. The colored photosensitive resin composition according to the above 1, wherein the second resin is contained in one molecule, and further comprises a resin having a compound having an unsaturated bond and an epoxy group or a compound having an unsaturated bond and a hydroxyl group. .

A color filter produced by the colored photosensitive resin composition as described in any one of the above 1 to 7.

An image display device comprising the color filter of the above 8. Effect of invention

The colored photosensitive resin composition of the present invention contains an epoxy resin comprising: a first resin comprising an epoxy group; and a second resin containing an acid group reactive with the epoxy group; thereby developing property, Sensitivity and adhesion are good.

Further, the colored photosensitive resin composition of the present invention contains Pigment Green 7 as a coloring agent, and has good coloring power and pattern formation property, and may be at least one yellow in a group further comprising Pigment Yellow 129 and Pigment Yellow 139 as needed. In the case of pigments, it reproduces the green color that has not been presented in the past, and it also maintains brightness and contrast excellently.

Form for implementing the invention

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent; and the (A) colorant comprises a green pigment of Pigment Green 7 The (B) alkali-soluble resin (A) contains: a first resin comprising an epoxy group; and a second resin containing an acid group reactive with the epoxy group, and the acid value is 170 to 300 mgKOH/g; whereby the colored photosensitive resin composition of the present invention can have a wide range of color reproduction, and also exhibits high contrast and brightness, and coloring power, pattern formation, developability, sensitivity and density. Good sex.

The invention is described in detail below. Colored photosensitive resin composition The colored photosensitive resin composition of the present invention may comprise (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. Of course, it is not limited to add additional components, such as additives, which are generally used in the field.

<(A) Colorant> Colorant (A) The coloring agent of the present invention contains a green pigment of Pigment Green 7 as an essential component. Pigment green 7 exhibits a green function as a coloring composition, and when used together with the alkali-soluble resin of the present invention described later, it exhibits high brightness and contrast, and good coloring power and pattern formation property.

If desired, as a preferred embodiment of the present invention, the coloring agent of the present invention may further comprise at least one yellow pigment selected from the group consisting of Pigment Yellow 129 and Pigment Yellow 139. Pigment Yellow 129 and Pigment Yellow 139 display a tone adjustment function.

By further adding the above-mentioned specific yellow pigment as a coloring agent, the composition of the present invention can exhibit a wide range of color reproduction in green without using the environmentally harmful substance Pigment Yellow 150, and more excellently display brightness, contrast, and graph. Form formation.

In the present invention, when the yellow pigment is further included, the mass ratio of the green pigment to the yellow pigment is preferably from 100:0 to 80:20. The foregoing range can most significantly exhibit a wide range of color reproduction, high brightness and contrast, and good coloring power.

The coloring agent of the present invention may further contain, in addition to the above pigments, pigments and dyes which will be used in the field without departing from the object of the present invention.

(a1) Pigment The pigment (a1) which can be additionally used in the present invention contains an organic pigment and an inorganic pigment. As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include phthalocyanine (water-soluble azo pigment, insoluble azo pigment), phthalocyanine pigment, quinophthalone pigment, and isoindole. Anthrone pigments, isoporphyrin pigments, anthraquinone pigments, anthraquinone pigments, dioxazine pigments, anthraquinone pigments, diterpene based pigments, pyrimidine pigments, anthrones pigments, indanthrone a pigment, a yellow ketone pigment, a pyranthrone pigment or a diketopyrrolopyrrole pigment.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal-stack salts, and specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. Oxide or composite metal oxide, etc.

In particular, the above-mentioned organic pigments and inorganic pigments are specifically exemplified as a pigment which is classified as a color index (published by The Society of Dyers and Colourists), and more specifically, a pigment having the following color index (CI) number is exemplified. However, it is not necessarily limited to such pigments.

In the pigment used in the pigment dispersion composition of the present invention, an organic pigment or an inorganic pigment which is generally used in the field can be used, and these pigments can be used alone or in combination of two or more.

The pigment may be subjected to a treatment such as a resin treatment, a surface treatment such as a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of a pigment surface by a polymer compound or the like, and a sulfuric acid micronization method. The micronization treatment, the organic solvent for removing impurities, the washing treatment by water, the ion exchange method, the plasma impurity removal treatment, and the like.

Specific examples of the pigments include: CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, 173, 180 and 185; CI Pigment Orange 13, 13, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71; CI Pigment Red 9, 97, 105, 122, 123 , 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 32, 33, 36 and 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 64, and 76; CI Pigment Green 10, 15, 25, 36, 47, and 58; and CI Pigment Brown 28 and the like.

It is preferred to use a pigment dispersion liquid in which the particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the pigment particle diameter is a method of dispersing a pigment dispersion liquid, and the like. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

In the colored photosensitive resin composition of the present invention, the above (a1) pigment can be contained in the form of a pigment dispersion composition.

The pigment dispersion composition contains (a1) a pigment, (a2) a dispersant, (a3) a dispersing aid, and (a4) a dispersing solvent; and (a5) a dispersing resin may be added for storage stability and easy dispersion.

Further, the pigment (a1) may be contained in an amount of from 20 to 90% by mass, more preferably from 30 to 70% by mass, based on the total mass of the solid matter in the pigment dispersion composition. When the content of the pigment is not included in the above range, the viscosity is high, the storage stability is poor, the dispersion efficiency is low, and the light-dark ratio is also adversely affected.

(a2) Dispersant The dispersant is added for the anti-aggregation and stability of the pigment, and the materials generally used in the field can be used without limitation. The dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate dispersant), and the acrylate dispersant contains butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate. (DMAEMA). The commercially available product of the acrylic dispersant may, for example, be DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, and the acrylate-based dispersant may be used alone or in combination of two or more. use.

The dispersant of the present invention may use other resin type pigment dispersants in addition to the above acrylate dispersant. The above-mentioned other resin type pigment dispersing agents include conventional resin type pigment dispersing agents, and in particular, polyurethane, polycarboxylate represented by polyacrylate, unsaturated polyamine, polycarboxylic acid, polycarboxylic acid An amine salt, an ammonium salt of a polycarboxy acid, an alkylamine salt of a polycarboxy acid, a polyoxyalkylene oxide, a long-chain polyamine phthalamide phosphate, a hydroxy-substituted polycarboxylate or a modified substance thereof. A guanamine or a salt thereof formed by reacting a polyester having a free carboxyl group with a poly(lower alkylenimine), a (meth)acrylic acid-styrene copolymer, or a (meth)acrylic acid-(meth)acrylic acid a water-soluble resin or a water-soluble polymer compound such as an ester copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol or a polyvinylpyrrolidone; a polyester; a modified polyacrylate; an ethylene oxide/propylene An additional product of an oxide, a phthalate ester, or the like.

As a commercial product of the above-mentioned resin type pigment dispersant, the cationic resin dispersant may, for example, be BYK-Chemie: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA -4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Lubirzol trade name: SOLSPERS- 24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemicals trade name: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto trade name: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha Chemical: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.

The dispersant is contained in an amount of from 5 to 60 parts by mass, more preferably from 15 to 50 parts by mass, based on 100 parts by mass of the pigment in the colorant. When the amount of the dispersant exceeds 60 parts by mass, the viscosity becomes high, and when it is less than 5 parts by mass, the pigment fine particles are difficult to be formed, or the gelation after dispersion or the like is caused.

In addition to the above-mentioned dispersing agent, a surfactant such as a cationic, anionic, nonionic, amphoteric, polyester or polyamine may be used as a dispersing agent; these may be used alone or in combination of two or more. To use.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters. Amine-modified urethanes, polyethyleneimine, etc., and KP (made by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (made by Toyo Co., Ltd.), EFTOP (made by Tohkem Products), MEGAFAC (DAINIPPON) (manufactured by INK AND CHEMICALS), Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (manufactured by Asahi Glass), SOLSPERSE (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto), and the like.

(a3 Dispersing Aid) The dispersing aid is a preparation which exhibits an action of dispersing a pigment into fine particles and preventing reaggregation. The dispersing aid is effective for forming a coloring layer having a high light-dark ratio and a good transparency.

Dispersing aids which can be used in the present invention include {[2-(diethylamine)ethyl]amino} 蒽-9,10-fluorene, 1,8-bis(benzamide) hydrazine, 1,4- Bis{[2-(dimethylamine)ethyl]amino}-5,8-dihydroxyindole-9,10-indole, 1,8-dihydroxy-4-[4-(2-hydroxyethyl) Anilino]-5-nitroguanidine-9,10-oxime, 1,4-dihydroxyindole, 1,4-bis(4-butylanilino)-5,8-dihydroxyindole, 4' -(4-hydroxy-1-indolylamino)-acetamid benzene, 1,4-bis{[2,6-diethyl-4-methylphenyl)amino] hydrazine, 1, 4-bis(butylamino)-fluorenyldiyl, 1,4-bis(4-butylanilino)-5,8-dihydroxyindole, 1,5-bis[(3-methylphenyl) Amino] -9,10-nonanedione, 1,5-dicyclohexylaminopurine, 1,4-bis(isopropylamino)phosphonium, 1,4-bis(methylamino)蒽醌, 1,4-bis(2,6-diethyl-4-methylanilino)indole, 2,2'-(9,10-dioxo-1,4-diyldi Amino)bis(5-methylsulfonate), 1-anilino-4-hydroxyindole, 1-hydroxy-4-[(4-methylphenyl)amino]-9,10-anthracene Ketone, 1,4-bis(p-amino)anthracene, 1-amino-4-methylaminopurine, N-[4-[(4-hydroxy-indol-1-yl)amino Phenyl]acetamide, 1-(methylamino)-4-(4-A Anilino) 9,10-dione and 1,4,5,8-tetrahydro-anthraquinone.

In addition to the aforementioned dispersing aids, commercially available dispersing aids may be further included as needed. Specific examples include Lubrizol's SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000, BYK's BYK-SYNERGIST2100, BYK-SINERGIST2105, BASF's EFKA-6745 or EFKA-6750.

The dispersing aid is contained in an amount of from 1 to 30 parts by mass based on 100 parts by mass of the pigment in the colorant. When the dispersing aid exceeds 30 parts by mass, the color inherent to the coloring agent (A) is deteriorated, and discoloration occurs due to hard baking during the production step of the colored layer.

(a4) Dispersing solvent The above-mentioned dispersing solvent is not particularly limited, and various organic solvents which will be used in the field can be used.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether; , diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl sarbuta acetate, ethyl sarbuta acetate Diethylene glycol alkyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxybenzyl acetate, etc. Alkylene glycol alkyl ether acetates; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; methyl ketone, acetone, methyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ethyl alcohol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol and other alcohols; 3-ethoxypropionic acid ethyl, 3-methoxypropionic acid methyl esters; and g- Cyclic esters such as butyrolactone. It is preferred to use an alkylene glycol alkyl ether acetate, a ketone, an ethyl 3-ethoxypropionate or a methyl 3-methoxypropionate, and it is more preferred to use propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate or methyl 3-methoxypropionate.

These dispersion solvents may be used alone or in combination of two or more. The dispersion solvent is contained in an amount of from 60 to 90% by mass, more preferably from 70 to 85% by mass, based on the total mass of the pigment dispersion composition. If it is out of the above range, there is a disadvantage that the storage stability of the pigment dispersion composition is not good.

(a5) Dispersion resin The dispersion resin functions as a dispersion medium of the (A) colorant, and can be selectively added. The dispersant (a2) is used alone, and if the dispersion resin (a5) is used, it can be produced more preferably. The pigment dispersion composition. In the case of dispersing a resin, if it can be used as a dispersion medium, it can be used without limitation. However, it is considered that the developability of the colored photosensitive resin composition produced by the pigment dispersion composition is preferably an acid value in order to have solubility in an alkali developer. .

Here, the acid value is a value measured as the amount of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is generally determined by titration using a potassium hydroxide aqueous solution.

In the case of an acid resin-dispersed resin, a compound (b1) having a carboxyl group bonded to the unsaturated group and a compound (b2) having an unsaturated bond copolymerizable with the compound (b1) can be produced by copolymerization.

Specific examples of the compound (b1) having a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and fumaric acid, mesaconic acid, and itaconic acid. a carboxylic acid; and an anhydride of the above dicarboxylic acid; a mono(meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals, such as an ω-carboxylic acid polycaprolactone mono(meth) acrylate, etc., preferably Acrylic acid, methacrylic acid. In the present invention, (meth) acrylate refers to acrylate, methacrylate or both.

The compounds exemplified for the above compound (b1) may be used alone or in combination of two or more. The compound (b2) having an unsaturated bond copolymerizable with the above compound (b1) may, for example, be styrene, vinyl toluene, a-methylstyrene, p-chlorostyrene, o-methoxystyrene or m-methoxy. Styrene, p-methoxystyrene, o-methoxystyrene, o-vinyl anisole, m-vinyl anisole, p-vinyl anisole, o-vinyl phenyl epoxy propyl ether, m-vinyl benzene An aromatic vinyl compound such as a epoxidized propyl ether or a p-vinyl phenyl epoxy propyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso (a) (meth)acrylic acid propyl ester, butyl (meth) acrylate, butyl (meth) acrylate, butyl (meth) acrylate or butyl (meth) acrylate Esters; benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclo(hexyl) hexyl acrylate, tricyclo[5.2.1.02,6]decane-8-yl ( An alicyclic (meth) acrylate such as methyl acrylate, 2-bicyclophenetanyl (meth) acrylate or isobutyl methacrylate; phenyl (meth) acrylate or (methyl) propylene (A) aryl (meth) acrylates; hydroxy (meth) acrylates such as 2-hydroxy (meth) acrylate or 2-hydroxy (meth) acrylate; N-cyclohexyl cis Equinone imine, N-benzyl maleimide, N-phenyl maleimide, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl Maleimide, N-p-hydroxyphenyl maleimide, N-o-methylphenyl maleimide, N-m-methylphenyl-butylene Amine, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N - N-substituted maleimide compound such as p-methoxyphenyl maleimide; (meth) acrylamide, N, N-dimethyl (meth) acrylamide Isounsaturated guanamine compound; 3-(methacrylomethoxymethyl)oxetane, 3-(methacrylomethoxyethyl)-3-ethyloxetane, 3-(A Acryloxyethyl)-2-trifluoromethyloxetane, 3-(methacrylomethoxyethyl)-2-phenyloxetane, 2-(methacrylofluorene) Ethyl) oxalate An unsaturated oxetane compound such as cyclobutane or 2-(methacrylomethoxyethyl)-4-trifluoromethyloxetane; and the like; however, it is not limited thereto.

The compounds exemplified in the above compound (b2) may be used alone or in combination of two or more.

The dispersion resin is contained in an amount of 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the pigment solid content in the colorant. When the amount of the dispersion resin exceeds 60 parts by mass, the viscosity is increased by the dispersion resin. When the amount is less than 5 parts by mass, the amount of the dispersion resin is insufficient, and the finely divided pigment dispersion composition cannot be obtained.

(a6) Dye The above dye may be used without limitation if it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and ensures reliability with respect to solubility in an alkali developing solution, heat resistance, solvent resistance, and the like.

The dye may be selected from an acid dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a derivative thereof, or an azo system may be selected. , acid dyes of xanthene, phthalocyanine and derivatives thereof.

The aforementioned dyes are preferably classified as a dye compound in the excellent index (published by The Society of Dyers and Colourists), and a conventional dye described in DYEING NOTE.

As a specific example of the above dye, the C.I. solvent dye may be exemplified by the following dyes. CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI Solvent Red 8, 45, 49, 122, 125 and 130; CI Solvents Orange 2, 7, 11, 15, 26 and 56; CI Solvent Blue 35, 37, 59 and 67; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35, etc. Green dyes, etc.

Further, CI acid dyes include: CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, and 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73 , 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211 , 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341 , 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422 and 426; CI acid orange 6, 6, 8, 10, 12, 26, 50, 51, 52, 56, 62 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256 , 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335 and 340; CI Acid Violet 6B, 7, 9, 17 and 19; CI Acid Green 1, 3, 5, 9, 16 Dyes such as 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

Further, CI Direct dyes can be exemplified by: CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94 , 95, 98, 102, 108, 109, 129, 136, 138, and 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250; CI Direct Orange 34, 39 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107; CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260 268, 274, 275 and 293; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104; CI Directly green, such as dyes 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

Further, CI mordant dyes can be exemplified by: CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95; CI moring orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23 , 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48; CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84; CI mordant purple 1, 2 , 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58; CI mord green 1, 3, 4, 5, 10, Dyes such as 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

The colorant (A) is contained in an amount of 20 to 80% by weight, more preferably 35 to 70% by weight based on the total mass of the solid matter in the colored photosensitive resin composition of the present invention.

<(B) Alkali-Soluble Resin> The alkali-soluble resin has reactivity with light or heat and alkali solubility, and functions as a dispersion medium for each component in the composition of the present invention. The alkali-soluble resin of the present invention comprises: (B-1) a first resin comprising an epoxy group; and (B-2) a second resin containing an acid group reactive with the aforementioned epoxy group And the acid value is 170 to 300 mgKOH/g.

(B-1) First Resin The first resin is a resin containing an epoxy group and having alkali solubility. If such a resin is a resin known in the art, it can be used without particular limitation. For example, (B-1-1) may be a resin containing a compound having an unsaturated bond and a carboxyl group, and (B-1-2) a compound copolymerized with at least one of the following Chemical Formulas 1 to 2.

[Chemical Formula 1]

(wherein R ₁ is hydrogen, or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group with or without a hetero atom; and R ₂ is a single bond, or a carbon number of 1 to 20 with or without a hetero atom; An alkylene group or a cycloalkylene group; the above R ₁ and the aforementioned R ₂ as an alkylene group or a cycloalkylene group may each be further substituted by a hydroxyl group)

[Chemical Formula 2]

(wherein R ₁ is hydrogen, or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group with or without a hetero atom; and R ₂ is a single bond, or a carbon number of 1 to 20 with or without a hetero atom; An alkylene group or a cycloalkylene group; the above R ₁ and the aforementioned R ₂ as an alkylene group or a cycloalkylene group may each be further substituted by a hydroxyl group).

(B-1-1) A carboxylic acid compound having a compound having an unsaturated bond and a carboxyl group which has an unsaturated bond and a carboxyl group, and which has a polymerizable unsaturated double bond, is not limited, and specific examples thereof include A saturated monocarboxylic acid or an unsaturated carboxylic acid or an unsaturated tricarboxylic acid, or a polyvalent carboxylic acid having two or more carboxyl groups in its molecule.

The unsaturated monocarboxylic acid may, for example, be acrylic acid, methacrylic acid or crotonic acid.

The unsaturated polyvalent carboxylic acid may, for example, be maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid.

The polyvalent carboxylic acid may be an acid anhydride, and examples of the unsaturated polyvalent acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride.

Further, the unsaturated polyvalent carboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester, and examples thereof include succinic acid mono(2-propenyloxyethyl) and succinic acid mono(2- Methyl propylene oxiranyl ethyl), fumaric acid mono(2-propenyl oxiranyl), fumaric acid mono(2-methylpropene oxiranyl), and the like.

The unsaturated polyvalent carboxylic acid may also be a mono (meth) acrylate of a di-terminal polymer thereof, and examples thereof include ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethyl. Acrylate and the like.

Further, the unsaturated polyvalent carboxylic acid may be an unsaturated acrylate containing a hydroxyl group or a carboxyl group in the same molecule, and examples thereof include α-(hydroxymethyl)acrylic acid.

Among these carboxylic acids, acrylic acid, methacrylic acid, maleic acid, and the like are preferably used from the viewpoint of high copolymerization reactivity.

The compound having an unsaturated bond and a carboxyl group in the present invention may be used alone or in combination of two or more.

(B-1-2) At least one compound of Chemical Formula 1 to Chemical Formula 2 At least one of the compounds of Chemical Formulas 1 to 2 of the present invention is a compound containing a polymerizable unsaturated bond and an epoxy group having an increased bridging density.

In the above Chemical Formula 1 and Chemical Formula 2, more specific examples of R ₁ may each be: hydrogen; methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, etc. And hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl, A hydroxyl group-containing alkyl group such as 2-hydroxy-isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl or the like. Wherein R _{1 is} each preferably hydrogen, methyl, hydroxymethyl, 1-hydroxyethyl or 2-hydroxydiethyl, and particularly preferably hydrogen or methyl.

In the above Chemical Formula 1 and Chemical Formula 2, more specific examples of R ₂ may each be: a single bond; an alkylene group such as a methylene group, a vinyl group, or a propylene group; a hydroxymethylene group, a 1-hydroxyvinyl group, and a 2-hydroxyethylene group; a hydroxyalkylene group such as a 1-hydroxy-n-propenyl group, a 2-hydroxy-n-propenyl group or a 3-hydroxy-n-propenyl group; a formaldehyde group, an acetaldehyde group, a propionaldehyde group, a thiomethylene group, a sulfur vinyl group An alkylene group containing a hetero atom such as a thiopropenyl group, an aminomethylene group, an aminovinyl group or an aminoacryl group. Wherein R _{2 is} particularly preferably a single bond, a methylene group, a vinyl group, a formaldehyde group or an acetaldehyde group, and particularly preferably a single bond or an acetaldehyde group. In the present invention, when R ₂ is a single bond, it means that the carbon at the 8-position or the 9-position of the tricyclodecyl group is directly bonded to the oxygen of the acrylate group.

More specific examples of the compound represented by Chemical Formula 1 include the following Chemical Formula 1-1 to Chemical Formula 1-15.

[Chemical Formula 1-1] [Chemical Formula 1-2]

[Chemical Formula 1-3] [Chemical Formula 1-4]

[Chemical Formula 1-5] [Chemical Formula 1-6]

[Chemical Formula 1-7] [Chemical Formula 1-8]

[Chemical Formula 1-9] [Chemical Formula 1-10]

[Chemical Formula 1-11] [Chemical Formula 1-12]

[Chemical Formula 1-13] [Chemical Formula 1-14]

[Chemical Formula 1-15]

More specifically, the compound represented by the above Chemical Formula 2 is exemplified by the following Chemical Formula 2-1 to Chemical Formula 2-15.

[Chemical Formula 2-1] [Chemical Formula 2-2]

[Chemical Formula 2-3] [Chemical Formula 2-4]

[Chemical Formula 2-5] [Chemical Formula 2-6]

[Chemical Formula 2-7] [Chemical Formula 2-8]

[Chemical Formula 2-9] [Chemical Formula 2-10]

[Chemical Formula 2-11] [Chemical Formula 2-12]

[Chemical Formula 2-13] [Chemical Formula 2-14]

[Chemical Formula 2-15]

The chemical compounds exemplified in the above Chemical Formula 1 and Chemical Formula 2 may be used alone or in combination of two or more.

Further, in the first resin (A), the copolymers of the above (B-1-1) and (B-1-2) are in addition to the above (B-1-1) and (B-1-2). The compound having an unsaturated bond which can be polymerized with the above-mentioned (B-1-1) and (B-1-2) polymerization can be copolymerized together.

There are compounds which can be unsaturatedly bonded to the above (B-1-1) and (B-1-2) polymerization, and specific examples thereof include ethyl 2-aminoacrylate and ethyl 2-aminoethyl methacrylate. , ethyl 2-dimethylaminoacrylate, ethyl 2-dimethylaminoacrylate, propyl 2-aminoacrylate, propyl 2-aminopropyl methacrylate, propyl 2-diaminoacrylate, Unsaturated carboxylic acid amine group such as 2-diaminopropyl methacrylate, propyl 2-dimethylamino acrylate, propyl 3-dimethylamino acrylate or propyl 3-dimethylamino acrylate Alkyl esters; vinyl acetates such as vinyl acetate, ethylene propionate, ethylene butyrate, ethylene benzoate; unsaturated ethers such as vinyl methyl ether, ethylene ether, allyl glycidyl ether; acrylonitrile, methacryl A vinyl cyanide compound such as nitrile, α-chloroacrylonitrile or dicyanethylene; acrylamide, methacrylamide, α-chloropropenylamine, N-2-hydroxyethyl decylamine, N-2- Unsaturated guanamines such as hydroxyethylmethyl acrylamide; maleimide, benzyl maleimide, N-phenyl maleimide, N-cyclohexyl cis Butylenediamine Unsaturated quinoids; aliphatic conjugated pentadienes such as 1,3-butadiene, isoprene, chloropentadiene; and polystyrene, polymethyl acrylate, polymethyl methacrylate The polymer molecular chain end of the ester, poly-n-butyl acrylate, poly-n-butyl methacrylate, polyoxymethane, and a macromonomer having a monopropenyl fluorenyl group or a monomethacryl fluorenyl group.

In the acrylic acid-soluble resin of the present invention, the first resin (A) is a copolymer obtained by copolymerizing the above (B-1-1) and (B-1-2) (further containing B-1-1 and B-1- When the monomer other than 2 is copolymerized, if it is also included in the present invention, the ratio of the constituent units derived from each of (B-1-1) and (B-1-2) in the copolymer is relative to The total number of moles constituting the constituent units of the copolymer is preferably in the following range in terms of the molar fraction. Constituent unit derived from (B-1-1): 5 to 75 mol% constituting unit derived from (B-1-2): 25 to 95 mol%

In particular, the ratio of the aforementioned constituent units is preferably in the following range. Component unit derived from (B-1-1): 10 to 70 mol% Constituent unit derived from (B-1-2): 30 to 90 mol%

When the ratio of the above-mentioned constituent unit is within the above range, a photosensitive resin composition excellent in developability, solvent resistance, heat resistance, and mechanical strength can be produced.

For the first resin (A), for example, the document "The method of polymer synthesis" (Dazu Takashi, issue: Chemical Tongren Distribution Co., Ltd., 1st edition, 1st brush, issued on March 1, 1972) The method described is to manufacture.

Specifically, a predetermined amount of the units (B-1-1) and (B-1-2) constituting the copolymer, a polymerization initiator and a solvent are placed in a reaction vessel, and oxygen is replaced by nitrogen in oxygen. In the absence of the polymer, the polymer is obtained by stirring, heating, and heat preservation. Further, the obtained copolymer may be directly used as a solution after the reaction, or may be a solution obtained by concentration or dilution, or may be used as a solid (powder) extract by reprecipitation or the like.

The acid value of the first resin is preferably in the range of 20 to 200 (KOH mg/g). When the acid value is in the above range, it is possible to produce a green coating film which is excellent in developability to a developing solution, excellent in sensitivity and adhesion, and free from pattern peeling.

The weight average molecular weight of the first resin in terms of polystyrene may be 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the first resin is within the above range, the film is prevented from being reduced during development, and the peeling property of the pattern portion is good.

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

(B-2) Second resin The second resin contains a compound which can open an acid group of an epoxy group of the first resin and is copolymerized, and has an acid value of 170 to 300 mgKOH/g. Acid resin. The acid-based group contained in the above-mentioned compound opens the epoxy group of the first resin to increase the bridging density, and the adhesion is excellent. When the acid value is in the above range, the developability is improved during development. The pattern can form a green coating film with good sensitivity and no pattern peeling.

More specific examples of the second resin may be a resin containing polymerization as described in the following (B-2-1), (B-2-2), and (B-2-3); (B-2-1): In one molecule, one or more kinds of skeletons selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton, and compounds having an unsaturated bond; (B-2-2): containing aromatic a compound of a vinyl group; (B-2-3): a compound containing an acid group which can ring-open the epoxy group of the first resin.

One molecule or more selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton, and having an unsaturatedly bonded compound (B-2-1), for example, as a molecule In one molecule, a compound having an unsaturated bond with a tricyclodecane skeleton and/or a dicyclopentadiene skeleton, specifically, a dicyclopentyl (meth) acrylate or a dicyclopentenyl group ( Methyl) acrylate, cyclopentaoxy (meth) acrylate, cyclopentaoxyalkenyl (meth) acrylate, tricyclodecane mono (meth) acrylate, and the like. Here, (meth) acrylate means acrylate and/or methacrylate.

Further, examples of the compound (B-2-2) containing an aromatic vinyl group include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene.

Further, the compound (B-2-3) containing an acid-acting group capable of ring-opening the epoxy group of the first resin is a carboxylic acid having an unsaturated double bond capable of polymerizing a compound having an unsaturated bond with a hydroxyl group. The compound is not limited, and specific examples thereof include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid, and a polyvalent carboxylic acid having two or more carboxyl groups in the molecule.

The unsaturated monocarboxylic acid may, for example, be acrylic acid, methacrylic acid or crotonic acid.

The unsaturated polyvalent carboxylic acid may, for example, be maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid.

The polyvalent carboxylic acid may be an acid anhydride, and examples of the unsaturated polyvalent acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride.

Further, the unsaturated polyvalent carboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester, and examples thereof include succinic acid mono(2-propenyloxyethyl) and succinic acid mono(2- Methyl propylene oxiranyl ethyl), fumaric acid mono(2-propenyl oxiranyl), fumaric acid mono(2-methylpropene oxiranyl), and the like.

The unsaturated polyvalent carboxylic acid may also be a mono (meth) acrylate of a di-terminal polymer thereof, and examples thereof include ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethyl. Acrylate and the like.

Further, the unsaturated polyvalent carboxylic acid may be an unsaturated acrylate containing a hydroxyl group or a carboxyl group in the same molecule, and examples thereof include α-(hydroxymethyl)acrylic acid.

Among these carboxylic acids, acrylic acid, methacrylic acid, maleic acid, and the like are preferably used from the viewpoint of high copolymerization reactivity.

The compound having an unsaturated bond and a carboxyl group in the present invention may be used alone or in combination of two or more.

The second resin of the present invention may be a resin which is further polymerized by containing a monomer other than the above (B-2-1) to (B-2-3). a compound having an unsaturated bond capable of polymerizing with (B-2-1) to (B-2-3), specifically methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) An unsubstituted or substituted alkyl ester of an unsaturated carboxylic acid such as butyl acrylate or ethyl (meth) acrylate;

Containing benzyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, cyclobutyl (meth) acrylate, octyl (meth) acrylate, (A Base) acrylic acid menthyl acetate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, heptene (meth) acrylate, octene (meth) acrylate, ring (A) Pentyl acrylate, isobornyl (meth)acrylate, decyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, bismuth (meth) acrylate An unsaturated carboxylic acid ester compound of an alicyclic substituent such as an ester; a monosaturated carboxylic acid ester compound of a diol such as an oligoethylene glycol mono(meth)acrylic acid alkyl ester; comprising benzyl (meth) acrylate, An unsaturated carboxylic acid ester compound having a substituent of an aromatic ring such as phenoxy methacrylate; a vinyl carboxylate such as vinyl acetate or vinyl propionate; and an ethylene cyanide such as (meth)acrylonitrile or α-chloroacrylonitrile; a compound; and a maleimide compound such as N-cyclohexylmethyleneimine or N-phenylmethyleneimine. These compounds may be used alone or in combination of two or more.

The ratio of the constituent components derived from each of (B-2-1) to (B-2-3) used in the present invention is in terms of the molar percentage with respect to the total number of moles constituting the constituent components of the copolymer. It should be in the following range. Component unit derived from (B-2-1): 10 to 80 mol% Constituent unit derived from (B-2-2): 10 to 80 mol% Constituent unit derived from (B-2-3) :10~80m%%

In particular, the ratio of the aforementioned constituent units is preferably in the following range. Component unit derived from (B-2-1): 20 to 40 mol% Constituent unit derived from (B-2-2): 20 to 50 mol% Constituent unit derived from (B-2-3) :10~60mol%%

When the ratio of the above-mentioned constitution is within the above range, the balance between developability, solubility, and heat resistance is good, and thus a preferable copolymer can be obtained.

As an embodiment of the present invention, the copolymer can be produced by the following method. The flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping tube, and a nitrogen introduction tube is introduced together with a total amount of (B-2-1) to (B-2-3), and the mass reference is 0.5 to 20 times. The solvent azobisisobutyronitrile was used to replace the atmosphere in the flask from nitrogen to nitrogen. Thereafter, the temperature of the solvent was raised to 40 to 140 ° C, and the tube was dropped from the tube for 0.1 to 8 hours, and the total amount of the bottle was dropped with respect to (B-2-1) to (B-2-3). 0 to 20 times the amount of the solvent, and for the total of (B-2-1), (B-2-2) and (B-2-3), the addition of azoisobutyronitrile or tertiary butyl A 0.1 to 10 mol% solution of a polymerization initiator such as peroxy2-ethylhexyl carbonate (stirred at room temperature or under heating) is further stirred at 40 to 140 ° C for 1 to 10 hours to obtain a copolymer.

Further, in the foregoing step, a part or the whole amount of the polymerization initiator may be placed in the flask, and one or the whole of (B-2-1), (B-2-2) and (B-2-3) may be placed. It can also be entered into the flask. Further, in order to control the molecular weight or the molecular weight distribution, an α-methylstyrene dimer or a ruthenium compound may be used as the chain transfer agent. The amount of α-methylstyrene dimer or ruthenium compound used is based on the total amount of (B-2-1), (B-2-2) and (B-2-3), and the mass basis is 0.005. ~5%. Further, the polymerization conditions described above may be appropriately adjusted in terms of the production method or the reaction temperature in consideration of the heat generation amount of the production equipment or the polymerization.

The second resin (B-2) of the present invention is not limited, and the copolymer obtained by copolymerizing (B-2-1), (B-2-2) and (B-2-3) is subjected to A resin having an unsaturated group bonded to an epoxy group (B-2-4a) or a compound having an unsaturated group bonded to a hydroxyl group (B-2-4b) in one molecule is more preferable. By adding the above (B-2-4) to the above copolymer, light/thermosetting property can be imparted to the second resin.

Specific examples of the compound (B-2-4a) having an unsaturated bond and an epoxy group in the above-mentioned one molecule of the present invention include glycidyl (meth)acrylate and 3,4-epoxy ring (A). Benzyl acrylate, methyl 3,4-epoxyhexyl (meth)acrylate, glycidyl methyl (meth)acrylate, and the like. Among these compounds, glycidyl (meth)acrylate is preferably used. These compounds may be used alone or in combination of two or more.

Further, specific examples of the compound (B-2-4b) having an unsaturated bond and a hydroxyl group in the above-mentioned one molecule include 2-hydroxyethyl (meth)acrylate and glycerol (meth)acrylate. A glycerin (meth) acrylate or the like, which is applicable, is not limited, and is included in the present invention.

Further, the ratio of the constituent units derived from (B-2-4) in the second resin (B-2) is derived from (B-2-3) in the binder resin (B-2). The number of moles of the constituent components is preferably from 5 to 80 mol%, more preferably from 10 to 70 mol%.

When the composition of (B-2-4) is within the above range, a green photosensitive resin composition having sufficient developability, good adhesion, and excellent exposure sensitivity and having no pattern peeling can be produced.

In the embodiment of the present invention, the second resin (B-2) can be produced by reacting the copolymer with (B-2-4), for example, by the following method.

The atmosphere in the flask is replaced with nitrogen from air, and the copolymer is 5 to 80 mol% in terms of molar fraction with respect to the constituent unit derived from (B-2-3) (B-2) -4) a reaction catalyst of a carboxyl group and an epoxy group, for example, hydroquinone is placed in a flask, which is relative to (B-2-1), (B-2-2) and (B-2-3) The total amount is 0.01 to 5%, and as a polymerization inhibitor, for example, hydroquinone is added, which is relative to (B-2-1), (B-2-2), and (B-2). The total amount of -3) is 0.001 to 5% by mass, and is reacted at 60 to 130 ° C for 1 to 10 hours, whereby the copolymer can be reacted with (B-2-4). Further, in the same manner as the polymerization conditions, the production method or the heat generation amount of the polymerization may be considered, and the input method or the reaction temperature may be appropriately adjusted.

The weight average molecular weight of the second resin in terms of styrene may be 3,000 to 100,000, more preferably 5,000 to 50,000. When the second resin (B-2) is in the range of 3,000 to 100,000, film formation is less likely to occur during development, and the non-pixel portion peeling property tends to be good at the time of development, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the second resin is preferably from 1.5 to 6.0, more preferably from 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is from 1.5 to 6.0, the developability is good, which is preferable.

In the present invention, the alkali-soluble resin may be appropriately mixed with the first resin and the second resin, and as a specific example, the first resin: the second resin may be used in a mixed weight ratio of 1:0.5 to 1:2.

The content of the alkali-soluble resin is from 5 to 90% by weight, more preferably from 10 to 70% by weight, based on the total solid matter in the colored photosensitive resin composition. When the content of the alkali-soluble resin is 5 to 90% by weight based on the above-mentioned standard, the solubility in the developer is sufficient, the developability is excellent, and as the stability of the coating film is increased, the pattern is less likely to be peeled off.

<(C) Photopolymerizable Compound> The photopolymerizable compound contained in the colored photosensitive resin composition of the present invention is a compound which can be polymerized by the action of light and a photopolymerization initiator described later, and examples thereof include a monofunctional single Body, difunctional monomer, other polyfunctional monomer, and the like.

The photopolymerizable compound used in the present invention may have two or more different structures or functional groups in which the functional group is mixed in order to improve the developability, sensitivity, adhesion, surface problem, and the like of the colored photosensitive resin composition. The photopolymerizable compound is not limited in scope. Specific examples of the monofunctional monomer include mercaptophenyl carbitol, 2-hydroxy-3-phenoxy propyl acrylate, 2-ethylhexyl acrylic acid carbamide, 2-hydroxyethyl acrylate, N- Vinyl quinone and the like. Specific examples of the difunctional monomer include hexamethylenedi(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethyl ethane. Diol (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentane diol (meth) acrylate, and the like. Specific examples of the other polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated (ethoxylated) trimethylolpropane tri(meth)acrylate, and propoxylation ( Propoxylated) Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated (B) Oxidation) dipentaerythritol hexa(meth) acrylate, propoxylated (propoxylated) dipentaerythritol hexa(meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among these monomers, a difunctional or higher polyfunctional monomer is preferably used.

The photopolymerizable compound is used in an amount of from 1 to 90 parts by weight, more preferably from 10 to 80 parts by weight, based on 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound, based on the solid content of the colored photosensitive composition. use.

<(D) Photopolymerization initiator> The photopolymerization initiator can be applied without limitation to those generally used in the field. One or more compounds selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a biimidazole-based compound, and an anthracene compound can be used. The photosensitive resin composition containing the aforementioned photopolymerization initiator is high in sensitivity.

The aforementioned triazine-based compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloromethane). (6)(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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamine-2-methylphenyl)vinyl]-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1. -[4-(2-Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinepropane-1-ketone, 2-benzyl-2-dimethylamine-1-(4-morpholinylphenyl)butane-1-one, 2-hydroxy-2-methyl-1-[ An oligomer of 4-(1-methylvinyl)phenyl]propan-1-one or the like.

Moreover, the acetophenone-based compound may, for example, be a compound represented by the following Chemical Formula 4.

[Chemical Formula 4]

In Chemical Formula 4, R ₁ to R ₄ each represent a phenyl group which may be substituted by a hydrogen atom, a halogen atom, a hydroxyl group or an alkyl group having 1 to 12 carbon atoms, or a benzyl group substituted with an alkyl group having 1 to 12 carbon atoms, or A naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by the above Chemical Formula 4 include 2-methyl-2-amino (4-methylthiophenyl)ethane-1-ketone and 2-ethyl-2-amino group (4). -methylthiophenyl)ethane-1-ketone, 2-propyl-2-amino (4-methylthiophenyl)ethane-1-ketone, 2-butyl-2-amino group (4 -methylthiophenyl)ethane-1ketone, 2-methyl-2-amino (4-methylthiophenyl)propane-1 1-one, 2-methyl-2-amino group (4- Methylthiophenyl)butane-1 Ketone, 2-ethyl-2-amino (4-methylthiophenyl)propane-1 Ketone, 2-ethyl-2-amino group (4-A Thiophenyl)butane-1 Ketone, 2-methyl-2-dimethylamino (4-methylthiophenyl)propane-1 Ketone, 2-methyl-2-diethylamine ( 4-methylthiophenyl)propane-1 1-ketone, and the like.

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrabenzimidazole or 2,2'-bis(2,3-dichlorobenzene). -4,4',5,5'-tetrabenzimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene)biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxybenzene)biimidazole, 4,4',5,5' position of phenyl group by carboxy alkoxy group Substituted biimidazole compounds and the like. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrabenzimidazole, 2,2'-bis(2,3-dichlorobenzene)-4 is preferably used. , 4', 5, 5'-tetrabenzimidazole.

Examples of the hydrazine compound include o-ethoxycarboxy-a-hydroxyimino-1-phenylpropan-1-one, and the following chemical formulas 5, 6, and the like.

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 7]

Further, other photopolymerization initiators and the like which are generally used in the field can be used in combination with the extent that the effects of the present invention are not impaired. Other photopolymerization initiators include, for example, a benzo compound, a benzophenone compound, a thioxanthone compound, an anthraquinone compound, and the like. These compounds may be used alone or in combination of two or more.

Examples of the benzo compound include benzo, benzomethyl ether, benzoethyl ether, benzoisopropyl ether, and benzoisobutyl ether.

The aforementioned benzophenone-based compound may, for example, be benzophenone, o-benzylidenebenzoic acid methyl, 4-phenylbenzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide. , 3,3', 4,4'-tetrakis (tertiary butylperoxycarboxy)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

The aforementioned thioxanthone-based compound may, for example, be 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone or 1-chloro-4-propoxythioxene Ketones, etc.

The aforementioned lanthanoid compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxy oxime, 2-ethyl-9,10-di Ethoxylated oxime, etc.

Further, other photopolymerization initiators may be exemplified by 2,4,6-trimethylbenzoepoxyphenylphosphine, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9 , 10-phenanthrenequinone, camphorquinone, phenylglyoxylate methyl, titanocene compound, and the like.

Further, as the photopolymerization initiator, a photopolymerization initiator having a group capable of causing chain transfer can also be used. Such a photopolymerization initiator is exemplified by, for example, Japanese Patent Publication No. 2002-544205.

The photopolymerization initiator having a group capable of causing chain transfer may, for example, be a compound represented by the following Chemical Formulas 8 to 13.

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

Further, in the present invention, the photopolymerization initiator may be used in combination with a photopolymerization initiator. When the photopolymerization initiator is used in combination with photopolymerization to form an auxiliary agent, the photosensitive resin composition containing the above is further highly sensitive, and a pattern of a green coating film having a good sensitivity can be formed.

The photopolymerization is preferably carried out using an amine compound or a carboxylic acid compound. In the above-mentioned photopolymerization initiator, specific examples of the amine compound include an aliphatic amine compound such as triethylolamine, methyldiethanolamine or triisopropanolamine, and methyl 4-dimethylaminobenzoate. , 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylamino Ethyl, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (general name: mazakirone), 4,4'-bis(diethyl An aromatic amine compound such as an amino)benzophenone. Among them, the above amine compound is preferably an aromatic amine compound.

In the above-mentioned photopolymerization initiator, specific examples of the carboxylic acid compound include phenylthioacetic acid, methylbenzenesulfuric acid, ethylbenzenesulfuric acid, methylethylbenzenesulfuric acid, dimethylphenylsulfuric acid, and A. Oxybenzene thioacetate, dimethoxybenzene sulphuric acid, chlorophenyl sulphuric acid, dichlorobenzene sulphuric acid, N-phenylglycine, phenoxyacetic acid, naphthalene thioacetate, N-naphthylglycine, naphthyloxyacetate, etc. Family of acetic acid.

The content of the photopolymerization initiator is 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound, based on the solid content of the colored photosensitive resin composition. unit. The photopolymerization has a content of the auxiliary agent of 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight, based on the previous number. When the content of the photopolymerization initiator is within the above range, the photosensitive resin composition becomes highly sensitive, and the coating film formed using the composition is excellent in sensitivity and does not cause pattern peeling, which is preferable. Further, when the content of the auxiliary agent in the photopolymerization is within the above range, the sensitivity of the photosensitive resin composition is further improved, and the pattern stability of the coating film formed using the composition is advantageous.

<Solvent (E)> If the solvent is generally used in the field, any one can be used without limitation.

Specific examples of the solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monoalkyl ether of ethylene glycol monobutyl ether; diethylene glycol Diethylene glycol dialkyl ethers such as dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl sarbuta acetate, ethyl 赛路苏Ethylene glycol alkyl ether acetates such as acetate, ethylene glycol monobutyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl An alkylene glycol alkyl ether acetate such as acetate or methoxybenzyl acetate; a propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as methyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether; propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, Propylene glycol butyl ether propionate and other propylene glycol alkyl ether propionates; methoxybutanol, ethoxybutanol, propoxybutanol, butoxybutanol, etc. Alcohol monoalkyl ethers; butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate; methoxy Butanediol monoalkane propionate such as butyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate; dipropylene glycol dimethyl ether, dipropylene glycol II Dipropylene glycol dialkyl ethers such as diethyl ether, dipropylene glycol methyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; methyl ethyl ketone, acetone, methyl ketone, methyl isobutyl ketone, and ring Ketones such as ketone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropyl Acid ethyl, 2-hydroxy-2-methylpropionic acid methyl, 2-hydroxy-2-methylpropionic acid ethyl, hydroxyacetic acid ethyl, hydroxyacetic acid ethyl, hydroxyacetic acid butyl, lactate ethyl, lactic acid Propyl, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylpropanoate Base, ethyl methoxyacetate, A Acetate propyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxypropyl acetate, butyl ethoxyacetate, methyl propyl oxyacetate, ethyl propyl oxyacetate, propyl propyl acetate Base, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, butyl acetoacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid propyl, 2-methoxypropionic acid butyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-ethoxypropionic acid propyl, 2-ethoxypropane Acid butyl, 2-butoxypropionic acid methyl, 2-butoxypropionic acid ethyl, 2-butoxypropionic acid propyl, 2-butoxypropionic acid butyl, 3-methoxypropionic acid methyl, 3 -ethyl methoxypropionate, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid ethyl, 3-ethoxypropionic acid Propyl, 3-ethoxypropionic acid butyl, 3-propoxypropionic acid methyl, 3-propoxypropionic acid ethyl, 3-propoxypropionic acid propyl, 3-propoxypropionic acid butyl, 3- Esters such as methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and piper; g-butyl Lactone ring Esters. The solvent exemplified herein may be used alone or in combination of two or more.

When the solvent is used in consideration of coatability and drying property, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, 3-ethoxypropane are preferably used. Ethyl esters such as acid ethyl and 3-methoxypropionic acid, and further preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol , 3-ethoxypropionic acid ethyl, 3-methoxypropionic acid methyl, and the like.

The content of the solvent is from 50 to 90% by weight, and more preferably from 60 to 85% by weight based on the total weight of the photosensitive resin composition containing the same. When the content of the solvent is within the above range, it is applied by a coating device such as a spin coater, a slit and a spin coater, a slit coater (sometimes referred to as a die coater or a curtain coater), or an inkjet. Sex is better, so it is more suitable.

<Additive (F)> The photosensitive resin composition of the present invention may further contain a filler, another polymer compound, a hardener, a leveling agent, a adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, or the like, if necessary. Additives such as chain transfer agents.

Specific examples of the filler include glass, cerium oxide, aluminum oxide, and the like. Specific examples of the other polymer compound include a curable resin such as an epoxy resin or a maleimide resin; and polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. , thermoplastic resins such as polyester and polyurethane.

The curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound as the curing agent include a bisphenol A epoxy resin, a brominated bisphenol A epoxy resin, a bisphenol F epoxy resin, and a brominated bisphenol F epoxy resin. Examples of the phenolic epoxy resin include an aromatic epoxy resin, an alicyclic epoxy resin, and a glycidyl ester resin, and examples thereof include a brominated derivative of the epoxy resin and an epoxy resin. An aliphatic, alicyclic or aromatic epoxy compound other than a brominated derivative thereof, a butadiene (co)polymer epoxide, an isoprene (co)polymer epoxide, a glycidyl group (A) Acrylate (co)polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound as the curing agent include carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, and terephthalic acid. Ester dioxetane, cyclohexane dicarboxylic acid dioxetane, and the like.

The hardener may be used in combination with a hardening auxiliary compound to effect ring-opening polymerization of an epoxy group of an epoxy compound or an oxetane skeleton of an oxetane compound. The hardening auxiliary compound may, for example, be a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride or an acid generator.

The carboxylic acid anhydride is commercially available as an epoxy resin hardener. The epoxy resin curing agent is, for example, a trade name (ADEKA HARDENER EH-700) (manufactured by ADEKA INDUSTRIAL CO., LTD.), a trade name (RIKACID HH) (manufactured by Shin-Nippon Chemical Co., Ltd.), and a trade name (MH-700). ) (manufactured by New Japan Physical and Chemical Co., Ltd.), etc. The hardeners exemplified above may be used alone or in combination of two or more.

A commercially available surfactant can be used as the leveling agent, and examples thereof include a surfactant such as an anthracene-based, a fluorine-based, an ester-based, a cationic-based, an anionic-based, nonionic-based or amphoteric surfactant. These surfactants may be used alone or in combination of two or more.

In addition to the above surfactants, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine upgrading In addition to polyurethanes and polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), EFTOP (manufactured by Tohkem Products), and MEGAFAC (manufactured by DAINIPPON INK AND CHEMICALS) are also available. Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (manufactured by Asahi Glass), SOLSPERSE (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto), and the like.

The adhesion promoter is preferably a decane compound, and specific examples thereof include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene tris(2-methoxyethoxy) decane, and N-(2-amine). Ethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3– Glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2–(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3– Chloropropylmethyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methacrylate propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

Specific examples of the antioxidant include 2-tributylbutyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-phenyl acrylate, 2-[1 -(2-hydroxy-3,5-di-tri-pentylphenyl)ethyl]-4,6-di-trisylpentyl phenyl acrylate, 6-[3-(3-tertiary butyl- 4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldiphenyl[d,f][1,3,2]dioxin ,3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxime-1,1-dimethylethyl]-2,4 , 8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tributyl-4-methylphenol), 4,4'-butylene double (6 -Tris-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tertiary Benzyl 4-methylphenol), dilauryl 3,3'-thiodipropionate, tetrakis-based 3,3'-thiodipropionate, distearyl 3,3'-sulfur Propionate, neopentyl pentoxide (3-lauryl thiopropionate), 1,3,5-tris(3,5-di-tri-butyl-4-hydroxybenzyl)-1,3, 5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''-hexa-tertiary butyl-a,a' , a''-(trimethyl-2,4,6-triyl)tri-pair New store pentaerythritol [3- (3,5-di - tert.butyl-4-hydroxyphenyl) propionate], 2,6-di - tert.butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2 - (3 - tris-butyl - 2 - hydroxy-5-methylphenyl) - 5 - chlorobenzotriazole, alkoxybenzophenol, and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like. Specific examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

(Color Filter and Image Display Device) The present invention provides a color filter manufactured using the above-described colored photosensitive resin composition, and an image display device including the above-described color filter.

The image display device including such a color filter may include a liquid crystal display device, an OLED, a flexible display, etc., but is not limited thereto, and all of the drawings known in the art can be exemplified. Like a display device.

The color filter can be produced by applying the coloring photosensitive resin composition of the present invention to the substrate, photohardening and developing it to form a pattern.

First, a colored photosensitive resin composition is applied onto a substrate, and then dried by heating to remove volatile components such as a solvent to obtain a smooth coating film.

The coating method can be carried out, for example, by spin coating, cast coating, roll coating, slit and spin coating, slit coating, or the like. After coating, it is heated and dried (prebaked), or dried under reduced pressure, and heated to volatilize volatile components such as a solvent. Here, the heating temperature is usually 70 to 200 ° C, more preferably 80 to 130 ° C. The thickness of the coating film after heat drying is generally about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. In this case, a device such as a mask aligner or a stepper should be used in order to uniformly illuminate the entire exposed portion or to align the mask with the correct position of the substrate. When it is irradiated with ultraviolet rays, it hardens at the part irradiated with ultraviolet rays.

As the ultraviolet light, a g line (wavelength: 436 nm), an h line, an i line (wavelength: 365 nm), or the like can be used. The amount of ultraviolet irradiation can be appropriately selected as needed, and the present invention is not limited thereto. When the coating film which has been hardened is brought into contact with the developing solution, and the non-exposed portion is dissolved and developed, a target pattern shape can be formed.

The development method may be any of a liquid addition method, a dropping method, a spray method, and the like. Further, at the time of development, the substrate may be inclined at an arbitrary angle. The developer is generally an aqueous solution containing a basic compound and a surfactant. The basic compound may be any of an inorganic and an organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, and cesium. Potassium acid, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Further, specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and trisole. Ethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic basic compounds may be used alone or in combination of two or more. The concentration of the basic compound in the alkali developing solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and oxyethylene/oxypropylene block copolymers. A sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a glycerin fatty acid ester, a polyoxyethylene fatty acid ester, a polyoxyethylene alkylamine, or the like.

Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl sulfate or sodium oleyl sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, and dodecylsulfonate. An alkyl allylate such as sodium or sodium dodecyl sulfonate.

Specific examples of the cationic surfactant include an amine salt such as stearylamine hydrochloride or lauryl trimethylammonium chloride or a quaternary ammonium salt. These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developing solution is usually from 0.01 to 10% by mass, more preferably from 0.05 to 8% by mass, even more preferably from 0.1 to 5% by mass. After the development, the water is washed, and further, it may be pre-baked at 150 to 230 ° C for 10 to 60 minutes as needed.

In the following, the preferred embodiments are presented to facilitate the understanding of the present invention, but the embodiments are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. Within the scope of the technical idea, various modifications and corrections are made to the embodiments, and such variations and modifications are of course subject to the scope of the appended claims.

<Synthesis Example 1: Synthesis of the first resin (B-1) in the alkali-soluble resin> A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping tube, and a nitrogen introduction tube was prepared, and a tube was dropped as a monomer, and 3 was charged. a mixture of 4-epoxytricyclodecane-8-yl (meth) acrylate (chemical formula 1) and 3,4-epoxytricyclodecane-9-yl (meth) acrylate (chemical formula 2) ( 50:50 molar ratio) 40 parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of tertiary butyl-2-hexanoic acid ethyl ester, propylene glycol single After 40 parts by weight of methyl ether acetate (PGMEA), the mixture was stirred and mixed to prepare a dropping tank as a chain transfer agent, and a mixture of 6 parts by weight of n-dodecylmer and 24 parts by weight of PGMEA was prepared. Thereafter, the weight of PGMEA 395 was introduced into the flask, and the atmosphere in the flask was changed from air to nitrogen, and the temperature in the flask was raised to 90 ° C while stirring. Next, the monomer and chain transfer agent are dropped from the dropping tube. The dropping system was maintained at 90 ° C for 2 hours, and after 1 hour, the temperature was raised to 110 ° C for 5 hours to obtain a resin (B-1-1) having an acid value of 75 mg KOH/g of the solid matter. The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

<Synthesis Example 2: Synthesis of second resin (B-2-a) in alkali-soluble resin> A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping tube, and a nitrogen introduction tube was prepared, and propylene glycol monomethyl ether acetate 182 g was introduced. After the atmosphere in the flask was changed from air to nitrogen, the temperature was raised to 100 ° C, and then 66.0 g (0.3 m) of monomethacrylate (manufactured by Hitachi Chemical Co., Ltd.) containing a (B-2-1) tricyclodecane skeleton. (B-2-2) a mixture of 35.0 g (0.30 mol) of α-methyl styrene, 28.8 g (0.40 mol) of (B-2-3) acrylic acid, and 136 g of propylene glycol monomethyl ether acetate, added A solution of 3.6 g of azobisisobutyronitrile was dropped from the dropping tube to the flask over 2 hours, and stirring was further continued from 100 ° C for 5 hours. Next, after changing the atmosphere in the flask from nitrogen to air, (B-2-4) glycidyl methacrylate 42.0 g (0.28 mol) and tridimethylamine methylphenol 0.9 g and the like were placed in the flask. 0.145 g of hydroquinone was further reacted at 110 ° C for 6 hours to obtain a resin (B-2-a) having an acid value of 170.7 mgKOH/g of a solid matter. The weight average molecular weight in terms of polystyrene measured by GPC was 22,180, and the molecular weight distribution (Mw/Mn) was 2.3.

<Synthesis Examples 3 to 18: Synthesis of Second Resin (B-2-b to q) in Alkali-Soluble Resin> As shown in the following Table 1, except for the components and ratios of (B-2-1 to 4) The same procedure as in the above Synthesis Example 2 was carried out.

[Table 1]

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin were measured by the GPC method under the following conditions. Device: HLC-8120GPC Pipe column: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection) Column temperature: 40°C Transfer phase solvent: Tetrahydrofuran Flow rate: 1.0ml/min Injection volume: 50μl Detector: RI Determination of sample concentration: 0.6 Mass % (solvent = tetrahydrofuran) Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH)

The ratio of the weight average molecular weight and the number average molecular weight obtained as described above was (Mw/Mn).

<Example 1: Production of colored photosensitive resin composition> A colored photosensitive resin composition (unit: weight) was produced by the components and compositions described in Table 2 below.

[Table 2]

<Example 2: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-b.

<Example 3: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-c in Example 1.

<Example 4: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-d in Example 1.

<Example 5: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-e in Example 1.

<Example 6: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-f in Example 1.

<Example 7: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-g in Example 1.

<Example 8: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-h in Example 1.

<Example 9: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-i in Example 1.

<Example 10: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-j in Example 1.

<Example 11: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-k in Example 1.

<Example 12: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-1 in Example 1.

<Example 13: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-m in Example 1.

<Example 14: Production of colored photosensitive resin composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-n in Example 1.

<Comparative Example 1: Production of Colored Photosensitive Resin Composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-o in Example 1.

<Comparative Example 2: Production of Colored Photosensitive Resin Composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-p in Example 1.

<Comparative Example 3: Production of Colored Photosensitive Resin Composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-2-q in Example 1.

<Comparative Example 4: Production of Colored Photosensitive Resin Composition> The same procedure as in Example 1 was carried out except that the resin B-2-a was changed to the resin B-1 in Example 1.

<Experimental Example 1> A glass substrate having a length of 2 inches (EAGLE 2000; manufactured by Corning) was washed successively with a neutral detergent, water, and ethanol, and then dried. The photosensitive resin composition prepared in the above Examples and Comparative Examples was spin-coated on the glass substrate, and then prebaked at 90 ° C for 3 minutes in a dust-free oven. After the pre-baked substrate was cooled to room temperature, the distance from the quartz glass mask was set to 150 μm, and an exposure apparatus (TME-150RSK; manufactured by TOPCON) was used to irradiate at 60 mJ/cm ² (405 nm basis). Light. At this time, the irradiation of the polymerizable resin composition is carried out by passing the emitted light from the ultrahigh pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Separation) and blocking light of 400 nm or less. At this time, the reticle is a reticle that is formed on the same plane using the next pattern.

a light-transmitting portion (pattern) having a regular square shape of 10 μm on one side, and the interval between the regular squares is 100 μm, and the coating film is immersed in a non-ionic surfactant 0.12% at 25 ° C after light irradiation. Potassium hydroxide 0.04% aqueous developer was used for 100 seconds, developed, washed with water, and then post-baked at 220 ° C for 20 minutes in an oven. The resulting film thickness was 3.6 μm. The film thickness was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). The pattern thus obtained was evaluated as described below, and the results are shown in Table 2 below.

1. Evaluation of developability (residue property) After development, the portion to be developed was observed for the presence or absence of residuals and residuals remaining without being washed away. When there is no residual, it is said to be good, and if there is a residual, it is evaluated as bad.

2. Adhesion evaluation When the pattern generated was evaluated by an optical microscope, it was evaluated by the degree of peeling of the following 20 μm pattern, and is shown in Table 1 below. ○: There is no peeling on the pattern. △: There are 1 to 3 peelings on the pattern. ×: There are 4 or more peelings on the pattern.

3. Line width and cross-sectional shape The cured film obtained as described above was measured for the line width of the pattern formed by Mask 14 μm using a scanning electron microscope (S-4600: manufactured by Hitachi, Ltd.), and the cross-sectional shape was evaluated as follows. When the cross-sectional shape is less than 90 degrees with respect to the pattern angle of the substrate, it is regarded as a forward taper, and when it is 90 degrees or more, it is judged to be a reverse taper. In the case of a forward taper, it is preferable because the pattern peeling is less likely to occur when the display device is formed.

4. Sensitivity of the developmental adhesion is evaluated by a microscope, and there are 1000 masks each having a diameter of 5 μm to 20 μm and a gap of 1 μm, and the pattern formed by the film thickness of 3 μm is leak-free and 100% residual. The pattern size formed by the mask. The smaller the diameter of the mask, the better the sensitivity.

[table 3]

With reference to the above-mentioned Table 3, in the case of the embodiment containing the second resin of the present invention, the exposure amount was low, and the adhesion to the substrate and the shape of the pattern were good as compared with the comparative example not including the above, and it was confirmed that the sensitivity was good.

Examples 15-23 and Comparative Examples 5-10 A colored photosensitive resin composition (unit: mass%) was produced by the components and contents described in the following Tables 4 and 5.

[table 5]

(Experimental Example 2) Measurement of test piece Preparation The colored photosensitive resin composition manufactured by the above Examples 15 to 23 and Comparative Examples 5 to 10 was used to produce a colored layer. That is, at this time, it was apply|coated to the glass plate by the spin-coating method, and it carried on the heating board, and was hold|maintained at the temperature of 100 degreeC for 3 minutes, and the film formation. Next, a 1 kw high pressure mercury lamp containing all of g, h, and i rays was used, and irradiation was performed at an illuminance of 100 mJ/cm ² . At this time, no special optical filter is used. The ultraviolet ray-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to develop. The glass plate coated with the above film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C for 30 minutes. The coloring layer thus obtained has a thickness of 1 to 5 μm, more preferably 2 to 4 μm.

1. Brightness measurement was measured using a microscopic spectrometer OSP‒SP2000. The brightness is shown in Table 3 below, and the color coordinates are Gx = 0.1670 and Gy = 0.6610.

The evaluation criteria for brightness (Y) are as follows. ○: Y≧24, △: 20≦Y <24, X:Y <20

2. Comparative measurement The measurement was performed using the TOPCON contrast measuring device BM-5A model, and the reference standard was based on a comparison of 1/30,000 of the glass substrate (before the formation of the colored layer). The results are shown in Table 3 below.

The evaluation criteria for comparison (CR) are as follows. ◎: CR≧10000, ○: 7000≦CR <10000, △: 5000≦CR <7000, X:CR <5000

3. Tint strength measurement The weight ratio of the pigment in the colored photosensitive resin composition to which the target coating film thickness (3.5 to 3.8 μm) was placed was measured. ○: coloring power <0.35, Δ: 0.35 ≦ coloring power <0.45, X: coloring power> 0.45

4. Pattern Formability Measurement The produced colored photosensitive resin composition was applied onto a glass substrate (#1737, manufactured by Corning) by a spin coating method, and then placed on a heating substrate and maintained at a temperature of 100 ° C for 3 minutes. A film is formed. Next, a test mask having a pattern having a stepwise change in the range of 1 to 100% was placed on the film, and the interval between the test mask and the test mask was set to 1000 mm, and an ultrahigh pressure mercury lamp (USH-250D) was used. , manufactured by USHIO Motor, irradiated with light at an exposure amount (365 nm) of 40 mJ/cm ² in an air atmosphere. The solution was developed with a KOH aqueous solution of pH 12.5, and the ultraviolet-irradiated film was developed by a spray developing machine for 80 seconds. The glass substrate covered with the film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C for 20 minutes to produce a color filter. The thickness of the pattern (film) of the manufactured color filter is 3.5 to 3.8 μm.

The pattern formation was performed while reducing the exposure amount with respect to the initial exposure amount at the time of formation of the pattern, and the pattern formation property was evaluated based on the ratio (%) of the exposure amount of the pattern formed with respect to the initial exposure amount. ○: pattern formation <0.2 △: 0.2 ≦ pattern formation <0.6 X: pattern formation> 0.6

As shown in the above Table 6, the examples of the present invention were excellent in overall physical properties such as brightness, contrast, coloring power, and pattern property as compared with the comparative examples.

However, it can be seen that in the case of Examples 18, 20, and 23 in which the mixing ratio of the green pigment and the yellow pigment was slightly deviated from 100:0 to 80:20, the contrast and pattern formation characteristics were slightly lowered.

As is clear from Table 6, from the viewpoint of the same color coordinate, when the comparative example and the comparative example were observed, the brightness and the contrast value of the examples were better than those of the comparative examples, and the coloring power was also good, and it was found that the display failure occurred in the liquid crystal display device. Possibility is low.

no

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Claims (9)

A colored photosensitive resin composition comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent; (A) a colorant a green pigment comprising Pigment Green 7; the (B) alkali-soluble resin (A) comprising: a first resin comprising an epoxy group; and a second resin containing a reactive group capable of reacting with the epoxy group An acid group having an acid value of 170 to 300 mgKOH/g. The colored photosensitive resin composition according to claim 1, wherein the colorant further comprises at least one yellow pigment of Pigment Yellow 129 and Pigment Yellow 139. The colored photosensitive resin composition according to claim 2, wherein the mass ratio of the green pigment to the yellow pigment in the colorant is from 100:0 to 80:20. The colored photosensitive resin composition according to the first aspect of the invention, wherein the first resin comprises a resin having a compound having an unsaturated bond and a carboxyl group, and a resin copolymerized with at least one of the following Chemical Formulas 1 to 2; ; [Chemical Formula 1] (wherein R ₁ is hydrogen, or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group with or without a hetero atom; and R ₂ is a single bond, or a carbon number of 1 to 20 with or without a hetero atom; An alkylene group or a cycloalkylene group; the above R ₁ and the aforementioned R ₂ as an alkylene group or a cycloalkylene group may each be further substituted by a hydroxyl group) [Chemical Formula 2] (wherein R ₁ is hydrogen, or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group with or without a hetero atom; and R ₂ is a single bond, or a carbon number of 1 to 20 with or without a hetero atom; An alkylene group or a cycloalkylene group; the above R ₁ and the aforementioned R ₂ as an alkylene group or a cycloalkylene group may each be further substituted by a hydroxyl group). The colored photosensitive resin composition according to claim 1, wherein the second resin is one molecule selected from the group consisting of a dodecane skeleton and a cyclopentadiene skeleton. The above skeleton includes a compound having a compound having an unsaturated bond, a compound containing an aromatic vinyl group, and a compound containing a compound capable of ring-opening an acid group of the epoxy group of the first resin. The colored photosensitive resin composition according to claim 5, wherein the aforementioned acid-containing compound is selected from the group consisting of an unsaturated monocarboxylic acid, or an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid. Select at least one compound. The colored photosensitive resin composition according to claim 1, wherein the second resin is contained in one molecule, and further comprises a compound having an unsaturated bond and an epoxy group, or a compound having an unsaturated bond and a hydroxyl group. Copolymerized resin. A color filter manufactured by using the colored photosensitive resin composition according to any one of the items 1 to 7. An image display device comprising the color filter of claim 8 of the patent application.