TWI489213B - Photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Description

Photosensitive resin composition, color filter, and liquid crystal display element thereof

The present invention relates to a photosensitive resin composition for a black matrix and a color filter and a liquid crystal display element formed using the black matrix. In particular, a photosensitive resin composition for a black matrix having high reliability, high optical density, and high impedance, and a color filter and a liquid crystal display element formed using the black matrix are provided.

In recent years, various liquid crystal display technologies have flourished, and in order to improve the contrast and display quality of current liquid crystal displays, black is generally placed in the gap between the stripes and dots of the color filters in the display. matrix. The black matrix described above can prevent problems such as a decrease in contrast and a decrease in color purity caused by light leakage between pixels. Conventionally, materials used for the black matrix are mainly vapor-deposited films containing chromium or chromium oxide. However, when the vapor deposited film is used as a material of a black matrix, there are disadvantages such as complicated process and high material cost. In order to solve this problem, it has been proposed to form a black matrix by means of photolithography using a photosensitive resin composition. technology.

At present, the industry's requirements for the shading of black matrices are increasing. One of the solutions is to increase the content of black pigments, thereby improving the shading of the black matrix. For example, Japanese Laid-Open Patent Publication No. 2006-259716 discloses a photosensitive resin composition for a black matrix comprising a high content of a black pigment, an alkali-soluble resin, a photopolymerization initiator, and a reaction having a difunctional group. Sex monomers and organic solvents. Among them, a reactive monomer having a difunctional group can improve the reaction between the compounds to form a high-definition pattern. Thereby, in the photosensitive resin composition, the sensitivity of the photosensitive resin composition can be maintained while increasing the light-shielding property so as to increase the content of the black pigment.

In addition, Japanese Laid-Open Patent Publication No. 2008-268854 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition contains an alkali-soluble resin having a carboxylic acid group and an unsaturated group, a photopolymerizable monomer containing an ethylenically unsaturated group, a photopolymerization initiator, and a high content of a black pigment. In the photosensitive resin composition for a black matrix, the resolution of the photosensitive resin composition of a high content of black pigment is improved by using a specific alkali-soluble resin.

Although the photosensitive resin composition having a black pigment content in the prior art can increase the light-shielding property and the like, the photosensitive resin composition of each of the above-mentioned prior methods still has poor reliability and insufficient optical density (OD) value. And the problem that the impedance value is too low. In view of this, there is still a need to develop a photosensitive resin composition for a black matrix which is excellent in reliability, high in OD, and high in resistance.

Therefore, an aspect of the present invention provides a photosensitive resin composition which has good reliability, high optical density, and high resistance value.

Another aspect of the present invention provides a black matrix which is produced by using the above-described photosensitive resin composition.

Yet another aspect of the present invention is to provide a color filter comprising the aforementioned black matrix.

Still another aspect of the present invention provides a liquid crystal display element comprising the aforementioned color filter.

According to the above aspect of the present invention, there is provided a photosensitive resin composition comprising an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, and a photoinitiator (C). Solvent (D), black pigment (E) and black dye (F) are described below.

Photosensitive resin composition Alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention contains a resin (A-1) having an unsaturated group and a polyoxyalkylene polymer (A-2).

Resin with unsaturated group (A-1)

The unsaturated group-containing resin (A-1) can be obtained by subjecting a mixture to a polymerization reaction, wherein the mixture comprises an epoxy compound (i) having at least two epoxy groups and having at least one carboxylic acid group and at least one The ethylenically unsaturated group compound (ii). Preferably, the mixture optionally comprises a carboxy group An acid anhydride compound (iii) and/or a compound (iv) having an epoxy group.

Epoxy compound having at least two epoxy groups (i)

The aforementioned epoxy compound (i) having at least two epoxy groups may have a structure represented by the following formula (II) or formula (III):

In the formula (II), B ₁ , B ₂ , B ₃ and B ₄ are the same or different, respectively, and B ₁ , B ₂ , B ₃ and B ₄ represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 5, respectively. The alkyl group, an alkoxy group having 1 to 5 carbon atoms, an aromatic group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

The epoxy compound (i) having at least two epoxy groups of the formula (II) includes, but is not limited to, a bisphenol fluorene having an epoxy group. The bisphenol quinone compound having an epoxy group is composed of 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy- 3-methylphenyl)fluorene[9,9-bis(4-hydroxy-3-methylphenyl)fluorene], 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene [9,9-bis ( 4-hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9- Bis(4-hydroxy-3-fluorophenyl)fluorene[9,9-bis(4-hydroxy-3-fluorophenyl)fluorene], 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene [9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9-bis(4-hydroxy-) 3,5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene], 9 a compound such as 9-9-bis(4-hydroxy-3,5-dibromophenyl)fluorene is reacted with a halogenated propylene oxide (epihalohydrin) Got it. The halogenated propylene oxide includes, but is not limited to, 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-epoxyhydrin (epibromohydrin). The epoxy group-containing bisphenol quinone type compound includes, but is not limited to, (1) manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, etc.; (2) manufactured by Osaka Gas, model PG-100, EG-210, etc. (3) Manufactured by SMS Technology Co., the model is SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.

In the formula (III), D ₁ to D ₁₄ are the same or different, respectively, and D ₁ to D ₁₄ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 to 15. An aryl group, and n represents an integer from 0 to 10.

Preferably, the epoxy compound (i) having at least two epoxy groups represented by the formula (III) is a compound having a structure represented by the following formula (IV) in the presence of an alkali metal hydroxide The halogenated propylene oxide is reacted to obtain:

In the formula (IV), D ₁ to D ₁₄ and n are as described above, respectively, and are not described herein.

Preferably, the epoxy compound (i) having at least two epoxy groups represented by the formula (III) is a compound having a structure represented by the following formula (V) and a phenol in the presence of an acid catalyst ( The phenol compound is subjected to a condensation reaction to form a compound having a structure represented by the above formula (IV). Next, an excess of halogenated propylene oxide is added for dehydrohalogenation to obtain an epoxy compound (i) having at least two epoxy groups as shown in formula (III):

In the formula (V), D ₁₅ and D ₁₆ are the same or different, and D ₁₅ and D ₁₆ each represent a hydrogen atom, a halogen, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; X ₁ and X ₂ are the same or different, and X ₁ and X ₂ each represent a halogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. This halogen means chlorine or bromine. The alkyl group means a methyl group, an ethyl group or a t-butyl group. The alkoxy group means a methoxy or ethoxy group.

The aforementioned phenolic compounds may include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, and tertiary butyl phenol. (t-butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol (vinylphenol), propenylphenol, ethnylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The phenolic compound may be used singly or in combination of plural kinds.

The compound having a structure represented by the formula (V) is used in an amount of 1 mol, and the phenol compound is preferably used in an amount of from 0.5 mol to 20 mol, more preferably from 2 mol to 15 mol. .

The foregoing acid catalyst may include, but is not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous or Zinc chloride, etc. The acid catalyst may be used singly or in combination of plural kinds. The acid catalyst is preferably selected from p-toluenesulfonic acid, sulfuric acid or hydrochloric acid.

The amount of the acid catalyst used is not particularly limited, but the amount of the compound having a structure represented by the formula (V) is 100% by weight, and the acid catalyst is preferably used in an amount of 0.1% by weight to 30% by weight. Weight percentage.

The aforementioned condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. The organic solvent may include, but is not limited to, toluene, xylene or methyl isobutyl ketone. The organic solvent may be used singly or in combination of plural kinds.

Based on a compound having a structure as shown in formula (V) and a phenolic compound The total amount of the substance used is 100% by weight, and the organic solvent is preferably used in an amount of 50% by weight to 300% by weight, more preferably 100% by weight to 250% by weight. Preferably, the condensation reaction is operated at a temperature of from 40 ° C to 180 ° C, and the operation time of the condensation reaction is from 1 hour to 8 hours.

After the completion of the aforementioned condensation reaction, a neutralization treatment or a water washing treatment may be carried out. The neutralization treatment adjusts the pH of the solution after the reaction to 3 to 7, preferably 5 to 7. The water washing treatment is carried out using a neutralizing agent, and the neutralizing agent is an alkaline substance including, but not limited to, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline, benzene An organic amine compound such as phenylene diamine or a compound such as ammonia or sodium dihydrogen phosphate. The water washing treatment may be carried out by a conventional method. For example, an aqueous solution containing a neutralizing agent may be added to the solution after the reaction, and extraction may be carried out repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenol compound and the solvent are distilled off under reduced pressure and concentrated to obtain a compound having a structure represented by the formula (IV).

The aforementioned halogenated propylene oxide is preferably selected from 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or any combination of the above.

The total equivalent weight of the hydroxyl group in the compound having a structure represented by the formula (IV) is 1 equivalent, and the halogenated propylene oxide is used in an amount of 1 mol to 20 moles, preferably 2 moles to 10 moles.

An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance before the dehydrohalogenation reaction is carried out, or may be added during the reaction. The operation temperature of the dehydrohalogenation reaction is preferably from 20 ° C to 120 ° C. The operation time of the dehydrohalogenation reaction is preferably from 1 hour to 10 hours.

An alkali metal hydroxide to be added to the dehydrohalogenation reaction may also be an aqueous solution thereof. In this case, the aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system while under reduced pressure or The water and the halogenated propylene oxide are continuously distilled under normal pressure, and the water and the halogenated propylene oxide are further separated, and the halogenated propylene oxide is continuously refluxed into the reaction system.

The total equivalent weight of the hydroxyl group in the compound having the structure represented by the formula (IV) is 1 equivalent, and the alkali metal hydroxide added in the dehydrohalogenation reaction is used in an amount of from 0.8 mol to 15 mol, preferably From 0.9 to 11 moles.

The quaternary ammonium salt such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, or trimethyl benzyl ammonium chloride may be added before the dehydrohalogenation reaction is carried out. The salt is used as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is carried out at a temperature of 20 ° C to 120 ° C for 1 hour to 10 hours. The dehydrohalogenation reaction is carried out.

In addition, in order to smoothly carry out the dehydrohalogenation reaction, in addition to alcohols such as methanol or ethanol, dimethylhydrazine may be added. The reaction is carried out by using an aprotic polar solvent such as (dimethyl sulfone) or dimethyl sulfoxide. In the case of using an alcohol, the total amount of the halogenated propylene oxide used is 100% by weight, and the alcohol is used in an amount of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight. In the case of using an aprotic polar solvent, the total amount of the halogenated propylene oxide used is 100% by weight, and the aprotic polar solvent is used in an amount of 5 to 100% by weight, preferably 10% by weight. Percentage to 90 weight percent.

In order to avoid the presence of unreacted starting materials such as halogenated propylene oxide, the solution after dehydrohalogenation may be further added to a solvent such as toluene or methyl isobutyl ketone, and The dehydrohalogenation reaction is carried out again by adding an aqueous alkali metal hydroxide solution such as sodium hydroxide or potassium hydroxide. Preferably, in the dehydrohalogenation reaction, the total equivalent weight of the hydroxyl group in the compound having the structure represented by the formula (IV) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol. Ears are more preferably from 0.05 moles to 0.2 moles. Preferably, the dehydrohalogenation reaction is operated at a temperature of from 50 ° C to 120 ° C. Preferably, the operation time of the dehydrohalogenation reaction is from 0.5 hours to 2 hours.

After the end of the dehydrohalogenation reaction, the filtration treatment or the water washing treatment may be selectively performed. Thereafter, by heating and decompressing, the temperature is 110 ° C to 250 ° C and the pressure is 1.3 kPa (10 mmHg) or less, and the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed, and the like can be obtained. An epoxy compound (i) having at least two epoxy groups as shown in (III). The formula (II) has The at least two epoxy group-containing epoxy compounds (i) include, but are not limited to, those manufactured by Nippon Kayaku Co., Ltd.: NC-3000, NC-3000H, NC-3000S, and NC-3000P.

a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (ii)

The compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from the group consisting of (1) acrylic acid, methacrylic acid, 2-methaacryloyloxyethylsuccinic acid (2-methaacryloyloxyethylsuccinic acid). 2-Methyl propylene oxime butyl succinic acid, 2-methyl propylene oxirane adipic acid, 2-methyl propylene oxybutyl adipate, 2-methyl propylene oxiranyl hexahydro Phthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropene oxime Oxypropyl succinic acid, 2-methyl propylene oxime adipic acid, 2-methyl propylene oxybutyl adipate, 2-methyl propylene oxypropyl tetrahydro phthalic acid, 2 - methacrylic acid propyl phthalate, 2-methyl propylene oxybutyl phthalic acid or 2-methyl propylene oxy butyl hydrogen phthalate; (2) a compound obtained by reacting a methyl acrylate with a dicarboxylic acid compound; (3) a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound.

The aforementioned dicarboxylic acid compound may include, but is not limited to, adipic acid, maleic acid, succinic acid, or phthalic acid. The hydroxyl group-containing (meth) acrylate may include, but is not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 -hydroxypropyl acrylate [(2-hydroxypropyl) Acrylate], 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl acrylate [(4-hydroxybutyl)] Methacrylate] or pentaerythritol trimethacrylate.

The carboxylic anhydride compound may be the same as the carboxylic anhydride compound (iii) contained in the mixture of the unsaturated group-containing resin (A-1) described below, and will not be further described herein.

Carboxylic anhydride compound (iii)

The carboxylic anhydride compound (iii) is preferably selected from the group consisting of succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrogen. Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl bridged methylene tetrahydrogen Dicarboxylic anhydrides such as methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride or 1,3-dioxoisobenzofuran-5-carboxylic anhydride a compound; a quaternary carboxylic anhydride compound such as benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride.

Compound with epoxy group (iv)

The epoxy group-containing compound (iv) is preferably selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and an unsaturated group. A glycidyl ether compound, other epoxy group-containing unsaturated compound or any combination of the above. The unsaturated group-containing glycidyl ether compound may include, but is not limited to, manufactured by Nagase Chemical Co., Ltd., model No. Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192 and other products.

In the present invention, the unsaturated group-containing resin (A-1) may be an epoxy compound (i) having at least two epoxy groups of the formula (II) and having at least one carboxylic acid group and at least one ethylenic unsaturated group. The base compound (ii) is subjected to a polymerization reaction to form a hydroxyl group-containing reaction product, followed by addition of the carboxylic anhydride compound (iii) to carry out a reaction. The total number of hydroxyl groups on the hydroxyl group-containing reaction product is 1 equivalent, and the number of equivalents of the acid anhydride group contained in the carboxylic anhydride compound (iii) is preferably from 0.4 equivalents to 1 equivalent, more preferably from 0.75 equivalents to 1 equivalent. When a plurality of carboxylic anhydride compounds (iii) are used, the manner of addition at the time of the reaction may be added sequentially or simultaneously. Preferably, when the carboxylic anhydride compound (iii) is a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is from 1/99 to 90/10. More preferably 5/95 to 80/20. Preferably, the reaction is operated at a temperature of from 50 ° C to 130 ° C.

In the present invention, the unsaturated group-containing resin (A-1) may be an epoxy compound (i) having at least two epoxy groups of the formula (III) and having at least one carboxylic acid group and at least one ethylenic unsaturated group. The base compound (ii) is reacted to form a hydroxyl group-containing reaction product, and then a carboxylic anhydride compound (iii) and/or an epoxy group-containing compound (iv) are added to carry out a polymerization reaction. Based on formula (III) The total equivalent weight of the epoxy group on the epoxy compound (i) having at least two epoxy groups is 1 equivalent, and the acid equivalent weight of the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is compared It is preferably from 0.8 equivalents to 1.5 equivalents, more preferably from 0.9 equivalents to 1.1 equivalents. The carboxylic acid anhydride compound (iii) is used in an amount of from 10 mole percent to 100 mole percent, preferably from 20 mole percent to 100 moles, based on the total amount of hydroxyl groups on the hydroxyl-containing reaction product of 100 mole percent. The percentage of ears, more preferably from 30 mole percent to 100 mole percent.

In the preparation of the unsaturated group-containing resin (A-1), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The reaction catalyst may include, but is not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride. , benzyltriethylammonium chloride or the like. The reaction catalyst may be used singly or in combination of plural kinds. The total amount of the epoxy compound (i) having at least two epoxy groups and the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight, the reaction catalyst The amount used is preferably from 0.01 part by weight to 10 parts by weight, more preferably from 0.3 part by weight to 5 parts by weight.

Further, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The polymerization inhibitor may include, but is not limited to, p-methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di-t-butyl-p-cresol) or phenothiazine. The polymerization inhibitor may be used singly or in combination of plural kinds.

The polymerization inhibitor is based on the total amount of the epoxy compound (i) having at least two epoxy groups and the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group in an amount of 100 parts by weight. The amount used is preferably from 0.01 part by weight to 10 parts by weight, more preferably from 0.1 part by weight to 5 parts by weight.

In the preparation of the unsaturated group-containing resin (A-1), a polymerization solvent can be used as necessary. The polymerization solvent may include, but is not limited to, an alcohol compound such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; a ketone such as methyl ethyl ketone or cyclohexanone a compound; an aromatic hydrocarbon compound such as toluene or xylene; a cellosolve compound such as celecin or butyl cellosolve; a carbaryl or butyl carbazine; Carbene-like compound; propylene glycol alkyl ether compound such as propylene glycol methyl ether; poly(propylene glycol alkyl ether) such as di(propylene glycol methyl ether) a compound; an acetate compound such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate; A lactate compound or a dialkyl glycol ether compound such as ethyl lactate or butyl lactate. The polymerization solvent may be used singly or in combination of plural kinds.

The acid value of the unsaturated group-containing resin (A-1) is preferably from 50 mgKOH/g to 200 mgKOH/g, more preferably from 60 mgKOH/g to 150 mg KOH / g.

The unsaturated group-containing resin (A-1) is used in an amount of 30 parts by weight to 90 parts by weight, preferably 35 parts by weight to 87 parts by weight, based on 100 parts by weight of the alkali-soluble resin, more preferably 40 parts by weight to 85 parts by weight.

In the photosensitive resin composition of the present invention, when the resin (A-1) having an unsaturated group is not used at all, the photosensitive resin composition obtained has a defect of poor reliability in an environment of high temperature and high humidity.

Polyoxane polymer (A-2)

The polyoxyalkylene polymer (A-2) of the present invention is formed by hydrolysis and partial condensation reaction of a reactant, wherein the reactant comprises a decane monomer, a polyoxyalkylene prepolymer and any mixture of the above materials. And the decane monomer comprises at least one decane monomer having a structure represented by the following formula (I): Si(R ₁ ) _t (OR ₂ ) _4-t (I)

In formula (I), t represents an integer from 1 to 3, and when t represents 2 or 3, each of R ₁ may be the same or different, wherein at least one R ₁ represents an anhydride group substituted with carbon An alkyl group of 1 to 10, an alkyl group substituted by an Epoxy group and having a carbon number of 1 to 10 or an oxyalkyl group substituted by an epoxy group, and the remaining R ₁ represents a hydrogen atom, and the carbon number is An alkyl group of 1 to 10, an alkenyl group having 2 to 10 carbon atoms or an aromatic group having 6 to 15 carbon atoms. When (4-t) represents 2 or 3, the plurality of R ₂ are each the same or different, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a mercapto group having 1 to 6 carbon atoms or carbon. The number is 6 to 15 of an aromatic group.

When the polyoxyalkylene polymer (A-2) has an acid anhydride group or an epoxy group, the polyoxyalkylene polymer has a good affinity with the SiOH functional group on the surface of the glass, and the adhesion can be improved, thereby increasing the high temperature. Moisture resistance and reliability in a wet environment. When the above R ₁ does not contain a functional group substituted with an acid anhydride group or an epoxy group, the photosensitive resin composition obtained has a disadvantage of poor reliability in an environment of high temperature and high humidity.

The alkyl group substituted with an acid anhydride group and having a carbon number of 1 to 10 may include, but not limited to, ethyl succinic anhydride, propyl succinic anhydride, propyl glutaric anhydride, and the like.

The alkyl group substituted with an epoxy group and having a carbon number of 1 to 10 may include, but is not limited to, oxetanylpentyl or 2-(3,4-epoxycyclohexyl)ethyl (2-(3). , 4-epoxycyclohexyl)ethyl) and the like.

The epoxy group-substituted oxyalkyl group may include, but is not limited to, glycidoxypropyl, 2-oxetanylbutoxy, and the like.

In the above R ₂ , the alkyl group may include, but is not limited to, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group. The thiol group can include, but is not limited to, an ethyl group. The aryl group can include, but is not limited to, a phenyl group.

The oxirane monomer as shown in formula (I) may include, but is not limited to, 3-glycidoxypropyltrimethoxysilane (TMS-GAA), 3-glycidoxypropyl 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, 2-epoxypropane 2-oxetanylbutoxypropyltriphenoxysilane; made by East Asia Synthetic Commercially available product: 2-oxetanylbutoxypropyltrimethoxysilane (trade name: TMSOX-D), 2-epoxypropoxybutoxypropyltriethoxy 2-oxetanylbutoxypropyltriethoxysilane (trade name: TESOX-D), 3-(triphenyloxyindenyl)propyl succinic anhydride; commercially available from Shin-Etsu Chemical Co., Ltd.: 3-(trimethoxydecyl) Propyl succinic anhydride (trade name: X-12-967); a commercial product manufactured by WACKER: 3-(triethoxyindolyl)propyl succinic anhydride (trade name GF-20) , 3-(trimethoxyindolyl)propylglutaric anhydride (abbreviated as TMSG), 3-(triethoxyindolyl)propylglutaric anhydride, 3-(triphenyloxyindenyl)propylpentane Diacid anhydride, diisopropoxy-di(2-oxetanylbutoxypropyl)silane; DIDOS], bis(3-epoxypropaneylpentyl) Di(3-oxetanylpentyl)dimethoxy silane, (di-n-butoxyfluorenyl) bis(propyl succinic anhydride), (dimethoxyindenyl) bis(ethyl succinic anhydride) 3-glycidoxypropyl dimethyl methoxy decane (3-gl Ycidoxypropyldimethylmethoxysilane), 3-glycidoxypropyldimethylethoxysilane, bis(2-propylene oxide butyloxypentyl)-2-epoxypropaneylpentyl ethoxylate [di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxysilane], tris(2-oxetanylpentyl)methoxysilane, (phenoxyindenyl) (propyl succinic anhydride) and (methyl methoxy decyl) bis (ethyl succinic anhydride) and the like. before The oxirane monomers shown in the formula (I) may be used singly or in combination of plural kinds.

Preferably, the siloxane monomer may optionally comprise a oxoxane monomer represented by the following formula (I-1): Si(R ₃ ) _u (OR ₄ ) _4-u (I-1)

In the formula (I-1), u represents an integer of 0 to 3. When u represents 2 or 3, a plurality of R ₃ are each the same or different, and R ₃ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a carbon number of 6 to 15 aromatic groups. When (4-u) represents 2, 3 or 4, the plurality of R ₄ are each the same or different, and R ₄ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 6 carbon atoms. Or an aromatic group having a carbon number of 6 to 15.

In R ₃ , the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-butyl, trifluoromethyl, 3,3 , 3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl or 3-isocyanatopropyl. The alkenyl group may include, but is not limited to, a vinyl group, a 3-propenyloxypropyl group, a 3-methylpropenyloxypropyl group, and the like. The aryl group may include, but is not limited to, phenyl, tolyl, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyphenyl)ethyl, 4-hydroxy-5- ( p-Hydroxyphenylcarbonyloxy)pentyl or naphthyl and the like.

In R ₄ , the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl groups and the like. The thiol group can include, but is not limited to, an ethyl group. The aryl group can include, but is not limited to, a phenyl group.

The oxoxane monomer represented by the formula (I-1) may include, but is not limited to, tetramethoxy decane, tetraethoxy decane, tetraethoxy decane, tetraphenoxy decane, methyl trimethoxy. Decane (MTMS), methyl triethoxy decane, Methyl triisopropoxy decane, methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane , n-propyltrimethoxydecane, n-propyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, Mercapto trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, phenyl trimethoxy decane (PTMS for short), phenyl triethoxy decane (PTES for short), p-hydroxyphenyl Trimethoxydecane, 1-(p-hydroxyphenyl)ethyltrimethoxydecane, 2-(p-hydroxyphenyl)ethyltrimethoxydecane, 4-hydroxy-5-(p-hydroxyphenylcarbonyl Oxy)pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, 3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, dimethyldimethoxydecane (DMDMS for short), dimethyldiethoxydecane, dimethyldiethoxydecane, di-n-butyl Dimethoxydecane, diphenyldimethoxydecane, trimethylmethoxydecane, tri-n-butylethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-propenyloxypropyl Trimethoxy decane, 3-methacryloxypropyltrimethoxydecane or 3-methylpropenyloxypropyltriethoxydecane. The above-mentioned oxirane monomers represented by the formula (I-1) may be used singly or in combination of plural kinds.

Preferably, the polyoxyalkylene prepolymer may optionally comprise a polyoxyalkylene prepolymer of the following formula (I-2):

In the formula (I-2), R ₅ , R ₆ , R ₇ and R ₈ are the same or different. When s represents an integer from 2 to 1000, each R ₅ or R ₆ may be the same or different.

The above R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, wherein Any of an alkyl group, an alkenyl group, and an aromatic group may optionally have a substituent. The alkyl group can include, but is not limited to, methyl, ethyl or n-propyl groups and the like. The alkenyl group may include, but is not limited to, a vinyl group, a propylene methoxy propyl group, a methacryloxypropyl group, and the like. The aromatic group may include, but is not limited to, a phenyl group, a tolyl group or a naphthyl group.

The above R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a mercapto group having 1 to 6 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and the alkyl group, the mercapto group and Any of the aromatic groups may optionally have a substituent. The alkyl group can include, but is not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl, and the like. The thiol group can include, but is not limited to, an ethyl group. The aryl group can include, but is not limited to, a phenyl group.

Further, s represented by the formula (I-2) is an integer of 1 to 1000. Preferably, s is an integer from 3 to 300. More preferably, s is an integer from 5 to 200.

The polyoxyalkylene as shown in the formula (I-2) may include, but is not limited to, 1,1,3,3-tetramethyl-1,3-dimethoxydioxane, 1, 1, 3 , 3-tetramethyl-1,3-diethoxydioxane, 1,1,3,3-tetraethyl-1,3-diethoxydioxanane, decyl alcohol manufactured by Gelest Commercially available terminal polyoxyalkylene [commercial names such as DM-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (molecular weight 4200), DMS-S27 (molecular weight for 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight: 43500), DMS-S35 (molecular weight: 49,000), DMS-S38 (molecular weight: 58,000), DMS- S42 (molecular weight: 77000), PDS-9931 (molecular weight: 1,000 to 1400), etc. The polyoxyalkylene represented by the formula (I-2) may be used singly or in combination of plural kinds.

Preferably, the polyaluminoxane polymer (A-2) can be prepared by a polymerization reaction by the aforementioned decane monomer and/or a polyoxyalkylene prepolymer, or a combination of cerium oxide particles via a copolymerization reaction. preparation. The average particle diameter of the cerium oxide particles is not particularly limited, and the average particle diameter thereof may be from 2 nm to 250 nm, preferably from 5 nm to 200 nm, more preferably from 10 nm to 100 nm.

The cerium oxide particles may include, but are not limited to, commercially available products manufactured by Catalyst Corporation [trade names such as OSCAR 1132 (having a particle diameter of 12 nm and a dispersing agent of methanol), OSCAR 1332 (having a particle diameter of 12 nm, and The dispersant is n-propanol), OSCAR 105 (particle size is 60 nm, and the dispersant is γ-butyrolactone), OSCAR 106 (particle size is 120 nm, and the dispersant is diacetone alcohol), etc.], Fuso Chemical Company Commercially available product [trade name such as Quartron PL-1-IPA (particle size 13 nm, and dispersant is isopropanone), Quartron PL-1-TOL (particle size 13 nm, and dispersant is toluene), Quartron PL-2L-PGME (particle size 18nm, dispersant is propylene glycol monomethyl ether), Quartron PL-2L-MEK (particle size 18nm, dispersant is methyl ethyl ketone), etc.], manufactured by Nissan Chemical Co., Ltd. Sales [Product name such as IPA-ST (particle size 12nm, and dispersant is isopropanol), EG-ST (particle size 12nm, and dispersant is ethylene glycol), IPA-ST-L (particle size) It is 45 nm, and the dispersing agent is isopropyl alcohol), IPA-ST-ZL (particle diameter is 100 nm, and the dispersing agent is isopropyl alcohol), etc.].

A general method can be used for the condensation reaction. For example, a solvent, water, or a catalyst is further added to the oxoxane monomer component, followed by heating and stirring at 50 ° C to 150 ° C for 0.5 hour to 120 hours. When stirring, by-products (alcohols, water, etc.) can be further removed by distillation.

The solvent is not particularly limited and may be the same as or different from the solvent (D) of the photosensitive resin composition of the present invention described below. The solvent is used in an amount of 15 g to 1200 g, preferably 20 g to 1100 g, more preferably 30 g to 1000 g, based on the total amount of the siloxane monomer used.

The water for hydrolysis is used in an amount of from 0.5 mol to 2 mol based on 1 mol of the hydrolyzable group contained in the siloxane monomer.

The aforementioned catalyst is not particularly limited, and the catalyst is preferably selected from an acid catalyst or a base catalyst. The acid catalyst may include, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, ion exchange resin, and the like. The base catalyst may include, but is not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, Potassium hydroxide, an alkoxysilane containing an amine group, an ion exchange resin, or the like.

The catalyst is used in an amount of from 0.005 g to 15 g, preferably from 0.01 g to 12 g, more preferably from 0.05 g to 10 g, based on the total amount of the rhodium oxide monomer used.

From the viewpoint of stability, the polyaluminoxane polymer (A-2) obtained by the condensation reaction is preferably free from by-products (such as alcohols or water) and a catalyst, and thus the obtained polyfluorene is obtained. The oxane polymer (A-2) can be selectively purified. The purification method is not particularly limited, and preferably, the hydrophobic solvent may be used to dilute the solution. The polyoxyalkylene polymer (A-2) is then concentrated with an evaporator to remove the organic layer washed several times with water to remove the alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.

The polysiloxane polymer (A-2) is used in an amount of 10 parts by weight to 70 parts by weight, preferably 13 parts by weight to 65 parts by weight, more preferably 15%, based on 100 parts by weight of the alkali-soluble resin. Parts by weight to 60 parts by weight.

Since the polyoxyalkylene polymer (A-2) has good water vapor resistance, the swelling effect of the photosensitive resin composition can be reduced, and the adhesion can be improved. Therefore, when the alkali-soluble resin (A) is not used in combination with the unsaturated group-containing resin (A-1) and the polyoxyalkylene polymer (A-2), the photosensitive resin composition obtained has reliability. Good shortcomings.

Other alkali soluble resin (A-3)

The alkali-soluble resin (A) of the present invention may contain other alkali-soluble resin (A-3). The other alkali-soluble resin (A-3) may include, but is not limited to, a resin having a carboxylic acid group or a hydroxyl group, and specific examples thereof include an unsaturated group (A-1) and a polysiloxane polymer (A-2). Acrylic resin, urethane resin, and novolac resin other than acrylic acid.

The acrylic resin may be manufactured by Toagosei Co., Ltd., and the model number is ARUFON UC-3910 or ARUFON UH-2032. The polyurethane resin may be a product manufactured by Nogakura Kogyo Co., Ltd., model number UN-904, UN-952, UN-333 or UN1255. The novolak type resin can be manufactured by Asahi Organic Materials Co., Ltd., and the model is EP4020G, EP4080G, TR40B45G or EP30B50.

The amount of the alkali-soluble resin (A) used is 100 parts by weight, which is The alkali-soluble resin (A-3) is used in an amount of from 0 part by weight to 40 parts by weight, preferably from 0 part by weight to 30 parts by weight, more preferably from 0 part by weight to 20 parts by weight.

Compound having ethylenically unsaturated group (B)

The compound (B) having an ethylenically unsaturated group is selected from the group consisting of a compound (B-1) having one ethylenically unsaturated group or a compound having two or more (including two) ethylenically unsaturated groups (B) -2).

The compound (B-1) having one ethylenically unsaturated group may include, but is not limited to, acrylamide, propylene morpholine, methacryl morpholine, acryl-7-amino-3,7-dimethyl Kesin ester, -7-amino-3,7-dimethyloctyl methacrylate, isobutoxymethyl acrylamide, isobutoxymethyl methacrylamide, isobornyl acrylate Ethyl ester, isobornyl oxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyl diglycol Acrylate, ethyl diglycol methacrylate, third octyl acrylamide, third octyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, dimethylamino acrylate Ester, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentene oxyethyl acrylate, dicyclopentene oxyethyl methacrylate, bicyclic acrylate Pentene ester, dicyclopentenyl methacrylate, N,N-dimethyl decylamine, N,N-dimethyl methacrylamide, tetrachlorophenyl acrylate, methyl Tetrachlorophenyl acrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tetrabromo acrylate Phenyl ester, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl acrylate, A Base Ethyl-2-trichlorophenoxyethyl ester, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, 2-tribromophenoxy methacrylate Ethyl ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinyl caprolactam, N-vinyl Pyrrolidone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromyl acrylate, pentabromophenyl methacrylate, polyethyl methacrylate Glycol ester, polyethylene monomethacrylate, poly propylene glycol monoacrylate, poly propylene glycol monomethacrylate, borneol acrylate or borneol methacrylate. The compound (B-1) having one ethylenically unsaturated group may be used singly or in combination of plural kinds.

The compound (B-2) having 2 or more (including 2) ethylenically unsaturated groups may include, but is not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate. , dicyclopentenyl dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris(2-hydroxyethyl)isocyanate diacrylate, three (2 -Hydroxyethyl)isocyanate dimethacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, tris(2-hydroxyethyl)isocyanate trimethacrylate,caprolactone modified three (2- Hydroxyethyl)isocyanate triacrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate trimethacrylate, trimethylolpropyl triacrylate, trimethylolpropyl trimethacrylate, Ethylene oxide (hereinafter referred to as EO) modified trimethylol propyl triacrylate, EO modified trimethylol propyl trimethacrylate, propylene oxide (hereinafter referred to as PO) modified triacrylate three Hydroxymethyl propyl ester, PO modified trimethylol propyl trimethacrylate, triethylene glycol dipropyl Ethyl ester, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol II Methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethyl Acrylate, polyester diacrylate, polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modification Dipentaerythritol hexamethacrylate, caprolactone modified dipentaerythritol pentaacrylate, caprolactone modified dipentaerythritol pentamethacrylate, ditrimethylol propyl tetraacrylate Ester, ditrimethylol propyl tetramethacrylate, EO modified bisphenol A diacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO Modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethacrylate, PO modified triglyceride, EO modified bisphenol F diacrylate, EO modified bisphenol F dimethacrylate, phenolic polymerization Glycidyl ether acrylate, or phenolic polyglycidyl ether methacrylate, and the like. The compound (B-2) having two or more (including two) ethylenically unsaturated groups may be used singly or in combination of plural kinds.

Preferably, the ethylenically unsaturated group-containing compound (B) is selected from the group consisting of trimethylolpropyl acrylate, EO-modified trimethylolpropyl acrylate, and PO-modified tris-trisyl triacrylate. Methyl propyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrihydroxy hydroxytetraacrylate Methyl propyl ester, propylene oxide modified glycerol triacrylate or a combination of these.

The compound (B) having an ethylenically unsaturated group is used in an amount of 20 parts by weight to 180 parts by weight, preferably 25 parts by weight to 160 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). More preferably, it is 30 parts by weight to 140 parts by weight.

Photoinitiator (C)

The photoinitiator (C) of the present invention is selected from the group consisting of oxime compounds (C-1), acetophenone compounds (C-2), other photoinitiators (C-3) or the above materials. Any combination.

The lanthanide compound (C-1) may include, but is not limited to, 1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]-ethanone-1 -(O-Ethylamino){1-[9-ethyl-6-(2-methylbezoyl)-9H-carbozole-3-yl]-ethanone-1-(o-acetyl oxime)} (eg Ciba Specialty Chemicals Produced by the company, model OXE-02), 1-[9-ethyl-6-(2-chloro-4-phenylsulfobenzoyl)-9H-indazol-3-yl]-ethane Ketone-1-(O-acetamidopurine) {1-[9-ethyl-6-(2-chloro-4-benzylsulfonyl benzoyl)-9H-carbozole-3-yl]-ethanone-1-(o-acetyl Oxime)} (for example: goods manufactured by Asahi Chemical Co., Ltd.), 1-(4-phenyl-thiobenzene) -butane-1,2-dione 2-indole-oxy-benzoic acid ester, 1-(4-phenyl-thiophenyl)-octane-1,2-dione 2-indole-oxygen - benzoate (for example, manufactured by Ciba Specialty Chemicals, model OXE-01), 1-(4-phenyl-thiophenyl)-octane-1-one oxime-oxy-acetate, 1 -(4-Phenyl-thiophenyl)-butan-1-one oxime-oxy-acetate. The oxime compound (C-1) may be used singly or in combination of plural kinds.

The acetophenone-based compound (C-2) may include, but is not limited to, p-dimethylamine acetophenone, α , α' -dimethoxy acetophenone, 2,2'-dimethyl-2 - acetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (2-methyl-1-(4) -methylthiophenyl)-2-morpholino-1-propanone), 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone [2-benzyl-2 -N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone] and the like. The acetophenone-based compound (C-2) may be used singly or in combination of plural kinds. Preferably, the acetophenone compound (C-2) is selected from the group consisting of 2-methyl-1-(4-methylthiophenyl)-2- morpholino-1-propanone or 2-benzyl Base-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone.

The other photoinitiator (C-3) may include, but is not limited to, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2' - bis(o-fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5' -tetraphenyldiimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxy Phenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4' , 5,5'-tetraphenyldiimidazole or diimidazole of 2,2'-bis(2,2'-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole ( Biimidazole) compound; thioxantone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4'-bis(dimethylamine)benzol a ketone or a benzophenone compound such as 4,4'-bis(diethylamine)benzophenone; an α -diketone compound such as benzil or an ethenyl group; a acyloin compound such as benzoin; a acyloin ether compound such as diphenylethanol ketone methyl ether, benzophenone ether or diphenylethanol ketone isopropyl ether; , 4,6-trimethylphenylhydrazine diphenylphosphine oxide or bis-(2,6-dimethoxy a compound having an acylphosphine oxide such as anthraquinone)-2,4,4-trimethylbenzylphosphine oxide; an anthraquinone compound such as hydrazine or 1,4-naphthoquinone; a halide compound such as phenacyl chloride, tribromomethylphenylhydrazine or tris(trichloromethyl)-s-triazine; di-t-butyl group A peroxide such as a peroxide or any combination of the above compounds.

The photoinitiator (C) is used in an amount of 10 parts by weight to 80 parts by weight, preferably 12 parts by weight to 75 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), more preferably 15 parts by weight to 70 parts by weight.

Solvent (D)

The solvent (D) of the present invention dissolves the alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, and the photoinitiator (C), and does not react with the components, and has an appropriate volatilization. Sex is better.

The solvent (D) may include, but is not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol single n-Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether (referred to as PGEE), Alkylene glycol monobutyl ether monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether An alkyl ether compound; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc. Alkyl glycol monoalkyl ether acetate compound; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ether compounds; methyl ethyl ketone, a ketone compound such as cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone (abbreviated as DAA); methyl 2-hydroxypropionate, An alkyl lactate compound such as ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxyethylpropionate (EEP), ethoxyethyl acetate, hydroxyacetic acid Ester, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid Other esters of propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate, etc. a compound; an aromatic hydrocarbon compound such as toluene or xylene; a guanamine compound such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide or the above solvent Any combination. The solvent (D) may be used singly or in combination of plural kinds.

The solvent (D) is used in an amount of from 1000 parts by weight to 7,000 parts by weight, based on the total amount of the alkali-soluble resin (A), preferably from 1300 parts by weight to 6,000 parts by weight, more preferably 1600 parts by weight. Parts to 5000 parts by weight.

Black pigment (E)

The black pigment (E) suitable for use in the present invention is preferably a black pigment having heat resistance, light resistance and solvent resistance.

Specific examples of the black pigment (E) described above, such as black organic pigments such as perylene black, cyanine black, and aniline black; red, blue, green, and purple Among the pigments such as yellow, cyanine, and magenta, two or more pigments are selected and mixed to form a nearly blackened mixed color organic pigment; carbon black, chromium oxide, a light-shielding material such as iron oxide, titanium black or graphite, wherein the carbon black may include, but is not limited to, CIpigment black 7, etc., and the carbon black is, for example, a commercially available product manufactured by Mitsubishi Chemical Corporation (the trade name thereof) It is MA100, MA230, MA8, #970, #1000, #2350 or #2650). The aforementioned black pigment (E) may be used singly or in combination of plural kinds.

The black pigment (E) is used in an amount of 100 parts by weight to 600 parts by weight, preferably 130 parts by weight to 550 parts by weight, more preferably 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Parts to 500 parts by weight.

In the photosensitive resin composition of the present invention, if the black pigment (E) is not used, the obtained photosensitive resin composition has a high temperature and high humidity condition. The shortcomings of poor reliability.

Black dye (F)

The black dye (F) of the present invention is preferably a dye other than the black pigment (E), and may include, but is not limited to, an acid dye, a basic dye, a disperse dye, an oil-soluble dye, or any combination of the above dyes.

Preferably, the black dye (F) may be an acid dye or a basic dye. The acid dye may be an azo metal complex dye such as chromium, copper or cobalt. The basic dye may be a polymethine dye having an amino or amino substituted quaternary ammonium salt, an azo dye, a azomethine dye, an anthraquinone dye or a triphenylmethane dye.

Specific examples of the azo-based metal complex dyes are: manufactured by Hodogaya Chemical Co., Ltd., models of Aizen Spilon Black BNH, MH, RLH, BH; manufactured by BASF, model No. NeoZapon X55, NeoZapon X51, A commercial product of an azo-based chromium metal complex dye such as Basantol Black X82.

Specific examples of the basic dye include, for example, manufactured by Hodogaya Chemical Co., Ltd., and models of Aizen Cathilon Black SBH, BXH, SH, NH, MH, AWH, and KBH.

Specific examples of the disperse dye may include, but are not limited to, those manufactured by Mitsui BASF Dyestuff Co., Ltd., models of Miketon Polyester dye, Miketon Fast dye, Dispersol dye, Palanil dye, etc.; and products manufactured by Sumitomo Chemical Co., Ltd., model Sumikaron dyes; Made by Nippon Kayaku Co., Ltd., model of Kayal on Polyester dye; Dystar Co., Ltd., model of Dianix dye; Ciba A product of the type Terasil dyes manufactured by Speciality Chemical; a product of the type Foron dye manufactured by Clariant.

Specific examples of the aforementioned oil-soluble dyes are: those manufactured by BASF Corporation, modeled after by Sudan Black X60; manufactured by Orient Chemical Industries, and sold under the trademarks of Nubian Black PC-0850, Oil Black HBB, etc.; CISolvent Black-3, - 7, -22: 1, -27, -29, -34, -50 and other commercial products.

The black dye (F) is used in an amount of 20 parts by weight to 200 parts by weight, preferably 25 parts by weight to 180 parts by weight, more preferably 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). 160 parts by weight.

When the photosensitive resin composition does not contain the black dye (F), the obtained photosensitive resin has a defect that the optical density value and the resistance value are low.

Additive (G)

The photosensitive resin composition of the present invention may optionally contain the additive (G) without affecting the effects of the present invention. The additive (G) may include, but is not limited to, a surfactant, a filler, a adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, or an alkali-soluble resin (A), which can increase various properties (such as mechanical properties). Polymers, etc.

Preferably, the surfactant is selected from the group consisting of cationic, anionic, nonionic, amphoteric, polyoxyalkylene, fluoro or any combination of the above surfactants. The surfactant may include, but is not limited to, a polyethoxylated alkyl ether surfactant such as polyethoxydodecyl ether, polyethoxylated oxime ether or polyethoxy oleyl ether; Polyethoxylated alkylphenyl ether surfactants such as oxyoctylphenyl ether or polyethoxylated nonylphenyl ether; Polyethylene glycol diester surfactant such as ethylene glycol dilaurate or polyethylene glycol distearate; sorbitan fatty acid ester surfactant; fatty acid modified polyester surfactant And a tertiary amine modified polyurethane surfactant. The surfactant may be used singly or in combination of plural kinds.

The surfactant may include, but is not limited to, a product of the type KP manufactured by Shin-Etsu Chemical Co., Ltd.; a product of the model SF-8427 manufactured by Toray Dow Corning Silicon Co., Ltd.; a product of the model Polyflow manufactured by Kyoritsu Oil & Fat Chemical Industry Co., Ltd.; Manufactured by Tochem Product Co., Ltd., model F-Top; manufactured by Dainipa INK Chemical Industry Co., Ltd., model of Megafac; manufactured by Sumitomo 3M, model of Fluorade; manufactured by Asahi Glass, model is Asahi Guard, Surflon Commodities; manufactured by Sino-Japanese Synthetic Chemicals, model SINOPOL E8008.

The total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the surfactant is used in an amount of from 0 part by weight to 6 parts by weight, preferably from 0 part by weight to 4 parts by weight.

The filler may include, but is not limited to, glass or aluminum or the like. The adhesion promoter may include, but is not limited to, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 -glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloro Propylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxy Decane or 3-thiolpropyltrimethoxydecane, and the like. The antioxidant may include, but is not limited to, 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol, and the like. The ultraviolet absorber may include, but is not limited to, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole [2-(3-t-butyl-5-). Methyl-2-hydroxyphenyl)-5-chloro benzotriazole] or alkoxybenzophenone. The anti-agglomerating agent may include, but is not limited to, sodium polyacrylate or the like.

The total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the polymer other than the filler, the adhesion promoter, the antioxidant, the ultraviolet absorber, the anti-aggregation agent, or the alkali-soluble resin (A) is used. It is 0 parts by weight to 10 parts by weight, preferably 0 parts by weight to 6 parts by weight.

Preparation of photosensitive resin composition

The method for producing a photosensitive resin composition of the present invention is the above-mentioned alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment ( E) and the black dye (F) are placed in a stirrer to be stirred and uniformly mixed into a solution state, and if necessary, a surfactant, a filler, a adhesion promoter, an antioxidant, an ultraviolet absorber, or the like may be selectively added. An additive (G) other than the anti-aggregation agent or the alkali-soluble resin (A), which can increase various properties such as mechanical properties.

Preparation of black matrix and pixel layer

The black matrix of the present invention is obtained by sequentially pre-baking, exposing, developing and post-baking the above-mentioned photosensitive resin composition.

The preparation of the black matrix can be carried out by applying a photosensitive resin composition onto a substrate by a coating method such as spin coating or cast coating, and removing the solvent therein by drying under reduced pressure and pre-baking, and further A pre-baked coating film is formed on the substrate. Among them, the conditions of drying under reduced pressure and pre-baking vary depending on the type and blending ratio of each component, and drying under reduced pressure is generally carried out for 1 second to 20 seconds in an environment having a pressure of less than 200 mmHg, and pre-baking treatment at 70 °C. It is carried out at a temperature of 110 ° C for 1 minute to 15 minutes. Then, the coating film is placed under a designated mask for exposure, and immersed in a developer at a temperature of 21 ° C to 25 ° C for 15 seconds to 5 minutes to remove unnecessary portions to form a specific pattern. The light used for the exposure is preferably ultraviolet rays such as g-line, h-line or i-line, and the ultraviolet irradiation device may be an (ultra) high-pressure mercury lamp and a metal halide lamp.

The developer used in the preparation of the black matrix of the present invention may include, but is not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, and Amine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7 a basic compound such as undecene. The concentration of the developer is from 0.001% by weight to 10% by weight, preferably from 0.005% by weight to 5% by weight, more preferably from 0.01% by weight to 1% by weight.

When a developer composed of the above-mentioned basic compound is used, it is usually washed with water after development, and air-dried with compressed air or compressed nitrogen. Next, post-baking treatment is carried out using a heating device such as a hot plate or an oven, and the heating temperature is usually from 150 ° C to 250 ° C. Among them, the heating time using the hot plate is 1 minute to 60 minutes, and the heating time using the oven is 5 minutes to 90 minutes. through After the above processing steps, a black matrix can be formed.

The glass substrate used for the black matrix can be an alkali-free glass, a soda-lime glass, a tempered glass (Pyrex glass), a quartz glass, a glass having a transparent conductive film attached to the surface, or a solid-state photographic element applied to a liquid crystal display. A photoelectric conversion element substrate (for example, a germanium substrate).

Preparation of color filters

The color filter of the present invention comprises the above-described black matrix, wherein the black matrix has a surface resistance value of 10 ¹⁰ Ω/cm ² to 10 ¹⁷ Ω/cm ² .

The color filter can be prepared according to a general preparation method, for example, the black matrix described above is formed on a substrate, and the colors (mainly including red, green, and blue colors) are formed on the substrate in the same manner. Further, a pixel colored layer of a color filter is obtained. Next, an indium tin oxide (ITO) deposited film is formed on the pixel colored layer in a vacuum environment of 220 ° C to 250 ° C, and if necessary, the ITO vapor deposited film is etched and etched, and then coated. A color filter for a liquid crystal display can be obtained by using a polyimide film for a liquid crystal alignment film.

Preparation of liquid crystal display elements

The liquid crystal display device of the present invention comprises the color filter described above, and can be obtained in accordance with a conventional method. For example, the color filter and the driving substrate provided with a thin film transistor (TFT) are firstly connected to each other. In contrast, a cell gap is interposed between the two substrates for opposite direction, and the surrounding portions of the two substrates are bonded together with a sealing agent, leaving only A liquid crystal injection hole is filled with a liquid crystal injected into the gap between the surface of the substrate and the sealing agent, and the liquid crystal injection hole is sealed to form a liquid crystal cell. Then, a liquid crystal display element can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell, that is, on the other side surface of the substrate constituting the liquid crystal cell.

The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

110‧‧‧ incident light

120‧‧‧Black matrix

130‧‧‧Out of light

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a side elevational view showing the manner in which optical density values are evaluated in accordance with the present invention.

Preparation of resin with unsaturated groups (A-1) Synthesis Example A-1-1

100 parts by weight of a ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, having an epoxy equivalent of 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight of benzyltriethyl chloride Ammonium, 0.1 parts by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous addition to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight / minute, the temperature of the reaction process is maintained at 100 ° C to 110 ° C, after 15 hours of reaction, a solid concentration of 50 can be obtained Light yellow transparent mixture of weight percent.

Next, 100 parts by weight of the above pale yellow transparent mixed solution was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone were simultaneously added. The tetracarboxylic dianhydride was heated to 110 ° C to 115 ° C, and after reacting for 2 hours, a resin (A-1-1) having an unsaturated group was obtained, and its acid value was 98.0 mgKOH/g.

Synthesis Example A-1-2

100 parts by weight of a ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, having an epoxy equivalent of 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight of benzyltriethyl chloride Ammonium, 0.1 parts by weight of 2,6-di-t-butyl-p-cresol, and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous manner to a 500 mL four-necked flask, and the feed rate was controlled. At 25 parts by weight/minute, the temperature of the reaction was maintained at 100 ° C to 110 ° C, and after reacting for 15 hours, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above pale yellow transparent mixture is dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride is added, and the reaction is carried out at 90 ° C to 95 ° C. 2 hours. Next, 6 parts by weight of tetrahydrophthalic anhydride is added and reacted at 90 ° C to 95 ° C for 4 hours to obtain a resin (A-1-2) having an unsaturated group, and the acid value thereof is 99.0 mg KOH / g.

Synthesis Example A-1-3

400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., model: NC-3000, and having an epoxy equivalent of 288) and 102 parts by weight Acrylic acid, 0.3 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and 264 parts by weight of propylene glycol monomethyl ether acetate were placed in a reaction flask, and the temperature of the reaction was maintained at 95 ° C. After 9 hours, an intermediate product having an acid value of 2.2 mgKOH/g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain an unsaturated group-containing resin (A-1-3) having an acid value of 102 mgKOH/g. And the weight average molecular weight was 3,200.

Preparation of polyaluminoxane polymer (A-2)

The polyaluminoxane polymers of Synthesis Examples A-2-1 to A-2-6 were prepared according to Table 1 below.

Synthesis Example A-2-1

In a 500 ml three-necked flask, 0.30 mol of methyltrimethoxydecane (hereinafter referred to as MTMS), 0.45 mol of phenyltrimethoxydecane (hereinafter referred to as PTMS), 0.05 mol of 3- (Triethoxy decyl) propyl succinic anhydride (hereinafter referred to as GF-20), 0.20 mol of 3-(trimethoxyindolyl) propyl methacrylate (hereinafter referred to as KBM-503) and 180 g 4-Hydroxy-4-methyl-2-pentanone (hereinafter abbreviated as DAA), and an aqueous oxalic acid solution (0.4 g of oxalic acid / 75 g of water) was added over 30 minutes while stirring at room temperature. Next, the flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes, and then the oil bath was heated to 120 ° C in 30 minutes. When the internal temperature of the solution reached 110 ° C, heating and stirring were continued for polycondensation for 6 hours. The polysiloxane polymer (A-2-1) can be obtained by removing the solvent by distillation. The types of raw materials and the amounts thereof used in Preparation Example A-2-1 are shown in Table 1.

Synthesis Example A-2-2 to Synthesis Example A-2-6

Synthesis Examples A-2-2 to A-2-6 were prepared in the same manner as in the production method of the polyaluminoxane polymer of Synthesis Example A-2-1 except that Synthesis Example A-2-2 was A-2-6 changes the type and amount of the raw material in the polyoxyalkylene polymer, and the formulation thereof is shown in Table 1, and will not be further described herein.

Preparation of photosensitive resin composition

The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 9 were prepared according to Tables 2 and 3 below.

Example 1

30 parts by weight of the unsaturated group-containing resin (A-1-1) of Synthesis Example A-1-1, 35 parts by weight of the polyaphoxylate polymer of Synthesis Example A-2-1, and 35 parts by weight The polyaluminoxane polymer of Synthesis Example A-2-4, 20 parts by weight of trimethylolpropyl acrylate (hereinafter abbreviated as B-1), and 10 parts by weight of 1-[9-ethyl-6- (2-Methylbenzylidene)-9H-indazole-3-substituted]-ethanone 1-(oxo-ethenylhydrazine) (manufactured by Ciba Specialty Chemicals, Inc., model OXE-02, Hereinafter, it is abbreviated as C-1), 1000 parts by weight of propylene glycol methyl ether acetate (hereinafter abbreviated as D-1), 100 parts by weight of MA100 (black pigment manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as E-1), and 20 parts by weight. The NeoZapon X55 (black dye manufactured by BASF Corporation, hereinafter abbreviated as F-1) was formed into a uniform solution state by a shaking stirrer to obtain a photosensitive resin composition of Example 1. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 2, and the methods for detecting the reliability, the surface resistance value, and the optical density value will be described later.

Examples 2 to 7 and Comparative Examples 1 to 9

In Examples 2 to 7 and Comparative Examples 1 to 9, the same production method as that of the photosensitive resin composition of Example 1 was used, except that Examples 2 to 7 and Comparative Examples 1 to 9 changed the photosensitivity. The types and amounts of the raw materials in the resin composition, and the other dyes (F') were added to Comparative Examples 6 and 7, and the formulations and evaluation results are shown in Tables 2 and 3, respectively, and are not described here.

Preparing a black matrix

The above-mentioned photosensitive resin composition was applied onto a glass substrate having a size of 100 mm × 100 mm by spin coating in a coater (model: MS-A150; available from Shinko Trading), and was 100 mmHg. Drying under reduced pressure for 5 seconds. Then, it was prebaked in an oven at 100 ° C for 2 minutes to form a prebaked coating film having a film thickness of 1.2 μm. Next, the prebaked coating film was irradiated with ultraviolet light (exposure model: AG500-4N; manufactured by M&R Nano Technology), wherein the intensity of the ultraviolet light was 100 mJ/cm ² . Thereafter, it was immersed in a developing solution (0.04% of potassium hydroxide) at 23 °C. After 2 minutes, it was washed with pure water and post-baked at 230 ° C for 60 minutes in an oven to form a black matrix having a film thickness of 1.0 μm on the glass substrate.

Evaluation method Reliability

The black matrix prepared by using the photosensitive resin compositions of the above Examples 1 to 7 and Comparative Examples 1 to 9 was placed at a temperature of 121 ° C and the pressure was In an oven of 2 atm and a relative humidity of 100%, after 8 hours, the aforementioned black matrix was cut into 100 by a knife according to the method of 8.5.2 in the adhesion test method of JIS. 5400 (1900) 8.5. After the base of the substrate, the tape was peeled off and peeled off, and the residue of the base was observed, and evaluated according to the following criteria:

○:>4B.

△: 3B to 2B.

×: 1B to 0B.

Among them, >4B: 0% ≦ fell off the number of bases ≦ 5%.

3B: The number of bases of 5% ≦ shed is ≦ 15%.

2B: The number of bases where 15% of the cockroaches fell off was 5%35%.

1B: The number of bases on which 35% of the cockroaches fell off was ≦65%.

0B: The number of bases where 65% of the cockroaches fall off is %100%.

2. Surface impedance value

The black matrix having the film thickness of 1.0 μm obtained by the use of Examples 1 to 7 and Comparative Examples 1 to 9 was measured using a high-impedance meter (Model: MCP-HT450 type Hiresta-UP; manufactured by Mitsubishi Chemical Corporation). For measurement, take three measurement points on the above black matrix, measure the average value of the surface resistance (Ω _S ), and evaluate according to the following criteria:

○: 1.0E+10≦Ω _S .

△: 1.0E+8≦Ω _S <1.0E+10.

×: Ω _S <1.0E+8.

3. Optical Density Value (Optical Density Value)

Please refer to Fig. 1, which is a side view showing the evaluation method of the optical density value according to the present invention. First, the black matrix 120 (the film thickness is 1.0 μm) obtained in the above Examples 1 to 7 and Comparative Examples 1 to 9 is irradiated with the incident light 110 having an intensity of I _{0 , and} the light emitted through the black matrix 120 is measured. Strength of 130 (I). Then, the optical density value of the black matrix 120 is calculated by the following formula (VI) and evaluated according to the following criteria:

○: 4.0 ≦ optical density value.

△: 3.8 ≦ optical density value < 4.0.

×: Optical density value <3.8.

From the results of the second table and the third table, it is understood that the photosensitive resin composition is used together with a resin (A-1) having an unsaturated group, a polysiloxane polymer (A-2), a black pigment (E), and black. In the case of the dye (F), the photosensitive resin composition obtained has good reliability, surface resistance value and optical density value in a high-temperature and high-humidity environment.

Next, when the photosensitive resin composition is used in combination with the unsaturated group-containing resin (A-1) and the polyoxyalkylene polymer (A-2), the obtained photosensitive resin composition can have good reliability. When the polyoxyalkylene polymer (A-2) has an acid anhydride group or an epoxy group, the acid anhydride group or the epoxy group can further improve the reliability of the photosensitive resin composition in an environment of high temperature and high humidity.

Further, when the photosensitive resin composition contains the black pigment (E), the photosensitive resin composition obtained can have a higher temperature and high humidity environment. The reliability is good, and when the photosensitive resin composition contains the black dye (F), the black dye (F) can increase the surface resistance value and the optical density value of the photosensitive resin composition.

It should be noted that the present invention describes a photosensitive resin composition for a color filter of the present invention and an application thereof by using specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments as examples, but the present invention belongs to It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds may be used for the photosensitive resin composition for color filters of the present invention and applications thereof without departing from the spirit and scope of the present invention. , composition, reaction conditions, process, analytical methods or instruments.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

Claims (6)

A photosensitive resin composition comprising: an alkali-soluble resin (A) comprising: a resin (A-1) having an unsaturated group, which is obtained by performing a polymerization reaction on a mixture, and the mixture contains at least two Epoxy group-containing epoxy compound (i) and compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group; and polyoxyalkylene polymer (A-2), which is a reactant Forming by hydrolysis and partial condensation reaction, wherein the reactant comprises a monodecane monomer, a polyoxyalkylene prepolymer and any mixture of the above materials, and the decane monomer comprises at least one of the following formula (I) The decane monomer of the structure: Si(R ₁ ) _t (OR ₂ ) _4-t (I) In the formula (I), the t represents an integer of 1 to 3, and when t represents 2 or 3, the plural Each of R ₁ is the same or different, wherein at least one R ₁ represents an alkyl group substituted with an acid anhydride group and having a carbon number of 1 to 10, an alkyl group substituted with an epoxy group and having a carbon number of 1 to 10, and an epoxy group. a substituted oxyalkyl group, and the remaining R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aromatic group having 6 to 15 carbon atoms; When the (4-t) represents 2 or 3, the plurality of R ₂ are each the same or different, and the R ₂ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a fluorenyl group having 1 to 6 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms; a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); a black pigment (E); and a black dye (F), selected from the group consisting of an acid dye, a basic dye, a disperse dye, an oil-soluble dye, or any combination of the above dyes, wherein the acid dye comprises an azo-based metal complex dye of chromium, copper, cobalt or the like, the base The dye includes a polymethine dye having an amino group or an amino-substituted quaternary ammonium salt, an azo dye, a azomethine dye, an anthraquinone dye or a triphenylmethane dye, and the amount of the alkali-soluble resin (A) used is 100. The black dye (F) is used in an amount of from 20 parts by weight to 200 parts by weight per part by weight. The photosensitive resin composition according to claim 1, wherein the epoxy compound (i) having at least two epoxy groups has a structure represented by the following formula (II) or formula (III): In the formula (II), the B ₁ , B ₂ , B ₃ and B ₄ are the same or different, respectively, and the B ₁ , B ₂ , B ₃ and B ₄ represent a hydrogen atom, a halogen atom and a carbon number, respectively. An alkyl group of 1 to 5, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms; In the formula (III), the D ₁ to the D ₁₄ are the same or different, respectively, and the D ₁ to D ₁₄ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a carbon number, respectively. An aromatic group of 6 to 15, and the n represents an integer of 0 to 10. The photosensitive resin composition according to claim 1, wherein the amount of the unsaturated group-containing resin (A-1) is 30, based on 100 parts by weight of the alkali-soluble resin (A). The polyadenine polymer (A-2) is used in an amount of 10 parts by weight to 70 parts by weight, and the ethylenically unsaturated group-containing compound (B) is used in an amount of 20 parts by weight. To 180 parts by weight, the photoinitiator (C) is used in an amount of 10 parts by weight to 80 parts by weight, the solvent (D) is used in an amount of 1000 parts by weight to 7000 parts by weight, and the black pigment (E) is used. The amount used is from 100 parts by weight to 600 parts by weight. A black matrix formed of the photosensitive resin composition according to any one of claims 1 to 3. A color filter comprising the black matrix as described in claim 4 of the patent application. A liquid crystal display element comprising the color filter of claim 5 of the patent application.