TWI539235B - Photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display device - Google Patents

Description

Photosensitive resin composition, color filter and preparation thereof Method, liquid crystal display device

The present invention relates to a photosensitive resin composition, a color filter, a method of producing the same, and a liquid crystal display device including the color filter. In particular, the present invention relates to a pixel formed of a photosensitive resin composition for a color filter having a low surface roughness and a high-definition pattern, a color filter produced therefrom, a method for producing the same, and a liquid crystal display. Device.

At present, color filters are widely used in applications such as color liquid crystal displays, color facsimile machines, and color cameras. With the increasing market demand for color liquid crystal displays, the production techniques of color filters are also diversified, such as dyeing, printing, electroplating, and dispersion methods, among which the dispersion method is the mainstream.

In the dispersion process, a pigment is dispersed in a photosensitive resin to form a photosensitive resin composition, and a photosensitive resin composition is applied onto a glass substrate, and a specific pattern is obtained by exposure, development, and the like. After repeatedly performing the above processes of coating, exposure, and development three times, the system is prepared. Red (R), green (G), and blue (B) pixel coloring patterns in the color filter. In general, in order to further improve the contrast of the color filter, a black matrix (or a light shielding layer) is disposed between the pixel coloring patterns.

In recent years, with the miniaturization and weight reduction of personal digital assistants and digital cameras, color filters need to be further thinned and highly colored, and therefore it is necessary to increase the amount of pigment in the photosensitive resin composition. However, when the amount of the pigment is increased, the amount of the photosensitive resin in the photosensitive resin composition is relatively small, and when the amount of the photosensitive resin contributing to the adhesion of the pixel coloring pattern is small, the pixel coloring pattern is The adhesion is lowered, so that the pixel coloring pattern is easily peeled off, resulting in poor linearity of the high-definition pattern. The existing technical solutions for solving the above problems are as follows: (1). Japanese Patent Laid-Open No. 2005-316012 selects the type of photoinitiator and increases the amount of photoinitiator; (2). Japanese Patent No. 3390514 improves the pixel coloring pattern. (3). Japanese Patent Laid-Open No. 2006-258916 adds an exposure process between development and post-baking to prevent deformation of the pixel coloring pattern; (4). Japanese Patent Laid-Open No. 2007-139906, JP-A-2007-138051, Patent No. 3,372,221 and JP-A-2000-162429 improve the photosensitive resin composition by a polymer pigment; however, the technical solution of the above patent makes the surface roughness of the pixel coloring pattern high.

From the above, it is known how to improve the surface roughness of the pixel formed by the photosensitive resin composition and the poor linearity of the high-definition pattern to meet the requirements of the current industry, which is currently highly sought by by those skilled in the art. problem.

In view of the above, the present invention provides a photosensitive resin composition for a color filter used in a liquid crystal display device, which can improve the problem of poor linearity of the surface roughness and the high-definition pattern.

Thus, the present invention provides a photosensitive resin composition for a color filter comprising: an alkali-soluble resin (A); and an ethylenically unsaturated group-containing compound (B) comprising a first compound containing an ethylenically unsaturated group (B-1); a photoinitiator (C); an organic solvent (D); and a pigment (E); wherein the ethylenically unsaturated group-containing first compound (B-1) has the formula (I) The structure shown,

In the formula (I), R ¹¹ represents hydrogen or a methyl group, and R ¹² represents an alkylene group having a carbon number of 1 to 20 and substituted or unsubstituted with a hydroxyl group, or a carbon number of 6 to 20 and substituted by a hydroxyl group or not Substituted aryl, one or more -CH ₂ - groups in the alkyl and aryl groups may each independently be -O-, -S-, -CO-, -O-CO- or - CO-O-substituted, X represents a decyloxy group.

In an embodiment of the invention, X represents a decyloxy group represented by formula (I-1), (I-2), or (I-3), In the formulae (I-1) to (I-3), R ²¹ to R ²⁵ each independently represent a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₂₀ aryl group, and n represents an integer of 1 to 50.

In one embodiment of the present invention, the ethylenically unsaturated group-containing first compound (B-1) is used in an amount ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). .

In an embodiment of the invention, the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1) having an unsaturated group, and the first alkali-soluble resin having an unsaturated group (A-1) It is prepared by a polymerization of a first mixture comprising an epoxy compound having at least two epoxy groups, and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group.

In one embodiment of the present invention, the epoxy compound having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (V), and is represented by the formula (VI). An epoxy compound having at least two epoxy groups, or a combination of the above,

In the formulae (V) and (VI), R ⁴¹ to R ⁴⁴ each independently represent hydrogen, halogen or a C ₁ to C ₅ alkyl group, and R ⁵¹ to R ⁶⁵ each independently represent hydrogen, halogen, C ₁ to C _{8 .} An alkyl group or a C ₆ to C ₁₅ aryl group, and n represents an integer of 0 to 10.

In one embodiment of the present invention, the total alkali-soluble resin (A-1) having an unsaturated group is contained in an amount ranging from 5 to 70 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). .

In an embodiment of the invention, the ethylenically unsaturated group-containing compound (B) further comprises a second compound (B-2) containing an ethylenically unsaturated group, and the second ethylenically unsaturated group-containing compound The compound (B-2) is a combination selected from the formula (II), the formula (III) or the above; wherein the formula (II) and the formula (III) are as follows:

In the formulae (II) and (III), R ³¹ represents -[(CH ₂ ) _y CH ₂ O]- or -[(CH ₂ ) _y CH(CH ₃ )O]-, and y represents an integer of 1 to 10 R ³² represents hydrogen, a carboxyl group or a (meth) acrylonitrile group, and in the formula (II), the total number of the (meth) acryl fluorenyl groups is 3 or 4, and m1 to m4 each independently represent an integer of 0 to 10. And the total of m1 to m4 is an integer of 1 to 40; in the formula (III), the total of the (meth)acryl fluorenyl groups is 5 or 6, and n1 to n6 each independently represent an integer of 0 to 10, And the sum of n1 to n6 is an integer of 1 to 60.

In one embodiment of the present invention, the ethylenically unsaturated group-containing second compound (B-2) is used in an amount ranging from 10 to 100% by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). Share.

In one embodiment of the present invention, the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 30 to 300 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A); The starting agent (C) is used in an amount ranging from 10 to 200 parts by weight; the organic solvent (D) is used in an amount ranging from 500 to 5000 parts by weight; and the pigment (E) is used in an amount ranging from 50 to 500 parts by weight.

The present invention further provides a method of producing a color filter comprising the pixel layer formed using the photosensitive resin composition for a color filter described above.

The present invention further provides a color filter which is produced by the above-described manufacturing method.

The present invention further provides a liquid crystal display device comprising the above-described color filter.

Based on the above, the photosensitive resin composition of the present invention is used for the shape When the color filter is formed, the problem of poor surfaceness of the surface roughness and the high-definition pattern can be improved, and the color filter and the liquid crystal display device can be applied.

The above described features and advantages of the invention will be apparent from the following description.

Alkali Soluble Resin (A)

The alkali-soluble resin (A) includes a first alkali-soluble resin (A-1), a second alkali-soluble resin (A-2), or a combination of the two.

[First alkali-soluble resin (A-1) having an unsaturated group]

The first alkali-soluble resin (A-1) having an unsaturated group is obtained by a polymerization reaction of a first mixture, the first mixture comprising an epoxy compound having at least two epoxy groups, and one having At least one carboxylic acid group and at least one ethylenically unsaturated group compound. The first mixture may also optionally include a carboxylic anhydride compound, an epoxy compound having an epoxy group, or a combination of the two.

<Epoxy compound having at least two epoxy groups>

The epoxy compound having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (V), and having at least two epoxy groups represented by the formula (VI). An epoxy compound, or a combination of the foregoing.

The epoxy compound having at least two epoxy groups represented by the formula (V) is as follows:

Wherein R ⁴¹ to R ⁴⁴ each independently represent hydrogen, halogen or C ₁ to C ₅ alkyl.

The epoxy compound having at least two epoxy groups represented by the formula (V) is obtained by reacting a first reactant comprising a bisphenol fluorene and an epihalohydrin.

The bisphenol quinoid compound can be used singly or in combination, such as, but not limited to, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis ( 4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)indole [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-methoxy Phenyl) 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)indole [9,9-bis(4-hydroxy-3,5-dichlorophenyl) Fluorene], or 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, etc.

The halogenated propylene oxide can be used singly or in combination, such as, but not limited to, 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-propylene oxide (epibromohydrin).

Specific examples of the epoxy compound having at least two epoxy groups represented by the formula (V) are: (1) ESF-300 manufactured by Nippon Steel Chemical Co., Ltd.; (2) PG-100 manufactured by Osaka Gas Co., Ltd. , EG-210, etc.; (3) SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc., manufactured by SMS Technology Co., Ltd.

The epoxy compound having at least two epoxy groups represented by the formula (VI) is as follows:

Wherein R ⁵¹ to R ⁶⁵ each independently represent hydrogen, halogen, C ₁ to C ₈ alkyl or C ₆ to C ₁₅ aryl, and n represents an integer of 0 to 10.

The epoxy compound having at least two epoxy groups represented by the formula (VI) is reacted by a second reactant comprising a compound represented by the formula (VI-1), a halogenated propylene oxide and an alkali metal hydroxide. Made by. More specifically, the reaction is carried out by dehydrohalogenation using an excess of halogenated propylene oxide and a compound represented by the formula (VI-1) in the presence of an alkali metal hydroxide.

Among them, the compound represented by the formula (VI-1) is as follows:

Wherein R ⁵¹ to R ⁶⁵ each independently represent hydrogen, halogen, C ₁ to C ₈ alkyl or C ₆ to C ₁₅ aryl, and n represents an integer of 0 to 10.

The compound represented by the formula (VI-1) is obtained by a condensation reaction of a third reactant including a compound represented by the formula (VI-2), a phenol compound, and an acid catalyst.

Among them, the compound represented by the formula (VI-2) is as follows:

Wherein R ⁵³ to R ⁵⁶ each independently represent hydrogen, halogen, C ₁ to C ₈ alkyl or C ₆ to C ₁₅ aryl; Y ¹ and Y ² each independently represent a halogen, a C ₁ to C ₆ alkane a group or a C ₁ to C ₆ alkoxy group. Preferably, the halogen is chlorine or bromine. The C ₁ to C ₆ alkyl group is a methyl group, an ethyl group or a tert-butyl group. The C ₁ to C ₆ alkoxy group is a methoxy group or an ethoxy group.

The phenolic compound can be used singly or in combination, such as but not limited to: phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t -t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol , vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol.

The total amount of the compound represented by the formula (VI-2) is 1 mol, and the phenol compound is used in an amount ranging from 0.5 mol to 20 mol. Preferably, the phenolic compound is used in an amount ranging from 2 moles to 15 moles.

The acid catalyst can be used singly or in combination, such as, but not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride ( Aluminium chloride anhydrous) or zinc chloride. Preferably, the acid catalyst is selected from the group consisting of p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or a combination thereof. The amount of the acid catalyst used is not particularly limited. Preferably, the total amount of the compound represented by the formula (VI-2) is 100% by weight, and the acid catalyst is used in an amount ranging from 0.1 to 30% by weight.

The condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. The organic solvent can be used singly or in combination, such as, but not limited to, toluene, xylene or methyl isobutyl ketone. The total amount of the compound and the phenol compound represented by the formula (VI-2) is 100% by weight, and the organic solvent is used in an amount ranging from 50 to 300% by weight. Preferably, the organic solvent is used in an amount ranging from 100 to 250% by weight.

The condensation reaction has an operating temperature of 40 to 180 ° C and an operation time of 1 hour to 8 hours. After completion of the condensation reaction, the solution obtained after the reaction is subjected to a neutralization treatment or a water washing treatment, and then the unreacted phenol compound and the solvent are distilled off by heat treatment under reduced pressure, followed by concentration to obtain a formula ( The compound shown in VI-1). Among them, the neutralization treatment is to adjust the pH range of the solution after the reaction to 3 to 7, preferably, the pH is in the range of 5 to 7. The water washing treatment is carried out using a neutralizing agent which is an alkaline substance such as, but not limited to, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; calcium hydroxide; (alkaline earth metal hydroxides such as (calcium hydroxide), magnesium hydroxide, etc.; diethylene triamine, triethylenetetramine, aniline, phenylene diamine And other organic amines; and ammonia, sodium dihydrogen phosphate, and the like.

The halogenated propylene oxide can be used singly or in combination, such as, but not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane, and the like. Before the dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction, and the operation temperature ranges from 20 to 120 ° C, and the operation time ranges from 1 hour to 10 hours. .

In one embodiment of the present invention, the alkali metal hydroxide used in the dehydrohalogenation reaction may also be an aqueous solution of an alkali metal hydroxide. In this case, an alkali metal hydroxide aqueous solution is continuously added to the reactor. At the same time, water and halogenated propylene oxide can be continuously distilled under reduced pressure or normal pressure, thereby removing water, and the halogenated propylene oxide obtained by distillation can be continuously refluxed into the reactor.

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

Based on the total hydroxyl equivalent of the compound represented by the formula (VI-1) The equivalent amount of the halogenated propylene oxide is from 1 to 20 equivalents. Preferably, the halogenated propylene oxide is used in an amount ranging from 2 to 10 equivalents. The total equivalent weight of the hydroxyl group in the compound represented by the formula (VI-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount ranging from 0.8 to 15 equivalents. Preferably, the alkali metal hydroxide is used in an amount ranging from 0.9 to 11 equivalents.

Further, in order to smoothly carry out the dehydrohalogenation reaction, an alcohol such as methanol or ethanol may be added, and an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide may be added. Wait for the reaction. In the case of using an alcohol, the alcohol is used in an amount ranging from 2 to 20% by weight based on the total amount of the halogenated propylene oxide being 100% by weight. Preferably, the alcohol is used in an amount ranging from 4 to 15% by weight. In the case of using an aprotic polar solvent, the aprotic polar solvent is used in an amount ranging from 5 to 100% by weight based on 100% by weight of the total amount of the halogenated propylene oxide. Preferably, the aprotic polar solvent is used in an amount ranging from 10 to 90% by weight.

After the dehydrohalogenation reaction is completed, the water washing treatment can be selectively performed. Thereafter, by heating and depressurizing, for example, at a temperature of 110 to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less, halogenated propylene oxide, an alcohol, and an aprotic polar solvent are removed.

In order to avoid the presence of unreacted starting materials such as halogenated propylene oxide to affect physical properties, the dehydrohalogenated reaction solution may be added to a solvent such as toluene or methyl isobutyl ketone, and sodium hydroxide is added. An aqueous alkali metal hydroxide solution such as potassium hydroxide is again subjected to a dehydrohalogenation reaction. In the dehydrohalogenation reaction, based on the compound represented by the formula (VI-1) The total equivalent weight of the hydroxyl group is 1 equivalent, and the alkali metal hydroxide is used in an amount ranging from 0.01 to 0.3 mol. Preferably, the alkali metal hydroxide is used in an amount ranging from 0.05 to 0.2 mol. Further, the dehydrohalogenation reaction has an operating temperature in the range of 50 to 120 ° C and an operating time in the range of 0.5 to 2 hours.

After the dehydrohalogenation reaction is completed, the salts are removed by filtration, washing, and the like. An epoxy compound having at least two epoxy groups represented by the formula (VI) can be obtained by distilling off a solvent such as toluene or methyl isobutyl ketone by heating and pressure reduction. Commercial products of the epoxy compound having at least two epoxy groups represented by the formula (VI) are, for example but not limited to, NC-3000, NC-3000H, NC-3000S, and NC-3000P manufactured by Nippon Kayaku.

<Compound having at least one carboxylic acid group and at least one ethylenically unsaturated group>

The compound having at least one carboxylic acid group and at least one ethylenically unsaturated group may be used singly or in combination, such as, but not limited to, (1) acrylic acid, methacrylic acid, 2-methylpropenyloxyethyl succinic acid ( 2-methacryloyloxyethylbutanedioic acid), 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate, 2-methylpropenyloxybutyl adipate, 2-methylpropene Ethoxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methylpropenyloxybutyl maleic acid, 2-Methyl propylene oxypropyl succinic acid, 2-methyl propylene sulfoxypropyl adipate, 2-methyl propylene oxypropyl tetrahydrophthalic acid, 2-methyl propylene oxy propylene Phthalic acid, 2-methylpropenyloxybutylphthalate, or 2-methylpropenyloxybutylphthalic acid; or (2). a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound is, for example but not limited to, adipic acid, succinic acid, maleic acid or phthalic acid a formic acid ester or the like; or (3) a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group-containing (meth) acrylate is, for example but not limited to: 2- Hydroxyethyl acrylate [2-hydroxyethyl) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol Trimethacrylate and the like.

Here, the carboxylic anhydride-based compound is selected from a dicarboxylic acid anhydride compound, a tetracarboxylic acid anhydride compound, or a combination thereof. (1) The dicarboxylic anhydride compound may be used singly or in combination, such as but not limited to: butanedioic anhydride, maleic anhydride, itaconic anhydride, orthophthalic anhydride. Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride , methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride or glutaric anhydride or trimellitic anhydride (1,3-dioxoisobenzofuran-5- Carboxyl anhydride). (2). The quaternary carboxylic anhydride compound may be used singly or in combination, and is, for example, but not limited to, benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride.

<Carboxylic anhydride compound>

The carboxylic anhydride-based compound is as described above and will not be described again.

<Epoxy compound having one epoxy group>

The epoxy compound having one epoxy group is selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, and an epoxy group-containing compound. An unsaturated compound, or a combination of the above. Commercially available products of the unsaturated group-containing glycidyl ether compound are, for example but not limited to, Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, and Denacol EX- manufactured by Nagase Chemical Industry Co., Ltd. 146, Denacol EX-171, Denacol EX-192, and the like.

The first alkali-soluble resin (A-1) having an unsaturated group may be an epoxy compound having at least two epoxy groups represented by the formula (V) and having at least one carboxylic acid group and at least one ethylenic unsaturated group The base compound is subjected to a polymerization reaction (operating at a temperature of 50 ° C to 130 ° C) to form a hydroxyl group-containing reaction product, followed by addition of the carboxylic anhydride compound to carry out a reaction. Preferably, the total hydroxyl group equivalent of the hydroxyl group-containing reaction product is 1 equivalent, and the acid anhydride group in the carboxylic anhydride compound has an equivalent weight ranging from 0.4 to 1 equivalent. More preferably, the acid anhydride group in the carboxylic anhydride-based compound has an equivalent weight ranging from 0.75 to 1 equivalent. When more than one of the carboxylic anhydride-based compounds is used, It may be added sequentially or simultaneously in the reaction. Preferably, when the carboxylic anhydride-based compound is a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is in the range of 1/99 to 90/10. More preferably, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound ranges from 5/95 to 80/20.

The first alkali-soluble resin (A-1) having an unsaturated group may be an epoxy compound having at least two epoxy groups represented by the formula (VI) and having at least one carboxylic acid group and at least one ethylenic unsaturated group The compound of the group is reacted to form a hydroxyl group-containing reaction product, followed by addition of the carboxylic anhydride compound and/or the epoxy compound having one epoxy group for polymerization. Preferably, the epoxy group having at least two epoxy groups represented by the formula (VI) has a total epoxy equivalent of 1 equivalent, the at least one carboxylic acid group and the at least one ethylenically unsaturated group. The acid value equivalent of the compound is from 0.8 to 1.5 equivalents. More preferably, it is from 0.9 to 1.1 equivalents. The total amount of hydroxyl groups based on the hydroxyl group-containing reaction product is 100 mol%, and the carboxylic anhydride compound is used in an amount ranging from 10 to 100 mol%, preferably from 20 to 100 mol%, more preferably, It is 30 to 100 mol%.

In the preparation of the first alkali-soluble resin (A-1) having an unsaturated group, in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The reaction catalyst can be used singly or in combination, such as but not limited to: triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethyl chloride. Tetramethylammonium chloride or benzyltriethylammonium chloride Chloride) and so on. Preferably, the total amount of the reaction catalyst is based on 100 parts by weight of the total of the epoxy compound having at least two epoxy groups and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. It is from 0.01 to 10 parts by weight, more preferably from 0.3 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 can be used singly or in combination, such as but not limited to: methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol ( 2,6-di-t-butyl-p-cresol), or phenothiazine or the like. The polymerization inhibitor is used in an amount ranging from 0.01 to 10 based on 100 parts by weight of the total of the epoxy compound having at least two epoxy groups and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. The parts by weight are preferably from 0.1 to 5 parts by weight.

In the preparation of the first alkali-soluble resin (A-1) having an unsaturated group, a polymerization solvent can be used as necessary. The polymerization solvent can be used singly or in combination, such as, but not limited to, an alcohol compound such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; methyl ethyl ketone or ring a ketone compound such as ketone; an aromatic hydrocarbon compound such as toluene or xylene; a cellosolve compound such as celecin or butyl cellosolve; carbitol or butyl Carbitol-like compounds such as butyl carbito; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; and polypropylene glycol alkyl ethers such as dipropylene glycol monoether [di(propylene glycol) methyl ether] Poly(propylene glycol) alkyl ether] compound; ethyl acetate, butyl acetate, ethylene glycol ether Acetate compound such as ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate; alkyl lactate such as ethyl lactate or butyl lactate a compound; or a dialkyl glycol ether. Further, the acid value of the first alkali-soluble resin (A-1) having an unsaturated group ranges from 50 mgKOH/g to 200 mgKOH/g, preferably from 60 mgKOH/g to 150 mgKOH/g.

When the alkali-soluble resin (A) contains the first alkali-soluble resin (A-1), the pixel formed by the obtained photosensitive resin composition has a low surface roughness. The content of the first alkali-soluble resin (A-1) having an unsaturated group is from 5 to 70 parts by weight, based on the total amount of the alkali-soluble resin (A), in an amount of from 5 to 70 parts by weight; preferably, 5 parts by weight. Up to 60 parts by weight; more preferably, from 5 parts by weight to 50 parts by weight.

[Second alkali soluble resin (A-2)]

The second alkali-soluble resin (A-2) is obtained by polymerization of a second mixture comprising an ethylenically unsaturated monomer having at least one carboxylic acid group, and other copolymerizable ethylene. Unsaturated monomers, solvents and starters. The total amount of the ethylenically unsaturated monomer having at least one carboxylic acid group and the other copolymerizable ethylenically unsaturated monomer is 100 parts by weight.

<Ethylene unsaturated monomer having at least one carboxylic acid group>

The ethylenically unsaturated monomer having at least one carboxylic acid group can be used singly or in combination, for example, but not limited to: (1). Unsaturated monocarboxylic acid compound: acrylic acid, methacrylic acid, crotonic acid, α-chloro Acrylic acid, ethyl Acrylic acid, cinnamic acid, 2-propenyl ethoxy succinate or 2-methyl propylene ethoxy succinate; (2) unsaturated dicarboxylic acid (anhydride) a compound: maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, aconitic acid or citraconic anhydride; or (3) trivalent or higher unsaturated polyvalent carboxylic acid (anhydride) compound. Preferably, the ethylenically unsaturated monomer having at least one carboxylic acid group is selected from the group consisting of acrylic acid, methacrylic acid, 2-propenyl ethoxy succinate, 2-methyl propylene ethoxylate Diacid ester or a combination of the above.

Other copolymerizable ethylenically unsaturated monomers can be used singly or in combination, such as but not limited to: (1). Dicyclopentyl acrylate, dicyclopentyl ethoxy acrylate, dicyclopentenyl acrylate (dicyclopentenyl acrylate) ), dicyclopentenyloxyethyl acrylate, dicyclopentyl methacrylate, dicyclopentyl ethoxy methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl ethoxylate (meth) methacrylate, etc.; (2) aromatic vinyl compound: styrene, α-methyl styrene, vinyl toluene, p-chlorostyrene or methoxy styrene; (3). Malay Imine compound: N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenyl Malay Yttrium, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o- Methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide or N-cyclohexylmaleimide Wait (4) an unsaturated carboxylic acid ester compounds: methyl acrylate, methyl methacrylate, benzyl methacrylate, ethyl acrylate, methacrylic Ethyl ethyl ester, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate Ester, second butyl acrylate, second butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid - 2-hydroxypropyl ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate Ester, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, Benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene methacrylate Glycol methacrylate), lauryl mecaprol Thacrylate), tertadecyl methacrylate, cetyl methacrylate, octadecylmethacrylate, eicosyl methacrylate Eicosyl methacrylate) or docosyl methacrylate; (5). N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate , N,N-diethylaminopropyl acrylate, N,N-dimethylaminopropyl methacrylate, N-N-dibutylaminopropyl acrylate or N-isobutyl methacrylate Aminoethyl ester; (6). Unsaturated carboxylic acid glycidyl ester compound: epoxy acrylate or methacrylic acid epoxy a propyl ester or the like; (7) a vinyl carboxylate-based compound: vinyl acetate, vinyl propionate or vinyl butyrate; (8) an unsaturated ether-based compound: vinyl methyl ether, vinyl ethyl ether, Allylepoxypropyl ether or methallyloxypropyl ether; (9). Vinyl cyanide compound: acrylonitrile, methacrylonitrile, α-chloroacrylonitrile or vinyl cyanide (10). Unsaturated amide compound: acrylamide, methacrylamide, α-chloropropenylamine, N-hydroxyethyl acrylamide or N-hydroxyethyl methacrylamide (11). An aliphatic conjugated diene compound: 1,3-butadiene, isoamylene or chlorinated butadiene. Preferably, the other copolymerizable ethylenically unsaturated monomer is selected from the group consisting of dicyclopentyl acrylate, dicyclopentyl ethoxy acrylate, dicyclopentenyl acrylate, dicyclopentenyl ethoxy acrylate Ester, dicyclopentyl methacrylate, dicyclopentyl ethoxy methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl ethoxy methacrylate, styrene, N-phenyl horse An imine, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate or a combination thereof.

The solvent used to prepare the second alkali-soluble resin (A-2) can be used singly or in combination, for example, but not limited to: (1). alkylene glycol monoalkyl ether or polyalkylene Polyalkylene glycol monoalkyl ether: ethylene glycol methyl ether, ethylene glycol ether, diethylene glycol methyl ether, diethylene glycol ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether , triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, two Tripropylene glycol monomethyl ether or tripropylene glycol mono ethyl ether; (2). alkylene glycol monoalkyl ether acetate [(poly)alkylene glycol monoalkyl ether acetate )] or polyalkylene glycol monoalkyl ether acetate: ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate Etc.; (3) Other ethers: diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether or tetrahydrofuran; (4). Ketones: methyl ethyl ketone, cyclohexanone , 2-heptanone or 3-heptanone, etc.; (5). alkyl lactate: methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; (6). ester: 2-hydroxy-2 -methyl methacrylate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionic acid ethyl ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetic acid Ester, 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 , isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate or ethyl 2-oxybutyrate (7) aromatic hydrocarbons: toluene or xylene, etc.; or (8). carboxylic acid amides: N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethyl Ethylamine and the like.

Preferably, the solvent is selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination thereof.

The initiator 1 for preparing the second alkali-soluble resin (A-2) It is a radical polymerization initiator. The radical polymerization initiator can be used singly or in combination, for example but not limited to: (1) azo compound: 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile)[2,2'-azobis-(2,4-dimethyl-valeronitrile), 2,2'-azobis(4-A [2,4-'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile 2,2'-azobis-2-methyl butyronitrile); (2) Peroxy compound: benzoylperoxide or the like.

The content of the second alkali-soluble resin (A-2) is in the range of 30 to 95 parts by weight; preferably 40 parts by weight to 95 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A); More preferably, it is 50 parts by weight to 95 parts by weight.

"Ethylene-unsaturated group-containing compound (B)"

The ethylenically unsaturated group-containing compound (B) includes a first compound (B-1) containing an ethylenically unsaturated group. Further, the ethylenically unsaturated group-containing compound (B) may further include a second compound (B-2) having an ethylenically unsaturated group and a first compound (B-1) other than the ethylenically unsaturated group. A third compound (B-3) containing an ethylenically unsaturated group other than the second compound (B-2) containing an ethylenically unsaturated group.

[First compound (B-1) containing an ethylenically unsaturated group]

The first compound (B-1) having an ethylenically unsaturated group has a structure represented by the following formula (I): In the formula (I), R ¹¹ represents hydrogen or a methyl group, and R ¹² represents an alkylene group having a carbon number of 1 to 20 and substituted or unsubstituted with a hydroxy group, or a carbon number of 6 to 20 and substituted by a hydroxy group or not By substituted aryl, one or more -CH ₂ - groups in the alkyl and aryl groups may each independently be -O-, -S-, -CO-, -O-CO- or -CO-O-substituted, X represents a decyloxy group.

R ^{20 is,} for example but not limited to, methyl, ethyl, propyl, isopropyl, butyl, alkyl having 1 to 20 carbon atoms and substituted with at least one hydroxy group (eg, hydroxymethyl) , hydroxy-extension ethyl), benzene, toluene, xylyl, naphthyl, an extended aryl group having 6 to 20 carbon atoms and substituted with at least one hydroxyl group. One or more -CH ₂ - groups in the above alkyl and extended aryl groups may each be independently substituted with -O-, -S-, -CO-, -O-CO- or -CO-O-. Preferably, R ¹² is selected from an alkylene group having 2 to 5 carbon atoms or -CH ₂ -OC ₃ H ₆ -; more preferably a propyl group or a -CH ₂ -OC ₃ H ₆ -.

Preferably, X represents a decyloxy group represented by the formula (I-1), (I-2) or (I-3), In the formulae (I-1) to (I-3), R ²¹ to R ²⁵ each independently represent a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₂₀ aryl group, and n represents an integer of 1 to 50.

Specific examples of the ethylenically unsaturated group-containing first compound (B-1) are, for example but not limited to:

When the ethylenically unsaturated group-containing first compound (B-1) is not used, the surface roughness of the pixel formed by the photosensitive resin composition and the linearity of the high-definition pattern are not good. The ethylenically unsaturated group-containing first compound (B-1) is used in an amount of from 0.1 to 10 parts by weight, based on the total amount of the alkali-soluble resin (A), based on 100 parts by weight; preferably from 0.1 to 8 parts by weight. More preferably, it is 0.1 to 5 parts by weight. When the amount of the ethylenically unsaturated group-containing first compound (B-1) is in the above range, the pixel formed by the subsequently obtained photosensitive resin composition has better surface roughness and high definition. The linearity of the pattern.

[Second compound (B-2) containing an ethylenically unsaturated group]

The second unsaturated compound-containing compound (B-2) is selected from the group consisting of formula (II), formula (III) or a combination thereof. Among them, formula (II) and formula (III) are as follows:

In the formulae (II) and (III), R ³¹ represents -[O(CH ₂ ) _y CH ₂ ]- or -[O(CH ₂ ) _y CH(CH ₃ )]-, and y represents an integer of 1 to 10. R ³² represents hydrogen, a carboxyl group or a (meth) acrylonitrile group, and in the formula (II), the total number of the (meth) acryl fluorenyl groups is 3 or 4, and m1 to m4 each independently represent an integer of 0 to 10. And the total of m1 to m4 is an integer of 1 to 40; in the formula (III), the total of the (meth)acryl fluorenyl groups is 5 or 6, and n1 to n6 each independently represent an integer of 0 to 10, And the sum of n1 to n6 is an integer of 1 to 60.

The compound represented by the formula (II) and the formula (III) may be subjected to the following synthesis method: (1) pentaerythritol or dipentaerythritol by ring opening of ethylene oxide or propylene oxide (Propylene oxide) The addition reaction is carried out to bond the ring-opening skeleton; and (2), for example, (meth)acrylofluorene chloride is reacted with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth)acrylonitrile group.

Preferably, the compound represented by the formula (II) and the formula (III) is a pentaerythritol derivative and/or a dipentaerythritol derivative.

Specific examples of the formula (II) are a compound represented by the formula (II-1), a compound represented by the formula (II-2), an Ethoxylated Pentaerythritol tetraacrylate or a propoxylated pentaerythritol IV. Propoxylated Pentaerythritol tetraacrylate. Wherein the total of m1 to m4 in the formula (II-1) is 4; and the total of m1 to m4 in the formula (II-2) is 12.

Specific examples of the formula (III) are compounds represented by the formula (III-1) to the formula (III-4). The total of n in the formula (III-1) and the formula (III-4) is 6; the total of n in the formula (III-2) and the formula (III-3) is 12. Preferably, the specific example of the formula (III) is a compound represented by the formula (III-1) or the formula (III-2).

When the ethylenically unsaturated group-containing compound (B) contains the ethylenically unsaturated group-containing second compound (B-2), the obtained photosensitive resin composition forms a pixel with better high definition. The linearity of the pattern.

The ethylenically unsaturated group-containing second compound (B-2) is used in an amount of from 10 parts by weight to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A); preferably 15 parts by weight to 80 parts by weight; more preferably 20 parts by weight to 50 parts by weight.

[Other third compound (B-3) containing an ethylenically unsaturated group]

The other ethylenically unsaturated group-containing third compound (B-3) is selected from the group consisting of a polyol modified by caprolactone and (meth)acrylic acid. The obtained (meth) acrylate compound, a compound having the structure of the formula (IV), or a combination of the two.

The compound having the structure of formula (IV) is as follows:

Wherein R ⁷¹ represents hydrogen or methyl.

The compound having the structure of the formula (IV) can be used singly or in combination, such as, but not limited to, acrylamide, (meth) propylene morpholine, (meth) acrylate-7-amino-3,7-dimethyl Octyl ester, isobutoxymethyl (meth) acrylamide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , ethyl diglycol (meth) acrylate, third octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl amino (meth) acrylate, (meth) acrylate Dodecyl ester, dicyclopenteneoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl(meth)acrylamide, (meth)acrylic acid Tetrachlorophenyl ester, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetramethyl (meth)acrylate Bromophenoxyethyl ester, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, ( 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactone , nitrogen-vinyl tyrosinone, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, poly (mono) (meth) acrylate Alcohol ester, poly(propylene) propylene glycol (meth) acrylate, methacrylate (di) methacrylate , Tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone modification Tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, trimethylolpropyl tri(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(methyl) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid Ester, polyester di(meth) acrylate, polyethylene glycol di(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (methyl) Acrylate, ditrimethylolpropyl tetra(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, EO modification Hydrogenated bisphenol A di(meth)acrylate, PO modified hydrogenated bisphenol A di(meth)acrylate, EO modified bisphenol F di(meth)acrylate, phenolic polyglycidyl ether (Meth) acrylate.

Preferably, the compound having the structure of formula (IV) is selected from the group consisting of trimethylolpropyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Tetraacrylate, ditrimethylolpropyl methacrylate, TO-1382 manufactured by Japan East Asia Synthetic Co., Ltd., or a combination thereof.

The caprolactone-modified polyol is obtained by reacting caprolactone with a polyol having four or more functional groups. The caprolactone is, for example but not limited to, γ-caprolactone, δ-caprolactone, or ε-caprolactone. Preferably, the caprolactone is ε-caprolactone. The polyol having four or more functional groups is, for example but not limited to, pentaerythritol, bis(trimethylolpropane), bis(pentaerythritol), and the like.

The (meth) acrylate compound obtained by reacting the caprolactone-modified polyol with (meth)acrylic acid can be used singly or in combination, such as but not limited to: pentaerythritol caprolactone modified tetra(methyl) An acrylate compound, a tetrakis (meth) acrylate compound modified with ditrimethylolpropane caprolactone, a poly(meth) acrylate compound modified with dipentaerythritol caprolactone, and the like.

Specific examples of the poly(meth) acrylate compound modified by the bis(pentaerythritol) caprolactone are di-pentaerythritol caprolactone-modified di(meth) acrylate compound and dipentaerythritol caprolactone modification. Tris(meth)acrylate compound, dipentaerythritol caprolactone modified tetra(meth)acrylate compound, dipentaerythritol caprolactone modified penta(meth)acrylate compound, dipentaerythritol A caprolactone-modified hexa(meth)acrylate compound or the like. The dipentaerythritol caprolactone modified poly(meth) acrylate compound is as shown in formula (VII):

In the formula (VII), R ⁸¹ and R ⁸² each independently represent hydrogen or a methyl group; m represents an integer of 1 to 2; a represents an integer of 1 to 6; and b represents an integer of 0 to 5, wherein a+b=2 To 6; preferably a+b=3 to 6; more preferably a+b=5 to 6; most preferably a+b=6.

Commercially available products of the (meth) acrylate-based compound obtained by reacting the caprolactone-modified polyol with (meth)acrylic acid are, for example, KAYARAD ^® DPCA-20, DPCA-30 manufactured by Nippon Kayaku Co., Ltd. , DPCA-60, DPCA-120, etc.

The other ethylenically unsaturated group-containing third compound (B-3) is used in an amount of 20 parts by weight to 190 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably 25 parts by weight Parts to 170 parts by weight; more preferably 30 parts by weight to 150 parts by weight.

The ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 30 parts by weight to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably 40 parts by weight to 250 parts by weight. More preferably, it is 50 parts by weight to 200 parts by weight.

"Photoinitiator (C)"

The photoinitiator (C) may be a radical type photoinitiator. Specifically, the photoinitiator (C) can be used singly or in combination, such as, but not limited to, an O-oxime-based compound, a triazine-based compound, and an acetophenone system. compounds, imidazole (biimidazole) based compound, benzophenone (benzophenone) compounds, α - dione (α -diketone) based compound, a ketone alcohol (acyloin) based compound, a ketone ether (acyloin ether) compounds, An acylphosphine oxide compound, a quinone compound, a halogen-containing compound, a peroxide, or the like.

The O-mercapto lanthanide compound can be used singly or in combination, such as but not limited to: 1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-benzene醯基肟), 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinium), 1-[4-(benzoyl) Phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-carbazole- 3-substituted]-ethane ketone 1-(O-ethylindenyl), 1-[9-ethyl-6-(3-methylphenylindenyl)-9H-indazol-3-yl]-ethanone-1-(O -Ethyl hydrazide), 1-[9-ethyl-6-phenylhydrazin-9H-indazol-3-yl]-ethane ketone-1-(O-ethyl fluorenyl), ethane ketone - 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9H-indazol-3-yl]-1-(O-ethylindenyl), ethane ketone- 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylphenyl)-9H-carbazol-3-yl]-1-(O-ethylindenyl), B Alkanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9H-indazol-3-yl]-1-(O-ethylindenyl), B Alkanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)-9H-indazol-3-yl]-1-(O-ethylindenyl) Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-indazol-3-yl]-1-(O-B Ethyl ketone), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl)]-9H-indazol-3-yl]- 1-(O-Ethylindole), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoinyl)-9H-indazole-3- ]]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenyl)--9H -carbazol-3-yl]-1-(O-B Ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoinyl} -9H-carbazol-3-yl]-1-(O-acetylindenyl) or ketone-1-[9-ethyl-6-{2-methyl-4-(2,2- Dimethyl-1,3-dioxolanyl)methoxybenzoin}}-9H-indazol-3-yl]-1-(O-ethylindenyl) and the like.

The triazine compound can be used singly or in combination, such as but not limited to: 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine [2,4- Bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine], 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3- Butadienyl)-s-triazine [2,4-bis(trichloromethyl)-6-(1-p-dimethyl- Aminophenyl-1,3-butadienyl)-s-triazine], or 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine [2-trichloromethyl-4-amino -6-(p-methoxy)styryl-s-triazine] and the like.

The acetophenone-based compound can be used singly or in combination, such as, but not limited to, p-dimethylacetone, α,α'-dimethoxyoxyazopropenone, 2,2'-di Methyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone or 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinylphenyl)-1-butanone or the like.

The diimidazole compound can be used singly or in combination, such as but 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(o-ethyl Phenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis ( 2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, or 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5' - Tetraphenyldiimidazole and the like.

The benzophenone compound can be used singly or in combination, such as, but not limited to, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4' - bis(dimethylamine)benzophenone or 4,4'-bis(diethylamine)benzophenone.

The α -diketone compound is, for example but not limited to, a benzil compound or an acetyl group compound. The ketol compound is, for example but not limited to, benzoin. The ketol ether compound is, for example but not limited to, benzoin methylether, benzoin ethylether or benzoin isopropyl ether. The phosphonium phosphide-based compound is, for example but not limited to, 2,4,6-trimethyl-benzoyl diphenylphosphine oxide or bis-(2,6-di Methoxybenzoquinone)-2,4,4-trimethoxy-benzoyl-2,4,4-trimethylbenzyl phosphineoxide, and the like. The lanthanoid compound is, for example but not limited to, anthraquinone, 1,4-naphthoquinone or the like. The halogen-containing compound is, for example but not limited to, phenacyl chloride, tribromomethyl phenylsulfone or tris(trichloromethyl)-s-triazatrix. -s-triazine]etc. The peroxide is, for example but not limited to, di-tertbutylperoxide. The α-diketone compound, the keto alcohol compound, the ketone ether compound, the phosphonium oxide compound, the oxime compound, the halogen-containing compound, the peroxide, or the like can be used singly or in combination.

Preferably, the photoinitiator (C) is selected from the group consisting of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 1-[4-( Phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinium), 1-[9-ethyl-6-(2-methylphenylhydrazino)- 9H-carbazol-3-yl]-ethanone-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl) Oxyl phenyl hydrazino)-9H-carbazol-3-yl]-1-(O-acetamido fluorene), ethane ketone-1-[9-ethyl-6-{2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl)methoxyphenylhydrazino}-9H-carbazole-3- 1,-1-(O-ethylindenyl), 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine, 2-benzyl-2 -N,N-dimethylamine-1-(4-morpholinylphenyl)-1-butanone, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5 '-Tetraphenyldiimidazole, 4,4'-bis(diethylamine)benzophenone or a combination of the above compounds.

. The photoinitiator (C) is used in an amount ranging from 10 parts by weight to 200 parts by weight, based on the amount of the alkali-soluble resin (A) used in an amount of 100 parts by weight; preferably 15 parts by weight to 150 parts by weight; more preferably It is 20 parts by weight to 100 parts by weight.

Organic Solvent (D)

The organic solvent (D) is capable of dissolving the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), and the pigment (E), and does not react with the above components. It is better to have appropriate volatility.

The organic solvent (D) can be the same as the organic solvent used for the preparation of the alkali-soluble resin (A-2), and therefore will not be described again. Preferably, the organic solvent (D) is selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination of the two.

The organic solvent (D) is used in an amount ranging from 500 parts by weight to 5000 parts by weight, based on the amount of the alkali-soluble resin (A) used, preferably from 600 parts by weight to 4,500 parts by weight; more preferably 700 parts by weight. Parts by weight to 4000 parts by weight.

Pigment (E)

The pigment (E) can be used singly or in combination, such as, but not limited to, an inorganic pigment or an organic pigment.

The inorganic pigment is for example but not limited to: metal oxide or metal A metal compound such as a salt of a wrong salt, for example, an oxide of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, or cerium, and a composite oxide of the foregoing metal.

The organic pigments can be used singly or in combination, such as but not limited to: (1). CI Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 , 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120 ,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175; (2). CI Pigment Orange 1, 5, 13, 14 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; (3). CI Pigment Red 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1 , 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4 , 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122 , 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; (4). CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39; (5). CI Pigment Blue 1, 2, 15, 15:3, 15:4, 15: 6, 16, 22, 60, 66; (6). CI pigment green 7, 36, 37, 58; (7.) CI Pigment browns 23, 25, 28; and (8).C.I. Pigment blacks 1, 7.

Preferably, the primary particles of the pigment (E) have an average particle diameter ranging from 10 nm to 200 nm; more preferably from 20 nm to 150 nm; most preferably from 30 nm to 130 nm.

The pigment (E) may optionally be accompanied by a dispersing agent such as, but not limited to, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric acid, a polyoxyalkylene system or a fluorine compound.

The surfactant can be used singly or in combination, for example but not limited to: (1). Polyethylene oxide alkyl ethers: polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, Polyethylene oxide ether ether, etc.; (2) Polyethylene oxide alkyl phenyl ethers: polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, etc.; (3). Polyethylene Glycol diesters: polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters; (5) fatty acid modified polyesters (6). Polyurethane modified by tertiary amine. Commercially available products of the surfactant are, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (manufactured by Toray Dow Corning Silicon), Polyflow (manufactured by Kyoei Oil & Fat Chemical Industry Co., Ltd.), and F-Top (Tochem Product Co., Ltd.), Megafac (manufactured by Dainippon INK Chemical Industry Co., Ltd.), Fluorade (manufactured by Sumitomo 3M), Asahi Guard, and Surflon (made by Asahi Glass).

The pigment (E) is used in an amount ranging from 50 to 500 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). Preferably, it is 80 parts by weight to 400 parts by weight; more preferably 100 parts by weight to 300 parts by weight.

Additives (F)

Sensitization of the present invention without affecting the efficacy of the present invention The resin composition is more selectively further added with the additive (F). Specific examples of the additive (F) include a filler, a polymer (refer to a polymer other than the above-described alkali-soluble resin (A)), an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, or a combination of the above additives.

Specific examples of the filler include glass or aluminum and the like.

Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or a combination of the above polymers.

Specific examples of the adhesion promoter include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxy Propyl propyl trimethoxy decane, 3-glycidyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 3-chloropropyl group Dimethoxy decane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane or a combination of the above compounds.

Specific examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol or a combination of the above compounds.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone or the above compounds. combination.

Specific examples of the anti-agglomerating agent include sodium polyacrylate and the like.

The additive (F) may be used in an amount of from 0.01 part by weight to 5 parts by weight, based on the amount of the alkali-soluble resin (A), preferably from 0.05 part by weight to 4 parts by weight, and more preferably 0.1 part by weight. Up to 3 parts by weight.

<<Preparation method of photosensitive resin composition for color filter>>

A method which can be used for preparing a photosensitive resin composition, for example, an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a pigment (E), and an organic solvent (D) The mixture is placed in a stirrer to be stirred, and uniformly mixed into a solution state. If necessary, an additive (F) may be added and uniformly mixed to obtain a photosensitive resin composition in a solution state.

Further, the method for preparing the photosensitive resin composition is not particularly limited. The photosensitive resin composition is prepared by, for example, dispersing a part of the alkali-soluble resin (A) and the ethylenically unsaturated group-containing compound (B) in a part of the organic solvent (D) to form a dispersion solution; and then The remaining pigment (E), the ethylenically unsaturated group-containing compound (B), the alkali-soluble resin (A), the photoinitiator (C), and the organic solvent (D) are mixed.

Alternatively, the photosensitive resin composition may be obtained by dispersing a part of the pigment (E) in a part of the organic solvent (D) to form a pigment dispersion; and mixing the remaining pigment (E), containing ethylenic unsaturation The compound (B), the alkali-soluble resin (A), the photoinitiator (C), and the remaining organic solvent (D) are prepared. Further, the dispersion step of the above pigment (E) can be carried out by mixing with a mixer such as a beads mill or a roll mill.

"Manufacturing method of pixel layer and color filter"

The color filter is made up of a photosensitive composition for a color filter. The pre-baked, exposed, developed, and post-baked treatments are applied to the substrate on which the black matrix has been formed, wherein the black matrix is used to isolate the pixel layers (hereinafter, the pixel layer is also referred to as a pixel coloring layer). ). The preparation method of the color filter will be described in detail below.

First, a photosensitive resin composition for a color filter in a solution state is uniformly applied onto a substrate by a coating method such as spin coating or cast coating or roll coating to form a coating film. The substrate is, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyles glass), a quartz glass, or a glass to which a transparent conductive film is attached, which is used for a liquid crystal display device, and the like, and is used for a photoelectric conversion device (such as a solid). A substrate (for example, a ruthenium substrate) of the photographic device; or a substrate having a black matrix for shielding light that can isolate a pixel colored layer such as red, green, or blue.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the residual solvent is completely removed by pre-baking to form a pre-baked coating film. It is worth noting that the conditions of drying under reduced pressure and pre-baking vary depending on the type and ratio of each component. In general, the vacuum drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the prebaking is performed at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes. Heat treatment.

Next, the prebaked coating film is exposed by a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet irradiation device may be a (ultra) high-pressure mercury lamp or a metal halide lamp.

Then, at the temperature of 23 ± 2 ° C, the above exposed pre-exposure The baking coating film is immersed in the developing solution to remove unnecessary portions of the prebaked coating film, whereby a specific pattern can be formed on the substrate. Specific examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, dimethyl Basicity of basic compounds such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo-(5.4.0)-7-undecene Aqueous solution. 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, and more preferably from 0.01% by weight to 1% by weight.

After the prebaked coating film is developed, the substrate having the specific pattern is washed with water, and the above specific pattern is air-dried with compressed air or compressed nitrogen. Then, post-bake (that is, heat treatment) is performed by a heating device such as a hot plate or an oven. The post-baking temperature is 100 to 280 ° C, and the heating time is 1 minute to 15 minutes to remove volatile components in the coating film and subject the unreacted ethylenic unsaturated double bond to a thermosetting reaction. After the above-described processing steps, a specific pattern can be fixed on the substrate, thereby forming a pixel colored layer. Repeating the above steps, sequentially forming red, green, blue and other pixel colored layers on the substrate.

Finally, an ITO (Indium Tin Oxide) protective film (evaporated film) was formed on the surface of the pixel colored layer by sputtering under a vacuum atmosphere at a temperature of 220 ° C to 250 ° C. When necessary, the ITO protective film is etched and wired, and a liquid crystal alignment film (polyimine for liquid crystal alignment film) is applied onto the surface of the ITO protective film, thereby forming a color filter having a pixel layer.

<<Manufacturing Method of Liquid Crystal Display Device>>

First, a color filter formed by the above-described method of forming a color filter and a substrate provided with a thin film transistor (TFT) are disposed oppositely, and a gap is provided between the two (crystal) Cell gap). Next, the color filter is attached to the peripheral portion of the above substrate with an adhesive and the injection hole is left. Then, liquid crystal is injected from the injection hole in the gap between the surface of the substrate and the adhesive, and the injection hole is sealed to form a liquid crystal layer. Subsequently, a polarizing plate is provided by contacting the other side of the color filter in contact with the other side of the liquid crystal layer in the color filter to form a liquid crystal display element. Next, a surface light source is provided on one side of the liquid crystal display element to form a liquid crystal display device. The liquid crystal used, that is, the liquid crystal compound or the liquid crystal composition, is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used in the production of the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any of inorganic substances or organic substances may be used, and the present invention is not limited thereto.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

Synthesis example of first alkali-soluble resin (A-1)

Hereinafter, a synthesis example of the first alkali-soluble resin (A-1) will be described. A-1-1 to Synthesis Example A-1-3:

Synthesis Example A-1-1

First, 100 parts by weight of a ruthenium epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion 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. The feed rate was controlled at 25 parts by weight/min, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid content of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was added to 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heated to 110 ° C to 115 ° C. After reacting for 2 hours, the first alkali-soluble resin A-1-1 having an acid value of 98 mgKOH/g and a weight average molecular weight of 2,205 was obtained.

Synthesis Example A-1-2

100 parts by weight of ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., model ESF-300; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added to a 500-mL four-necked flask. The feed rate was controlled at 25 parts by weight/min, and the temperature of the reaction was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate while 13 parts by weight of benzophenonetetracarboxylic dianhydride was added, and heated to 90 ° C to 95 ° C. After reacting for 2 hours, 6 parts by weight of tetrahydrophthalic anhydride is added, and the reaction is carried out at 90 ° C to 95 ° C for 4 hours to obtain a first alkali-soluble resin (A-1-2) having an acid value of 99.0 mgKOH/g and a weight average molecular weight of 2,630.

Synthesis Example A-1-3

400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., model: NC-3000; epoxy equivalent: 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight A portion of triphenylphosphine and 264 parts by weight of propylene glycol monomethyl ether acetate were added to the reaction flask and the temperature was maintained at 95 °C. After 9 hours of reaction, 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 a first alkali-soluble resin (A-1-3) having an acid value of 102 mgKOH/ g, and the weight average molecular weight is 3,200.

Synthesis example of second alkali-soluble resin (A-2)

Hereinafter, Synthesis Example A-2-1 of the second alkali-soluble resin (A-2) and Synthesis Example A-2-2 will be described:

Synthesis Example A-2-1

1 part by weight of 2,2'-azobisisobutyronitrile, 240 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, 15 parts by weight of styrene, 35 parts by weight of methyl group Benzyl acrylate, 10 parts by weight of glycerol monomethacrylate and 20 parts by weight of nitrogen-phenyl maleimide The flask was placed in a round bottom flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen gas. Thereafter, the mixture was slowly stirred and heated to 80 ° C to uniformly mix the respective reactants and carry out polymerization for 4 hours. Thereafter, the temperature is further raised to 100 ° C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile is added for polymerization for 1 hour to obtain a further alkali-soluble resin (hereinafter referred to as A-2-1). ).

Synthesis Example A-2-2

2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl ether, 15 parts by weight of methacrylic acid, 15 parts by weight of ethyl 2-hydroxyacrylate, and 70 parts by weight The benzyl methacrylate was placed in a round bottom flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen gas, and then slowly stirred and heated to 80 ° C to uniformly mix and polymerize the reactants. Reaction for 3 hours. Thereafter, the temperature is further raised to 100 ° C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile is added for polymerization for 1 hour to obtain an other alkali-soluble resin (hereinafter referred to as A-2-2). ).

Example of photosensitive resin composition

Hereinafter, Examples 1 to 9 and Comparative Examples 1 to 5 of the photosensitive resin composition will be described:

Example 1

100 parts by weight of the first alkali-soluble resin A-1-1 having an unsaturated group, 10 parts by weight of the first compound B-1-1 containing an ethylenically unsaturated group, and 10 parts by weight of 1-[4- (phenylthio)phenyl]-1,2-octanedione 2-(O-benzohydrazide) (hereinafter abbreviated as C-1), and 50 parts by weight of pigment (E-1) (by CI Pigment Red 254 and CI Pigment Yellow 39, the weight ratio of CI Pigment Red 254 to CI Pigment Yellow 139 is 80:20) 500 parts by weight of propylene In the alcohol methyl ether acetate (hereinafter abbreviated as D-1), the photosensitive resin composition of Example 1 was obtained by stirring uniformly with a shaking type stirrer. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 1.

Examples 2 to 9 and Comparative Examples 1 to 5

The photosensitive resin compositions of Examples 2 to 9 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, and were distinguished by changing the kinds of components of the photosensitive resin composition and the amount thereof (for example, Table 1 shows the compounds corresponding to the labels in Table 1 as shown below. The pixels formed by the obtained photosensitive resin composition were evaluated by the following evaluation methods, and the results are shown in Table 1.

[Evaluation method] 1. Linearity of high-definition patterns

The photosensitive resin compositions of the above respective Examples and Comparative Examples were applied by spin coating to a glass substrate having a length and a width of 100 mm. Then, it was dried under reduced pressure at a pressure of about 100 mmHg (mmHg) for about 30 seconds. Next, the above glass substrate was prebaked at 80 ° C for 3 minutes to form a prebaked film having a film thickness of 2.5 μm. Thereafter, using a photomask having a strip pattern of 25 μm [pitch 50 μm], an exposure machine (manufactured by Canon, model: PLA-501F) was used at 300 mJ/cm ² (mJ/cm ² ). The above pre-baked coating film is irradiated with ultraviolet light. After irradiation with ultraviolet light, the prebaked coating film was immersed in a developing solution at 23 ° C for 2 minutes. Thereafter, the prebaked coating film was washed with pure water, and the prebaked coating film was post-baked at 200 ° C for 80 minutes to form a photosensitive resin layer having a film thickness of 2.0 μm on the glass substrate.

The strip pattern formed by the above method was observed by an optical microscope, and the high definition pattern linearity was evaluated in accordance with the following criteria.

◎: 90% or more of the high-definition pattern has good linearity.

○: 80% or more, and a high-definition pattern of less than 90% has good linearity.

Δ: 70% or more, and the high-definition pattern of less than 80% has good linearity.

○ ×: The linearity of the high-definition pattern of less than 70% is good.

2. Surface roughness

The pre-baked coating film of the above evaluation mode (a) having a film thickness of 2.5 μm was irradiated with ultraviolet light of 100 mJ/cm ² (mJ/cm ² ) using an exposure machine (manufactured by Canon, model: PLA-501F), and then The prebaked coating film was immersed in a developing solution at 23 ° C for 1 minute, and washed with pure water. Then, by baking at 235 ° C for 30 minutes, a pixel layer having a film thickness of 2.0 μm was formed on the glass substrate. The surface roughness of the pixel layer was measured using an Atomic Force Microscope (AFM) (Dimension 3100, manufactured by Veeco Instruments Inc.). The measurement area was 10 μm ² . The surface roughness was evaluated based on the following criteria. The smaller the measured surface roughness is, the better the surface roughness of the pixel formed by the photosensitive resin composition is.

◎: Surface roughness ≦ 6nm

○: 6 nm < surface roughness ≦ 8 nm

△: 8 nm < surface roughness ≦ 10 nm

×: 10 nm < surface roughness

Note: B-1-1 Formula (I-4) B-1-2 Formula (I-5) B-1-3 Formula (I-7) B-1-4 Formula (I-8) B-1- 5 Formula (I-9) B-2-1 (II-1) B-2-2 (III-1) B-2-3 (III-3) B-2-4 (III-4) B-3 -1 caprolactone modified dipentaerythritol hexaacrylate B-3-2 pentaerythritol tetraacrylate B-3-3 C-1 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzohydrazide)C-2 2-methyl-[4-(methylthio) Phenol]2-morpholino-1-propanone C-3 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole C-4 4,4'-bis(diethylamine)benzophenone D-1 propylene glycol methyl ether acetate D-2 3-ethoxypropionate ethyl ester E-1 CIPigment R254/CIPigment Y139=80/20 E-2 CIPigment G36/CIPigment Y150=60/40 E-3 CIPigment B15:6

From the results of the experimental data in Table 1, the photosensitive resin composition of Examples 1 to 9 was formed into a pixel of the photosensitive resin composition by using the first compound (B-1) containing an ethylenically unsaturated group. The surface roughness is low and the linearity of the high-definition pattern is preferred.

The first compound (B-1) containing the ethylenically unsaturated group in Example 9 was used in an amount of 15 parts by weight, and Examples 1 to 8 were the first compound (B-1) containing an ethylenically unsaturated group. The amount is 0.1 to 10 parts by weight, so that the surface roughness of the pixel formed by the photosensitive resin composition is lower and the linearity of the high-definition pattern is better.

The photosensitive resin composition of Comparative Examples 1 to 5 was formed by using the first compound (B-1) containing the ethylenically unsaturated group. The high-definition pattern of the pixel formed by the photo-resin composition has poor linearity and high surface roughness.

In summary, the first compound (B-1) containing an ethylenically unsaturated group is used, and the alkali-soluble resin (A), photoinitiator (C), organic solvent (D) and pigment are blended. (E) Since the high-definition pattern of the pixel formed by the photosensitive resin composition has good linearity and low surface roughness, the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (12)

A photosensitive resin composition comprising: an alkali-soluble resin (A); an ethylenically unsaturated group-containing compound (B), comprising a first compound (B-1) containing an ethylenically unsaturated group; and a photoinitiator (C); an organic solvent (D); and a pigment (E); wherein the first compound (B-1) having an ethylenically unsaturated group has a structure represented by the formula (I), In the formula (I), R ¹¹ represents hydrogen or a methyl group, and R ¹² represents an alkylene group having a carbon number of 1 to 20 and substituted or unsubstituted with a hydroxyl group, or a carbon number of 6 to 20 and substituted by a hydroxyl group or not Substituted aryl, one or more -CH ₂ - groups in the alkyl and aryl groups may each independently be -O-, -S-, -CO-, -O-CO- or - CO-O-substituted, X represents a decyloxy group. The photosensitive resin composition according to claim 1, wherein X represents a decyloxy group represented by the formula (I-1), (I-2) or (I-3), In the formulae (I-1) to (I-3), R ²¹ to R ²⁵ each independently represent a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₂₀ aryl group, and n represents an integer of 1 to 50. The photosensitive resin composition according to claim 1, wherein the total amount of the ethylenically unsaturated group-containing first compound (B-1) is 100 parts by weight based on the total amount of the alkali-soluble resin (A). It is 0.1 to 10 parts by weight. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1) having an unsaturated group, and the first alkali-soluble resin having an unsaturated group The resin (A-1) is obtained by a polymerization reaction of a first mixture comprising an epoxy compound having at least two epoxy groups, and one having at least one carboxylic acid group and at least one ethyl group. An unsaturated group of compounds. The photosensitive resin composition according to claim 4, wherein the epoxy compound having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (V). An epoxy compound having at least two epoxy groups represented by the formula (VI), or a combination of the above, In the formulae (V) and (VI), R ⁴¹ to R ⁴⁴ each independently represent hydrogen, halogen or a C ₁ to C ₅ alkyl group, and R ⁵¹ to R ⁶⁵ each independently represent hydrogen, halogen, C ₁ to C _{8 .} An alkyl group or a C ₆ to C ₁₅ aryl group, and n represents an integer of 0 to 10. The photosensitive resin composition according to claim 4, wherein the content of the first alkali-soluble resin (A-1) having an unsaturated group is 100 parts by weight based on the total amount of the alkali-soluble resin (A). It is 5 to 70 parts by weight. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) further comprises a second compound (B-2) having an ethylenically unsaturated group, the ethylenic property. The unsaturated compound second compound (B-2) is selected from the group consisting of formula (II), formula (III) or a combination thereof; wherein formula (II) and formula (III) are as follows: In the formulae (II) and (III), R ³¹ represents -[(CH ₂ ) _y CH ₂ O]- or -[(CH ₂ ) _y CH(CH ₃ )O]-, and y represents an integer of 1 to 10 R ³² represents hydrogen, a carboxyl group or a (meth) acrylonitrile group, and in the formula (II), the total number of the (meth) acryl fluorenyl groups is 3 or 4, and m1 to m4 each independently represent an integer of 0 to 10. And the total of m1 to m4 is an integer of 1 to 40; in the formula (III), the total of the (meth)acrylinyl groups is 5 or 6, and n1 to n6 each independently represent an integer of 0 to 10. And the sum of n1 to n6 is an integer of 1 to 60. The photosensitive resin composition according to claim 7, wherein the amount of the ethylenically unsaturated group-containing second compound (B-2) is 100 parts by weight based on the total amount of the alkali-soluble resin (A). The range is from 10 to 100 parts by weight. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 30 to 300, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). Parts by weight; the photoinitiator (C) is used in an amount ranging from 10 to 200 parts by weight; the organic solvent (D) is used in an amount ranging from 500 to 5000 parts by weight; and the pigment (E) is used in an amount ranging from 50 to 500 parts by weight. Share. A method of producing a color filter, which comprises forming a pixel layer using the photosensitive resin composition according to any one of claims 1 to 9. A color filter produced by the method of claim 10. A liquid crystal display device comprising a color filter according to claim 11.