CN104062848A - Photosensitive resin composition, black matrix, color filter and liquid crystal display element - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a black matrix, a color filter and a liquid crystal display element. A photosensitive resin composition includes an alkali-soluble resin component, an ethylenically unsaturated group-containing compound, a photoinitiator, a pigment component and a solvent. The alkali-soluble resin component includes a resin with unsaturated groups prepared by polymerization of a mixture, and the mixture includes an epoxy compound with at least two epoxy groups, and at least one carboxylic acid group and at least one ethylene group. Compounds with sexually unsaturated groups. The pigment component includes black pigments and blue pigments. The composition uses a resin with unsaturated groups, and adjusts the weight ratio of the black pigment to the blue pigment to be in the range of 0.5 to 10, so that the composition has high sensitivity and the black matrix formed by the composition has high light shielding performance and high resolution.

Description

Photosensitive resin composition, black matrix, color filter and liquid crystal display element

technical field

The invention relates to a photosensitive resin composition for forming a black matrix, in particular to a photosensitive resin composition comprising an alkali-soluble resin and a pigment component. The pigment component includes a black pigment and a blue pigment.

Background technique

In order to improve the contrast and display quality of current liquid crystal displays, black matrices are generally arranged in the stripes and dots of the color filter. The role of the black matrix is to prevent defects such as a decrease in contrast and a decrease in color purity caused by light leakage between pixels. In the past, the black matrix was made by using materials containing chromium or chromium oxide to form an evaporated film on the substrate, but this method has disadvantages such as complicated manufacturing process and expensive materials. In order to solve the above disadvantages, a technique of forming a black matrix on a substrate with a photosensitive resin composition in a photolithographic manner has been proposed.

At present, the industry has higher and higher requirements for the light-shielding properties of the black matrix. The solution is to increase the content of black pigments to improve the light-shielding properties of the black matrix. Japanese Patent Application Laid-Open No. 2006-259716 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition comprises a high content of black pigment, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer with a difunctional group, and an organic solvent. The reactive monomer with a difunctional group is an acrylic acid containing a fluorenyl group. ester monomer. The photosensitive resin composition of the Japanese patent application uses a high content of black pigment to seek high light-shielding properties, and at the same time, it is necessary to use the fluorenyl-containing acrylate monomer to increase the degree of crosslinking of the photosensitive resin composition during exposure , and then increase the sensitivity to form a black matrix with a high-definition pattern.

Japanese Patent Application Laid-Open No. 2008-268854 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition includes alkali-soluble resin with carboxylic acid group and polymerizable unsaturated group, photopolymerizable monomer with ethylenically unsaturated group, photoinitiator and high-content black pigment. The photosensitive resin composition of the Japanese patent application uses a high content of black pigment to seek high light-shielding properties, and at the same time uses a specific alkali-soluble resin with carboxylic acid groups and polymerizable unsaturated groups to improve the photosensitive resin composition. The degree of cross-linking during exposure improves the sensitivity and enables the black matrix formed by the photosensitive resin composition to maintain the required resolution.

However, because the current industry requires a minimum line width of less than 10 μm for the resolution of the black matrix in order to provide higher resolution image quality for the liquid crystal display element, the black matrix disclosed in the above two patent applications is composed of photosensitive resin The black matrix formed by the object can no longer meet the industry's requirements for resolution.

In view of the above, improving the photosensitive resin composition to provide a higher resolution for the black matrix, and then providing a high-quality liquid crystal display device, is a subject for those skilled in the art to make further breakthroughs.

Contents of the invention

The first object of the present invention is to provide a photosensitive resin composition. The photosensitive resin composition has high sensitivity and can form a black matrix with high light-shielding property and high resolution.

The photosensitive resin composition of the present invention comprises:

The alkali-soluble resin component (A) includes a resin (A-1) with an unsaturated group, and the resin (A-1) with an unsaturated group is prepared by a polymerization reaction of a mixture, and the mixture includes at least two Epoxy compound (i) of epoxy group, and compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group;

Compound (B) containing an ethylenically unsaturated group;

Photoinitiator (C);

pigment component (D); and

solvent (E);

The pigment component (D) includes a black pigment (D-1) and a blue pigment (D-2), and the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) is The range is 0.5 to 10.

In the photosensitive resin composition of the present invention, the epoxy compound (i) having at least two epoxy groups is selected from epoxy compounds having at least two epoxy groups represented by formula (I), and epoxy compounds represented by formula (II) Epoxy compounds having at least two epoxy groups, or combinations thereof:

R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aryl alkyl,

R ⁵ to R ¹⁸ 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.

In the photosensitive resin composition of the present invention, the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by formula (I):

R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aryl alkyl.

In the photosensitive resin composition of the present invention, the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by formula (II):

R ⁵ to R ¹⁸ 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.

In the photosensitive resin composition of the present invention, based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the content of the resin (A-1) with unsaturated groups ranges from 50 to 100 parts by weight. The use amount of the ethylenically unsaturated group compound (B) ranges from 30 to 300 parts by weight, the use amount of the pigment component (D) ranges from 100 to 1000 parts by weight, and the use amount of the solvent (E) ranges from 1000 parts by weight. to 5000 parts by weight.

In the photosensitive resin composition of the present invention, based on the total amount of the ethyl unsaturated group-containing compound (B) being 100 parts by weight, the photoinitiator (C) is used in an amount ranging from 10 to 60 parts by weight.

In the photosensitive resin composition of the present invention, based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the amount of the black pigment (D-1) used ranges from 50 to 600 parts by weight, and the blue pigment ( D-2) is used in an amount ranging from 50 to 400 parts by weight.

The second object of the present invention is to provide a black matrix with high light-shielding properties and high resolution.

The black matrix of the present invention is formed from the above-mentioned photosensitive resin composition.

The third objective of the present invention is to provide a color filter.

The color filter of the present invention includes the above-mentioned black matrix.

A fourth object of the present invention is to provide a liquid crystal display element.

The liquid crystal display device of the present invention includes the above-mentioned color filter.

The beneficial effects of the present invention are: by using the resin (A-1), black pigment (D-1) and blue pigment (D-2) with unsaturated groups, and the amount of black pigment (D-1) is the same as The weight ratio of the amount of blue pigment (D-2) used is in the range of 0.5 to 10, so that the photosensitive resin composition has high sensitivity, and the black matrix formed by the photosensitive resin composition has high light-shielding properties and high resolution rate, so that the liquid crystal display element including the black matrix has good contrast and high-quality display quality.

Detailed ways

Herein, the (meth)acrylic acid [(meth)acrylic acid] means acrylic acid (acrylic acid) and/or methacrylic acid (methacrylic acid); the (meth)acrylate [(meth)acrylate] means acrylate (acrylate) and/or methacrylate; the (meth)acryloyl [(meth)acryloyl group] means acryloyl (acryloyl group) and/or methacryloyl group (methacryloyl group).

The photosensitive resin composition of the present invention comprises:

The alkali-soluble resin component (A) includes a resin (A-1) with an unsaturated group, and the resin (A-1) with an unsaturated group is prepared by a polymerization reaction of a mixture, and the mixture includes at least two Epoxy compound (i) of epoxy group, and compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group;

Compound (B) containing an ethylenically unsaturated group;

Photoinitiator (C);

pigment component (D); and

solvent (E);

The pigment component (D) includes a black pigment (D-1) and a blue pigment (D-2), and the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) is The range is 0.5 to 10.

Preferably, based on 100 parts by weight of the total amount of the alkali-soluble resin component (A), the content of the resin (A-1) with unsaturated groups ranges from 50 to 100 parts by weight, and the ethylenically unsaturated The usage range of the basic compound (B) is 30 to 300 parts by weight, the usage range of the pigment component (D) is 100 to 1000 parts by weight, and the usage range of the solvent (E) is 1000 to 5000 parts by weight .

The following will further describe each component in the photosensitive resin composition of the present invention one by one:

<<Alkali-soluble resin component (A)>>

[Resin (A-1) having an unsaturated group]

As mentioned above, the resin (A-1) having an unsaturated group is prepared by performing a polymerization reaction on the mixture, the mixture includes the epoxy compound (i) having at least two epoxy groups, and the epoxy compound (i) having at least In addition to the compound (ii) having one carboxylic acid group and at least one ethylenically unsaturated group, the mixture may optionally include a carboxylic acid anhydride compound (iii) and/or an epoxy compound (iv) having one epoxy group. The epoxy compound (i) having at least two epoxy groups, the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group, the carboxylic anhydride compound (iii) and the The oxy-epoxide compound (iv) is further described.

<Epoxy compound (i) having at least two epoxy groups>

Preferably, the epoxy compound (i) having at least two epoxy groups is selected from the epoxy compounds having at least two epoxy groups shown in formula (I), the epoxy compounds having at least two epoxy groups shown in formula (II) Epoxy compounds with epoxy groups, or combinations thereof:

R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aryl Alkyl group.

R ⁵ to R ¹⁸ 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.

Preferably, the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by formula (I). The epoxy compound having at least two epoxy groups represented by the formula (I) is the same as described above, so it will not be described again.

Preferably, the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by formula (II). The epoxy compound having at least two epoxy groups represented by the formula (II) is the same as above, so it will not be described again.

In more detail, the epoxy compound having at least two epoxy groups represented by the formula (I) is, for example but not limited to: the second compound comprising bisphenol fluorene and epihalohydrin An epoxy-containing bisphenol fluorene type compound prepared by polymerization reaction of a reactant.

The bisphenol fluorene compounds can be used alone or in combination, for example but not limited to: 9,9-bis(4-hydroxyphenyl)fluorene[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-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)fluorene[9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene[9,9-bis( 4-hydroxy-3,5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene[9,9-bis(4-hydroxy-3,5-dichlorophenyl) fluorene], or 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene[9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene], etc.

The halogenated propylene oxide can be used alone or in combination, for example but not limited to: 3-chloro-1,2-epoxypropylene (epichlorohydrin) or 3-bromo-1,2-epoxypropylene (epibromohydrin) and the like.

The epoxy-containing bisphenol fluorene compound can be used alone or in combination, such as but not limited to: (1). Products manufactured by Nippon Steel Chemical, such as: ESF-300, etc.; (2). Products manufactured by Osaka Gas , such as: PG-100, EG-210, etc.; (3). Products manufactured by S.M.S Technology Co., such as: SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.

In more detail, the epoxy compound having at least two epoxy groups represented by the formula (II) is for example but not limited to: a compound represented by the formula (II-1), a halogenated propylene oxide and an alkali metal hydrogen It is obtained by reacting the second reactant of the oxide. More specifically, the reaction is dehydrohalogenation using an excess amount of halogenated propylene oxide and the compound represented by the formula (II-1) in the presence of an alkali metal hydroxide.

The compound shown in the formula (II-1):

R ⁵ to R ¹⁸ 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.

More specifically, the compound represented by the formula (II-1) is prepared by condensation reaction of the second reactant comprising the compound represented by the formula (II-2), a phenol compound and an acid catalyst Its, the compound shown in this formula (II-2):

R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aryl group; X ¹ and X ² each independently represent a halogen atom, C ₁ to C ₆ Alkyl or C ₁ to C ₆ alkoxy. Preferably, the halogen atom is chlorine or bromine. The C ₁ to C ₈ alkyl group and C ₁ to C ₆ alkyl group are methyl, ethyl or tert-butyl. The C ₁ to C ₆ alkoxy group is methoxy or ethoxy.

The phenolic compound can be used alone or in combination, such as but not limited to: phenol (phenol), cresol (cresol), ethylphenol (ethylphenol), n-propylphenol (n-propylphenol), isobutylphenol (isobutylphenol), t -Butylphenol (t-butylphenol), octylphenol (octylphenol), nonylphenol (nonylphenol), stubble phenol (xylenol), methylbutylphenol (methylbutylphenol), di-tert-butylphenol (di-t-butylphenol), Vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol, cyclohexylcresol, etc.

Based on the total amount of the compound represented by the formula (II-2) being 1 mole, the amount of the phenolic compound used ranges from 0.5 moles to 20 moles. Preferably, the amount of the phenolic compound used ranges from 2 moles to 15 moles.

The acid catalyst can be used alone or in combination, such as but not limited to: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonic acid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous aluminum chloride ( aluminum chloride anhydrous) or zinc chloride (zinc chloride), etc. Preferably, the acid catalyst is selected from p-toluenesulfonic acid, sulfuric acid or hydrochloric acid. The amount of the acid catalyst used is not particularly limited. Preferably, based on the total amount of the compound represented by the formula (II-2) being 100wt%, the acid catalyst is used in an amount ranging from 0.1 to 30wt%.

The condensation reaction can be performed without a solvent or in the presence of an organic solvent. The organic solvent can be used alone or in combination, such as but not limited to: toluene, xylene, or methyl isobutyl ketone. Based on the total amount of the compound represented by the formula (II-2) and the phenolic compound as 100wt%, the usage amount of the organic solvent is in the range of 50 to 300wt%, preferably, the usage amount of the organic solvent is in the range of 100 to 300wt%. 250wt%. In addition, the operating temperature of the condensation reaction is 40 to 180° C., and the operating time is 1 hour to 8 hours. After the condensation reaction is completed, the solution obtained after the reaction is neutralized or washed with water, and then, the unreacted phenolic compound and the solvent are distilled off by heat treatment under reduced pressure, and then concentrated to obtain the formula (II - the compound shown in 1). The neutralization treatment is to adjust the pH range of the reacted solution to 3-7, preferably, the pH range is 5-7. The washing treatment is carried out using a neutralizing agent that is an alkaline substance, such as but not limited to: alkali metal hydroxides such as sodium hydroxide (sodium hydroxide) and potassium hydroxide (potassium hydroxide); calcium hydroxide (calcium hydroxide) Alkaline earth metal hydroxides such as magnesium hydroxide; organic amines such as diethylene triamine, triethylenetetramine, aniline, and phenylene diamine; And ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate), etc.

The halogenated propylene oxide is selected from 3-chloro-1,2-propylene oxide, 3-bromo-1,2-propylene oxide, or combinations thereof. Before the dehydrohalogenation reaction, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be added in advance or during the reaction process, and the operating temperature range is 20 to 120 ° C, and the operating time range is 1 hour to 10 hours .

In a specific example of the photosensitive resin composition of the present invention, the alkali metal hydroxide used in the dehydrohalogenation reaction can also be an aqueous alkali metal hydroxide solution. At this time, the aqueous alkali metal hydroxide solution is continuously added to the reaction In the reactor, at the same time, water and propylene oxide can be continuously distilled under reduced pressure or normal pressure, thereby removing the water, and the propylene oxide obtained by distillation can be continuously refluxed into the reactor.

Before the above-mentioned dehydrohalogenation reaction, tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride can also be added. The quaternary ammonium salt is used as a catalyst, and react at 50 to 150°C for 1 hour to 5 hours, then add alkali metal hydroxide or an aqueous solution of alkali metal hydroxide, and react at a temperature of 20°C to 120°C for 1 hour to 10 hours for the dehydrohalogenation reaction.

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

In addition, in order to make the dehydrohalogenation reaction go smoothly, in addition to alcohols such as methanol or ethanol, aprotic polar substances such as dimethyl sulfone and dimethyl sulfoxide can also be added. solvents, etc. to carry out the reaction. In the case of using alcohols, based on the total amount of the halogenated propylene oxide being 100 wt%, the alcohols are used in an amount ranging from 2 to 20 wt%. Preferably, the alcohols are used in an amount ranging from 4 to 15 wt%. In an example of using an aprotic polar solvent, based on the total amount of the halogenated propylene oxide being 100 wt%, the aprotic polar solvent is used in an amount ranging from 5 to 100 wt%. Preferably, the aprotic polar solvent is used in an amount ranging from 10 to 90 wt%.

After completion of the dehydrohalogenation reaction, a water washing treatment can be optionally performed. Then, by heating and reducing pressure, for example, at a temperature of 110 to 250° C. and a pressure of 1.3 kPa (10 mmHg) or less, the halogenated propylene oxide, alcohols, and aprotic polar solvents are removed.

In order to avoid the presence of unreacted starting materials such as halogenated propylene oxide and affect the physical properties, the solution after the dehydrohalogenation reaction can be added to a solvent such as toluene or methyl isobutyl ketone (methyl isobutyl ketone), and added Alkali metal hydroxide aqueous solution such as sodium, potassium hydroxide, carry out dehydrohalogenation reaction again. In the dehydrohalogenation reaction, based on the total equivalent of hydroxyl groups in the compound represented by the formula (II-1) being 1 equivalent, the use amount of the alkali metal hydroxide ranges from 0.01 to 0.3 moles, preferably, the alkali The metal hydroxide is used in an amount ranging from 0.05 to 0.2 moles. In addition, the operating temperature of the dehydrohalogenation reaction ranges from 50 to 120° C., and the operating time ranges from 0.5 hours to 2 hours.

After the dehydrohalogenation reaction is completed, the salts are removed through steps such as filtration and water washing. And utilizing the mode of heating and reducing pressure, solvents such as toluene and methyl isobutyl ketone are distilled off to obtain the epoxy compound represented by the formula (II) having at least two epoxy groups. Commercially available epoxy compounds having at least two epoxy groups represented by the formula (II) include, but are not limited to, NC-3000, NC-3000H, NC-3000S, and NC-3000P manufactured by Nippon Kayaku.

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

The compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group can be used alone or in combination, such as but not limited to (1). Acrylic acid, methacrylic acid, 2-methacryloyloxyethylbutyl 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxybutylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxybutylbutanedioic acid, 2- Methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxypropylmaleic acid, 2-methacryloyloxybutylmaleic acid Toric acid, 2-methacryloxypropyl succinic acid, 2-methacryloyloxypropyl adipic acid, 2-methacryloyloxypropyl tetrahydrophthalic acid, 2-methylpropene Acyloxypropylphthalic acid, 2-methacryloyloxybutylphthalic acid, or 2-methacryloyloxybutylhydrophthalic acid; or (2). A compound obtained by reacting with a dicarboxylic acid compound, such as but not limited to: adipic acid, succinic acid, maleic acid or phthalic acid, etc.; or (3). A half-ester compound obtained by reacting (meth)acrylate with a carboxylic acid anhydride compound (iii), the hydroxyl-containing (meth)acrylate is for example but not limited to: 2-hydroxyethyl acrylate [(2-hydroxyethyl) acrylate], 2-hydroxyethyl methacrylate [(2-hydroxyethyl)methacrylate], 2-hydroxypropyl acrylate [(2-hydroxypropyl)acrylate], 2-hydroxypropyl methacrylate [(2- hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl)acrylate], 4-hydroxybutyl methacrylate [(4-hydroxybutyl)methacrylate], or pentaerythritol trimethacrylate, etc.

The carboxylic anhydride compound (iii) is selected from dicarboxylic anhydride compounds, tetracarboxylic anhydride compounds, or combinations thereof. The dibasic carboxylic acid anhydride compound can be used alone or in combination, such as but not limited to butanedioic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride , tetrahydrophthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalicanhydride), methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl endomethylene Methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride, or 1,3-dioxoisobenzofuran-5-carboxylic anhydride, etc. The tetravalent carboxylic acid anhydride compound can be used alone or in combination, for example but not limited to benzophenone tetracarboxylic dianhydride (BTDA), bisbenzene tetracarboxylic dianhydride or bisphenyl ether tetracarboxylic dianhydride.

<Carboxylic anhydride compound (iii)>

The carboxylic acid anhydride compound (iii) is as described above, so it will not be described in detail.

<Epoxy compound (iv) having one epoxy group>

The epoxy compound (iv) having an epoxy group is selected from glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, glycidyl ether compounds containing unsaturated groups, epoxy-containing radical unsaturated compounds, or combinations thereof. Commercially available products of the unsaturated group-containing glycidyl ether compound include but are not limited to: Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146 manufactured by Nagase Chemical Industry Co., Ltd. , Denacol EX-171, Denacol EX-192, etc.

This resin (A-1) with unsaturated groups can be represented by the epoxy compound with at least two epoxy groups and the compound with at least one carboxylic acid group and at least one ethylenically unsaturated group ( ii) performing a polymerization reaction (the operating temperature range is 50° C. to 130° C.) to form a reaction product containing a hydroxyl group, and then adding a carboxylic acid anhydride compound (iii) for reaction. Preferably, based on the total hydroxyl equivalent of the hydroxyl-containing reaction product being 1 equivalent, the equivalent of the acid anhydride group in the carboxylic anhydride compound (iii) ranges from 0.4 to 1 equivalent. More preferably, the equivalent of the acid anhydride group in the carboxylic anhydride compound (iii) ranges from 0.75 to 1 equivalent. When using one or more kinds of the carboxylic acid anhydride compound (iii), they are added sequentially or simultaneously during the reaction. Preferably, when dicarboxylic anhydride compounds and tetracarboxylic anhydride compounds are used as the carboxylic anhydride compound (iii), the molar ratio of dicarboxylic anhydride compounds to tetracarboxylic anhydride compounds ranges from 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 resin (A-1) with unsaturated group can be represented by 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 ( ii) performing a reaction to form a reaction product containing a hydroxyl group, and then adding a carboxylic acid anhydride compound (iii) and/or an epoxy compound (iv) having an epoxy group to carry out a polymerization reaction. Preferably, the total equivalent weight of epoxy groups based on the epoxy compound having at least two epoxy groups represented by formula (II) is 1 equivalent, and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (ii) has an acid value equivalent of 0.8 to 1.5 equivalents. More preferably, it is 0.9 to 1.1 equivalents. Based on the total amount of hydroxyl groups in the hydroxyl-containing reaction product being 100 mol%, the amount of the carboxylic acid anhydride compound (iii) used ranges from 10 to 100 mol%, preferably from 20 to 100 mol%, more preferably, 30 to 100 mol%.

When preparing the resin (A-1) having an unsaturated group, in order to accelerate the reaction, a basic compound is usually added to the reaction solution as a reaction catalyst. The reaction catalyst can be used alone or in combination, such as but not limited to: triphenyl phosphine (triphenyl phosphine), triphenyl antimony (triphenyl stibine), triethylamine (triethylamine), triethanolamine (triethanolamine), tetramethyl chloride Ammonium (tetramethylammonium chloride) or benzyltriethylammonium chloride (benzyltriethylammoniumchloride), etc. Preferably, 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 is 100 parts by weight, the reaction The catalyst is used in an amount ranging from 0.01 to 10 parts by weight, more preferably, from 0.3 to 5 parts by weight.

In addition, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The polymerization inhibitor can be used alone or in combination, such as but not limited to: methoxyphenol (methoxyphenol), methylhydroquinone (methylhydroquinone), hydroquinone (hydroquinone), 2,6-di-tert-butyl p-cresol (2 , 6-di-t-butyl-p-cresol), or phenothiazine (phenothiazine), etc. 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 being 100 parts by weight, the use of the polymerization inhibitor The amount ranges from 0.01 to 10 parts by weight, preferably, from 0.1 to 5 parts by weight.

When preparing this resin (A-1) which has an unsaturated group, a polymerization reaction solvent can be used as needed. The polymerization solvent can be used alone or in combination, such as but not limited to: alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; methyl ethyl ketone or cyclic Ketone compounds such as hexanone; aromatic hydrocarbon compounds such as toluene or xylene; cellosolve compounds such as cellosolve or butyl cellosolve; carbitol or butyl carbitol (butylcarbito) and other carbitol compounds; propylene glycol monomethyl ether and other propylene glycol alkyl ether compounds; dipropylene glycol monomethyl ether [di(propylene glycol) methyl ether] and other polypropylene glycol alkyl ethers [poly(propylene glycol) )alkyl ether] compounds; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate and other acetate compounds; ethyl lactate (ethyllactate) or butyl lactate (butyl lactate) and other alkyl lactate compounds; or dialkyl glycol ethers. In addition, the acid value of the unsaturated resin (A-1) ranges from 50 mgKOH/g to 200 mgKOH/g, preferably, from 60 mgKOH/g to 150 mgKOH/g.

Because the resin (A-1) with unsaturated groups has good heat resistance, and contains unsaturated bonds, it can also undergo crosslinking reaction to improve the sensitivity of the photosensitive resin composition, and is composed of the photosensitive resin The black matrix formed by the material has good resolution. Therefore, when the photosensitive resin composition does not use the resin (A-1) with an unsaturated group, the sensitivity of the photosensitive composition will be poor, and due to the The black matrix formed by the photosensitive resin composition has the disadvantage of poor resolution. Preferably, based on the total amount of the alkali-soluble resin (A) component being 100 parts by weight, the content of the resin (A-1) with unsaturated groups ranges from 50 to 100 parts by weight, preferably 60 parts by weight. to 100 parts by weight, more preferably, 70 to 100 parts by weight.

[Other Alkali Soluble Resins (A-2)]

The alkali-soluble resin component (A) also includes other alkali-soluble resins (A-2). The other alkali-soluble resins (A-2) are, for example but not limited to, resins containing carboxylic acid groups or hydroxyl groups. Specific examples are: acrylic resins other than the resin (A-1) having unsaturated groups, polyurethane (urethane) Resin or novolac type (novolac) resin, etc.

Based on 100 parts by weight of the total amount of the alkali-soluble resin component (A), the content of the other alkali-soluble resin (A-2) ranges from 0 to 50 parts by weight, preferably from 0 to 40 parts by weight, more preferably Preferably, it is 0 to 30 parts by weight.

<<Ethylenically unsaturated group-containing compound (B)>>

Based on 100 parts by weight of the alkali-soluble resin component (A), the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 30 parts by weight to 300 parts by weight. When the amount of the ethylenically unsaturated group-containing compound (B) is less than 30 parts by weight, the degree of crosslinking of the photosensitive resin composition is insufficient to form a black matrix with a predetermined pattern; when the ethylenically unsaturated group-containing When the amount of the compound (B) used is greater than 300 parts by weight, the sensitivity of the photosensitive composition is too high, so that residues are likely to be generated after development of the non-illuminated parts. Preferably, based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 40 parts by weight to 280 parts by weight. More preferably, based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 50 parts by weight to 260 parts by weight.

The ethylenically unsaturated group-containing compound (B) is selected from a compound (B-1) having one ethylenically unsaturated group, a compound (B-2) having two or more (including two) ethylenically unsaturated groups , or a combination of them.

The compound (B-1) having an ethylenically unsaturated group can be used alone or in combination, such as but not limited to: (meth)acrylamide [(meth)acrylamide), (meth)acryloylmorpholine, (meth) base) 7-amino-3,7-dimethyloctyl acrylate, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate ester, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, (meth) ) dimethylaminoethyl acrylate, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-di Meth(meth)acrylamide, tetrachlorophenyl(meth)acrylate, 2-tetrachlorophenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate ], tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, trichlorophenoxyethyl (meth)acrylate Bromophenyl ester, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxy-ethyl (meth)acrylate, 2-hydroxy-propyl (meth)acrylate, vinyl caprolactam, nitrogen- Vinylpyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polymono(meth)acrylate base) propylene glycol acrylate or bornyl (meth)acrylate, etc.

The compound (B-2) having two or more (containing two) ethylenically unsaturated groups can be used alone or in combination, such as but not limited to: ethylene glycol di(meth)acrylate, di(meth)acrylic acid Dicyclopentenyl ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, (2-Hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tri(meth)acrylic acid Trimethylol propyl ester, trimethylol propyl tri(meth)acrylate modified by ethylene oxide (referred to as EO), tri(meth)acrylate tris(meth)acrylate modified by propylene oxide (referred to as PO) Methylol Propyl Ester, Tripropylene Glycol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, 1,4-Butanediol Di(meth)acrylate, 1,6-Hexanediol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate modified by caprolactone, modified by caprolactone dipentaerythritol penta(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate], bisphenol A modified with ethylene oxide Di(meth)acrylate, bisphenol A di(meth)acrylate modified with propylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with ethylene oxide, modified with propylene oxide Modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified glycerol tri(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate or Novolac polyglycidyl ether (meth)acrylate, etc.

The ethylenically unsaturated group-containing compound (B) is selected from trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified with ethylene oxide, trimethylolpropyl triacrylate modified with propylene oxide Methylol propyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate modified by caprolactone, tetraacrylate diacrylate Trimethylol propyl ester, glyceryl triacrylate modified with propylene oxide, or combinations thereof.

<<Photoinitiator (C)>>

The photoinitiator (C) can be used alone or in combination, for example but not limited to: O-acyl oxime compound (C-1), triazine benzene compound, acetophenone compound, diimidazole compound, Benzophenone-based compounds, α-diketone-based compounds, ketone-alcohol-based compounds, ketol-alcohol-based compounds, acylphosphine oxide-based compounds, quinone-based compounds, halogen-containing compounds, peroxides, and the like.

The O-acyl oxime compound (C-1) can be used alone or in combination, for example but not limited to: 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-( O-benzoyl oxime), 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (for example, OXE01 manufactured by Ciba Specialty Chemicals), 1-[4-(Benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazole-3-substituent]-ethanone 1-(O-acetyl oxime) (such as OXE02 from Ciba Specialty Chemicals), 1-[9-ethyl-6-(3-methylbenzene Acyl)-9H-carbazole-3-substituent]-ethanone 1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-substituent] -Ethanone 1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-carbazole-3-substituted Base]-1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3 -Substituent]-1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9H-carbazole-3- Substituent]-1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazole- 3-Substituent] -1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carba Azole-3-substituent]-1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl )-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxy Benzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyridine Acrylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), Ethanone-1-[9-ethyl-6-{2-methyl- 4-(2,2-Dimethyl-1,3-dioxolanyl)benzoyl}-9H-carbazole-3-substituent]-1-(O-acetyloxime), or ethane Keto-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carba Azole-3-substituent]-1-(O-acetyl oxime) and the like.

Preferably, the O-acyl oxime compound (C-1) is selected from 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime )[OXE01, manufactured by Ciba Specialty Chemicals], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone 1-(O-acetyl Oxime) [OXE02, manufactured by Ciba Specialty Chemicals], Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzoyl)-9H-carbazole-3-substituent] -1-(O-acetyl oxime), or ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxa Pentyl)methoxybenzoyl}-9H-carbazole-3-substituent]-1-(O-acetyloxime).

The triazine compounds can be used alone or in combination, such as but not limited to: vinyl-halomethyl-s-triazine compounds, 2-(naphtho-1-substituent)-4,6- Bis-halomethyl-s-triazabenzene compound, or 4-(p-aminophenyl)-2,6-bis-halomethyl-s-triazapine compound, etc.

The vinyl-halomethyl-s-triazine compounds can be used alone or in combination, such as but not limited to: 2,4-bis(trichloromethyl)-6-p-methoxystyryl- s-triazepine, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazepine, Or 2-trichloromethyl-3-amino-6-p-methoxystyryl-s-triazine, etc.

The 2-(naphtho-1-substituent)-4,6-bis-halomethyl-s-triazine compound can be used alone or in combination, such as but not limited to: 2-(naphtho-1- Substituent)-4,6-bis-trichloromethyl-s-triazepine, 2-(4-methoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl -s-triazepine, 2-(4-ethoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazepine, 2-(4-butane Oxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazepine, 2-[4-(2-methoxyethyl)-naphtho-1- Substituent] -4,6-bis-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl)-naphtho-1-substituent]-4,6- Bis-trichloromethyl-s-triazepine, 2-[4-(2-butoxyethyl)-naphtho-1-substituent]-4,6-bis-trichloromethyl-s -Triazabenzene, 2-(2-methoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazepine, 2-(6-methoxy -5-methyl-naphtho-2-substituent)-4,6-bis-trichloromethyl-s-triazine, 2-(6-methoxy-naphtho-2-substituent) -4,6-bis-trichloromethyl-s-triazine, 2-(5-methoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s- Triazine, 2-(4,7-dimethoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazine, 2-(6-ethyl Oxy-naphtho-2-substituent)-4,6-bis-trichloromethyl-s-triazepine, or 2-(4,5-dimethoxy-naphtho-1-substituent )-4,6-bis-trichloromethyl-s-triazepine, etc.

The 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazepine compound can be used alone or in combination, such as but not limited to: 4-[p-N,N-di (Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[o-methyl-p-N,N-bis(ethoxy Cylcarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-triazepine, 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(tri Chloromethyl)-s-triazepine, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4-(p -N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4-[p-N,N-bis(phenyl)aminophenyl ]-2,6-bis(trichloromethyl)-s-triazine, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl)-s -Triazabenzene, 4-[right-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[ m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[m-bromo-p-N, N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[m-chloro-p-N,N-bis( Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[m-fluoro-p-N,N-bis(ethoxycarbonyl) Methyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)amino Phenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2 ,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis (Trichloromethyl)-s-Triazabenzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)- s-triazine, 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-bromo- p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-chloro-p-N,N-di (Chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazepine, 4-[m-fluoro-p-N,N-bis(chloroethyl)aminobenzene base]-2,6-di (Trichloromethyl)-s-Triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s- Triazine, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4-(m -fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-ethoxy ylcarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)- 2,6-bis(trichloromethyl)-s-triazepine, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl Base)-s-triazepine, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4- (m-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4-(m-fluoro-p-N-chloroethyl Aminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis(tri Chloromethyl)-s-triazine, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazepine, or 2,4-bis(trichloromethyl) -6-[3-Bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazepine, etc.

Preferably, the triazine-based compound is selected from 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl )-s-triazepine or 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazepine.

The acetophenone compounds can be used alone or in combination, such as but not limited to: p-dimethylaminoacetophenone, α,α'-dimethoxyazoacetophenone, 2,2'-di Methyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, Or 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone, etc. Preferably, the acetophenone compound is selected from 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, or 2-benzyl-2- N,N-Dimethylamino-1-(4-morpholinophenyl)-1-butanone.

The diimidazole compounds can be used alone 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-methoxyphenyl) Phenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole 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. Preferably, the diimidazole compound is 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

The benzophenone-based compounds can be used alone or in combination, such as but not limited to: thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4' - Bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone or the like. Preferably, the benzophenone-based compound is 4,4'-bis(diethylamino)benzophenone.

The α-diketone compound is, for example but not limited to, benzil or acetyl. The ketol-based compound is, for example but not limited to, benzophenone. The ketoalcohol ether compound is, for example but not limited to: benzoethanol ketone methyl ether, benzobethanol ketone ethyl ether or benzobethanol ketone isopropyl ether and the like. The acylphosphine oxide compounds are such as but not limited to: 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis-(2,6-dimethoxybenzoyl)-2,4,4 - Trimethylphenylphosphine oxide and the like. The quinone compounds are, for example but not limited to, anthraquinone, 1,4-naphthoquinone and the like. The halogen-containing compound is, for example but not limited to: phenacyl chloride, tribromomethylphenyl sulfone or tris(trichloromethyl)-s-triazepine and the like. The peroxide is for example but not limited to: di-tert-butyl peroxide and the like. The aforementioned α-diketone compounds, ketone alcohol compounds, ketone alcohol ether compounds, acylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, and the like can be used alone or in combination.

The usage amount of the photoinitiator (C) can be prepared as needed, preferably, based on the total amount of the ethyl unsaturated group-containing compound (B) is 100 parts by weight, the amount of the photoinitiator (C) The usage amount ranges from 10 to 60 parts by weight. More preferably, based on the total amount of the ethylenically unsaturated group-containing compound (B) being 100 parts by weight, the photoinitiator (C) is used in an amount ranging from 15 to 55 parts by weight. Still more preferably, based on the total amount of the ethylenically unsaturated group-containing compound (B) being 100 parts by weight, the photoinitiator (C) is used in an amount ranging from 20 to 50 parts by weight.

<<Pigment component (D)>>

The pigment component (D) is used in an amount ranging from 100 to 1000 parts by weight. When the amount of the pigment component (D) used is less than 100 parts by weight, the light-shielding property of the black matrix formed by the photosensitive resin composition is not good. And when the usage amount of the pigment component (D) is higher than 1000 parts by weight, the viscosity of the photosensitive resin composition will be too high, so that it is not easy to disperse evenly when it is to be coated on the substrate later, which is not conducive to A thin film is formed on the substrate or the thickness of the formed thin film is uneven.

Preferably, based on 100 parts by weight of the total amount of the alkali-soluble resin component (A), the amount of the black pigment (D-1) used ranges from 50 to 600 parts by weight, preferably from 75 to 500 parts by weight, More preferably 100 to 400 parts by weight; the blue pigment (D-2) is used in an amount ranging from 50 to 400 parts by weight, preferably 60 to 350 parts by weight, more preferably 70 to 300 parts by weight. If no black pigment (D-1) is used at all, the light-shielding property of the black matrix formed by the photosensitive resin composition is not good; if no blue pigment (D-2) is used at all, the photosensitive resin composition The sensitivity of the object is not good, and the resolution of the formed black matrix is not good.

The pigment component (D) in the photosensitive resin composition uses the blue pigment (D-2) to make light energy in the wavelength range of 325 to 380 nm travel to the photosensitive resin composition in contact with the substrate when exposed, As a result, the degree of cross-linking reaction of the photosensitive resin composition is improved, and then the sensitivity of the overall photosensitive resin composition is improved, so that the line width smaller than 4 μm can be left on the substrate after development, and the resolution of the black matrix is improved. Rate.

When the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) is less than 0.5, the light-shielding property of the black matrix formed by the photosensitive resin composition is not good. When the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) is greater than 10, the sensitivity of the photosensitive resin composition is not good, and the photosensitive resin composition formed The resolution of the black matrix is poor. Below will be described in more detail for this black pigment (D-1) and this blue pigment (D-2):

[black pigment (D-1)]

The black pigment (D-1) preferably has heat resistance, light resistance and solvent resistance.

The black pigment (D-1) can be used alone or in combination, such as but not limited to: (1). Black organic pigments, such as: perylene black (perylene black), cyanine black (cyanine black) or aniline black ( anilineblack), etc.; (2). From red, blue, green, purple, yellow, cyanine (cyanine) or magenta (magenta) and other pigments, choose two or more pigments to mix to make nearly black (3). Shading material, such as: carbon black (carbon black), chromium oxide, iron oxide, titanium black (titanium black) or graphite, etc., carbon black such as but not limited to: C.I. Pigment Black 7, etc., Specific examples include MA100, MA230, MA8, #970, #1000, #2350, and #2650 manufactured by Mitsubishi Chemical Corporation.

[blue pigment (D-2)]

The blue pigment (D-2) is preferably selected not to absorb light sources with a wavelength range below 380nm. The blue pigment can be used alone or in combination, such as but not limited to blue pigment with copper phthalocyanine structure or indanthrone blue (indanthrone blue) blue pigment. The blue pigments with copper phthalocyanine structure are for example but not limited to: C.I. Pigment Blue 15:1 (C.I.PB15:1), C.I. Pigment Blue 15:2 (C.I.PB15:2), C.I. :3), C.I. Pigment Blue 15:4 (C.I.PB15:4), C.I. Pigment Blue 15:5 (C.I.PB15:5), or C.I. Pigment Blue 15:6 (C.I.PB15:6), etc.

The pigment component also includes violet pigments and/or red pigments.

The selection of the purple pigment is preferably not to absorb light sources with a wavelength range below 380nm. The purple pigments can be used alone or in combination, such as but not limited to: C.I. Pigment Violet 14 (C.I.PV14), C.I. Pigment Violet 19 (C.I.PV19), C.I. C.I. Pigment Violet 32 (C.I.PV32), C.I. Pigment Violet 33 (C.I.PV33), C.I. Pigment Violet 36 (C.I.PV36), C.I. Pigment Violet 37 (C.I.PV37), C.I. Pigment Violet 38 (C.I.PV38), C.I. Pigment Violet 40 ( C.I.PV40), or C.I. Pigment Violet 50 (C.I.PV50), etc.

The red pigment is selected from red pigments having an azo condensation structure, red pigments having an anthraquinone structure, quinacridone-based red pigments, perylene-based red pigments, pyranthracene-8,16-dione-based red pigments, or their The combination. The red pigment with azo condensation structure can be used alone or in combination, such as but not limited to: C.I. Pigment Red 83 (C.I.Pigment red83), C.I. Pigment Red 89 (C.I.Pigment red89), or C.I. Pigment Red 177 (C.I.Pigment red177) wait. Preferably, the red pigment with an azo condensation structure is selected from C.I. Pigment Red 89, C.I. Pigment Red 177, or a combination thereof. The red pigment with anthraquinone structure can be used alone or in combination, for example but not limited to: C.I. C.I.Pigment red220), C.I. Pigment red 221 (C.I.Pigment red221), C.I. Pigment red 242 (C.I.Pigment red242), C.I. Pigment red 248 (C.I.Pigment red248), or C.I. Pigment red 262 (C.I.Pigment red262), etc. Preferably, the red pigment with anthraquinone structure is selected from C.I. Pigment Red 166, C.I. Pigment Red 242, or a combination thereof.

<<Solvent (E)>>

The solvent (E) must be capable of dissolving the alkali-soluble resin component (A), the compound (B) containing ethylenically unsaturated groups, the photoinitiator (C) and the pigment component (D), and does not mix with the above-mentioned components Those that react and have appropriate volatility are preferred.

The solvent (E) can be used alone or in combination, such as but not limited to: alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, other ether compounds, ketone compounds, lactic acid alkyl Esters, other esters, aromatic hydrocarbons, carboxylic acid amines.

The alkyl glycol monoalkyl ether compounds can be used alone or in combination, such as but not limited to: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, Diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether , Dipropylene glycol mono-n-butyl ether, or tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether, etc.

The alkyl glycol monoalkyl ether acetate compounds can be used alone or in combination, such as but not limited to: ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate, or propylene glycol ether acetate, etc. .

The other ether compounds can be used alone or in combination, for example but not limited to: diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, etc.

The ketone compounds can be used alone or in combination, such as but not limited to: methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or diacetone alcohol.

The alkyl lactate compounds can be used alone or in combination, such as but not limited to: methyl lactate or ethyl lactate, etc.

The other ester compounds can be used alone or in combination, such as but not limited to: methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3 -methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, iso-acetate Propyl ester, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate or ethyl 2-oxybutyrate, etc.

The aromatic hydrocarbons can be used alone or in combination, such as but not limited to: toluene or xylene.

The carboxylic acid amine compounds can be used alone or in combination, such as but not limited to: N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

Preferably, based on 100 parts by weight of the total amount of the alkali-soluble resin (A), the amount of the solvent (E) used ranges from 1000 parts by weight to 5000 parts by weight. More preferably, based on 100 parts by weight of the total amount of the alkali-soluble resin (A), the usage amount of the solvent (E) ranges from 1200 parts by weight to 4800 parts by weight. Still more preferably, based on the total amount of the alkali-soluble resin (A) being 100 parts by weight, the amount of the solvent (E) used ranges from 1500 parts by weight to 4500 parts by weight.

<<Additive (F)>>

On the premise of not affecting the efficacy of the present invention, the photosensitive resin composition of the present invention also contains additives (F), such as but not limited to: surfactants, fillers, adhesion promoters, crosslinking agents, antioxidants, anti-coagulation agents , or a polymer other than the alkali-soluble resin component (A) and capable of increasing various properties such as mechanical properties, etc.

The surfactant is selected from cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane-based surfactants, fluorine-based surfactants, or combinations thereof. More specifically, the surfactant is such as but not limited to: polyethoxyalkyl ethers, polyethoxyalkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, Polyesters modified with fatty acids, or polyurethanes modified with tertiary amines. The polyethoxy alkyl ethers are, for example but not limited to: polyethoxy lauryl ether, polyethoxy stearyl ether, polyethoxy oleyl ether, etc. The polyethoxyalkylphenyl ethers are, for example but not limited to: polyethoxyoctylphenyl ether or polyethoxynonylphenyl ether and the like. The polyethylene glycol diesters are, for example but not limited to: polyethylene glycol dilaurate or polyethylene glycol distearate. The above surfactants can be used alone or in combination.

Commercially available surfactants to be used include KP (manufactured by Shin-Etsu Chemical), SF-8427 (manufactured by TorayDow Corning Silicon), Polyflow (manufactured by Kyoeisha Oleochemical Industry), F-Top (manufactured by Tochem Product Co., Ltd. Manufactured by Dainippon INK Chemical Industry), Megafac (manufactured by Dainippon INK Chemical Industry), Fluorade (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), or SINOPOL E8008 (manufactured by Sino-Nippon Synthetic Chemicals), etc.

The fillers can be used alone or in combination, such as but not limited to glass or aluminum.

The adhesion promoter can be used alone or in combination, such as but not limited to vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-amino Ethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidyl Propyl Trimethoxysilane, 3-Glycidyl Propyl Methyldiethoxy Silane, 2-(3,4-Epoxycyclohexyl) Ethyl Trimethoxy Silane, 3-Chloropropane Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropionyloxypropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane, etc.

The antioxidant can be used alone or in combination, such as but not limited to 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-tert-butylphenol and the like.

The anti-aggregation agent is for example but not limited to sodium polyacrylate.

The crosslinking agent is, for example, but not limited to epoxy-based compounds or resins such as 1031S and 157S-70 manufactured by Japan Epoxy Resin Co., Ltd.

Based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the use of any additive in the polymer other than the filler, adhesion promoter, antioxidant, anti-coagulant or alkali-soluble resin (A) The amount ranges from 0 parts by weight to 10 parts by weight, preferably, the amount used ranges from 0 parts by weight to 6 parts by weight.

Based on 100 parts by weight of the total amount of the alkali-soluble resin component (A), the amount of the surfactant used ranges from 0 parts by weight to 6 parts by weight. Preferably, the amount used of the surfactant ranges from 0 parts by weight parts to 4 parts by weight.

Based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the amount of the cross-linking agent used ranges from 0 parts by weight to 100 parts by weight. Preferably, the amount used of the cross-linking agent ranges from 0 parts by weight parts to 80 parts by weight.

The preparation method of the photosensitive resin composition of the present invention is not particularly limited. For example, the alkali-soluble resin component (A), the compound (B) containing ethylenically unsaturated groups, the photoinitiator (C), and the pigment can be used. Component (D) and solvent (E) are placed in a stirrer and stirred evenly to form a solution state, and additive (F) can be added if necessary to be evenly mixed. Alternatively, for example, the alkali-soluble resin component (A), the compound (B) containing ethylenically unsaturated group (B), the photoinitiator (C) and the solvent (E) are placed in a stirrer and stirred uniformly to form solution, and then directly add the pigment component (D) into the solution to disperse to obtain the photosensitive resin composition of the present invention. Or first disperse a part of the pigment component (D) in a part of the alkali-soluble resin component (A) and a part of the solvent (E) to form a pigment dispersion, and then mix the compound containing ethylenically unsaturated groups (B), the photoinitiator (C), and the remaining alkali-soluble resin component (A) and solvent (E), the photosensitive resin composition of the present invention is obtained.

The black matrix of the present invention is formed from the above-mentioned photosensitive resin composition.

When the film thickness of the black matrix of the present invention is 1 μm, the optical density (O.D value) ranges above 3.5; preferably, when the film thickness of the black matrix is 1 μm, the optical density ranges from 3.8 to 5.5.

The black matrix can be prepared by the following steps: (1). The photosensitive resin composition of the present invention is coated on the substrate by coating methods such as spin coating or casting coating, and dried under reduced pressure (pressure: less than 200mmHg, processing time: 1 second to 20 seconds), and pre-bake treatment (temperature: 70 to 110 ° C, processing time: 1 minute to 15 minutes) to remove the solvent (E) in the photosensitive resin composition, so that the substrate (2). Place the pre-baked coating film under the specified mask to irradiate with ultraviolet light [for example: g-line, h-line or i-line, and the ultraviolet irradiation device is: (ultra) high pressure mercury lamp and metal Halogen lamp] irradiation exposure; (3). Dip in developer for development (processing temperature: 23±2°C, processing time: 15 seconds to 5 minutes), to remove the unexposed part, and then wash it with pure water , to form the pattern of the specified mask, and then air-dry the pattern with compressed air or compressed nitrogen; (4.) Use a heating device (such as a hot plate or oven) for post-baking treatment (processing temperature: 150 to 250 ° C, Processing time: 150 to 250° C. when using a hot plate, and 15 minutes to 150 minutes when using an oven), that is, the black matrix is formed on the substrate.

The developer is for example but not limited to sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine, dimethyl Ethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene, etc. The developer has a concentration ranging from 0.001 to 10 wt%, preferably, the developing solution has a concentration ranging from 0.005 to 5 wt%, more preferably, the developing solution has a concentration ranging from 0.01 to 1 wt%.

The substrates suitable for the black matrix of the present invention are: non-alkali glass, soda lime glass, hard glass (Piles glass) and quartz glass used in liquid crystal display devices, etc., and a transparent conductive film is attached to the glass. or for a photoelectric conversion device substrate (for example, a silicon substrate) for a solid-state imaging device or the like.

The color filter of the present invention includes the above-mentioned black matrix.

The color filter of the present invention is made according to the general preparation method, for example: the above-mentioned black matrix is formed on the substrate first, and then each color (mainly including red, green and blue) is formed on the substrate in the same formation method Then, the pixel coloring layer of the color filter is obtained. Next, in a vacuum at 220°C to 250°C, an indium tin oxide (ITO) vapor-deposited film is formed on the pixel colored layer. Imide, which is used to make color filters for liquid crystal displays.

The liquid crystal display device of the present invention includes the above-mentioned color filter.

In the liquid crystal display element of the present invention, the above-mentioned color filter and the drive substrate provided with thin film transistors (thinfilm transistor; TFT) are opposed to each other, and a cell gap (cell gap) is interposed between the color filter and the drive substrate. Arranging facing each other, and using a sealant to bond the color filter to the surrounding parts of the drive substrate, leaving only the liquid crystal injection hole, and then filling and injecting liquid crystal into the gap defined by the surface of the substrate and the sealant, The liquid crystal injection hole is then sealed to form a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on the other side surfaces of the respective substrates constituting the liquid crystal cell, a polarizing plate is bonded to produce a liquid crystal display element.

The aforementioned liquid crystals and liquid crystal alignment films are not particularly limited, and they can be used in the field, and are not the focus of the present invention, so no further description is given.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only, and should not be construed as limitations on the implementation of the present invention.

<Example>

[Synthesis Example 1] Preparation of Resin (A-1-1) Having Unsaturated Groups

With 100 parts by weight of fluorene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol, and the propylene glycol methyl ether acetate of 130 weight parts join in the four-necked flask of 500mL with continuous addition mode, and feed rate is controlled at 25 weight parts/minute, and this reaction The temperature of the process was maintained at 100 to 110° C., and the reaction was carried out for 15 hours to obtain a light yellow transparent mixed liquid (solid content concentration: 50 wt %).

Then, 100 parts by weight of the above-mentioned light yellow transparent mixed solution was dissolved in 25 parts by weight of ethylene glycol ether acetate to form a mixed solution, and simultaneously 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of dihydrophthalic anhydride were added. Put benzophenone tetracarboxylic dianhydride in the mixed solution, then heat the mixed solution to 110°C to 115°C, and react for 2 hours to obtain a resin with unsaturated groups (acid value: 98.0mgKOH/g; hereinafter referred to as A -1-1).

[Synthesis Example 2] Preparation of Resin (A-1-2) Having Unsaturated Groups

100 parts by weight of the light yellow transparent mixed solution obtained in Preparation Synthesis Example 1 was dissolved in 25 parts by weight of ethylene glycol ether acetate to form a mixed solution, and 13 parts by weight of benzophenone tetracarboxylic dianhydride was added to the mixed solution. In the liquid, first react the mixed solution at 90 to 95°C for 2 hours, then add 6 parts by weight of tetrahydrophthalic anhydride to the mixed solution, and react at 90 to 95°C for 4 hours to obtain A resin having an unsaturated group (acid value: 99.0 mgKOH/g; hereinafter abbreviated as A-1-2).

[Synthesis Example 3] Preparation of Resin (A-1-3) Having Unsaturated Groups

400 parts by weight of epoxy compound [model NC-3000, produced by Nippon Kayaku (Co., Ltd.); epoxy equivalent 288], 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol (methoxyphenol), 5 parts by weight of Triphenylphosphine and 264 parts by weight of propylene glycol methyl ether acetate were added into the reaction flask, the temperature during the reaction was maintained at 95° C., and the reaction was carried out for 9 hours to obtain an intermediate product (acid value: 2.2 mgKOH/g). Next, 151 parts by weight of tetrahydrophthalic anhydride (tetrahydrophthalic anhydride) was added and reacted at 95° C. for 4 hours to obtain a resin with unsaturated groups (acid value: 102 mgKOH/g, weight average molecular weight: 3,200; below Abbreviated as A-1-3).

[Synthesis Example 4] Preparation of other alkali-soluble resins (A-2-1)

1 part by weight of 2,2'-azobisisobutyronitrile, 240 parts by weight of propylene glycol methyl ether acetate, 20 parts by weight of methacrylic acid, 15 parts by weight of styrene, 35 parts by weight of styrene methacrylate The glycerin monomethacrylate of methyl ester, 10 weight parts and the N-phenylmaleimide of 20 weight parts join in the round bottom flask that stirrer and condenser are equipped with, and make this flask inside be full of nitrogen, Next, the temperature was raised to 80° C. under slow stirring, and the components were uniformly mixed and polymerized for 4 hours. Then the temperature was raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added to carry out polymerization for 1 hour to obtain another alkali-soluble resin (hereinafter referred to as A-2-1).

[Synthesis Example 5] Preparation of Other Alkali-Soluble Resins (A-2-2)

2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol monomethyl ether, 15 parts by weight of methacrylic acid, 15 parts by weight of 2-hydroxyethyl acrylate and 70 parts by weight of Add benzyl methacrylate to a round-bottomed flask equipped with a stirrer and a condenser, and fill the flask with nitrogen, then stir slowly and raise the temperature to 80°C to mix the ingredients uniformly and carry out polymerization reaction for 3 hours . Then the temperature was raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added to carry out polymerization for 1 hour to obtain another alkali-soluble resin (hereinafter abbreviated as A-2-2).

[Example 1] Preparation of photosensitive resin composition and black matrix

<Photosensitive resin composition>

100 parts by weight of the resin (A-1-1) with unsaturated groups in Synthesis Example 1, 60 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as B-1), 30 parts by weight of 1-[9-ethyl Base-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone 1-(O-acetyl oxime) (hereinafter referred to as C-1-1), 50 parts by weight Pigment Black 7 (hereinafter referred to as D-1-1), 100 parts by weight of C.I. Pigment Blue 15:1 (hereinafter referred to as D-2-1), 5 parts by weight of C.I. Pigment Violet 23 (hereinafter referred to as D-3- 1), and 1000 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as E-1) were placed in a shaker and stirred evenly to form a solution, which was the photosensitive resin composition of Example 1. Table 1 shows the test results of the properties of the photosensitive resin composition in Example 1.

<Black Matrix>

Put the photosensitive resin composition of Example 1 into a coating machine (manufactured by Shinko Trading; model MS-A150), apply it on a glass substrate of 100mm×100mm by spin coating, and then dry it under reduced pressure at 100mmHg , lasted for 5 seconds, and then pre-baked in an oven at 100° C. for 2 minutes to form a pre-baked coating film with a film thickness of about 1.2 μm.

Then, place the pre-baked coating film under a designated photomask, irradiate the pre-baked coating film with ultraviolet light (exposure machine model: AG500-4N; manufactured by M&R Nano Technology) at 100mJ/ ^cm2 , and then, the pre-baked coating film The baked coating film was immersed in developer (0.04% potassium hydroxide) at 23°C for 2 minutes to remove the part of the pre-baked coating film that was not irradiated by ultraviolet light, and then washed with pure water, and then placed in the oven at 230 ℃ for 60 minutes to form a black matrix with a film thickness of 1.0 μm on the substrate. The properties test results of the obtained black matrix are shown in Table 1.

[Examples 2 to 7 and Comparative Examples 1 to 5] Preparation of photosensitive resin composition and black matrix

Examples 2 to 7 and Comparative Examples 1 to 5 prepared the photosensitive resin composition and black matrix with the same steps as Example 1, the difference lies in: changing the types and usage amounts of each raw material, see Table 1. Table 1 shows the properties test results of the obtained photosensitive resin composition and black matrix.

[nature test]

For the convenience of describing the measurement process, the following example 1 is used for illustration, and the rest of the examples and comparative examples are all measured according to this method.

1. Optical Density value (Optical Density value, referred to as O.D value):

After irradiating the black matrix of Example 1 with incident light, measure the intensity of the outgoing light penetrating from the black matrix of Example 1 (film thickness: 1 μm), and then calculate the O.D value of the black matrix of Example 1 by the following formula:

OD=－log(I/I ₀ )

I ₀ is the intensity of the incident light, and I is the intensity of the outgoing light after the incident light passes through the black matrix.

2. Resolution:

Place the pre-baked coating film in Example 1 under a photomask with different wire widths, irradiate the pre-baked coating film with an exposure dose capable of forming a 20 μm wire width, and then immerse the pre-baked coating film at 23° C. In the developer (0.04% potassium hydroxide) for 2 minutes to remove the part of the pre-baked coating film that has not been irradiated by ultraviolet light, then wash it with pure water, and then perform post-baking treatment in an oven at 230 ° C for 60 minutes . Next, observe with a microscope (manufactured by Nikon, model Eclipse50i) and a scanning electron microscope (manufactured by Hitachi, model S-3000N), and the evaluation method is as follows:

○: minimum line width ≤ 4μm;

△: 4μm≤minimum line width<10μm;

╳: Minimum line width >10μm.

3. Place the pre-baked coating film in Example 1 under the designated half-tone mask (passing rate 50%), and utilize ultraviolet light (exposure machine model AG500-4N of exposure machine model AG500-4N; M & R NanoTechnology manufacture ) to perform a weak exposure process to form a test coating film. Then, take a measurement point on the test coating film to measure the film thickness δ, then immerse the test coating film in a developer solution (0.045%KOH) at 23°C for 50 seconds, and measure it at the same measurement point Film thickness δ _d . Then the residual film rate can be obtained through the following formula:

Residual film rate (%)=[(δ _d )/(δ)]×100%

Evaluation is based on the following benchmarks:

○: Exposure amount ≤ 80mJ/cm ² , which means that when the exposure amount of the photosensitive resin composition is below 80mJ/cm ² , the residual film rate of the formed test coating film can reach more than 90%, which means that the photosensitive resin composition good sensitivity;

╳: Exposure amount > 80mJ/cm ² , which means that the photosensitive resin composition needs an exposure amount above 80mJ/cm ² to make the residual film rate of the formed test film reach more than 90%, which means that the photosensitive resin composition The sensitivity is not good.

Table 1

Note: "--": means no addition; B-1: dipentaerythritol hexaacrylate; B-2: dipentaerythritol tetraacrylate; C-1-1: 1-[9-ethyl-6-(2- Toluyl)-9H-carbazole-3-substituent]-ethanone 1-(O-acetyl oxime) (trade name OXE02, manufactured by Ciba Specialty Chemicals); C-1-2: 1-[4 -(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (trade name OXE01, manufactured by Ciba Specialty Chemicals); C-1-3: Ethanone-1 -[9-Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime); C-2 -1: 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone (trade name IRGACURE369; manufactured by Ciba Specialty Chemicals); C-2-2 : 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (trade name IRGACURE907; manufactured by Ciba Specialty Chemicals); D-1-1: trade name MA100 (Mitsubishi D-1-2: trade name MA230 (manufactured by Mitsubishi Chemical); D-1-3: trade name MA8 (manufactured by Mitsubishi Chemical); D-2-1: C.I. Pigment Blue 15:1; D-2 -2: C.I. Pigment Blue 15:3; D-2-3: C.I. Pigment Blue 15:6; D-3-1: C.I. Pigment Violet 23; D-3-2: C.I. Pigment Red 89; E-1: Propylene Glycol Methyl ether acetate; E-2: ethyl 3-ethoxypropionate.

The results of the experimental data in Table 1 show that the photosensitive resin compositions of Examples 1 to 7 contain the resin (A-1), black pigment (D-1) and blue pigment (D-2) with unsaturated groups. ), and the weight ratio of the amount of black pigment (D-1) to the amount of blue pigment (D-2) is in the range of 0.5 to 10, the photosensitive resin composition has better sensitivity, and the photosensitive resin The black matrix formed by the composition has high light-shielding properties (O.D value of 4.0 to 4.8) and high resolution (the minimum line width is below 4 μm).

The photosensitive resin composition of Comparative Example 1 is poor in sensitivity because it does not contain the resin (A-1) with this unsaturated group, and the resolution of the black matrix formed by the photosensitive resin composition is not good (minimum line width greater than 10 μm).

Because the photosensitive resin composition of Comparative Example 2 does not contain black pigment (D-1), the O.D value of the black matrix formed by its photosensitive resin composition is only 2.0, so the light-shielding property is not good, and the photosensitive resin The resolution of the black matrix formed by the composition is poor.

Since the photosensitive resin composition of Comparative Example 3 does not contain blue pigment (D-2), the sensitivity of the photosensitive resin composition is not good, and the resolution of the black matrix formed by the photosensitive resin composition is also not good .

For the photosensitive resin composition of Comparative Example 4, the O.D value of the black matrix formed by the photosensitive resin composition is Only for 3.3 and poor resolution.

In the photosensitive resin composition of Comparative Example 5, the weight ratio of the amount of black pigment (D-1) used to the amount of blue pigment (D-2) used was 11.0, the sensitivity of the photosensitive resin composition was not good, and the The resolution of the black matrix formed by the permanent resin composition is poor.

In summary, the photosensitive resin composition of the present invention uses the resin (A-1), the black pigment (D-1) and the blue pigment (D-2) with the unsaturated group, and the black pigment (D- 1) The weight ratio of the amount used to the blue pigment (D-2) is in the range of 0.5 to 10, so that the photosensitive resin composition has high sensitivity, and the black matrix formed by the photosensitive resin composition has high light-shielding Sex (O.D value 4.0 to 4.8) and high resolution.

Only the above description is a preferred embodiment of the present invention, and it cannot be used to limit the scope of the present invention. Still belong to the scope that the patent of the present invention covers.

Claims (10)

1. A photosensitive resin composition, characterized in that it comprises: The alkali-soluble resin component (A) includes a resin (A-1) with an unsaturated group, and the resin (A-1) with an unsaturated group is prepared by a polymerization reaction of a mixture, and the mixture includes at least two Epoxy compound (i) of epoxy group, and compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group; Compound (B) containing an ethylenically unsaturated group; Photoinitiator (C); pigment component (D); and solvent (E); The pigment component (D) includes a black pigment (D-1) and a blue pigment (D-2), and the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) is The range is 0.5 to 10. 2. The photosensitive resin composition according to claim 1, wherein the epoxy compound (i) having at least two epoxy groups is selected from compounds having at least two epoxy groups represented by formula (I). The epoxy compound, the epoxy compound with at least two epoxy groups shown in formula (II), or their combination: R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aryl alkyl, R ⁵ to R ¹⁸ 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. 3. The photosensitive resin composition according to claim 1, characterized in that, the epoxy compound (i) having at least two epoxy groups is represented by formula (I) having at least two epoxy groups Epoxy compound: R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aryl alkyl. 4. The photosensitive resin composition according to claim 1, characterized in that, the epoxy compound (i) having at least two epoxy groups is represented by formula (II) having at least two epoxy groups Epoxy compound: R ⁵ to R ¹⁸ 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. 5. The photosensitive resin composition according to claim 1, characterized in that, based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the resin (A-1) having an unsaturated group The content ranges from 50 to 100 parts by weight, the used amount of the ethylenically unsaturated group-containing compound (B) ranges from 30 to 300 parts by weight, the used amount of the pigment component (D) ranges from 100 to 1000 parts by weight, The solvent (E) is used in an amount ranging from 1000 to 5000 parts by weight. 6. The photosensitive resin composition according to claim 1, characterized in that, based on the total amount of the ethyl unsaturated group-containing compound (B) being 100 parts by weight, the use of the photoinitiator (C) The amount ranges from 10 to 60 parts by weight. 7. The photosensitive resin composition according to claim 1, characterized in that, based on the total amount of the alkali-soluble resin component (A) being 100 parts by weight, the usage range of the black pigment (D-1) is 50 to 600 parts by weight, the blue pigment (D-2) is used in an amount ranging from 50 to 400 parts by weight. 8. A black matrix formed of the photosensitive resin composition according to any one of claims 1 to 7. 9. A color filter comprising the black matrix according to claim 8. 10. A liquid crystal display element comprising the color filter according to claim 9.