TWI544281B - Photosensitive resin composition for black matrix and application thereof - Google Patents

Description

Photosensitive resin composition for black matrix and application thereof

The present invention relates to a photosensitive resin composition for a black matrix and an application thereof, and more particularly to a photosensitive resin composition for a black matrix having good development resistance and surface resistance, and a color filter formed using the composition. A light sheet and a liquid crystal display having the color filter.

In recent years, with the vigorous development of various technologies of liquid crystal displays, and in order to improve the contrast and display quality of liquid crystal displays, strips and dots of color filters of black matrix in liquid crystal displays are usually set ( In the gap between dots). The black matrix described above can prevent defects such as a decrease in contrast ratio and a decrease in color purity caused by light leakage between pixels.

In general, the black matrix may be a vapor deposited film having chromium or chromium oxide or the like. However, when a black matrix is produced by the vapor deposition film described above, it has a drawback that the process is complicated and the material is expensive. To solve this problem, the black matrix is formed by a photo lithographic technique.

However, in the process of making color filters, black matrix and color The ends of the color pixels (i.e., the three color pixels of red, green, and blue) have a large level difference, and a defect that the color is unevenly displayed is generated. In order to solve the problem, a photo-curable resin composition having a high cross-linking density is disclosed in Japanese Laid-Open Patent Publication No. Hei 5-78483, and a protective film composition having an epoxy compound is disclosed in Japanese Patent Laid-Open No. Hei 10-133372. Improve the defects caused by the aforementioned step. However, such photosensitive resin compositions are still defective in development resistance and surface resistance.

Japanese Patent Publication No. Hei 5-070528 discloses the use of an epoxy acrylate compound having an anthracene ring to react with an acid anhydride to produce an alkali-soluble resin. However, this technique still suffers from defects in developability and surface resistance.

In view of the above, there is an urgent need to develop a photosensitive resin composition for a black matrix having excellent development resistance and high surface resistance value to overcome the above-mentioned problems of the conventional black matrix.

Therefore, an aspect of the present invention provides a photosensitive resin composition for a black matrix. This photosensitive resin composition has good developability and surface resistance.

Another aspect of the present invention provides a black matrix formed by the above-described photosensitive resin composition.

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

Still another aspect of the present invention is to provide a liquid crystal display package Contains the aforementioned color filter.

According to the above aspect of the invention, there is provided a photosensitive resin composition for a black matrix, which comprises an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, and a photoinitiator. (C), a solvent (D), a black pigment (E), and an oxetane compound (F) having a halogen atom, which are described below.

Photosensitive resin composition Alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention may comprise a first alkali-soluble resin (A-1). Next, the alkali-soluble resin (A) may optionally contain a second alkali-soluble resin (A-2) and other alkali-soluble resin (A-3).

First alkali soluble resin (A-1)

The first alkali-soluble resin (A-1) may be a compound having a structure as shown in the formula (I):

In the formula (I), R ₁ represents a phenyl group or a phenyl group having a substituent, wherein the substituent may be an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and R ₂ represents a -CO- group. , -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-anthracene or a single bond; R ₃ represents a tetravalent carboxylic acid residue; R ₄ represents a divalent carboxylic acid residue, wherein at least one of R ₃ and R ₄ has a fluorine atom; R ₅ represents a hydrogen atom or a methyl group; and m represents 1 An integer of up to 20.

R ₃ may be a tetravalent carboxylic acid residue having a fluorine atom or a tetravalent carboxylic acid residue having no fluorine atom, preferably a tetravalent aromatic group having a fluorine atom, and more preferably a benzene having a fluorine atom. ring.

The alkali-soluble resin (A-1) is obtained by reacting a first mixture, and the first mixture may comprise a diol compound (a-1) having a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride thereof (a) And 2) and a dicarboxylic acid or its anhydride (a-3), wherein at least one of the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its anhydride (a-3) has a fluorine atom.

A diol compound having a polymerizable unsaturated group (a-1)

The diol compound (a-1) having a polymerizable unsaturated group is a bisphenol compound (a-1-1) having two epoxy groups and having at least one carboxylic acid group and at least one ethylenically unsaturated group. The compound (a-1-2) is obtained by reacting. The reactant for synthesizing the diol compound (a-1) having a polymerizable unsaturated group may also contain other compounds.

The bisphenol compound (a-1-1) having two epoxy groups can be obtained, for example, by dehydrohalogenation of a bisphenol compound with a halogenated propylene oxide in the presence of an alkali metal hydroxide.

Specific examples of the bisphenol used for the synthesis of the bisphenol compound (a-1-1) having two epoxy groups may include, but are not limited to, bis(4-hydroxyphenyl)one, bis(4-hydroxy-). 3,5-Dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-di Methylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyphenyl)hexafluoropropane, double (4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethyl decane , bis(4-hydroxy-3,5-dimethylphenyl)dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, bis(4-hydroxyphenyl) Methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-dual (4 -hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5- Dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3) -dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-double (4-Hydroxy-3-fluorophenyl)indole, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene or any combination of the above compounds.

Specific examples of the halogenated propylene oxide used for the synthesis of the bisphenol compound (a-1-1) having two epoxy groups may include, but are not limited to, 3-chloro-1,2-epoxypropane and 3-bromo. -1,2-propylene oxide or any combination of the above compounds. The halogenated propylene oxide may be used in an amount of 1 equivalent to 20 equivalents, and preferably 2 equivalents to 10 equivalents, based on 1 equivalent of the total hydroxyl group in the bisphenol compound.

Specific examples of the alkali metal hydroxide may include sodium hydroxide, potassium hydroxide or any combination of the above compounds. The alkali metal hydroxide to be added in the dehydrohalogenation reaction may be used in an amount of from 0.8 to 15 equivalents, and preferably from 0.9 to 11 equivalents, based on 1 equivalent of the total hydroxyl group of the bisphenol compound.

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

In one embodiment, an aqueous solution of the alkali metal hydroxide added by the above dehydrohalogenation reaction may also be used. In this embodiment, while the above aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing. Water, at the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction is carried out, the reaction system may also add tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethylbenzyl ammonium chloride, etc. The quaternary ammonium salt acts as a catalyst. Next, the reaction is carried out at 50 ° C to 150 ° C for 1 hour to 5 hours, and an alkali metal hydroxide or an aqueous solution thereof is further added. Then, the reaction is carried out at a temperature of from 20 ° C to 120 ° C for 1 hour to 10 hours to carry out a dehydrohalogenation reaction.

Further, in order to smoothly carry out the above-described dehydrohalogenation reaction, an aprotic substance such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol. Aprotic) is a polar solvent to carry out the reaction. In the case of using an alcohol, the total amount of the halogenated propylene oxide used is 100% by weight, and the alcohol may be used in an amount of 2 to 20% by weight, and preferably 4 weight percent to 15 weight percent. In the embodiment using an aprotic polar solvent, the total amount of the halogenated propylene oxide used is 100% by weight, and the aprotic polar solvent may be used in an amount of 5 to 100% by weight, and preferably 10% by weight to 90% by weight.

After the completion of the dehydrohalogenation reaction, the water washing treatment can be selectively carried out. Then, the polar solvent such as halogenated propylene oxide, alcohol, and aprotic is removed by heating and decompression, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg).

In order to prevent the formed epoxy resin from having a hydrolyzable halogen, the solution after the dehydrohalogenation reaction may be added to a solvent such as benzene, toluene or methyl isobutyl ketone, and sodium hydroxide is added. Or an aqueous solution of an alkali metal hydroxide such as potassium hydroxide to carry out a dehydrohalogenation reaction again. In the dehydrohalogenation reaction, the alkali metal hydroxide may be used in an amount of from 0.01 mol to 1 mol, and preferably from 0.05 mol to 0.9 mol, based on 1 equivalent of the total hydroxyl group of the bisphenol compound. . Secondly, the above dehydrohalogenation reaction may be carried out at a temperature of from 50 ° C to 120 ° C, and its operation time may be from 0.5 hours to 2 hours.

After completion of the dehydrohalogenation reaction, the salts can be removed by filtration, washing, and the like. Further, a solvent such as benzene, toluene or methyl isobutyl ketone can be distilled off by heating under reduced pressure to obtain a bisphenol compound (a-1-1) having two epoxy groups.

The bisphenol compound (a-1-1) having two epoxy groups is preferably a bisphenol compound having two epoxy groups having the structure represented by the following formula (I-11), or having the following A bisphenol compound having at least two epoxy groups represented by the formula (I-12) is a polymer obtained by polymerizing a monomer:

In the formula (I-11) and the formula (I-12), A ₁ to A ₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group. R ₂ represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9, 9-indenylene or a single bond. m ₁ may represent an integer of 1 to 10, and more preferably may represent an integer of 1 to 2.

The bisphenol compound having two epoxy groups having a structure represented by the formula (I-11) is preferably a bisphenol having two epoxy groups having the structure represented by the following formula (I-13). Class compound:

In the formula (I-13), A ₁ , A ₂ , A ₃ , A ₄ , A ₇ and A ₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

A bisphenol compound having two epoxy groups having a structure represented by the formula (I-13) can be obtained by reacting a bisphenol fluorene with an epihalohydrin having two epoxy groups. Bisphenolphthalein type compound.

Specific examples of the aforementioned bisphenol quinoid type compound may include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3- [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-double (9,9-bis(4-hydroxy-3-bromophenyl)fluorene] 4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene [9] ,9-bis(4-hydroxy-3-methoxyphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9-bis(4-hydroxy-3, 5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9 - bis(4-hydroxy-3,5-dibromophenyl)fluorene or a combination of the above compounds.

Specific examples of the halogenated propylene oxide may include 3-chloro-1,2-epoxypropane (epichlorohydrin), 3-bromo-1,2-epoxypropan (epibromohydrin) or any combination of the above.

Specific examples of the bisphenol quinoid compound having an epoxy group may include, but are not limited to, (1) a product manufactured by Nippon Steel Chemical Co., Ltd., and its model number is ESF-300 or the like; (2) a product manufactured by Osaka Gas, And its model is PG-100, EG-210 or the like; or (3) a product manufactured by SMS Technology Co., and its model is SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.

The compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group may include, but is not limited to, acrylic acid, methacrylic acid, 2-methacryloyloxyethylbutanedioic acid (2-methacryloyloxyethylbutanedioic) Acid), 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate, 2-methylpropenyloxybutyl adipate, 2-methylpropene oxime Hexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methylpropenyloxybutyl maleic acid, 2-methyl Acryloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropenyloxypropyltetrahydrophthalic acid, 2-methylpropenyloxypropyl phthalate Dicarboxylic acid, 2-methylpropenyloxybutylphthalic acid or 2-methylpropenyloxybutylphthalic acid; obtained by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound a compound wherein the dicarboxylic acid compound may include, but is not limited to, adipic acid, succinic acid, maleic acid, phthalic acid; a (meth) acrylate having a hydroxyl group and a carboxylic anhydride compound The resulting half ester compound, wherein the (meth) acrylate having a hydroxyl group may include, but is not limited to, 2-hydroxyethyl acrylate [(2-hydroxyethyl)acrylate], 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropylmethyl Acrylate [(2-hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate or pentaerythritol trimethacrylate . Further, specific examples of the carboxylic anhydride compound described herein may be specific examples of the tetracarboxylic dianhydride in the other tetracarboxylic acid or its acid dianhydride (a-2-2) described later, and other dicarboxylic acids described later or The specific examples of the dicarboxylic acid anhydride in the acid anhydride (a-3-2) are the same, and therefore will not be further described.

Tetracarboxylic acid or its acid dianhydride (a-2)

The tetracarboxylic acid or its acid dianhydride (a-2) comprises a tetracarboxylic acid having a fluorine atom or an acid dianhydride thereof (a-2-1) and a tetracarboxylic acid having a fluorine atom or an acid dianhydride thereof (a-2) Other tetracarboxylic acids other than -1) or their acid dianhydrides (a-2-2).

The tetracarboxylic acid having a fluorine atom or the acid dianhydride (a-2-1) thereof may include, but is not limited to, a tetracarboxylic acid compound having a fluorine atom having a structure represented by the following formula (I-1), and having the following formula ( A group consisting of a fluorine atom-containing tetracarboxylic dianhydride compound having the structure shown in I-2) and a combination thereof;

In the formula (I-1) and the formula (I-2), X ₁ may represent a group having the following formula (I-3) to formula (I-8):

In the formulae (I-3) to (I-8), X ₂ represents a fluorine atom or a trifluoromethyl group, respectively, and "*" represents a position bonded to a carbon atom.

Specific examples of the tetracarboxylic acid having a fluorine atom or its acid dianhydride (a-2-1) may include, but are not limited to, 4,4'-hexafluoroisopropylidene diphthalic acid (4,4'-hexafluoro Isopropylidene diphthalic acid), 1,4-difluoropyromellitic acid, 1-monofluoropyromellitic acid, 1,4-bis(trifluoromethyl) An aromatic tetracarboxylic acid having a fluorine atom such as 1,4-ditrifluoromethylpyromellitic acid, or a dianhydride compound of the above tetracarboxylic acid, or any combination of the above compounds.

Specific examples of the tetracarboxylic acid having a fluorine atom or its acid dianhydride (a-2-1) may further contain 3,3'-hexafluoroisopropylidene phthalate [3,3'-(hexafluoro isopropylidene) )diphthalic acid], 5,5'-{2,2,2-trifluoro-1-[3-(three Fluoromethyl)phenyl]ethylidene}diphthalic acid {5,5'-{2,2,2-trifluoro-1-[3-(trifluoromethyl)phenyl]ethylidene}diphthalic acid}, 5,5 '-[2,2,3,3,3-pentafluoro-1-(trifluoromethyl)propylene]diphthalic acid {5,5'-[2,2,3,3,3- Pentafluoro-1-(trifluoromethyl)propylidene]diphthalic acid}, 5,5'-oxybis(4,6,7-trifluoro-pyromellitic acid) [5,5'-oxybis(4,6,7- Trifluoro-pyromellitic acid)], 3,6-bis(trifluoromethyl)pyromellitic acid, 4-(trifluoromethyl)perbenzenetetracarboxylic acid [4- (trifluoromethyl)pyromellitic acid], 1,4-bis(3,4-dicarboxylic acid trifluorophenoxy)tetrafluorobenzene, etc. a tetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid, or any combination of the above compounds.

The other tetracarboxylic acid or acid dianhydride (a-2-2) thereof may comprise a saturated linear hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid. Or any combination of the above compounds.

Specific examples of the above-mentioned saturated linear hydrocarbon tetracarboxylic acid may include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid or any combination of the above compounds. The saturated linear hydrocarbon tetracarboxylic acid may also have a substituent.

Specific examples of the aforementioned alicyclic tetracarboxylic acid may include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, norbornanetetracarboxylic acid, or any combination of the above compounds. The alicyclic tetracarboxylic acid may also have a substituent.

Specific examples of the aromatic tetracarboxylic acid may include pyromellitic acid, benzophenone tetracarboxylic acid, and biphenyl tetracarboxylic acid (Biphenyl tetracarboxylic acid). Acid), diphenyl ether tetracarboxylic acid, diphenyl phosphonium tetracarboxylic acid, 1,2,3,6-tetrahydrophthalic acid or any combination of the above compounds. The aromatic tetracarboxylic acid may have a substituent.

Dicarboxylic acid or its anhydride (a-3)

The dicarboxylic acid or its anhydride (a-3) may contain a dicarboxylic acid having a fluorine atom or an anhydride thereof (a-3-1) and the dicarboxylic acid having a fluorine atom or an anhydride thereof (a-3-1) Other dicarboxylic acids or their anhydrides (a-3-2).

The dicarboxylic acid having a fluorine atom or its anhydride (a-3-1) may include, but is not limited to, a dicarboxylic acid compound having a fluorine atom having a structure represented by the following formula (I-9), having the following formula (I-10) a dicarboxylic anhydride compound having a fluorine atom of the structure shown or any combination of the above:

In the formula (I-9) and the formula (I-10), X ₃ may represent an organic group having a fluorine atom of 1 to 100 carbon atoms.

Specific examples of the dicarboxylic acid having a fluorine atom or its anhydride (a-3-1) may include 3-fluorophthalic acid, 4-fluorophthalic acid, Tetrafluorophthalic acid, 3,6-difluorophthalic acid, tetrafluoro succinic acid, or an acid anhydride compound of the above dicarboxylic acid, or Any combination of the above compounds.

Specific examples of the other dicarboxylic acid or its anhydride (a-3-2) may include a saturated linear hydrocarbon dicarboxylic acid, a saturated cyclic hydrocarbon dicarboxylic acid, an unsaturated dicarboxylic acid or an acid anhydride of the above dicarboxylic acid compound, or Any combination of the above compounds.

Specific examples of the saturated linear hydrocarbon dicarboxylic acid may include succinic acid, acetyl succinic acid, adipic acid, sebacic acid, Citramalic acid, malonic acid, glutaric acid, citric acid, Tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or any combination of the above compounds. The hydrocarbon group in the saturated linear hydrocarbon dicarboxylic acid may also be substituted.

Specific examples of the saturated cyclic hydrocarbon dicarboxylic acid may include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and hexahydrotrimellitic acid. Or any combination of the above compounds. The saturated cyclic hydrocarbon dicarboxylic acid may also be an alicyclic dicarboxylic acid substituted with a saturated hydrocarbon group.

Specific examples of the unsaturated dicarboxylic acid may include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl endo-methylene tetrahydro phthalic acid. ), chlorendic acid, trimellitic acid, or any combination of the above.

Specific examples of the other dicarboxylic acid or its anhydride (a-3-2) may include trimethoxydecylpropyl succinic anhydride, triethoxydecyl propyl succinic anhydride, methyl dimethoxy decyl alkyl group Propyl succinic anhydride, methyl diethoxy decyl propyl succinic anhydride, trimethoxy decyl butyl succinic anhydride, triethoxy decyl butyl succinic anhydride, methyl diethoxy decane Butyl succinic anhydride, p-(trimethoxydecyl)phenyl succinic anhydride, p-(triethoxydecyl)phenyl succinic anhydride, p-(methyldimethoxydecyl)phenyl butyl Diacid Anhydride, p-(methyldiethoxydecyl)phenyl succinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, inter A dicarboxylic acid anhydride such as methyldiethoxyalkylalkyl)phenylsuccinic anhydride or a dicarboxylic acid compound of the above dicarboxylic anhydride or any combination of the above compounds.

The dicarboxylic acid compound is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid or any combination of the above compounds, and more preferably Diacid, itaconic acid, tetrahydrophthalic acid or a combination of the above compounds.

The dicarboxylic anhydride is preferably succinic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, trimellitic anhydride or any combination of the above compounds.

The method for synthesizing the alkali-soluble resin (A-1) is not particularly limited as long as the diol compound (a-1) having a polymerizable unsaturated group, tetracarboxylic dianhydride or its tetracarboxylic acid (a-2), and The dicarboxylic anhydride or its dicarboxylic acid (a-3) can be obtained by reaction.

In the preparation of the aforementioned alkali-soluble resin (A-1), in order to accelerate the reaction rate, a basic compound is usually added as a reaction catalyst to the reaction solution. Specific examples of the reaction catalyst may include triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride. Any combination of benzyltriethylammonium chloride or the above reaction catalyst. The reaction catalyst may be used singly or in combination of plural kinds.

Secondly, in order to control the degree of polymerization, a reaction inhibitor is usually added to the reaction solution. Specific examples of the polymerization inhibitor may include methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di- Tert-butyl-p-cresol), phenothiazine or an analogue thereof. The above polymerization inhibitors may be used singly or in combination of plural kinds.

In the preparation of the alkali-soluble resin (A-1), a polymerization solvent can be used as necessary. Specific examples of the polymerization solvent may include, but are not limited to, an alcohol compound such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, ethylene glycol or the like; methyl ethyl ketone; a ketone compound such as cyclohexanone or the like; an aromatic hydrocarbon compound such as toluene, xylene or the like; a race of celecin, butyl cellosolve or the like a cellosolve compound; a carbitol compound such as carbital, butyl carbitol or the like; a propylene glycol alkyl ether compound such as propylene glycol monomethyl ether or the like; dipropylene glycol monomethyl ether [ Poly(propylene glycol alkyl ether) compound such as di(propylene glycol)methyl ether] or the like; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether Acetate compound such as acetate), propylene glycol methyl ether acetate, propylene glycol methyl monoether acetate or the like; ethyl lactate, milk An alkyl lactate compound such as butyl lactate or the like; or a dialkyl glycol ether, or a methyl 2-hydroxy-2-methylpropionate or a 2-hydroxy-2 -methylpropionic acid Ethyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethoxyacetic acid Other esters such as ethyl ester. The above polymerization solvent may be used singly or in combination of plural kinds. The acid value of the alkali-soluble resin (A-1) is from 50 mgKOH/g to 200 mgKOH/g, and preferably from 60 mgKOH/g to 180 mgKOH/g.

Further, the synthesis method of the first alkali-soluble resin (A-1) can be carried out, for example, by a method described in Japanese Patent Laid-Open Publication No. Hei 9-325494, at a reaction temperature of 90 ° C to 140 ° C to obtain a diol compound and a tetracarboxylic acid. A well-known method for the reaction of acid dianhydride. At a reaction temperature of from 90 ° C to 130 ° C, the first mixture is uniformly dissolved and allowed to react. Next, the reaction and aging are carried out at 40 ° C to 80 ° C.

The first alkali-soluble resin (A-1) obtained by the reaction of the first mixture is an alkali-soluble resin having a fluorine atom, and is preferably an alkali-soluble resin having an aromatic structure of a fluorine atom.

In the respective components of the first mixture forming the first alkali-soluble resin (A-1), at least one of a tetracarboxylic acid or an acid dianhydride (a-2) and a dicarboxylic acid or an anhydride thereof (a-3) The fluorine atom is contained, and preferably the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its anhydride (a-3) each contain a fluorine atom.

In particular, when the tetracarboxylic acid or its acid dianhydride (a-2) has a fluorine atom, the tetracarboxylic acid or its acid dianhydride (a-2) may contain a tetracarboxylic acid having a fluorine atom or an acid dianhydride thereof. (a-2-1), when the dicarboxylic acid or its anhydride (a-3) has a fluorine atom, the dicarboxylic acid or its anhydride (a-3) may contain a dicarboxylic acid having a fluorine atom or an anhydride thereof (a) -3-1).

When tetracarboxylic acid or its acid dianhydride (a-2) or dicarboxylic acid or its anhydride When none of the (a-3) fluorine atoms is present, the photosensitive resin composition obtained has poor developability.

The first alkali-soluble resin (A-1) is used in an amount of 10 parts by weight to 100 parts by weight, preferably 12 parts by weight to 95 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A), and More preferably, it is 15 parts by weight to 90 parts by weight.

The first alkali-soluble resin (A-1) has water repellency, and the development resistance of the photosensitive resin composition can be improved. Secondly, the first alkali-soluble resin (A-1) and the black pigment (E) described later have a stronger van der Waals force, and the black pigment (E) forms a better protection, thereby enhancing the surface resistance of the photosensitive resin composition. .

When the alkali-soluble resin (A) does not contain the first alkali-soluble resin (A-1), the obtained photosensitive resin composition has defects in development resistance and surface resistance.

Further, the molar number of the diol compound (a-1) having a polymerizable unsaturated group, the molar number of a tetracarboxylic acid having a fluorine atom or its acid dianhydride (a-2-1), and a fluorine atom When the molar number of the dicarboxylic acid or its anhydride (a-3-1) satisfies the relationship [(a-2-1)+(a-3-1)]/(a-1)=0.4 to 1.6, The development resistance of the photosensitive resin composition can be further improved.

Second alkali soluble resin (A-2)

The alkali-soluble resin (A) of the present invention may optionally contain a second alkali-soluble resin (A-2). The second alkali-soluble resin (A-2) contains a structure represented by the following formula (V):

In the formula (V), Z ₁ and Z ₂ each independently represent a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group or a halogen atom.

The second alkali-soluble resin (A-2) is obtained by reacting a compound having a structure represented by the formula (V) with another compound which can be copolymerized. The above compound having a structure represented by the formula (V) may be a bisphenol quinoid compound having two epoxy groups represented by the following formula (V-1) or having two as shown in the formula (V-2) Hydroxyl bisphenol quinone type compound:

In the formula (V-1), the definitions of Z ₁ and Z ₂ are as described above, and are not described herein.

In the formula (V-2), the definitions of Z ₁ and Z ₂ are as described above, and are not described herein. Z ₃ and Z ₄ each independently represent an alkylene group or an extended aliphatic ring group having a carbon number of 1 to 20, and p and q each independently represent an integer of 1 to 4.

Specific examples of the other copolymerizable compound may include an unsaturated monocarboxylic acid compound such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid or cinnamic acid; maleic acid and itaconic acid; , succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methyl hexahydrophthalic acid, methyl bridged methylene tetrahydrophthalic acid (methyl endo-methylene tetrahydro phthalic acid), dicarboxylic acids such as chlorendic acid and glutaric acid, and anhydrides thereof; tricarboxylic acids such as trimellitic acid and anhydrides thereof; Tetracarboxylic acid such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenylether tetracarboxylic acid or the like And its anhydride or a combination of the above compounds.

Preferably, the second alkali-soluble resin (A-2) may be a product manufactured by Nippon Steel Chemical Co., Ltd., and its model number is V259ME or V301ME.

The second alkali-soluble resin (A-2) may be used in an amount of from 0 part by weight to 90 parts by weight, preferably from 5 parts by weight to 88 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). And it is preferably from 10 parts by weight to 90 parts by weight.

Other alkali soluble resin (A-3)

The alkali-soluble resin (A) of the present invention may optionally contain other alkali-soluble resin (A-3). The other alkali-soluble resin (A-3) is a resin other than the first alkali-soluble resin (A-1) and the second alkali-soluble resin (A-2).

Other alkali-soluble resins (A-3) may include, but are not limited to, having a carboxylic acid Base or hydroxyl resin. Specific examples of the other alkali-soluble resin (A-3) may include resins such as an acrylic resin, a urethane resin, and a novolac resin.

The amount of the other alkali-soluble resin (A-3) to be used is 0 parts by weight to 30 parts by weight, preferably 0 parts by weight to 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), and more preferably It is 0 parts by weight to 10 parts by weight.

Compound having ethylenically unsaturated group (B)

The compound (B) having an ethylenically unsaturated group of the present invention may contain the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups.

Compound (B-1) having an acidic group and at least three ethylenically unsaturated groups

The acidic group in the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups can react with an alkaline developer. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group or a phosphoric acid group. Among them, the acidic group is preferably a carboxyl group which can exert a good effect with an alkaline developer.

The compound (B-1) having an acidic group and at least three ethylenically unsaturated groups may be (1) a polyfunctional (meth) acrylate having a hydroxyl group and a dicarboxylic acid anhydride or a dibasic acid. To synthesize a carboxyl group-containing polyfunctional (meth) acrylate, or (2) to modify an aromatic polyfunctional (meth) acrylate with concentrated sulfuric acid or fuming sulfuric acid to synthesize a sulfonic acid group. Polyfunctional (meth) acrylate.

Preferably, the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups contains a compound having a structure represented by the following formula (VI) or (VII):

In the formula (VI), B ₁ represents -CH ₂ -, -OCH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ - or -OCH ₂ CH ₂ CH ₂ CH ₂ -; B ₂ represents a structure represented by the following formula (VI-1) or formula (VI-2); n represents an integer of 0 to 14; and B ₃ represents a formula (VI-3), a formula (VI-4) or a formula (VI-) 5) The structure shown:

In the formula (VI-3) and the formula (VI-4), r represents an integer of 1 to 8; in the formula (VI-5), the benzene ring may be tetrahydrogen or hexahydrogen.

In the formula (VII), B ₁ , B ₂ , B ₃ , n and r are as defined above, and are not described herein. B ₄ represents a structure represented by -O- or the following formula (VII-1) and s represents an integer of 1 to 8:

In formula (VI) or formula (VII), when B is _{present. 1} and ₂ a plurality of B, B ₁ and B ₂ may be the same or different, respectively.

In a specific example of the compound having an acidic group and at least three (above) ethylenically unsaturated groups represented by the above formula (VI) or formula (VII), a specific example of the compound having three ethylenically unsaturated groups may be Monohydroxy oligoacrylate or monohydroxy oligo methacrylate such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol penta methacrylate, and malonic acid, succinic acid, a carboxyl group-containing monoester compound formed from a diacid such as glutaric acid, isophthalic acid, terephthalic acid or phthalic acid; a specific example of a commercially available product may be manufactured by Toagosei Co., Ltd., model number TO- 756 products or manufactured by Kyoeisha Chemical Co., Ltd., model PE3A-MS or PE3A-MP; specific examples of compounds having five ethylenically unsaturated groups can be manufactured by Toagosei Co., Ltd., model number TO-1382 Or a product of TO-1385 or manufactured by Kyoeisha Chemical Co., Ltd., model number DPE6A-MS or DPE6A-MP.

The above compound (B-1) having an acidic group and at least three (or more) ethylenically unsaturated groups is preferably pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate. A monoester compound having a carboxyl group formed by ester and succinic acid or phthalic acid.

Use of the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups based on 100 parts by weight of the alkali-soluble resin (A) The amount is from 15 parts by weight to 150 parts by weight, preferably from 20 parts by weight to 130 parts by weight, and more preferably from 25 parts by weight to 110 parts by weight.

When the compound (B) having an ethylenically unsaturated group contains the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups, the photosensitive resin composition obtained has a better surface resistance.

Other compounds having an ethylenically unsaturated group (B-2)

The compound (B) having an ethylenically unsaturated group may optionally contain another compound (B-2) having an ethylenically unsaturated group.

The other ethylenically unsaturated group-containing compound (B-2) may be selected from a compound having one ethylenically unsaturated group or a compound having two or more (including two) ethylenically unsaturated groups.

The aforementioned compound having an ethylenically unsaturated group may include, but is not limited to, (meth)acrylamide, (meth)acryloquinone morpholine, (meth)acrylic acid-7-amino-3 , 7-dimethyloctyl ester, isobutoxymethyl (meth) acrylamide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate - 2-ethylhexyl ester, ethyl diethylene glycol (meth) acrylate, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl (meth) acrylate Aminoethyl ester, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl (A) Base) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( Tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate (meth)acrylic acid-2- Tribromophenoxyethyl ester, ethyl 2-hydroxy-(meth)acrylate, propyl 2-hydroxy-(meth)acrylate, vinyl caprolactam, N-vinylpyrrolidone, (meth)acrylic acid Phenoxyethyl ester, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene mono(meth) acrylate, poly (mono) (meth) acrylate or (A) A compound such as acrylic acid borneol ester. The compound having one ethylenically unsaturated group may be used singly or in combination of plural kinds.

The above compound having two or more (including two) ethylenically unsaturated groups may include, but is not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, and triethylene glycol II. (Meth) acrylate, tetraethylene glycol di(meth) acrylate, tris(2-hydroxyethyl)isocyanate di(meth) acrylate, tris(2-hydroxyethyl)isocyanate (Meth) acrylate, caprolactone modified tris(2-hydroxyethyl) isocyanate tri(meth) acrylate, tris(meth) acrylate trimethylol propyl ester, ethylene oxide ( EO) modified tris (meth) acrylate trimethylol propyl acrylate, propylene oxide modified (PO) tris (meth) acrylate trimethylol propyl ester, tripropylene glycol di (meth) acrylate Ester, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyester di(methyl) ) acrylate, polyethylene glycol di(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone Dipentaerythritol hexa(methyl) propylene Acid ester, caprolactone modified dipentaerythritol penta (meth) acrylate, di(trimethylolpropane) tetra(meth)acrylate], modified by ethylene oxide Bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, ethylene oxide modified hydrogenated bisphenol A di(methyl) Acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate or novolak polyglycidyl ether (methyl a compound such as an acrylate. The compound having two or more (including two) ethylenically unsaturated groups may be used singly or in combination of plural kinds.

Specific examples of the other ethylenically unsaturated group-containing compound (B-2), such as: trimethylolpropyl acrylate, trimethylolpropyl acrylate triacrylate modified with ethylene oxide, epoxy Propane-modified trimethylolpropyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol Acrylate, ditrimethylolpropyl methacrylate, propylene oxide modified glycerol triacrylate or any combination of the above.

The compound (B) having an ethylenically unsaturated group is used in an amount of 20 parts by weight to 200 parts by weight, preferably 25 parts by weight to 180 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). More preferably, it is 30 parts by weight to 160 parts by weight.

Photoinitiator (C)

The photoinitiator (C) of the present invention is not particularly limited. In one embodiment, the photoinitiator (C) may include, but is not limited to, an O-mercapto lanthanide compound, a triazabenzene compound, and a phenylethyl group. Alkanone compounds, diimidazole compounds, benzophenone compounds, α-diketone compounds, keto alcohol compounds, keto alcohol ether compounds, phosphonium oxide compounds, terpenoids, halogen-containing compounds Or peroxides, etc. The following is described.

Specific examples of the above O-indenyl lanthanide compound are, for example, 1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-phenylhydrazinium), 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinyl), 1-[4-(phenylindenyl)phenyl]- Heptane-1,2-dione-2-(O-phenylhydrazinium), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazole-3-substituent ]-Ethyl ketone-1-(O-acetamidoxime), 1-[9-ethyl-6-(3-methylphenylhydrazino)-9H-indazole-3-substituted]-ethane Keto-1-(O-ethylindenyl), 1-[9-ethyl-6-benzoin-9H-indazole-3-substituted]-ethanone-1-(O-ethenyl)肟), Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-indazole-3-substituted]-1-(O-acetonitrile) Ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)-9H-indazole-3-substituted]-1-( O-Ethyl hydrazide), Ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylphenyl)-9H-indazole-3-substituted]-1- (O-Ethyl hydrazine), Ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)-]H-indazole-3-substituent ]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoinyl)-9H-oxime Zyridin-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyl methoxybenzene) Mercapto)-9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranyl) Methoxybenzoinyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl- 5-tetrahydropyranylmethoxybenzoinyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-{9-ethyl-6 -[2-Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)phenylindenyl]-9H-indazole-3-substituted}-1-(O- Ethyl hydrazide), ethane ketone-1-{9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxy Benzimidyl]-9H-indazole-3-substituted}-1-(O-ethylindenyl) and the like. Above The O-indenyl lanthanide compounds may be used singly or in combination of plural kinds.

The above O-fluorenyl lanthanide compound is preferably 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoinhydrazino) (for example: A product manufactured by Ciba Specialty Chemicals, model number OXE 01), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-carbazole-3-substituted]-ethane ketone -1-(O-ethinylhydrazine) (for example, a product manufactured by Ciba Specialty Chemicals Co., Ltd., and its model number is OXE 02), ethane ketone-1-[9-ethyl-6-(2-methyl- 4-tetrahydrofuranmethoxyphenylmercapto)-9H-indazole-3-substituted]-1-(O-acetamidoxime) or ethanoketone-1-{9-ethyl-6-[2- Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoinyl]-9H-indazole-3-substituted}-1-(O-B醯基肟) and so on.

The above triazabenzene compound may include, but is not limited to, a vinyl-halomethyl-s-triazabenzene compound, 2-(naphtho-1-substituted)-4,6-bis-halo A bis-s-triazabenzene compound or a 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound or the like.

Specific examples of the aforementioned vinyl-halomethyl-s-triazabenzene compound, such as: 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazo Heterobenzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene or 2-tri Chloromethyl-3-amino-6-p-methoxystyryl-s-triazabenzene and the like.

Specific examples of the aforementioned 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-triazabenzene compound, such as 2-(naphtho-1-substituted)- 4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-three Azabenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-trichloro Methyl-s-triazabenzene, 2-(4-butoxy-naphthyl-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4 -(2-methoxyethyl)-naphtho-1-substituted]-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-ethoxy B -naphthyl-1-substituted]-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1- Substituent]-4,6-bis-trichloromethyl-s-triazabenzene, 2-(2-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl -s-triazabenzene, 2-(6-methoxy-5-methyl-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2 -(6-methoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(5-methoxy-naphtho-1-substituted -4,6-bis-trichloromethyl-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-bis-trichloro Methyl-s-triazabenzene, 2-(6-ethoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene or 2-(4) , 5-dimethoxy-naphthyl-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene and the like.

Specific examples of the aforementioned 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound, such as 4-[p-N,N-di(ethoxy) Alkylcarbonyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(ethoxycarbonyl) Methyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(chloroethyl)aminophenyl]-2,6-di ( Trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4- (p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(phenyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-[p-N-(p-methoxy) Phenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-N,N-bis(ethoxycarbonylmethyl)amino group Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-di(ethoxycarbonylmethyl)aminophenyl] -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2, 6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di (trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2,6-di(trichloromethyl)- S-triazabenzene, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-three Azabenzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4- [o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-pair -N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triaza , 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m- Chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N, N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethyl) Aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2, 6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl) )-s-triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene , 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(three Chloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-three Azabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro- p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl) -2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethane) -s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4 -(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene or 2,4-bis(trichloromethyl)- 6-{3-Bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl}-1,3,5-triazabenzene and the like. The above triazabenzene compounds may be used singly or in combination of plural kinds.

The above triazabenzene compound is preferably 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl). -s-triazabenzene or 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene and the like.

Specific examples of the above-mentioned acetophenone-based compound are, for example, p-dimethylacetophenone, α,α'-dimethoxyoxyazopropenone, 2,2'-dimethyl-2. -Phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propanone or 2- Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone and the like. The above-mentioned acetophenone compounds may be used singly or in combination of plural kinds. The aforementioned acetophenone compound is preferably 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propanone or 2-benzyl-2-N. N-dimethylamine-1-(4-morpholinophenyl)-1-butanone or the like.

Specific examples of the above diimidazole compounds are as follows: 2,2'-bis(o-chloro Phenyl)-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-ethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-double (p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2 '-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole and the like. The above-mentioned diimidazole compounds may be used singly or in combination of plural kinds. The above-mentioned diimidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

Specific examples of the above benzophenone compounds, such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4'-bis(dimethyl Amine) benzophenone or 4,4'-bis(diethylamine) benzophenone. The above benzophenone compounds may be used singly or in combination of plural kinds. The aforementioned benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone.

Specific examples of the above α-diketone compound are, for example, benzoin or ethenyl. Specific examples of the ketol compound are, for example, benzophenone. Specific examples of the above ketol ether compound include benzophenone methyl ether, benzophenone ether or diphenylethanol ketone isopropyl ether. Specific examples of the above fluorinated phosphonium oxide compound are, for example, 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide or bis-(2,6-dimethoxybenzoquinone)-2,4, 4-trimethylphenylphosphine oxide or the like.

Specific examples of the above terpenoids include hydrazine or 1,4-naphthoquinone.

Specific examples of the halogen-containing compound include phenylhydrazine methyl chloride, tribromomethylphenylhydrazine or tris(trichloromethyl)-s-triazabenzene. Specific examples of the above peroxides include di-tert-butyl peroxide and the like. The above-mentioned α-diketone compound, keto alcohol compound, keto alcohol ether compound, ruthenium phosphine oxide compound, hydrazine compound, halogen-containing compound or peroxide may be used singly or in combination of plural kinds.

The photoinitiator (C) is used in an amount of from 5 parts by weight to 55 parts by weight, based on the total amount of the alkali-soluble resin (A), and preferably from 7 parts by weight to 50 parts by weight, and more preferably 10 parts by weight to 45 parts by weight.

Solvent (D)

The solvent (D) to which the present invention is applied is a compound (B) which can dissolve the aforementioned alkali-soluble resin (A), has an ethylenically unsaturated group, and a photoinitiator (C), and a black pigment (E) which will be described later and have An oxetane compound (F) of a halogen atom, and does not react with each of the above components. The solvent (D) is preferably one having a suitable volatility.

Specific examples of the solvent (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, and three Ethylene 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, tripropylene glycol An alkyl diol monoalkyl ether solvent such as monomethyl ether or tripropylene glycol monoethyl ether; an alkyl group such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate or propylene glycol diethyl ether acetate Alcohol monoalkyl ether acetate solvent; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrogen An ether solvent such as furan; a ketone solvent such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or 4-hydroxy-4-methyl-2-pentanone; methyl lactate or Ethyl lactate solvent such as ethyl lactate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyric acid Ester, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate Ester, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate An ester solvent such as ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate or ethyl 2-oxybutyrate; an aromatic hydrocarbon solvent such as toluene or xylene; Carboxylic acid amines such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide Agents. The aforementioned solvent (D) may be used singly or in combination of plural kinds.

The solvent (D) is used in an amount of from 1000 parts by weight to 5000 parts by weight, preferably from 1100 parts by weight to 4,500 parts by weight, and more preferably 1200 parts by weight based on 100 parts by weight of the total amount of the alkali resin (A). Parts to 4000 parts by weight.

Black pigment (E)

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

Specific examples of the black pigment (E) of the present invention, such as perylene black, cyanine black or aniline (aniline) Black); such as red, blue, green, purple, yellow, cyanine or magenta, two or more pigments are mixed to make them close to black. Mixed color organic pigment; light black material such as carbon black, chromium oxide, iron oxide, titanium black or graphite, wherein the aforementioned carbon black may include, but not limited to, CIpigment black 7 and the like. Specific examples of the carbon black described above are commercially available from Mitsubishi Chemical Corporation, and the models thereof are MA100, MA230, MA8, #970, #1000, #2350, and #2650. The aforementioned black pigment (E) may be used singly or in combination of plural kinds.

The black pigment (E) is used in an amount of from 60 parts by weight to 600 parts by weight, based on the total amount of the alkali-soluble resin (A), preferably from 80 parts by weight to 550 parts by weight, and more preferably 100 parts by weight. Parts to 500 parts by weight.

Oxetane compound having a halogen atom (F)

The oxetane compound (F) having a ruthenium atom of the present invention may comprise a first oxetane compound (F-1) having a ruthenium atom and a second oxetane compound having a ruthenium atom (F) -2) or a combination of the two.

The first oxetane compound having a halogen atom (F-1)

The first oxetane compound (F-1) having a halogen atom has a compound of the formula (II) or a condensate of the compound: Si(Y ₁ ) _a (OY ₂ ) _4-a Formula (II)

In the formula (II), Y ₁ and Y ₂ each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number of An alkylcarbonyl group of 2 to 7 or an organic group having an oxetanyl group, wherein at least one of Y ₁ and Y ₂ is an organic group having an oxetanyl group, and a represents 0 to 3 The integer.

Specific examples of the compound having a structure represented by the formula (II) may include, but are not limited to, 3-[(3-ethyloxetan-3-yl)methoxy]propyltrimethoxydecane, 3 -[(3-ethyloxetan-3-yl)methoxy]propyltriethoxydecane, 3-[(3-ethyloxetan-3-yl)methoxy ]propyltriethoxydecane, 3-[(3-ethyloxetan-3-yl)methoxy]propylmethyldimethoxydecane, 3-[(3-ethyl Oxetane-3-yl)methoxy]propylmethyldiethoxydecane, 3-[(3-ethyloxetan-3-yl)methoxy]propylmethyl Diethoxydecane, 3-[(3-ethyloxetan-3-yl)methoxy]propyldimethylmethoxydecane, 3-[(3-ethyloxocyclo) Butan-3-yl)methoxy]propyldimethylethoxydecane, 3-[(3-ethyloxetan-3-yl)methoxy]propyldimethylethoxime Oxydecane, (3-ethyloxetan-3-yl)methoxytrimethoxydecane, (3-ethyloxetan-3-yl)methoxytriethoxydecane , bis[(3-ethyloxetan-3-yl)methoxy]dimethoxydecane, bis[(3-ethyloxetan-3-yl)methoxy]di B Baseline, tris[(3-ethyloxetan-3-yl)methoxy]methoxydecane, tris[(3-ethyloxetan-3-yl)methoxy] Ethoxy decane, or any combination of the above. From the viewpoint of hydrolysis, the compound having the formula (1) preferably has a methoxy group.

The second oxetane compound having a halogen atom (F-2)

The second oxetane compound (F-2) having a ruthenium atom is subjected to a thermal condensation reaction by a compound having a structure represented by the formula (III), and further having a formula (IV) The oxetane compound having a hydroxyl group of the structure shown is subjected to an ester-interchange reaction: Si(Y ₃ ) _b (OY ₄ ) _4-b (III)

In the formula (III), Y ₃ each independently represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; Y ₄ independently represents An alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an alkylcarbonyl group having 2 to 5 carbon atoms, and b represents an integer of 0 to 2 ;

In the formula (IV), Y ₅ to Y ₁₀ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having a hydroxyl group or a phenyl group, wherein at least Y ₅ to Y ₁₀ One represents an alkyl group having a hydroxyl group.

Specific examples of the compound having a structure represented by the formula (III) may include tetramethoxynonane, tetraethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, methyltriethoxycarbonyl. Base decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, cyclohexyl trimethoxy decane, benzene Trimethoxy decane, phenyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, diethyl dimethoxy decane, diethyl diethoxy decane, Diphenyldimethoxydecane, diphenyldiethoxydecane or any combination of the above. Stereoscopic barrier based on transesterification (steric hindrance), a compound having a structure represented by the formula (III) may preferably be tetramethoxydecane, tetraethoxydecane, methyltrimethoxydecane or methyltriethoxy. Decane, ethyltrimethoxydecane, ethyltriethoxydecane or any combination of the above.

From the viewpoint of easy synthesis, a specific example of the oxetane compound having a hydroxyl group as shown in the formula (IV) may preferably contain (3-methyloxetan-3-yl)methanol, (3-Ethyloxetane-3-yl)methanol, 2-hydroxymethyloxetane or any combination of the above compounds.

The weight average molecular weight of the oxetane compound (F) having a halogen atom is preferably from 200 to 4,000.

The total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the oxetane compound (F) having a halogen atom is used in an amount of 1 part by weight to 10 parts by weight, preferably 1.2 parts by weight to 9 parts by weight. Parts, and more preferably from 1.5 parts by weight to 8 parts by weight.

When the baking treatment is carried out as described later, the oxetane compound (F) having a halogen atom can form a better protection against the aforementioned black pigment (E) and increase the surface resistance.

When the photosensitive resin composition does not contain the oxetane compound (F) having a ruthenium atom, the photosensitive resin composition obtained has a defect that surface resistance is poor.

a compound having at least two oxiranes in the molecule (G)

The photosensitive resin composition of the present invention may optionally contain a compound (G) having at least two oxiranes in the molecule.

a compound (G) having at least two oxiranes in the molecule Specific examples may be bisphenol A type oxirane resin, bisphenol F type oxirane resin, phenol novolac type oxirane resin, cresol novolac type oxirane resin or aliphatic oxyheterocyclic ring. A compound such as a propane resin.

A commercially available product of the compound (G) having at least two oxiranes in the molecule may be commercially available from Mitsubishi Chemical Corporation, and may be of a model number JER152, JER157S70, JER157S65, JER806, JER828 or JER1007; Commercial product of paragraph No. 0189 of No. 2011-221494; manufactured by Nagase ChemteX Co., Ltd., and its model number can be DENACOL EX-611, EX-612, EX-614, EX-614B, EX -622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850 , EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX -321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, or DLC-402; or a product manufactured by Nippon Steel Chemical Co., Ltd., and its model number It can be YH-300, YH-301, YH-302, YH-315, YH-324 or YH-325.

The compound (G) having at least two oxiranes in the molecule may be used singly or in combination of plural kinds.

The compound (G) having at least two oxiranes in the molecule is used in an amount of 30 parts by weight to 120 parts by weight, preferably 35 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). It is up to 110 parts by weight, and more preferably 40 parts by weight to 100 parts by weight.

When the post-baking treatment is carried out, the compound (G) having at least two oxiranes in the molecule can provide better protection against the aforementioned black pigment (E) and increase the surface resistance.

When the photosensitive resin composition contains the compound (G) having at least two oxiranes in the molecule, the photosensitive resin composition obtained has a better surface resistance.

Additive (H)

The photosensitive resin composition for a black matrix of the present invention can be further selectively added with an additive (H) before the effect of the present invention is effected. The additive (H) may include, but is not limited to, a surfactant, a filler, a adhesion promoter, an antioxidant, an anti-aggregation agent, and the like.

Specific examples of the surfactant may include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a fluorine-containing surfactant, or the above-mentioned interface activity. Any combination of agents.

Specific examples of the surfactant may include, but are not limited to, polyethoxylated alkyl ethers such as polyethoxydodecyl ether, polyethoxylated decyl ether or polyethoxy oleyl ether; Polyethoxylated alkylphenyl ethers such as oxyoctyl phenyl ether or polyethoxylated phenyl ether; polyethylene glycol dilaurate or polyethylene glycol distearate Ethylene glycol diesters; sorbitan fatty acid ester compounds; fatty acid modified polyester compounds; tertiary amine modified polyurethane compounds; or commercially available products. The commercially available product may be a product manufactured by Shin-Etsu Chemical Co., Ltd., and its model is KP; a product manufactured by Toray Dow Corning Silicon, and its model number is SF-8427; product manufactured by Kuraei Oil & Fat Chemical Industry Co., Ltd., and its model is Polyflow; Tochem Product's product, and its model is F-Top; it is manufactured by Dainippon Ink Chemical Industry and its model is Megafac. Sumitomo 3M manufactures products of the type manufactured by Asahi Glass Co., Ltd., and its model is Asahi Guard or Surflon; or a product manufactured by Sino-Japanese Synthetic Chemical Co., Ltd., and its model number is SINOPOL E8008. The surfactant may be used singly or in combination of plural kinds.

The above fluorosurfactant may include, but is not limited to, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluoro Octyl hexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, Octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl sulfate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzene sulfonate, Sodium fluoroalkaneate, sodium fluorocarbonate, fluoroalkane polyoxyethylene ether, diglycerol tetrakis(fluoroalkane polyoxyethylene ether), fluoroalkylammonium iodine, fluoroalkane betaine, perfluoroalkane polyoxyethylene ether, Perfluoroalkyl alkanol, or a product manufactured by BM CHEMIE, and its model number is BM-1000 or BM-1100; it is manufactured by Dainippon Ink and Chemical Industries Co., Ltd., and its model is Megafac F142D, F172, F173, F183, F178, F191, F471 or F476; a product manufactured by Sumitomo Chemical Co., Ltd., and its model number is Fluorad FC 170C, FC-171, FC-430 or FC-431; the product manufactured by Asahi Glass Co., Ltd., and its model is chlorine. Fluorocarbon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 Or SC-106; a product manufactured by New Akita Chemical Co., Ltd., and its model is F Top EF301, 303 or 352; a product manufactured by NEOSU, and its model is Ftergent FT-100, FT-110, FT-140A, FT -150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310 or FT-400S; or DIC's products, and their models are F-410, F-444, F-445, F-552, F-553 or F-554. The fluorine-containing surfactants may be used singly or in combination of plural kinds.

Specific examples of the aforementioned filler may include glass or aluminum or the like.

Specific examples of the adhesion promoter include a melamine compound and a decane compound, and the adhesion promoter can increase the adhesion between the photosensitive resin composition and the substrate having the semiconductor material. The melamine may include, but is not limited to, a product manufactured by Mitsui Chemicals Co., Ltd., and its model is Cymel-300 or Cymel-303; a product manufactured by Sanwa Chemical Co., Ltd., and its model number is MW-30MH, MW-30, MS- 11, MS-001, MX-750 or MX-706. The decane-based compound may include, but is not limited to, vinyltrimethoxydecane, vinyltriethoxydecane, 3-(meth)acryloxypropyltrimethoxydecane, vinyltris(2-methoxyl). Ethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Baseline, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidylpropyltrimethoxydecane, 3-epoxypropoxydimethylene Methoxy decane, 3-glycidyl propyl methyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-chloropropylmethyl dimethyl Oxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-methylpropoxypropyl three Methoxy decane, 3-mercaptopropyltrimethoxy decane or a product manufactured by Shin-Etsu Chemical Co., Ltd., and its model number is KBM-403.

Specific examples of the antioxidant may be 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-tert-butylphenol.

A specific example of the anti-agglomerating agent may be sodium polyacrylate or the like.

The content of the filler, the adhesion promoter, the antioxidant, or the anti-agglomerating agent in the additive (H) is 10 parts by weight or less, and preferably 6 or more, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). Parts by weight or less.

The total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the surfactant used in the additive (H) is 6 parts by weight or less, preferably 4 parts by weight or less.

Preparation of a black matrix composition of the photosensitive resin

The photosensitive resin composition for a black matrix is prepared by using the above-mentioned alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment ( E) and an oxetane compound (F) having a halogen atom are placed in a stirrer and stirred to uniformly mix into a solution state, and if necessary, a compound having at least two oxirane groups in the molecule may be added ( G) and the additive (H) are uniformly mixed to obtain a photosensitive resin composition for a black matrix in a solution state.

The amount of the compound (B) having an ethylenically unsaturated group is from 20 parts by weight to 200 parts by weight, and the amount of the photoinitiator (C) is 5, based on 100 parts by weight of the alkali-soluble resin (A). The solvent (D) is used in an amount of from 1000 parts by weight to 5000 parts by weight, based on 55 parts by weight, of the black pigment (E) is used in an amount of from 60 parts by weight to 600 parts by weight, and the oxetane compound (F) having a halogen atom is used in an amount of from 1 part by weight to 10 parts by weight.

Next, the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the compound (B-1) having an acidic group and at least three or more ethylenically unsaturated groups is used in an amount of 15 parts by weight to 150 parts by weight. Further, the compound (G) having at least two oxiranes in the molecule is used in an amount of from 30 parts by weight to 120 parts by weight.

Preparation of black matrix

The black matrix of the present invention is obtained by sequentially pre-bake, expose, develop and post-bake the above-mentioned photosensitive resin composition. Among them, when the film thickness of the black matrix is 1 μm , the optical density thereof is 3.0 or more. Preferably, when the film thickness of the black matrix is 1 μm , the optical density is from 3.2 to 5.5. More preferably, when the film thickness of the black matrix is 1 μm , the optical density is from 3.5 to 5.5.

The black matrix of the present invention can be applied to a substrate by a coating method such as spin coating or cast coating, and the solvent can be removed by drying under reduced pressure and pre-baking. Further, a pre-baked coating film is formed on the substrate. Depending on the type of the above components or the blending ratio, the above-described vacuum drying and pre-baking treatment have different process conditions. The drying under reduced pressure is usually carried out at a pressure of less than 200 mmHg for 1 second to 20 seconds, and the pre-baking treatment is carried out at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes. After pre-baking, the coating film is placed under a designated mask for exposure treatment. Then, immersed in a developer at a temperature of 21 ° C to 25 ° C, It takes 15 seconds to 5 minutes to remove unwanted parts and form a specific pattern. The light used for the exposure is preferably ultraviolet rays such as g-line, h-line or i-line, and the ultraviolet irradiation device may be an (ultra) high-pressure mercury lamp and a metal halide lamp.

Specific examples of the above-mentioned suitable developer, such as: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, diethyl Amine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene A basic compound. The concentration of the developer is generally from 0.001% by weight to 10% by weight, preferably from 0.005% by weight to 5% by weight, more preferably from 0.01% by weight to 1% by weight.

When such a developer is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen. Then, the post-baking treatment is performed by a heating device such as a hot plate or an oven. The post-baking treatment temperature is usually from 150 ° C to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 60 minutes, and the heating time using the oven is from 15 minutes to 150 minutes. After the above processing steps, a black matrix can be formed on the substrate.

Specific examples of the substrate include an alkali-free glass, a soda-lime glass, a hard glass (Pyles glass), a quartz glass, and the like, and a transparent conductive film attached to the glass; or A photoelectric conversion device substrate (such as a germanium substrate) such as a solid-state imaging device.

Method for preparing color filter

The method for preparing the color filter of the present invention can be coated by rotary coating a coating method such as cloth, cast coating or roll coating, in which a color filter that has been mixed into a solution state is coated on a substrate with a photosensitive resin composition, wherein the substrate is previously composed of the aforementioned photosensitive resin The object forms a black matrix that separates the colored layers of each pixel. After coating, most of the solvent is removed by drying under reduced pressure. Next, the remaining solvent is removed by pre-baking to form a pre-baked film. Among them, depending on the type of each component and the formulation ratio, the vacuum drying and pre-baking treatment have different process conditions. The drying under reduced pressure is usually carried out at a pressure of from 0 mmHg to 200 mmHg for from 1 second to 60 seconds, and the prebaking treatment is carried out at a temperature of from 70 ° C to 110 ° C for from 1 minute to 15 minutes. After pre-baking, the pre-baked film is placed under a designated mask for exposure treatment. Next, the prebaked coating film is immersed in the above-mentioned developing solution at a temperature of 21 ° C to 25 ° C, and development is carried out for 15 seconds to 5 minutes to remove unnecessary portions to form a specific pattern. The light used for exposure is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet device may be (ultra) high-pressure mercury lamp and metal halide lamp.

After the above development treatment, it is washed with water, and air-dried with compressed air or compressed nitrogen, and then post-baked by a heating device such as a hot plate or an oven. The conditions of the post-baking treatment are as described above, and will not be further described herein. .

The color layer of the color filter can be obtained by repeating the above steps for each color (mainly including red, green, and blue colors). Next, in a vacuum environment having a temperature of 220 ° C to 250 ° C, an indium tin oxide (ITO) vapor deposited film is formed on the pixel layer, and if necessary, the ITO coating film is subjected to etching and wiring treatment, and then the liquid crystal alignment film is coated. The quinone imine, which is fired, can be used as a color filter for a liquid crystal display element.

Method for preparing liquid crystal display element

The liquid crystal display device of the present invention includes a color filter substrate formed by the above-described method of manufacturing a color filter, and a drive substrate provided with a thin film transistor (TFT). Next, an intervening gap (cell gap) is disposed between the two substrates, and a peripheral portion of the two substrates is bonded by a sealing agent, and the liquid crystal filling is injected into the surface of the substrate and the sealing agent is separated. Within the gap. Then, the injection hole is sealed to form a liquid crystal cell. Thereafter, a liquid crystal display element can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell, that is, on the other side surface of each of the substrates constituting the liquid crystal cell.

The liquid crystal used in the above, that is, the liquid crystal compound or the liquid crystal composition is not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and may be any inorganic or organic substance. The technique for forming a liquid crystal alignment film is well known to those of ordinary skill in the art to which the present invention pertains, and is not the focus of the present invention and will not be further described herein.

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

Preparation of a diol compound having a polymerizable unsaturated group (a-1) Preparation Example 1

First, 100 parts by weight of a ruthenium epoxy compound (commercially manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300; epoxy equivalent: 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight of benzyl chloride Ethylammonium, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous manner to a 500-mL four-necked flask. 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 concentration of 50% by weight was obtained. Then, the light yellow transparent mixture is subjected to extraction, filtration, and heat drying to obtain a diol compound having a polymerizable unsaturated group of Preparation Example 1 having a solid content of 99.9 weight percent (a-1- 1).

Preparation Example 2

First, 100 parts by weight of a ruthenium epoxy compound (commercially manufactured by Osaka Gas, and its model number is PG-100; epoxy equivalent of 259), 35 parts by weight of methacrylic acid, and 0.3 parts by weight of benzyl chloride Ethylammonium, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 135 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 is controlled at 25 parts by weight per minute, and the temperature of the reaction process is maintained. After reacting for 15 hours at 100 ° C to 110 ° C, a pale yellow transparent mixture having a solid content of 50% by weight was obtained. The above-mentioned pale yellow transparent mixture is subjected to extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (a-1-2) of Preparation Example 2 having a solid content of 99.9 weight percent. .

Preparation Example 3

100 parts by weight of an antimony epoxy compound (commercially available from Nippon Steel Chemical Co., Ltd., model ESF-300; epoxy equivalent 231), 100 parts by weight of 2-methylpropenyl ethoxy succinate, 0.3 Parts by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 200 parts by weight of propylene glycol monomethyl ether acetate are added in a continuous manner to 500 ml of four In the 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 content of 50% by weight was obtained. The above-mentioned pale yellow transparent mixture was subjected to extraction, filtration, and heating and drying to obtain a polymerizable unsaturated group-containing diol compound (a-1-3) of Preparation Example 3 having a solid content of 99.9 weight%.

Preparation Example 4

First, 0.3 mol of bis(4-hydroxyphenyl)phosphonium, 9 mol of 3-chloro-1,2-epoxypropane was added to a 1000 ml three-necked flask equipped with mechanical stirring, a thermometer and a reflux condenser. And 0.003 mol of tetramethylammonium chloride. Subsequently, the mixture was heated to 105 ° C while stirring, and reacted at 105 ° C for 9 hours. Then, unreacted 3-chloro-1,2-epoxypropane was distilled off under reduced pressure. After that, the reaction system was cooled to room temperature, and 9 mol of benzene was added with stirring. 0.5 mol sodium hydroxide (an aqueous solution dissolved in water at a concentration of 30% by weight). Then, the temperature was raised to 60 ° C and maintained for 3 hours. Next, the reaction solution was washed with water repeatedly until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, and then dried at 75 ° C for 24 hours to obtain an bis(4-hydroxyphenyl)fluorene epoxy compound.

100 parts by weight of an epoxy compound of bis(4-hydroxyphenyl)fluorene (epoxy equivalent 181), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, and 0.1 part by weight of 2, 6-di-tert-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 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. The light yellow transparent mixed solution is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (a-1-4) having a solid content of 99.9 weight percent. .

Preparation Example 5

Add 0.3 mol of bis(4-hydroxyphenyl)hexafluoropropane, 9 mol of 3-chloro-1,2-epoxypropane and a 1000 ml three-necked flask equipped with mechanical stirring, thermometer and reflux condenser. 0.003 mole of tetramethylammonium chloride. Subsequently, the mixture was heated to 105 ° C while stirring, and reacted at 105 ° C for 9 hours. Next, unreacted 3-chloro-1,2-epoxypropane was distilled off under reduced pressure. Thereafter, the reaction system was cooled to room temperature, and 9 mol of benzene and 0.5 mol of sodium hydroxide (an aqueous solution having a concentration of 30% by weight in water) were added with stirring. Then, the temperature was raised to 60 ° C and maintained for 3 hours. Then, repeatedly wash with water The reaction solution was decanted until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, and then dried at 75 ° C for 24 hours to obtain an epoxy compound of bis(4-hydroxyphenyl)hexafluoropropane.

100 parts by weight of an epoxy compound of bis(4-hydroxyphenyl)hexafluoropropane (epoxy equivalent 224), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 135 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 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. The light yellow transparent mixed liquid was subjected to a step of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing di compound (a-1-5) of Preparation Example 5 having a solid content of 99.9 weight%.

Preparation Example 6

Add 0.3 mol of bis(4-hydroxyphenyl)dimethyl decane, 9 mol of 3-chloro-1,2-epoxypropane to a 1000 ml three-necked flask equipped with mechanical stirring, thermometer and reflux condenser. And 0.003 mol of tetramethylammonium chloride. Subsequently, the mixture was heated to 105 ° C while stirring, and reacted at 105 ° C for 9 hours. Next, unreacted 3-chloro-1,2-epoxypropane was distilled off under reduced pressure. Thereafter, the reaction system was cooled to room temperature, and 9 mol of benzene and 0.5 mol of sodium hydroxide (an aqueous solution having a concentration of 30% by weight in water) were added with stirring. Then, the temperature was raised to 60 ° C and maintained for 3 hours. Next, the reaction solution was washed with water repeatedly until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, and then dried at 75 ° C for 24 hours to obtain An epoxy compound of bis(4-hydroxyphenyl)dimethyl decane.

100 parts by weight of an epoxy compound of bis(4-hydroxyphenyl)dimethyl decane (epoxy equivalent 278), 100 parts by weight of 2-methylpropenyl ethoxy succinate, 0.3 parts by weight Benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 200 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 for 15 hours to obtain a pale yellow transparent mixture having a solid content of 50% by weight. The light yellow transparent mixed solution is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (a-1-6) having a solid content of 99.9 weight percent. .

Preparation of first alkali soluble resin (A-1)

The first alkali-soluble resin (A-1) of Synthesis Example 1 to Synthesis Example 10 was prepared according to the first table.

Synthesis Example 1

First, 1.0 mol of the diol compound (a-1-1) having a polymerizable unsaturated group prepared in the above Preparation Example 1, 0.1 mol of 4,4'-hexafluoroisopropylidene di-o-benzene. Dicarboxylic acid dianhydride (a-2-1-a), 0.2 mol of pyromellitic dianhydride (a-2-2-c), 0.4 mol of maleic acid (a-3-2-a) 1.0 mole of tetrahydrophthalic anhydride (a-3-2-b), 1.9 grams of benzyltriethylammonium chloride, 0.6 grams of 2,6-di-t-butyl-p-cresol and 750 g of propylene glycol monomethyl ether acetate was added to a 500 ml four-necked flask at the same time to form a reaction solution. liquid. Here, "simultaneous addition" means that tetracarboxylic acid or its acid dianhydride (a-2) and a dicarboxylic acid or its anhydride (a-3) are added at the same reaction time. Next, the reaction solution was heated to 110 ° C, and reacted for 2 hours to obtain a first alkali-soluble resin (A-1-1) of Synthesis Example 1 having an acid value of 129 mg KOH/g and a number average molecular weight of 2,368. .

Synthesis Example 2

1.0 mol of the diol compound (a-1-2) having a polymerizable unsaturated group prepared in the above Preparation Example 2, 2.0 g of benzyltriethylammonium chloride, and 0.7 g of 2,6-di The third butyl p-cresol and 700 g of propylene glycol methyl ether acetate were added to a 500 ml four-necked flask to form a reaction solution. Next, 0.2 mol of 1,4-difluorobenzenetetracarboxylic dianhydride (a-2-1-b), 0.2 mol of benzophenone tetracarboxylic dianhydride (a-2-2-b) was added. ) and reacted at 90 ° C for 2 hours. Then, 1.2 mol of tetrahydrophthalic anhydride (a-3-2-b) was added and reacted at 90 ° C for 4 hours. Here, "segmented addition" means adding tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its anhydride (a-3), respectively, at different reaction times, that is, adding tetracarboxylic acid first. Or its acid dianhydride (a-2), followed by the addition of a dicarboxylic acid or its anhydride (a-3). Through the above synthesis step, the first alkali-soluble resin (A-1-2) of Synthesis Example 2 having an acid value of 125 mgKOH/g and a number average molecular weight of 3,388 was obtained.

Synthesis Example 3, Synthesis Example 5, Synthesis Example 7, and Synthesis Example 9

Synthesis Example 3, Synthesis Example 5, Synthesis Example 7 and Synthesis Example 9 were prepared in the same manner as in the production method of the first alkali-soluble resin of Synthesis Example 1, except that Synthesis Example 3, Synthesis Example 5, and Synthesis Example 7 were used. And Synthesis Example 9 is to change the type and amount of the raw material in the first alkali-soluble resin, and the The parties are shown in Table 1, respectively, and will not be described here.

Synthesis Example 4, Synthesis Example 6, Synthesis Example 8, and Synthesis Example 10

In Synthesis Example 4, Synthesis Example 6, Synthesis Example 8, and Synthesis Example 10, the same production method as that of the first alkali-soluble resin of Synthesis Example 2 was used, except that Synthesis Example 4, Synthesis Example 6, and Synthesis Example 8 were used. And Synthesis Example 10 changes the kind and usage amount of the raw material in the first alkali-soluble resin, and the formulation thereof is as shown in Table 1, and will not be further described herein.

Preparation of a second alkali soluble resin (A-2)

The second alkali-soluble resin (A-2) of Synthesis Example 11 to Synthesis Example 13 was prepared according to the second table.

Synthesis Example 11

1.0 mol of the diol compound (a-1-1) having a polymerizable unsaturated group prepared in the above Preparation Example 1, 1.9 g of benzyltriethylammonium chloride, and 0.6 g of 2,6-di The third butyl p-cresol was dissolved in 700 g of propylene glycol methyl ether acetate, and 0.3 mol of biphenyltetracarboxylic acid (a-2-2-a) and 1.4 mol of maleic acid (a) were simultaneously added. -3-2-a). Subsequently, the mixture was heated to 110 ° C and reacted for 2 hours to obtain a second alkali-soluble resin (A-2-1) of Synthesis Example 11 having an acid value of 125 mg KOH/g and a number average molecular weight of 2,455.

Synthesis Example 12 and Synthesis Example 13

In Synthesis Example 12 and Synthesis Example 13, the same production method as that of the second alkali-soluble resin of Synthesis Example 11 was used, except that Synthesis Example 12 and Synthesis Example 13 changed the type of the raw material in the second alkali-soluble resin and The amount of use, the reaction parameters and the time of addition of the reactants, and the formulation thereof The reaction parameters are shown in Table 2, respectively, and are not described here. It is worth noting that "simultaneous addition" means adding tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its anhydride (a-3) at the same reaction time, and "segmented addition" means Adding tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its anhydride (a-3) separately at different reaction times, that is, adding tetracarboxylic acid or its acid dianhydride (a-2) first. Then, a dicarboxylic acid or its anhydride (a-3) is added.

Other alkali soluble resin (A-3)

The other alkali-soluble resin (A-3) of Synthesis Example 14 to Synthesis Example 16 was prepared according to Table 3 below.

Synthesis Example 14

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1000 ml. After introducing nitrogen, 30 parts by weight of 2-hydroxyethyl methacrylate (HEMA) and 10 parts by weight were added. Benzyl methacrylate (BzMA), 60 parts by weight of CF9BuMA, 3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) (AMBN) and 300 parts by weight of diethylene glycol II Methyl ether (Diglyme). Next, the above mixture was slowly stirred and the solution was allowed to warm to 80 °C. Next, this was polycondensed at 80 ° C for 6 hours. Then, after evaporating the solvent, the other alkali-soluble resin (A-3-1) of Synthesis Example 14 was obtained.

Synthesis Example 15 and Synthesis Example 16

In Synthesis Example 15 and Synthesis Example 16, the same production method as that of the other alkali-soluble resin of Synthesis Example 14 was used, except that Synthesis Example 15 and Synthesis Example 16 were used to change the raw materials of other alkali-soluble resins. The type and amount of use, and the formulas thereof are shown in Table 3, and are not described here.

Preparation of an oxetane compound having a halogen atom (F) Synthesis Example 17

Add 27.84 g (0.1 mol) of 3-[(3-ethyloxetan-3-yl)methoxy]propyltrimethoxynonane and 0.54 g (30.0 mmol) of water to 80 grams of Diacetone alcohol (DAA). After stirring at room temperature for a while, the temperature was raised to 60 ° C and stirred for 2 hours. Then, the temperature was raised to 160 ° C, and the diacetone alcohol and the methanol were azeotroped, and reacted for 6 hours to prepare a oxirane having a ruthenium atom of Synthesis Example 17 which was diluted with diacetone alcohol and had a solid content concentration of 20% by weight. The alkane compound (F-1-1) wherein the oxetane compound (F-1-1) having a ruthenium atom of Synthesis Example 17 has a structure represented by the following formula (VIII-1):

Synthesis Example 18

22.64 g (0.1 mol) of (3-ethyloxetan-3-yl)methoxytrimethoxydecane and 0.54 g (30.0 mmol) of water were added to 80 g of diacetone alcohol (Diacetone alcohol; DAA). After stirring at room temperature for a while, the temperature was raised to 60 ° C and stirred for 2 hours. Then, the temperature was raised to 160 ° C, and the diacetone alcohol and the methanol were azeotroped, and reacted for 6 hours to prepare a oxirane having a ruthenium atom of Synthesis Example 18 which was diluted with diacetone alcohol and had a solid content concentration of 20% by weight. The alkane compound (F-1-2) wherein the oxetane compound (F-1-2) having a ruthenium atom of Synthesis Example 18 has a structure represented by the following formula (VIII-2):

Synthesis Example 19

89.41 g (0.1 mol) of a compound having the structure represented by the following formula (VIII-3) (wherein t is 7 or 8) and 209.9 g (1.8 mol) of (3-ethyloxetane) The -3-yl)methanol was added to 400 grams of diacetone alcohol. After stirring at room temperature for a while, the temperature was raised to 60 ° C and stirred for 2 hours. Then, the temperature was raised to 160 ° C, and the diacetone alcohol and the methanol were azeotroped, and reacted for 6 hours to obtain a oxirane having a ruthenium atom of the synthesis example 19 which was diluted with diacetone alcohol and had a solid content concentration of 20% by weight. An alkane compound (F-2-1) wherein the oxetane compound (F-2-1) having a ruthenium atom of Synthesis Example 19 has a structure represented by the following formula (VIII-4), and t is 7 or 8:

Synthesis Example 20

95.01 g (0.1 mol) of a compound having the structure represented by the following formula (VIII-5) (wherein u is 7 or 8) and 183.8 g (1.8 mol) of (3-methyloxetane) The -3-yl)methanol was added to 400 grams of diacetone alcohol. After stirring at room temperature for a while, the temperature was raised to 60 ° C and stirred for 2 hours. Then, the temperature was raised to 160 ° C, and the diacetone alcohol and the methanol were azeotroped, and reacted for 6 hours to prepare a oxirane having a ruthenium atom of the synthesis example 20 diluted with diacetone alcohol and having a solid content concentration of 20% by weight. An alkane compound (F-2-2) wherein the oxetane compound (F-2-2) having a halogen atom of Synthesis Example 20 has a structure represented by the following formula (VIII-6), and u is 7 or 8:

Preparation of photosensitive resin composition

The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were prepared according to Tables 4 and 5 below.

Example 1

100 parts by weight of the aforementioned first alkali-soluble resin (A-1-1), 15 parts by weight of pentaerythritol triacrylate esterified with phthalic acid (B-1-1), and 5 parts by weight of trisacrylic acid Hydroxymethyl propyl ester (B-2-1), 5 parts by weight of 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3- substituent]- 1-(oxy-acetamidine) (C-1), 60 parts by weight of CIPigment BK7 (E-1) and 1 part by weight of the aforementioned oxetane compound (F-1-1) having a halogen atom The photosensitive resin composition of Example 1 was obtained by adding to 1000 parts by weight of propylene glycol monomethyl ether acetate (D-1) and stirring uniformly with a shaking type stirrer. The obtained photosensitive resin composition was evaluated by the following evaluation methods of development resistance and surface resistance, and the obtained results are shown in Table 4.

Example 2 to Example 10 and Comparative Example 1 to Comparative Example 6

In Examples 2 to 10 and Comparative Examples 1 to 6, the same production method as that of the photosensitive resin composition of Example 1 was used, except that Examples 2 to 10 and Comparative Examples 1 to 6 were used to change the photosensitivity. The type and amount of the raw materials in the resin composition, and the formulations and evaluation results thereof are shown in Tables 4 and 5, respectively, and are not described here.

Preparing a black matrix

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

Evaluation method Development resistance

The photosensitive resin compositions prepared in the above Examples 1 to 10 and Comparative Examples 1 to 6 were applied by spin coating in a coater (Model: MS-A150; available from Shinko Trading). On a glass substrate measuring 100 mm x 100 mm. Next, it was dried under reduced pressure at a pressure of 60 Pa for 15 seconds to form a coating film. Then, the substrate coated with the coating film was placed in an oven and prebaked at a temperature of 100 ° C for 2 minutes to form a prebaked coating film. Next, the prebaked coating film was exposed to ultraviolet light (exposure model: AG500-4N; manufactured by M&R Nano Technology) at 50 mJ/cm ² . At this time, the film thickness before development of the prebaked coating film (photosensitive resin layer) can be measured. Then, the exposed prebaked coating film was immersed in a developer (concentration: 0.045% potassium hydroxide) at 23 ° C for 1 minute to form a glass substrate having the developed coating film thereon. Next, the glass substrate on which the developed coating film was applied was washed with water, placed in an oven, and baked at 235 ° C for 30 minutes to form a photosensitive resin layer on the glass substrate. At this time, the film thickness after development of the photosensitive resin layer can be measured. Then, the film thickness ratio before and after development was calculated according to the following formula (IX), and evaluated according to the following criteria, wherein the larger the film thickness ratio, the better the development resistance of the photosensitive resin composition:

◎: 88% ≦ film thickness ratio.

○: 85% ≦ film thickness ratio <88%.

△: 80% ≦ film thickness ratio <85%.

×: The film thickness ratio was <80%.

2. Surface impedance

The black matrix having the film thickness of 1.0 μm obtained by the use of Examples 1 to 10 and Comparative Examples 1 to 6 was measured using a high-impedance meter (Model: MCP-HT450 type Hiresta-UP; manufactured by Mitsubishi Chemical Corporation). For measurement, take three measurement points on the above black matrix, measure the average value of the surface resistance (Ω _S ), and evaluate according to the following criteria:

◎: 1.0E+14≦Ω _S .

○: 1.0E+12≦Ω _S <1.0E+14.

△: 1.0E + 10 ≦ Ω _S < 1.0E + 12.

×: Ω _S <1.0E+10.

As is apparent from the results of the fourth and fifth tables, when the alkali-soluble resin (A) does not contain the first alkali-soluble resin (A-1), the photosensitive resin composition obtained has defects in development resistance and surface resistance. . In the first alkali-soluble resin (A-1), the molar number of the diol compound (a-1) having a polymerizable unsaturated group, the tetracarboxylic acid having a fluorine atom or its acid dianhydride (a-2) The molar number of -1) and the number of moles of the dicarboxylic acid having a fluorine atom or its anhydride (a-3-1) satisfy the relationship [(a-2-1)+(a-3-1)]/ When (a-1) = 0.4 to 1.6, the obtained photosensitive resin composition has better developability.

Secondly, when the compound (B) having an ethylenically unsaturated group contains the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups, the photosensitive resin composition obtained has a better surface resistance. .

In addition, when the photosensitive resin composition does not contain the oxetane compound (F) having a ruthenium atom, the photosensitive resin composition obtained has a defect that surface resistance is poor.

Further, when the photosensitive resin composition further contains the compound (G) having at least two oxiranes in the molecule, the photosensitive resin composition has a better surface resistance.

It should be noted that the present invention describes the photosensitive resin composition for a black matrix of the present invention and its application by using specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments as an example, but the technology of the present invention It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds may be used for the photosensitive resin composition for black matrix of the present invention and its application without departing from the spirit and scope of the present invention. The material, composition, reaction conditions, process, analytical method or instrument are carried out.

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

Claims (13)

A photosensitive resin composition for a black matrix comprising: an alkali-soluble resin (A) comprising a first alkali-soluble resin (A-1) having the formula (I): In the formula (I) in which R ₁ represents a phenylene or phenylene having a substituent, wherein the substituent having a carbon number of 1 to an alkyl group, a halogen atom or a phenyl 5; R ₂ represents the -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-Asia a mercapto or a single bond; the R ₃ represents a tetravalent carboxylic acid residue; the R ₄ represents a divalent carboxylic acid residue, wherein at least one of R ₃ and R ₄ has a fluorine atom; and R ₅ represents a hydrogen atom Or methyl; and m represents an integer from 1 to 20; a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); a black pigment (E); An oxetane compound (F) having a halogen atom, comprising a first oxetane compound (F-1) having a halogen atom, and a second oxetane compound having a halogen atom (F) -2) or a combination of the two, and the oxetane compound (F) having a halogen atom has a weight average molecular weight of from 200 to 4,000, wherein the first oxetane compound having a halogen atom ( F-1) is a compound having a structure represented by the following formula (II) or a condensate of the compound, and The second oxetane compound (F-2) having a halogen atom is subjected to a heat condensation reaction by a compound having a structure represented by the following formula (III), and further having a structure represented by the formula (IV). The oxetane compound having a hydroxyl group is subjected to transesterification to obtain: Si(Y ₁ ) _a (OY ₂ ) _4-a (II) In the formula (II), the Y ₁ and the Y ₂ are each independently The ground represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having 2 to 7 carbon atoms or having an oxetanyl group. An organic group, wherein at least one of Y ₁ and Y ₂ is an organic group having an oxetanyl group, and the a represents an integer of 0 to 3; Si(Y ₃ ) _b (OY ₄ ) _{4 -b} Formula (III) In the formula (III), the Y ₃ independently represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or a carbon number of 6 to 10 The Y ₄ independently represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an alkylcarbonyl group having 2 to 5 carbon atoms. And b represents an integer from 0 to 2; In the formula (IV), the Y ₅ to the Y ₁₀ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having a hydroxyl group or a phenyl group, wherein the Y ₅ to Y At least one of ₁₀ represents an alkyl group having a hydroxyl group. The photosensitive resin composition for a black matrix according to claim 1, wherein the first alkali-soluble resin (A-1) is obtained by reacting a first mixture, and the first mixture comprises: a diol compound (a-1) having a polymerizable unsaturated group; a tetracarboxylic acid or an acid dianhydride thereof (a-2); and a dicarboxylic acid or an anhydride thereof (a-3), and wherein the tetracarboxylic acid or The acid dianhydride (a-2) contains a tetracarboxylic acid having a fluorine atom or an acid dianhydride (a-2-1) and the tetracarboxylic acid having a fluorine atom or an acid dianhydride thereof (a-2-1) a tetracarboxylic acid or an acid dianhydride (a-2-2) thereof, the dicarboxylic acid or its anhydride (a-3) comprising a dicarboxylic acid having a fluorine atom or an anhydride thereof (a-3-1) and a dicarboxylic acid having a fluorine atom or an acid anhydride thereof (a-3-1) or an acid anhydride thereof (a-3-2), and the tetracarboxylic acid or acid dianhydride thereof (a-2) And at least one of the dicarboxylic acid or its anhydride (a-3) has a fluorine atom. The photosensitive resin composition for a black matrix according to claim 2, wherein the tetracarboxylic acid having a fluorine atom or the acid dianhydride (a-2-1) is selected from the group consisting of the following formula (I) -1) a tetracarboxylic acid compound having a fluorine atom of the structure shown, a tetracarboxylic dianhydride compound having a fluorine atom having a structure represented by the following formula (I-2), and a combination of the above: In the formula (I-1) and the formula (I-2), the X ₁ represents a group having the following formula (I-3) to formula (I-8): In the formula (I-3) to the formula (I-8), the X ₂ represents a fluorine atom or a trifluoromethyl group, respectively, and the "*" represents a position bonded to a carbon atom. The photosensitive resin composition for a black matrix according to claim 2, wherein the dicarboxylic acid having a fluorine atom or an anhydride thereof (a-3-1) is selected from the group consisting of the following formula (I-9) a dicarboxylic acid compound having a fluorine atom of the structure shown, a dicarboxylic anhydride compound having a fluorine atom having a structure represented by the following formula (I-10), and a combination of the above: In the formula (I-9) and the formula (I-10), the X ₃ represents an organic group having a fluorine atom of 1 to 100 carbon atoms. The photosensitive resin composition for a black matrix according to the second aspect of the invention, wherein the tetracarboxylic acid having a fluorine atom or an acid dianhydride (a-2-1) and the dicarboxylic acid having a fluorine atom; The molar ratio of the total mole number of its anhydride (a-3-1) to the molar number of the diol compound (a-1) having a polymerizable unsaturated group {[(a-2-1)+ (a-3-1)]/(a-1)} is 0.4 to 1.6. The photosensitive resin composition for a black matrix according to claim 1, wherein the compound (B) having an ethylenically unsaturated group contains a compound having an acidic group and at least three ethylenically unsaturated groups ( B-1). The photosensitive resin composition for a black matrix according to claim 1, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the first alkali-soluble resin (A-1) is used. The amount of the compound (B) having an ethylenically unsaturated group is from 20 parts by weight to 200 parts by weight, and the amount of the photoinitiator (C) used is from 10 parts by weight to 100 parts by weight. The solvent (D) is used in an amount of from 1000 parts by weight to 5000 parts by weight, the black pigment (E) is used in an amount of from 60 parts by weight to 600 parts by weight, and the oxime atom is used in an amount of from 55 parts by weight to 55 parts by weight. The cyclobutane compound (F) is used in an amount of from 1 part by weight to 10 parts by weight. The photosensitive resin composition for a black matrix according to claim 6, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the acidic group and at least three ethylenically unsaturated groups are used. The compound (B-1) is used in an amount of 15 parts by weight to 150 parts by weight. The photosensitive resin composition for a black matrix according to claim 1, further comprising a compound (G) having at least two oxiranes in one molecule. The photosensitive resin composition for a black matrix according to claim 9 of the invention, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the compound having at least two oxiranes in the molecule The amount of (G) used is from 30 parts by weight to 120 parts by weight. A black matrix is formed by a photosensitive resin composition for a black matrix according to any one of claims 1 to 10. A color filter comprising the eleventh item of the patent application scope The black matrix described. A liquid crystal display comprising the color filter of claim 12 of the patent application.