TWI557504B - Photosensitive resin composition and uses thereof - Google Patents

Description

Photosensitive resin composition and application thereof

The present invention relates to a photosensitive resin composition for a black matrix and a color filter and a liquid crystal display element formed using the black matrix. In particular, a photosensitive resin composition for a black matrix having improved resolution and a taper angle, and a color filter and a liquid crystal display element formed using the black matrix are provided.

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

At present, the industry has increasingly increased the shading requirements of the black matrix, and one of the solutions is to increase the amount of black pigment used, thereby improving the shading of the black matrix. For example, Japanese Laid-Open Patent Publication No. 2006-259716 discloses a photosensitive resin composition for a black matrix comprising a high-use black pigment, an alkali-soluble resin, a photopolymerization initiator, and a difunctional group. Reactive monomer and organic solvent. Among them, a reactive monomer having a difunctional group can improve the reaction between the compounds to form a high-definition pattern. Thereby, in the photosensitive resin composition, while increasing the light-shielding property so as to increase the amount of use of the black pigment, the taper angle of the photosensitive resin composition can be maintained.

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

Although the photosensitive resin composition in which the amount of the black pigment used is increased in the prior art, the resolution and the like can be increased. However, the resolution and the taper angle of the photosensitive resin composition of each of the above-mentioned prior methods have not yet been accepted by the industry. In view of this, there is still a need to develop a photosensitive resin composition for a black matrix which can improve the resolution and the taper angle.

The present invention provides a photosensitive resin composition for a black matrix having excellent resolution and taper angle by using a component which provides a special alkali-soluble resin and a special photoinitiator.

Accordingly, the present invention provides a photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment ( E); wherein: the alkali-soluble resin (A) comprises the first alkali-soluble resin (A-1) represented by the formula (1):

In the formula (1): A represents a phenyl group or a substituted phenyl group having a substituent, wherein the substituent is an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and B 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; ¹ represents a tetravalent carboxylic acid residue containing a fluorine atom or a tetravalent carboxylic acid residue not containing a fluorine atom; Y ¹ represents a divalent carboxylic acid residue containing a fluorine atom or a divalent carboxylic acid residue not containing a fluorine atom And R ¹ represents a hydrogen atom or a methyl group; and m represents an integer of 1 to 20; wherein at least one of L ¹ and Y ¹ contains a fluorine atom; and the photoinitiator (C) comprises the formula (7) Α-ketooxime ester compound (C-1):

In the formula (7): R ¹⁰ represents a methylphenyl group having 1 to 5 methyl groups; R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, a benzyl group or a carbon having 1 to 10 carbon atoms. a number from 3 to 6 cycloalkyl; R ¹² represents methyl, ethyl, propyl or benzamidine; and R ¹³ represents -H, , , , , Wherein a represents methyl or ethyl; and b represents -H or methyl.

The present invention also provides a black matrix formed of the aforementioned photosensitive resin composition.

The present invention further provides a color filter comprising the aforementioned black matrix.

The present invention further provides a liquid crystal display element comprising the aforementioned color filter.

1‧‧‧ taper angle (θ)

2‧‧‧Photograph

3‧‧‧Substrate

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Figure 1 is a graph showing the relationship between the taper angle and the resist pattern in a scanning electron microscope.

The present invention provides a photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment (E) Wherein: the alkali-soluble resin (A) comprises the first alkali-soluble resin (A-1) represented by the formula (1):

In the formula (1): A represents a phenyl group or a substituted phenyl group having a substituent, wherein the substituent is an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and B 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; ¹ represents a tetravalent carboxylic acid residue containing a fluorine atom or a tetravalent carboxylic acid residue not containing a fluorine atom; Y ¹ represents a divalent carboxylic acid residue containing a fluorine atom or a divalent carboxylic acid residue not containing a fluorine atom And R ¹ represents a hydrogen atom or a methyl group; and m represents an integer of 1 to 20; wherein at least one of L ¹ and Y ¹ contains a fluorine atom; and the photoinitiator (C) comprises the formula (7) Α-ketooxime ester compound (C-1):

In the formula (7): R ¹⁰ represents a methylphenyl group having 1 to 5 methyl groups; R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, a benzyl group or a carbon having 1 to 10 carbon atoms. a number of 3 to 6 cycloalkyl groups; R ¹² represents a methyl group, an ethyl group, a propyl group or a benzyl group; and R ¹³ represents -H, , , , , Wherein a represents methyl or ethyl; and b represents -H or methyl.

The alkali-soluble resin (A) according to the present invention comprises the first alkali-soluble resin (A-1) represented by the formula (1):

In the formula (1): A represents a phenyl group or a substituted phenyl group having a substituent, wherein the substituent is an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and B 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; ¹ represents a tetravalent carboxylic acid residue containing a fluorine atom or a tetravalent carboxylic acid residue not containing a fluorine atom; Y ¹ represents a divalent carboxylic acid residue containing a fluorine atom or a divalent carboxylic acid residue not containing a fluorine atom And R ¹ represents a hydrogen atom or a methyl group; and m represents an integer of 1 to 20; wherein at least one of L ¹ and Y ¹ contains a fluorine atom; it is noted that the L ¹ may be a fluorine atom-containing four The valence carboxylic acid residue or the tetravalent carboxylic acid residue not containing a fluorine atom is preferably a tetravalent aromatic group having fluorine, more preferably a benzene ring having fluorine.

Specifically, the alkali-soluble resin (A-1) is obtained by reacting the first mixture. The first mixture includes a diol compound (a-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or its acid dianhydride (a-2), and a dicarboxylic acid or an anhydride thereof (a-3). At least one of the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its anhydride (a-3) needs to contain a fluorine atom, and the diol which contains a polymerizable unsaturated group is described in detail below. Compound (a-1) is composed of two The epoxy group-containing bisphenol compound (a-1-i) and a compound (a-1-ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group are reacted. Among them, the reactant for synthesizing the diol compound (a-1) containing a polymerizable unsaturated group may also contain other compounds.

The bisphenol compound (a-1-i) 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 bisphenols used to synthesize the bisphenol compound (a-1-i) having two epoxy groups include 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-dimethylphenyl) ) bismuth, bis(4-hydroxy-3,5-dichlorophenyl)fluorene, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoro Propane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylnonane, bis(4-hydroxy-3,5-dimethylphenyl) Dimethyldecane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyloxane, 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-dimethyl Phenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-double (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-bromobenzene) A hydrazine, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene or a combination of the above compounds.

Specific examples of the halogenated propylene oxide used to synthesize the bisphenol compound (a-1-i) having two epoxy groups include 3-chloro-1,2-epoxypropane and 3-bromo-1,2. - propylene oxide or a combination of the above compounds. The above halogenated propylene oxide may be used in an amount of from 1 equivalent to 20 equivalents, and preferably from 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 include sodium hydroxide, potassium hydroxide or a combination of the above compounds. The alkali metal hydroxide added in the above 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 in the bisphenol compound. .

It is to be noted that 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 for the dehydrohalogenation reaction is from 20 ° C to 120 ° C, and the operation time ranges from 1 hour to 10 hours.

In one embodiment, an aqueous solution of the alkali metal hydroxide added to 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, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethylbenzyl ammonium chloride or the like may be added. The 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 allowed to proceed for 1 hour to 10 hours at a temperature of from 20 ° C to 120 ° C to carry out a dehydrohalogenation reaction.

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

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

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the dehydrohalogenated reaction solution may be added to a solvent such as benzene, toluene or methyl isobutyl ketone, and sodium hydroxide or potassium hydroxide may be added. An aqueous alkali metal hydroxide solution is used to carry out the 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, preferably from 0.05 mol to 0.9 mol, based on the total equivalent of the hydroxyl group in the above bisphenol compound. ear. Further, the above dehydrohalogenation reaction has an operating temperature in the range of 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

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

The bisphenol compound (a-1-i) having two epoxy groups is preferably a bisphenol compound having two epoxy groups represented by the following formula (1-1), or a formula The bisphenol compound having two epoxy groups shown in (1-2) is a polymer obtained by polymerizing a monomer:

In the formulae (1-1) and (1-2), 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; and B 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; M1 may represent an integer of 1 to 10, more preferably an integer of 1 to 2.

The bisphenol compound having two epoxy groups represented by the formula (1-1) is particularly preferably a bisphenol compound having two epoxy groups represented by the following formula (1-3).

In the formula (1-3), 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.

The bisphenol compound having two epoxy groups represented by the formula (1-3) is, for example, a reaction of a bisphenol fluorene and an epihalohydrin having two epoxy groups. Bisphenolphthalein type compound.

Specific examples of the bisphenol quinoid type compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methyl Phenyl) 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene [9,9-bis(4-hydroxy-) 3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis (4- 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methyl) 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9- Bis(4-hydroxy-3,5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)indole [9,9-bis(4-hydroxy-3,5- Dichlorophenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene or a combination of the above compounds.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxyhydrin, 3-bromo-1,2-epoxyhydrin (epibromohydrin) or a combination of the above compounds.

Specific examples of the bisphenol quinoid compound having an epoxy group include (1) a product manufactured by Nippon Steel Chemical Co., Ltd.: ESF-300 or the like; (2) a product manufactured by Osaka Gas: for example, PG-100, EG- 210 or an analogue thereof; or (3) a product manufactured by SMS Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.

The compound (a-1-ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is at least one compound selected from the group consisting of acrylic acid, methacrylic acid, and 2-methyl propylene hydride. 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutylsuccinic acid, 2-methylpropenyloxyethyl adipate, 2-methylpropenyloxybutylene Acid, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methylpropene oxime Oxybutyl butyl maleic acid, 2-methyl propylene methoxy succinic acid, 2-methyl propylene oxypropyl adipate, 2-methyl propylene oxypropyl tetrahydro phthalic acid, 2 -Methyl propylene oxime propyl phthalate, 2-methyl propylene oxy butyl phthalic acid, or 2-methyl propylene oxy butyl hydrogen phthalic acid; a compound obtained by reacting an acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, phthalic acid; Group of (meth) acrylate with a carboxylic acid anhydride half-ester compound obtained by reaction of a compound wherein hydroxyl group-containing The (meth) acrylate includes, but is not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Acrylate [(2-hydroxypropyl)acrylate], 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutylmethyl Acrylate [(4-hydroxybutyl)methacrylate], or pentaerythritol trimethacrylate, and the like. 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 below and other dicarboxylic acids described below 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.

The tetracarboxylic acid or its acid dianhydride (a-2) includes a tetracarboxylic acid containing a fluorine atom or an acid dianhydride (a-2-1), in addition to the fluorine atom-containing tetracarboxylic acid or its acid dianhydride. A tetracarboxylic acid other than (a-2-1) or an acid dianhydride (a-2-2) thereof, or a combination of the two.

The tetracarboxylic acid containing a fluorine atom or its acid dianhydride (a-2-1) is selected from the group consisting of a fluorine atom-containing tetracarboxylic acid compound represented by formula (2-1) and a fluorine atom represented by formula (2-2). a group of tetracarboxylic dianhydride compounds. Specifically, the fluorine atom-containing tetracarboxylic acid compound represented by the formula (2-1) and the fluorine atom-containing tetracarboxylic dianhydride compound represented by the formula (2-2) are as follows.

In the formulae (2-1) and (2-2), L ² is a tetravalent aromatic group having fluorine, and preferably has a benzene ring. Specifically, it is preferably one selected from the group consisting of the formula (L-1) to the formula (L-6).

In the formulae (L-1) to (L-6), E each independently represents a fluorine atom or a trifluoromethyl group; and * represents a position bonded to a carbon atom.

More specifically, specific examples of the fluorine-containing tetracarboxylic acid or its acid dianhydride (a-2-1) include 4,4'-hexafluoroisopropylidene diphthalic acid (4,4'-hexafluoro). Isopropylidene diphthalic acid), 1,4-difluoropyromellitic acid, 1-monofluoropyromellitic acid, 1,4-bis(trifluoromethyl) A fluorine-containing aromatic tetracarboxylic acid such as 1,4-ditrifluoromethylpyromellitic acid, a dianhydride compound of the above tetracarboxylic acid, or a combination of the above compounds.

Specific examples of the fluorine atom-containing tetracarboxylic acid or its acid dianhydride (a-2-1) further include 3,3'-hexafluoroisopropylidenephthalic acid (3,3'-(hexafluoroisopropylisopropylene). Diphthalic acid), 5,5'-[2,2,2-trifluoro-1-[3-(trifluoromethyl)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] bisphthalic 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)benzenedicarboxylic acid (3,6-bis(trifluoromethyl)pyromellitic acid), 4-(trifluoromethyl)pyromellitic acid, 1,4-bis(3,4-dicarboxylic acid trifluoride) A fluorine-containing tetracarboxylic acid such as 1,4-bis(3,4-dicarboxylic acid trifluorophenoxytetrafluorobenzene), a dianhydride compound of the above tetracarboxylic acid, or a combination of the above compounds.

The other tetracarboxylic acid or its acid dianhydride (a-2-2) includes a saturated linear hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, a dianhydride compound of the above tetracarboxylic acid, or a combination thereof. .

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

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

Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylphosphonium tetracarboxylic acid, 1, 2,3,6-tetrahydrophthalic acid, or a combination of the above compounds. The aromatic tetracarboxylic acid may also have a substituent.

The dicarboxylic acid or its anhydride (a-3) includes a dicarboxylic acid containing a fluorine atom or an anhydride thereof (a-3-1), in addition to the above-mentioned dicarboxylic acid containing a fluorine atom or an anhydride thereof (a-3-1) Other dicarboxylic acids, anhydrides thereof (a-3-2), or a combination of the two.

The dicarboxylic acid containing a fluorine atom or an acid anhydride thereof (a-3-1) is selected from the group consisting of a fluorine atom-containing dicarboxylic acid compound represented by formula (3-1) and a fluorine atom-containing compound represented by formula (3-2). A group consisting of carboxylic anhydride compounds. Specifically, the fluorine atom-containing dicarboxylic acid compound represented by the formula (3-1) and the fluorine atom-containing dicarboxylic acid anhydride compound represented by the formula (3-2) are as follows:

In the formula (3-1) and the formula (3-2), X ¹ represents an organic group of a fluorine atom having 1 to 100 carbon atoms.

Specific examples of the fluorine-containing dicarboxylic acid or its anhydride (a-3-1) include 3-fluorophthalic acid, 4-fluorophthalic acid, and tetra Tetrafluorophthalic acid, 3,6-difluorophthalic acid, tetrafluoro succinic acid, an acid anhydride compound of the above dicarboxylic acid, or the above compound The combination.

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

Specific examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, sebacic acid, Citramalic acid, malonic acid, glutaric acid, citric acid, and tartaric acid. , oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or a 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 include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and hexahydrotrimellitic acid. Or a combination of the above compounds. The saturated cyclic hydrocarbon dicarboxylic acid may also be a saturated hydrocarbon-substituted alicyclic dicarboxylic acid.

Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and methyl endo-methylene tetrahydro phthalic acid. , chlorendic acid, partial benzene Triacid, or a combination of the above compounds.

Specific examples of the other dicarboxylic acid or its anhydride (a-3-2) include trimethoxydecylpropyl succinic anhydride, triethoxydecyl propyl succinic anhydride, and methyl dimethoxy decyl propyl acrylate. Butane dianhydride, methyldiethoxydecyl succinic anhydride, trimethoxydecyl butyl succinic anhydride, triethoxy decyl butyl succinic anhydride, methyl diethoxy decyl Butyl succinic anhydride, p-(trimethoxydecyl)phenyl succinic anhydride, p-(triethoxydecyl)phenyl succinic anhydride, p-(methyldimethoxydecyl)phenyl butyl 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 a combination of the above compounds.

The dicarboxylic acid compound is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid or a combination of the above compounds, more preferably succinic acid. , 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 a 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) containing 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 above-mentioned alkali-soluble resin (A-1), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. Specific examples of the above reaction catalyst include triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride. , benzyltriethylammonium chloride or a combination of the above reaction catalysts. The above counter The catalyst may be used singly or in combination.

Further, in order to control the degree of polymerization, an inhibitor is usually added to the reaction solution. Specific examples of the above polymerization inhibitor 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 can be used singly or in combination of two or more.

In the preparation of the above alkali-soluble resin (A-1), a polymerization solvent can be used as necessary. Specific examples of the above polymerization solvent include: alcohol compounds of ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, ethylene glycol or the like; methyl ethyl ketone, cyclohexyl a ketone compound of a ketone or an analogue thereof; an aromatic hydrocarbon compound of toluene, xylene or the like; a cellosolve of celecin, butyl cellosolve or the like a compound; a carbitol compound of carbitol, butyl carbazine or the like; a propylene glycol alkyl ether compound of propylene glycol monomethyl ether or the like; dipropylene glycol monomethyl ether (di(propylene glycol) methyl) Poly(propylene glycol alkyl ether) compound of ether or its analogue; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate Acetate compound of propylene glycol methyl ether acetate, propylene glycol methyl monoether acetate or the like; ethyl lactate, butyl lactate An alkyl lactate compound of the same; or a dialkyl glycol ether; or methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethyl ethoxyacetate, etc. Other esters. The above polymerization solvent may be used singly or in combination of two or more. Further, the acid value of the above alkali-soluble resin (A-1) is from 50 mgKOH/g to 200 mgKOH/g, preferably from 60 mgKOH/g to 180 mg KOH / g.

Further, a known method of reacting a diol compound with a tetracarboxylic dianhydride at a reaction temperature of 90 ° C to 140 ° C can be employed, for example, as described in JP-A-H09-325494. Further, the first mixture is uniformly dissolved and allowed to react at a reaction temperature of from 90 ° C to 130 ° C, followed by carrying out the reaction and aging at a reaction temperature of from 40 ° C to 80 ° C.

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

On the other hand, among the respective components of the first mixture forming the alkali-soluble resin (A-1), among the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its anhydride (a-3), At least one of them contains a fluorine atom, and it is preferred that the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its anhydride (a-3) contain a fluorine atom. When the tetracarboxylic acid or its acid dianhydride (a-2) or the dicarboxylic acid or its anhydride (a-3) does not contain a fluorine atom, the resolution of the photosensitive resin composition is not good. In particular, when the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its anhydride (a-3) both contain a fluorine atom, the tetracarboxylic acid or its acid dianhydride (a-2) includes a tetracarboxylic acid containing a fluorine atom or an acid dianhydride thereof (a-2-1), and the dicarboxylic acid or its anhydride (a-3) includes a dicarboxylic acid containing a fluorine atom or an anhydride thereof (a-3-1) .

Since the fluorine atom can effectively improve the alkali resistance of the alkali-soluble resin (A), the development resistance of the photosensitive resin composition is further improved. Further, due to the development resistance of the photosensitive resin composition, a finer pattern can remain on the substrate during development, and the resolution of the photosensitive resin composition can be improved.

Further, the molar number of the diol compound (a-1) containing a polymerizable unsaturated group, the molar number of a fluorine atom-containing tetracarboxylic acid or its acid dianhydride (a-2-1), and a fluorine atom-containing group 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 resolution of the photosensitive resin composition can be further improved.

The first base is used based on 100 parts by weight of the alkali-soluble resin (A). The soluble resin (A-1) is used in an amount of 20 to 100 parts by weight; preferably 25 to 90 parts by weight; more preferably 30 to 80 parts by weight. When the first alkali-soluble resin (A-1) is not used, the resolution and the taper angle of the photosensitive resin composition are not good.

The alkali-soluble resin according to the present invention may optionally include a second alkali-soluble resin (A-2) and other alkali-soluble resins (A-3).

The second alkali-soluble resin (A-2) includes a derivative unit having the formula (4):

In the formula (4), R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom.

The second alkali-soluble resin (A-2) is obtained by reacting a compound represented by the formula (4) with another compound which can be copolymerized. The compound represented by the formula (4) may be a bisphenol quinoid compound containing two epoxy groups represented by the following formula (5) or a bisphenol quinoid compound containing two hydroxyl groups represented by the formula (6). .

In the formula (5), with the same formula R R ⁴ (4) ^2; R R ⁵ the same as in the formula (4) ^3.

In the formula (6), the same as R R ⁶ in the formula (4) ^2; R R ⁷ the same as in the formula (4) ^3; R ⁸ and R ⁹ each independently represent an alkylene group or a carbon number of 1 to 20 extending aliphatic Ring group; p and q each independently represent an integer from 1 to 4.

Specific examples of other copolymerizable compounds include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, itaconic acid, and succinic acid. , phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methyl hexahydrophthalic acid, methyl endomethyltetrahydrophthalic acid (methyl endo- Methylene tetrahydro phthalic acid), dicarboxylic acids such as chlorendic acid and glutaric acid and their anhydrides; tricarboxylic acids such as trimellitic acid and their anhydrides; and pyromellitic Acid), tetracarboxylic acid such as benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenylether tetracarboxylic acid, acid anhydride thereof or the like combination.

The second alkali-soluble resin (A-2) is preferably manufactured by Nippon Steel Chemical Co., Ltd. under the trade name of V259ME, V301ME, and the like.

The second alkali-soluble resin (A-2) is used in an amount of from 0 to 80 parts by weight, based on the amount of the alkali-soluble resin (A), and is preferably from 10 to 75 parts by weight; more preferably from 20 to 30 parts by weight. 70 parts by weight.

The other alkali-soluble resin (A-3) is the first alkali-soluble resin (A-1) and A resin other than the second alkali-soluble resin (A-2). The other alkali-soluble resin (A-3) is, for example, a resin having a carboxylic acid group or a hydroxyl group, but is not limited to a resin having a carboxylic acid group or a hydroxyl group. Specific examples of the other alkali-soluble resin (A-3) include resins such as an acrylic resin, a urethane resin, and a novolac resin.

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

The photosensitive resin composition according to the present invention contains a compound (B) having an ethylenically unsaturated group.

The compound (B) having an ethylenically unsaturated group according to the present invention may be selected from a compound having one ethylenically unsaturated group or a compound having two or more (including two) ethylenically unsaturated groups.

Specific examples of the aforementioned compound having one ethylenically unsaturated group include (meth)acrylamide, (meth)acryl morpholine, and (meth)acrylic acid-7-amino group- 3,7-Dimethyloctyl, isobutoxymethyl(meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid 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, nitrogen, nitrogen-dimethyl ( Methyl) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromobenzene (meth)acrylate Ester, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxy-(meth) propylene Ethyl ester, propyl 2-hydroxy-(meth)acrylate, vinyl caprolactam, nitrogen-vinylpyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, Pentabromophenyl methacrylate, poly Ethylene (meth) acrylate, poly (mono) (meth) acrylate, methacrylate (meth) acrylate, and the like. The above compound having one ethylenically unsaturated group may be used singly or in combination of two or more.

Specific examples of the compound having two or more (including two) ethylenically unsaturated groups include ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, and triethylene glycol di (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(methyl) acrylate trimethylol propyl ester, ethylene oxide ( Ethylene oxide, EO) modified trimethylolpropyl tris(meth)acrylate, propylene oxide (PO) modified tris (tri)methyl trimethacrylate, tripropylene glycol di Methyl) acrylate, neopentyl glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, pentaerythritol III (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta(meth) acrylate, Dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, tetra(meth) acrylate tris Di(trimethylolpropane)tetra(meth)acrylate, epoxide-modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(methyl) Acrylate, ethylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified Triglyceride (meth) acrylate, ethylene oxide modified bisphenol F di(meth) acrylate, novolak polyglycidyl ether (meth) acrylate or the like, or a combination thereof . The above compound having two or more (including two) ethylenically unsaturated groups may be used singly or in combination of two or more.

Specific examples of the above compound (B) having an ethylenically unsaturated group include: Trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified with ethylene oxide, trimethylolpropyl triacrylate modified with propylene oxide, pentaerythritol triacrylate, pentaerythritol tetraacrylate Ester, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropyl methacrylate, propylene oxide modified glycerol Triacrylate or an analog thereof, or a combination of the above compounds.

The compound (B) having an ethylenically unsaturated group is preferably trimethylolpropyl triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or a combination of the above compounds.

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

The photoinitiator (C) of the present invention comprises the α-ketoxime compound (C-1) represented by the formula (7):

R ¹⁰ represents a methylphenyl group having 1 to 5 methyl groups, and a specific example thereof is , or And R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, a benzyl fluorenyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Preferably, the aforementioned alkyl group may be, for example, a methyl group; R ¹² represents a methyl group, an ethyl group, a propyl group or a benzamidine group, wherein an ethyl group is preferred; and R ¹³ represents a -H group. , , , , Wherein a represents methyl or ethyl; and b represents -H or methyl.

In a preferred embodiment of the present invention, the α-ketooxime ester compound (C-1) represented by the formula (7) includes a structure represented by the following formulas (7-1) to (7-12):

In a specific example of the present invention, the α-ketooxime ester compound (C-1) represented by the formula (7) is obtained by the following reaction: first, an oxazole compound or a ruthenium chloride compound (acyl) Chloride) and n-methyl phenyl acyl chloride are sequentially placed in the presence of aluminum chloride, and the reaction can give a mercapto compound which is catalyzed by a base catalyst. The α-ketooxime compound is reacted with isoamyl nitrite; then, the α-ketooxime compound is reacted with a ruthenium chloride compound under the catalysis of a triethylamine catalyst to obtain the above formula (7). The α-ketooxime ester compound shown.

The α-ketooxime ester compound (C-1) having a structure represented by the formula (7) is used in an amount of 10 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably 12 to 65 parts by weight; more preferably 15 to 60 parts by weight. When the α-ketooxime ester compound (C-1) represented by the formula (7) is not used, the resolution and the taper angle of the photosensitive resin composition are not good.

In a preferred embodiment of the present invention, the photoinitiator (C) of the present invention further comprises a photoinitiator (C-2), which may include, but is not limited to, an embodiment of the present invention. O-mercapto lanthanide compound, triazabenzene compound, acetophenone compound, diimidazole compound, benzophenone compound, α-diketone compound, keto alcohol compound, keto alcohol ether The compound, the phosphonium oxide compound, the anthraquinone compound, the halogen-containing compound, the peroxide, and the like are described below.

Specific examples of the above O-indenyl lanthanide compound are: 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1 -(4-(phenylthio)phenyl)-octane-1,2-dione-2-indole-oxy-benzoate (for example, OXE-01 manufactured by Ciba Specialty Chemicals), 1-[4 -(phenylhydrazino)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1-[9-ethyl-6-(2-methylbenzhydryl) -9 hydrogen-carbazole-3-substituted]-1-(oxy-acetamidine) (for example, OXE-02 manufactured by Ciba Specialty Chemicals), 1-[9-ethyl-6-(3-methylbenzene) Mercapto)-9H-carbazole-3-substituted]-ethanone 1-(O-acetamidoxime), 1-[9-ethyl-6-benzoin-9H-carbazole-3- Substituent]-ethane ketone 1-(O-ethenyl hydrazine), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylphenyl fluorenyl)-9H-indole Zyridin-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylphenyl) -9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylphenyl) )-9H-carbazole-3-substituted]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyran) Benzo hydrazino)-9H-carbazole-3-substituted]-1-(O-ethenyl) Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-indazole-3-substituted]-1-(O-) Ethyl hydrazide), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl)-9H-carbazole-3- substituent ]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxyphenyl)-9H-carbazole- 3-Substituent]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenyl) )-9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2 - dimethyl-1,3-dioxolanyl)phenylhydrazinyl}-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[ 9-ethyl-6-{2-methyl-4- (2,2-Dimethyl-1,3-dioxolanyl)methoxybenzoinyl}-9H-indazole-3-substituted]-1-(O-ethylindenyl), etc. .

The aforementioned O-indenyl lanthanide compound is 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinyl)[OXE 01], 1 -[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazole-3-substituted]-ethanone 1-(O-ethylindenyl)[OXE 02], ethane Keto-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxyphenyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl) Ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoquinone} -9H-carbazole-3-substituted]-1-(O-ethylindenyl) and the like are preferred. The above O-indenyl lanthanide compounds may be used singly or in combination of plural kinds, depending on actual needs. If the O-mercaptoquinone-based compound is not used at all, the resulting photosensitive resin composition has a drawback that the adhesion after development is poor.

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

Specific examples of the aforementioned vinyl-halomethyl-s-triazabenzene compound are: 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triaza Benzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloro Methyl-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 are: 2-(naphtho-1-substituted)-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazole Heterobenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-butoxy-naphtho -l-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-yl]-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphthyl-1-substituted]-4,6-bis-trichloromethyl Base-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, 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 are: 4-[p-N,N-di(ethoxy) Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(ethoxycarbonyl) 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-bis(chloroethyl)aminophenyl]-2,6-di(three Chloromethyl)-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)amine Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloromethane) -s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-di(trichloromethyl)-s-triaza Benzene, 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[inter- Bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6- (trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl) -s-triazabenzene, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-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-triazabenzene, 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-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m- Bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N, N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-di(chloroethane) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)- 2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloro) Methyl)-s-triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole Benzene, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o- Chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxylate Carbocarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m- Bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-chloroethylamino group Phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(three Chloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-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, 2,4-bis(trichloromethyl)-6-[3-bromo-4- [N,N-Bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene and the like.

The aforementioned triazabenzene compound is 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s Triazine, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene and the like are preferred. The above-mentioned triazabenzene compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above-mentioned acetophenone compounds are: p-dimethylaminophenone, α,α'-dimethoxyoxyazopropenone, 2,2'-dimethyl-2- Phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propane Ketone, 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone and the like. The aforementioned acetophenone compound is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propanone, 2-benzyl-2-N,N- Dimethylamine-1-(4-morpholinophenyl)-1-butanone or the like is preferred. The above-mentioned acetophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above diimidazole compounds are: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o- Fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4 , 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(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 Wait. The above second imidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole. The above-mentioned diimidazole compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above benzophenone compounds are: thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4'-bis(dimethyl Amine) benzophenone, 4,4'-bis(diethylamine) benzophenone, and the like. The aforementioned benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone. The above benzophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.

Specific examples of the above-mentioned α-diketone compound are benzoin, ethenyl and the like. A specific example of the above ketone alcohol compound is benzophenone. Specific examples of the above ketol ether compound are benzophenone methyl ether, benzophenone ethyl ether, and diphenylethanol ketone isopropyl ether. Specific examples of the above fluorinated phosphonium oxide compound are: 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, bis-(2,6-dimethoxybenzoquinone)-2,4, 4-trimethylphenylphosphine oxide or the like. Specific examples of the above terpenoids are: hydrazine, 1,4-naphthoquinone, and the like. Specific examples of the above halogen-containing compound are: benzoquinone methyl chloride, tribromomethylphenylhydrazine, and tris(trichloromethyl) Base)-s-triazabenzene and the like. 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, phosphine oxide compound, quinone compound, halogen-containing compound, peroxide, or the like may be used singly or in combination of plural kinds. Depending on actual needs.

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

The solvent (D) suitable for the present invention is a compound (B) capable of dissolving the alkali-soluble resin (A), having an ethylenically unsaturated group, a photoinitiator (C), a black pigment (E), and a thermal initiator (F). It is preferred that it does not react with the above components and has a suitable volatility.

Specific examples of the aforementioned 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 triethyl ethane. 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 single An alkyl glycol monoalkyl ether compound such as methyl ether or tripropylene glycol monoethyl ether; an alkyl glycol monoalkane such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate or propylene glycol diethyl ether acetate Ether acetate compound; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether or tetrahydrofuran and other ether compounds; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone Or a ketone compound such as diacetone alcohol; an alkyl lactate compound such as methyl lactate or ethyl lactate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3 Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate , n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvate Other ester compounds such as ester, n-propyl pyruvate, methyl acetate, ethyl acetate or ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene or xylene; N-methylpyrrolidone a carboxylic acid amine compound such as N,N-dimethylformamide or N,N-dimethylacetamide; or any combination thereof. The aforementioned solvent (D) can be generally used singly or in combination of plural kinds.

The solvent (D) is used in an amount of from 1,000 to 8,000 parts by weight, based on the amount of the alkali-soluble resin (A), preferably from 1200 to 7,000 parts by weight; more preferably from 1,500 to 6,000 parts by weight.

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

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

The black pigment (F) is used in an amount of from 140 parts by weight to 1200 parts by weight, based on the amount of the alkali-soluble resin (A), preferably from 170 to 1100 parts by weight; more preferably from 200 to 1,000 parts by weight. .

The thermal initiator (F) of the present invention is not particularly limited, and in one embodiment of the present invention, it may include, but is not limited to, an azo compound, an organic peroxide, a hydrogen peroxide compound, and the like.

A specific example of the above azo compound is: 2,2'-azobisisobutyronitrile [2,2'- Azobis(isobutyronitrile), 2,2'-azobis-2-methylbutyronitrile, 1,1'-azobis(cyclohexane-2- [1,1'-azobis(cyclohexane-1-carbonitrile)], 2,2'-azobis(2,4-dimethylvaleronitrile)[2,2'-azobis(2,4- Dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl)azo]carbamamine {1-[(1-cyano-1-methylethyl)azo]formamide}, 2,2-azo {2-Methyl-nitro-[1,1-di(hydroxymethyl)-2-hydroxyethyl]propanamine {2,2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl) )-2-hydroxyethyl]propionamide}, 2,2'-azobis[nitro-(2-propenyl)-2-methylpropionamide]{2,2'-azobis[N-(2-propenyl) -2-methylpropionamide], 2,2'-azobis[nitro-(2-propenyl)-2-ethylpropionamide]{2,2'-azobis[N-(2-propenyl)-2- Ethyl propionamide], 2,2'-azobis(nitro-butyl-2-methylpropionamide) {2,2'-azobis(N-butyl-2-methylpropionamide)}, 2,2'-even 2,2'-azobis(N-cyclohexyl-2-methyl propionamide), 2,2'-azobis(dimethyl-2-) [2,2'-azobis(dimethyl-2-methyl propionamide)], 2,2'-azobis(dimethyl) -2-methylpropionate [2,2'-azobis(dimethyl-2-methylpropionate)] or 2,2'-azobis(2,4,4-trimethylpentene) [2,2 '-azobis (2, 4, 4-trimethyl pentene)] and the like.

Specific examples of the above organic peroxides include: benzamidine peroxide, dibutylbutyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1 ,3,3-tetramethylbutyl peroxyneodecanoate, di(4-tert-butylcyclohexyl)peroxydicarbonate [di(4- T-butyl cyclohexyl)peroxydicarbonate], 1-cyclohexyl-1-methylethyl peroxyneodecanoate, bis(2-ethoxyethyl)peroxydicarbonate [di(2-ethoxy- Ethyl)peroxydicarbonate], di(2-ethylhexyl)peroxydicarbonate, t-hexyl peroxyneodecanoate, dimethoxybutyl Dimethoxybutyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxidation T-butyl peroxypivalate, di(3,5,5-trimethyl hexanoyl)peroxide, di-n-peroxide -octanoyl peroxide), dilauroyl peroxide, distearoyl peroxide, 2-ethylperoxyhexanoic acid-1,1,3,3-tetramethylbutyl ester (1 , 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate), 2,5-dimethyl-2,5-di(2-ethylhexanoic acid peroxy)hexane [2,5-dimethyl-2,5- Di(2-ethylhexanoylperoxy)hexane], 2-ethylhexylperoxy-2-ethylhexanoate, di(4-methylbenzoyl) Peroxide], 2-ethylperoxyhexanoic acid T-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1,1-di(t-butyl 1,1-di(t-butylperoxy-2-methylcyclohexane), 1,1-di(t-butylperoxy)-3,3,5-trimethyl Cyclohexane [1,1-di(t-hexyl peroxy)-3,3,5-trimethylcyclohexane], 1,1-di(trihexylperoxy)cyclohexane [1,1-di(t-hexyl) Peroxy)cyclohexane], 1,1-di(t-butylperoxycyclohexane), 2,2-di[4,4-di(third) (2,2-di[4,4-di(t-butylperoxy)cyclohexyl] propane}, t-hexyl peroxy isopropyl monocarbonate, T-butylperoxy maleate, t-butyl peroxy-3,5,5-trimethyl hexanoate , t-butyl peroxy laurate, 2,5-dimethyl-2,5-di(3-methylbenzamide Oxidized hexane [2,5-dimethyl-2,5-di-(3-methyl benzoyl peroxy)hexane], t-butyl peroxy isopropyl monocarbonate, third butyl T-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxy benzoate, 2,5-dimethyl-2, 5-(2-dimethyl-2,5-di(benzoyl peroxy)hexane, t-butyl peroxy acetate, 2,2 -2,2-di(t-butylperoxy)butane, t-butyl peroxybenzoate, butyl-4,4 -2 (n-butyl-4,4-di(t-butylperoxy)valerate], di(2-tert-butylperoxyisopropyl)benzene [di(2- T-butyl peroxy isopropyl)benzene], dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di Tributyl peroxy hexane [2,5-dimethyl-2,5-di(t-butyl peroxy)hexane], di-t-butyl peroxide, 2,5- Dimethyl -2,5-di(t-butylperoxy)hexyne [2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3], tert-butyltrimethylperoxydecane (t -butyl trimethylsilyl peroxide), di(3-methylbenzoyl)peroxide [di(3-methylbenzoyl)peroxide] and benzamidine (3-methylpropionamyl) peroxide [benzoyl ( A mixture of 3-methylbenzoyl)peroxide and dibenzoyl peroxide.

Specific examples of the above hydrogen peroxide compound are: p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydrogen peroxide (1,1,3,3-tetramethyl butyl hydroperoxide), cumene hydroperoxide, t-butyl hydroperoxide, and the like.

The aforementioned thermal initiator (F) is 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis (2, 4-dimethylvaleronitrile), diisobutylphosphonium peroxide, peroxygen Dibenzoyl hydrazine, tert-butyl peroxyisobutyrate, cumene hydroperoxide, cumene peroxynonanoate, and the like are preferred. The above thermal initiators (F) may be used singly or in combination of plural kinds, depending on actual needs.

In one embodiment of the present invention, the amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the hot start agent (F) is from 4 parts by weight to 40 parts by weight; preferably from 5 to 35 parts by weight. Parts by weight; more preferably 6 to 30 parts by weight. When the thermal initiator (F) is used, the resolution of the photosensitive resin composition can be further improved.

The photosensitive resin composition of the present invention may be further optionally further added with an additive (G) including, but not limited to, a surfactant, a filler, a adhesion promoter, a bridging agent, and an anti-aging agent, without affecting the efficacy of the present invention. An oxidizing agent, an anti-agglomerating agent, or a polymer other than the alkali-soluble resin (A) which can increase various properties such as mechanical properties.

The surfactant may be selected from the group consisting of cationic, anionic, nonionic, amphoteric, polyoxyalkylene, fluorosurfactant or any combination thereof. Further, the aforementioned surfactant may include, but is not limited to, polyethoxylated alkyl ethers such as polyethoxydodecyl ether, polyethoxylated oxime ether or polyethoxylated oleyl ether; Polyethoxylated alkylphenyl ethers such as ethoxyoctylphenyl ether or polyethoxylated nonylphenyl ether; polyethylene glycol such as polyethylene glycol dilaurate or polyethylene glycol distearate Diol diesters; sorbitan fatty acid esters; fatty acid modified polyesters; and tertiary amine modified polyurethanes. The above surfactants may be used singly or in combination of plural kinds.

Specific examples of suitable surfactants include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (made by Dow Corning Dongli Polyxanthate Co., Ltd.), Polyflow (manufactured by Kyoei Oil & Fat Chemical Industry Co., Ltd.), F-Top (Tochem Product) Co., Ltd., Megafac (manufactured by Dainippon INK Chemical Industry Co., Ltd.), Fluorade (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), or SINOPOL E8008 (manufactured by Nippon Synthetic Chemical Co., Ltd.).

Specific examples of suitable fillers are, for example, glass or aluminum.

Specific examples of suitable adhesion promoters are, for example, vinyl trimethoxy decane, Vinyl triethoxy decane, vinyl tris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidylpropyltrimethoxydecane, 3-epoxypropanol Propylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxy Decane, 3-methylpropoxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane.

Specific examples of suitable antioxidants are, for example, 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol.

Specific examples of suitable anti-agglomerating agents are, for example, sodium polyacrylate.

Specific examples of suitable bridging agents include epoxy compounds such as 1031S and 157S-70 manufactured by Nippon Epoxy Co., Ltd., and resins.

The content of the polymer other than the filler, the adhesion promoter, the antioxidant, the anti-aggregation agent, or the alkali-soluble resin (A) in the additive (G) is 100 parts by weight based on the amount of the alkali-soluble resin (A). It is 10 parts by weight or less, preferably 6 parts by weight or less.

The content of the surfactant in the additive (G) is 6 parts by weight or less, preferably 4 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin (A).

The content of the bridging agent in the additive is 100 parts by weight or less, preferably 80 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin (A).

The photosensitive resin composition of the present invention generally comprises the above-mentioned alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a black pigment (E). And the hot initiator (F) is placed in a stirrer and stirred to uniformly mix into a solution state, and if necessary, a surfactant, a filler, a adhesion promoter, a bridging agent, an antioxidant, an anti-agglomerating agent, etc. may be added. The additive (G) is uniformly mixed to prepare a photosensitive resin composition in a solution state.

Secondly, the preparation method of the photosensitive resin composition of the present invention is not particularly By way of example, the black pigment (E) may be directly dispersed in the photosensitive resin composition, or a part of the black pigment (E) may be dispersed in a part of the alkali-soluble resin (A) and the solvent ( In the medium of D), after the pigment dispersion is formed, the compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a hot starter (F), an alkali-soluble resin (A), and a solvent are further mixed. Made from the rest of (D). The dispersion step of the above black pigment (E) can be carried out by mixing the above components by a mixer such as a beads mill or a roll mill.

The present invention also provides a black matrix formed of the aforementioned photosensitive resin composition.

The black matrix is obtained by sequentially pre-baking, exposing, developing, and post-baking the photosensitive resin composition as described above, wherein the optical density of the black matrix is in a film thickness of 1 μm. 3.0 or more. Preferably, the optical density of the black matrix ranges from 3.2 to 5.5 at a film thickness of 1 μm; more preferably, the optical density of the black matrix ranges from 3.5 to 5.5 at a film thickness of 1 μm.

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. The conditions for the drying under reduced pressure and the pre-baking are different depending on the type and blending ratio of each component. Usually, the drying under reduced pressure is carried out at a pressure of less than 200 mmHg for 1 second to 20 seconds, and the pre-baking treatment is performed at It 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 exposed to a designated mask, and then immersed in a developer at a temperature of 23±2° C. for 15 seconds to 5 minutes to remove unnecessary portions to form a specific one. 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 are: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia Water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0 a basic compound such as 7-undecene. The concentration of the developer is generally from 0.001% by weight (% 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, and then post-baked by a heating device such as a hot plate or an oven. The post-baking temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 60 minutes, and the heating time in 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: alkali-free glass, soda-lime glass, hard glass (Pyrus glass), 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 device.

The present invention further provides a color filter comprising the aforementioned black matrix.

The method for forming a color filter of the present invention can be applied to a color filter prepared by mixing the solution into a solution state by a coating method such as rotary coating, cast coating or roll coating. On the substrate, wherein the substrate has previously formed a black matrix separating the pixel colored layers by using the aforementioned photosensitive resin composition. After coating, most of the solvent is removed by drying under reduced pressure, and the solvent is removed by pre-bake to form a pre-baked coating film. Among them, the conditions of drying under reduced pressure and pre-baking vary depending on the type of each component and the blending ratio. Usually, the drying under reduced pressure is carried out at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the pre-bake is at 70. It is carried out at a temperature of from ° C to 110 ° C for 1 minute to 15 minutes. After pre-baking, the pre-baked coating film is exposed between the designated masks, and is immersed in the above-mentioned developing solution at a temperature of 23±2° C. for 15 seconds to 5 minutes for development, and is not partially removed to form pattern. For the light used for exposure, it is better to use ultraviolet rays such as g-line, h-line, and i-line. The ultraviolet device can be a (super) high pressure mercury lamp and a metal halide lamp.

After the above-mentioned development, it is washed with water, and the pattern is air-dried by compressed air or compressed nitrogen, and then subjected to post-baking treatment by a heating device such as a hot plate or an oven. The conditions of the post-baking treatment are as described above, and are not 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, an indium tin oxide (ITO) vapor-deposited film is formed on the pixel layer in a vacuum environment at a temperature of 220 ° C to 250 ° C, and if necessary, the ITO coating film is subjected to etching and wiring, and then the liquid crystal alignment film is coated with a polymerized film. The imine, which is further fired, can be used as a color filter for a liquid crystal display element.

The present invention further provides a liquid crystal display element comprising the aforementioned color filter.

The liquid crystal display device of the present invention is a color filter substrate formed by the method for producing a color filter, and a driving substrate provided with a thin film transistor (TFT), between the two substrates The intervening gap (cell gap) is disposed oppositely, and the peripheral portions of the two substrates are bonded together with a sealing agent, and the liquid crystal is filled in the gap between the surface of the substrate and the sealing agent to seal the injection hole. A liquid crystal cell is formed. Then, on the outer surface of the liquid crystal cell, that is, on the other side faces of the respective substrates constituting the liquid crystal cell, the polarizing plate is bonded to each other to obtain a liquid crystal display element.

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

Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and any of an inorganic substance or an organic substance may be used. 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 therefore will not be further described.

The invention will be described in detail by the following examples, which are not intended to illustrate It is limited to what is disclosed in these examples.

<Preparation example of diol compound (a-1) containing a polymerizable unsaturated group>

Preparation Example 1: Method for Producing Polymeric Unsaturated Group-Containing Diol Compound (a-1-1)

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 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 mixed solution is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound of Preparation Example 1 having a solid content of 99.9% by weight (a-1- 1).

Preparation Example 2: Method for producing diol compound (a-1-2) containing a polymerizable unsaturated group

100 parts by weight of an antimony epoxy compound (Model PG-100, manufactured by Osaka Gas; Epoxy equivalent 259), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 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 process was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid content of 50% by weight was obtained. The light yellow transparent mixed liquid is subjected to the steps of 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% by weight. .

Preparation Example 3: Production method of diol compound (a-1-3) containing a polymerizable unsaturated group

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 100 parts by weight of 2-methylpropenyl ethoxy succinate, 0.3 parts by weight of chlorine Benzyltriethylammonium, 0.1 parts by weight of 2,6-di-t-butyl group The 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 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 diol compound (a-1-3) of Preparation Example 3 having a solid content of 99.9% by weight.

Preparation Example 4: Process for producing diol compound (a-1-4) containing a polymerizable unsaturated group

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. Thereafter, the reaction system was cooled to room temperature, and 9 mol of benzene and 0.5 mol of sodium hydroxide (30 wt% aqueous solution formed 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 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 liquid 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% by weight. .

Preparation Example 5: Production method of diol compound (a-1-5) containing a polymerizable unsaturated group

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 (30 wt% aqueous solution formed 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)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 is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (a-1-5) having a solid content of 99.9% by weight. .

Preparation Example 6: Method for producing diol compound (a-1-6) containing a polymerizable unsaturated group

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 (30 wt% aqueous solution formed in water) were added with stirring. Then, the temperature was raised to 60 ° C and maintained for 3 hours. Then, repeatedly wash the reaction solution with water until 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 liquid 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% by weight. .

<Synthesis Example of First Alkali-Soluble Resin (A-1)>

Synthesis Example 1:

1.0 mol of a polymerizable unsaturated group-containing diol compound (a-1-1), 0.1 mol of 4,4'-hexafluoroisopropylidene diphthalic 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 mol of tetrahydroortylene Diacetic anhydride (a-3-2-b), 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2,6-di-t-butyl-p-cresol and 750 g of propylene glycol monomethyl ether acetate It was added to a 500 ml four-necked flask at the same time to form a reaction solution. 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 of Synthesis Example 1 having an acid value of 129 mg KOH/g and a number average molecular weight of 2,368 (hereinafter referred to as a first base) Soluble resin A-1-1).

Synthesis Example 2:

1.0 mol of a polymerizable unsaturated group-containing diol compound (a-1-2), 2.0 g of benzyltriethylammonium chloride, 0.7 g of 2,6-di-t-butyl-p-cresol as well as 700 g of propylene glycol methyl ether acetate was 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 of Synthesis Example 2 (hereinafter referred to as first alkali-soluble resin A-1-2) 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:

The first alkali-soluble resin of Synthesis Example 3, Synthesis Example 5, Synthesis Example 7, and Synthesis Example 9 was prepared in the same manner as in Synthesis Example 1, except that the component type and amount of the first alkali-soluble resin were changed. The reaction time, the reaction temperature and the reaction time of the reactants are as shown in Table 1, and are not described here.

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

The first alkali-soluble resin of Synthesis Example 4, Synthesis Example 6, Synthesis Example 8, and Synthesis Example 10 was prepared in the same manner as in Synthesis Example 2 except that the component type and amount of the first alkali-soluble resin were changed. The reaction time, the reaction temperature and the reaction time of the reactants are as shown in Table 1, and are not described here.

<Synthesis Example of Second Alkali-Soluble Resin (A-2)>

Synthesis Example 11

1.0 mol of a polymerizable unsaturated group-containing diol compound (a-1-1), 1.9 g of benzyltriethylammonium chloride, and 0.6 g of 2,6-di-t-butyl-p-cresol Dissolved in 700 g of propylene glycol methyl ether acetate with 0.3 mol of biphenyltetracarboxylic acid (a-2-2-a) and 1.4 mol of maleic acid (a-3-2-a) . Next, heating to 110 ° C and reacting for 2 hours gave a synthesis example 11 having an acid value of 125 mg KOH/g and a number average molecular weight of 2455. The second alkali-soluble resin (hereinafter referred to as a second alkali-soluble resin A-2-1).

Synthesis Example 12 to Synthesis Example 13

The second alkali-soluble resin of Synthesis Example 12 to Synthesis Example 13 was prepared in the same manner as in Synthesis Example 11, and was distinguished by changing the kind of the component of the second alkali-soluble resin and the amount thereof, the reaction time, and the reaction temperature. And the reactant addition time (as shown in Table 2). It should be noted that, "addition at the same time" means adding tetracarboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its anhydride (a-3) at the same reaction time, and "segment addition" </ RTI> 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 or its acid dianhydride (a) -2), followed by the addition of the dicarboxylic acid or its anhydride (a-3).

In Table 1 and Table 2:

<Synthesis Example of Other Alkali Soluble Resin (A-3)>

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, 15 parts by weight of acrylic acid (AA) and 15 parts by weight of 2-hydroxy methacrylate were added. Ethyl ester (HEMA), 10 parts by weight of benzyl methacrylate (BzMA), 60 parts by weight of CF ₉ BuMA, 3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) (AMBN) And 300 parts by weight of diethylene glycol dimethyl 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, another alkali-soluble resin (A-3-1) can be obtained.

Synthesis Example 15 to Synthesis Example 16

The other alkali-soluble resins of Synthesis Example 15 to Synthesis Example 16 were prepared in the same manner as in Synthesis Example 11, and were distinguished by changing the kinds of the components of the other alkali-soluble resin, the amount thereof, the reaction time, the reaction temperature, and the reaction. The addition time (as shown in Table 3), wherein the compounds corresponding to the labels in Table 3 are as follows.

<Synthesis Example of α-Ketone Ester Compound (C-1)>

First, 100 g of 2-(o-tolyl)acetic acid and 237 g of sulfinium chloride were placed under a nitrogen atmosphere, and the temperature was slowly raised to 95 ° C and refluxed for 4 hours. After four hours, the sulphur sulphate is then distilled at the normal temperature and the reactor is cooled to normal temperature, and the residual sulphur sulphide chlorine is removed by a vacuum distillation apparatus, and finally the residual viscous liquid is in petroleum ether. The precipitate was filtered to give 112 g of yellow crystals. The yellow crystal is 2-(o-tolyl)acetyl chloride. The GC purity was 99%; the GC mass spectrum was M/Z = 168.03.

Next, 20 g of N-ethylcarbazole was dissolved in 120 ml of CH ₂ Cl ₂ under a nitrogen atmosphere, and while the reaction was cooled to 0 ° C, 14.07 g of AlCl ₃ was slowly added. Under the condition that the internal temperature was less than 5 ° C, 16.31 g of o-tolylhydrazinyl chloride was slowly added dropwise, and after stirring at room temperature for about 5 hours, when the internal temperature was lowered to less than 0 ° C, 14.07 g of AlCl ₃ was slowly added. Under the condition that the internal temperature is less than 5 ° C, 17.79 g of 2-(o-tolyl)acetamidine chloride is slowly added dropwise, and after stirring at room temperature for about 8 hours, when the internal temperature drops to less than 0 ° C, 300 ml of ice is added. Water was slowly added to the solution in the reactor. After stirring for about 1 hour, the layers were separated and further neutralized with 200 ml of 1% NaOH. After washing, the organic layer was dried with MaSO ₄ and the solvent was removed using a rotary evaporator. After recrystallization from ethyl acetate and dichloromethane, 35 g of a white solid was obtained, yield 77%. The white solid is (1-(9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl)-2-(o-tolyl)ethanone) (1-( 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)-2-(o-tolyl)ethanone).

180 mL of dimethylformamide was placed in the reactor, 30 g of the above white solid was added to the reactor and dissolved, and 1.82 g of sodium methoxide was slowly added to the reaction water at a temperature of 15 ° C to maintain 15 The internal temperature of °C was slowly added to 8.13 g of isoamyl nitrite, then the temperature was raised to 25 ° C, stirred for 8 hours, 200 mL of ethyl acetate solvent and 200 mL of distilled water were added for water washing, and the reaction was carried out twice. after washing with water to remove additional dimethylformamide, and then saturated calcium carbonate, washing, drying the organic layer using MaSO _4, after distillation under reduced pressure to afford a liquid compound. Finally, methanol and dichloromethane were added and recrystallized to obtain 20 g of pale yellow crystals in a yield of 63%. The pale yellow crystal is (E)-1-(9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl)-2-(hydroxyimino)-2 -(o-tolyl)-2-(6-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)-2-(hydroxyimino)-2-(o-tolyl) Ethanone).

Finally, the internal temperature of the reactor was lowered to less than 0 ° C under a nitrogen atmosphere, and 20 g of the above pale yellow crystals, 120 mL of dichloromethane and 4.4 g of triethylamine were added, followed by 3.42 g of ethyl chloroform and A solution of 10 mL of dichloromethane was slowly added to the reactor. After the internal temperature was raised to 10 ° C, the mixture was stirred for 3 hours, and the reaction solution was passed through repeated addition of water, and the organic layer was washed and distilled under reduced pressure to obtain a solid compound. Things. After finally adding ethyl acetate and dichloromethane, it was recrystallized, and after filtration, 17 g of pale yellow solid was obtained, yield 78%. The pale yellow crystal is (E)-2-(ethyloxyimino)-1-(9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl -(E)-2-(acetoxyimino)-1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)-2-(o -tolyl)ethanone), which is an α-ketoxime compound represented by formula (7-1).

Synthesis Example 18 to Synthesis Example 22

The α-ketooxime ester compounds of Synthesis Example 18 to Synthesis Example 22 were prepared in the same manner as in Synthesis Example 17, and were respectively of the formulas (7-2), (7-4), (7-6), (7- 7), α-ketooxime ester compound represented by (7-10)

<Example of Photosensitive Resin>

Example 1

100 parts by weight of the first alkali-soluble resin (A-1-1), 20 parts by weight of trimethylolpropyl triacrylate (B-1), and 10 parts by weight of α represented by the formula (7-1) a ketoxime compound (C-1-1), 140 parts by weight of CIPigment BK7 (E-1), added to 1600 parts by weight of propylene glycol monomethyl ether acetate (D-1), and a shaker ( After shaking well, the photosensitive resin composition of Example 1 was obtained. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 4.

Embodiment 2 to Embodiment 10

The photosensitive resin compositions of Examples 2 to 10 were prepared in the same manner as in Example 1, and were different in that the composition of the photosensitive resin composition and the amount thereof were changed (as shown in Table 4). ), wherein the compounds corresponding to the labels in Table 4 are as follows. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 4.

Comparative Example 1 to Comparative Example 7

The photosensitive resin compositions of Comparative Examples 1 to 7 were prepared in the same manner as in Example 1, and were distinguished by changing the kinds of components of the photosensitive resin composition and the amounts thereof used (as shown in Table 5). ). The obtained photosensitive resin composition was evaluated in the following evaluation manners, and the results are shown in Table 5.

<Evaluation method>

Resolution:

Various photosensitive resin compositions obtained in the examples and the comparative examples were applied onto a glass substrate by spin coating. Next, prebaking at 100 ° C for 2 minutes gave a pre-baked coating film of about 1.2 μm. Then, the above prebaked coating film was placed under a line and space mask (manufactured by Nibbon Filcon, Japan), and ultraviolet light of 50 mJ/cm ² was used (exposure model AG500- 4N; manufactured by M&R Nano Technology) for exposure. Subsequently, development was carried out at 23 ° C for 1 minute in a 0.045% potassium hydroxide aqueous solution to remove the coating film on the unexposed portion of the substrate. Then, the glass substrate having a specific pattern is washed with water. Finally, the minimum value of the line width of the pattern formed on the glass substrate is defined as the resolution. The line amplitude was evaluated in the following manner. It is to be noted that the smaller the minimum pattern line width, the better the resolution of the photosensitive resin composition.

◎: Minimum pattern width ≦ 4μm

○: 4 μm < minimum pattern width ≦ 6 μm

△: 6 μm < minimum pattern width ≦ 8 μm

×: 8 μm < minimum pattern line width

Taper angle:

Various photosensitive resin compositions obtained in the examples and the comparative examples were applied onto a glass substrate by spin coating. Next, prebaking at 100 ° C for 2 minutes gave a pre-baked coating film of about 1.2 μm. Then, the prebaked coating film was placed under a reticle for exposure (exposure model AG500-4N; manufactured by M&R Nano Technology). Subsequently, development was carried out at 23 ° C for 1 minute in a 0.045% potassium hydroxide aqueous solution to remove the coating film on the unexposed portion of the substrate. Then, the glass substrate having a specific pattern was washed with water to obtain a photoresist pattern. The taper angle of the resist pattern was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies) (refer to Fig. 1).

◎: 50 degree ≦ taper angle ≦ 60 degrees

○: 60 degrees < taper angle ≦ 65 degrees or 45 degrees ≦ taper angle < 50 degrees

△: 65 degrees < taper angle ≦ 80 degrees or 30 degrees ≦ taper angle < 45 degrees

×: 80 degrees < taper angle or taper angle < 30 degrees

In Table 4 and Table 5:

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (14)

A photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); and a black pigment (E); The alkali-soluble resin (A) contains the first alkali-soluble resin (A-1) represented by the formula (1): In the formula (1): A represents a phenyl group or a substituted phenyl group having a substituent, wherein the substituent is an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and B 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; ¹ represents a tetravalent carboxylic acid residue containing a fluorine atom or a tetravalent carboxylic acid residue not containing a fluorine atom; Y ¹ represents a divalent carboxylic acid residue containing a fluorine atom or a divalent carboxylic acid residue not containing a fluorine atom And R ¹ represents a hydrogen atom or a methyl group; and m represents an integer of 1 to 20; wherein, at least one of L ¹ and Y ¹ contains a fluorine atom; and the photoinitiator (C) comprises the formula (7) Α-ketooxime ester compound (C-1): In the formula (7): R ¹⁰ represents a methylphenyl group having 1 to 5 methyl groups; R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, a benzyl group or a carbon having 1 to 10 carbon atoms. a number of 3 to 6 cycloalkyl groups; R ¹² represents a methyl group, an ethyl group, a propyl group or a benzyl group; and R ¹³ represents or Wherein a represents methyl or ethyl; and b represents -H or methyl. The photosensitive resin composition of claim 1, wherein the alkali-soluble resin (A-1) is obtained by a reaction of a first mixture comprising: a diol compound containing a polymerizable unsaturated group (a-1) a tetracarboxylic acid or an acid dianhydride thereof (a-2); and a dicarboxylic acid or an anhydride thereof (a-3); wherein: the tetracarboxylic acid or its acid dianhydride (a-2) comprises a fluorine atom a tetracarboxylic acid or an acid dianhydride thereof (a-2-1), or a tetracarboxylic acid other than the fluorine atom-containing tetracarboxylic acid or its acid dianhydride (a-2-1) or an acid dianhydride thereof ( A-2-2) or a combination of the two; The dicarboxylic acid or its anhydride (a-3) includes a dicarboxylic acid containing a fluorine atom or an anhydride thereof (a-3-1), in addition to the above-mentioned dicarboxylic acid containing a fluorine atom or an anhydride thereof (a-3-1) a dicarboxylic acid or an anhydride thereof (a-3-2) other than the above or a combination of the two; and the tetracarboxylic acid or its acid dianhydride (a-2) and the dicarboxylic acid or its anhydride (a) At least one of -3) contains a fluorine atom. The photosensitive resin composition of claim 2, wherein the fluorine-containing tetracarboxylic acid or acid dianhydride (a-2-1) thereof is selected from the formula (2- in the alkali-soluble resin (A-1) 1) a group of a tetracarboxylic acid compound containing a fluorine atom and a tetracarboxylic dianhydride compound containing a fluorine atom represented by the formula (2-2); In the formula (2-1) and the formula (2-2), the L ² is selected from one of the groups represented by the formula (L-1) to the formula (L-6); In the formulae (L-1) to (L-6), E each independently represents a fluorine atom or a trifluoromethyl group; and * represents a position bonded to a carbon atom. The photosensitive resin composition according to claim 2, wherein in the alkali-soluble resin (A-1), the fluorine-containing dicarboxylic acid or its anhydride (a-3-1) is selected from the formula (3-1) a group consisting of a fluorine atom-containing dicarboxylic acid compound and a fluorine atom-containing dicarboxylic anhydride compound represented by formula (3-2), In the formula (3-1) and the formula (3-2), X ¹ represents an organic group of a fluorine atom having 1 to 100 carbon atoms. The photosensitive resin composition according to claim 2, wherein the mole number of the polymerizable unsaturated group-containing diol compound (a-1), the fluorine atom-containing tetracarboxylic acid or the acid dianhydride thereof (a- The molar number of 2-1) and the molar number of the fluorine-containing dicarboxylic acid or its anhydride (a-3-1) satisfy the relationship [(a-2-1)+(a-3-1) ] / (a-1) = 0.4 to 1.6. The photosensitive resin composition of claim 1, further comprising a thermal initiator (F) selected from the group consisting of an azo compound, a peroxide, and a hydrogen peroxide compound At least one of the group's ethnic groups. The photosensitive resin composition according to claim 6, wherein the azo compound is selected from the group consisting of 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-2-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1-[(1-cyano-1- Methylethyl)azo]mercaptoamine, 2,2-azobis{2-methyl-nitro-[1,1-di(hydroxymethyl)-2-hydroxyethyl]propanamide, 2 , 2'-azobis[nitro-(2-propenyl)-2-methylpropionamide], 2,2'-azobis[nitro-(2-propenyl)-2-ethylpropionate Amine], 2,2'-azobis(nitro-butyl-2-methylpropionamide), 2,2'-azobis(nitro-cyclohexyl-2-methylpropionamide), 2 , 2'-azobis(dimethyl-2-methylpropanamide), 2,2'-azobis(dimethyl-2-methylpropionate), and 2,2'-azo At least one of the groups of bis(2,4,4-trimethylpentene). The photosensitive resin composition according to claim 6, wherein the peroxide is selected from the group consisting of Benzoyl peroxide, dibutylbutyl peroxide, diisobutylphosphonium peroxide, cumene peroxy neodecanoate, dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, peroxidation Dibutyl phthalate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, 1-cyclohexyl- 1-methylethyl peroxydicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate, peroxy neodecanoic acid Ester, dimethoxybutyl peroxydicarbonate, tert-butyl peroxy neodecanoate, third hexyl peroxypivalate, tert-butyl peroxypivalate, peroxidation 3,5,5-trimethylhexanide), dioctyl peroxide, dilaurate peroxide, distearate, 2-ethylperoxyhexanoic acid-1,1,3,3-tetra Methyl butyl ester, 2,5-dimethyl-2,5-di(2-ethylhexanoic acid peroxy)hexane, 2-ethylperoxyhexanoic acid trihexyl ester, peroxidized di(4- Methylbenzhydrazide), tert-butyl 2-ethylperoxyhexanoate, dibenzoguanidine peroxide, third isobutyl peroxybutyrate 1,1-di(t-butylperoxy)-2-methylcyclohexane, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(Third-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di[4,4-di(t-butyl) Oxidation) cyclohexyl]propane, third hexylperoxy isopropyl carbonate, tert-butylperoxymaleate, tert-butylperoxy-3,5,5-trimethylhexanoate, Tributyl peroxylaurate, 2,5-dimethyl-2,5-bis(3-methylbenzhydrazide peroxy)hexane, tert-butylperoxyisopropyl carbonate, third Butylperoxy-2-ethylhexyl carbonate, third hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzhydrazide peroxy)hexane, tert-butyl Peroxyacetate, 2,2-bis(t-butylperoxy)butane, tert-butylperoxybenzoate, butyl-4,4-di(t-butylperoxyvalerate , bis(2-tert-butylperoxyisopropyl)benzene, cumene peroxide, di-thylhexyl peroxide, 2,5-dimethyl-2,5-di (t-butyl) Oxidation) hexane, di-t-butyl peroxid e), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, tert-butyltrimethylperoxydecane, At least one of the group consisting of a mixture of bis(3-methylbenzhydryl)peroxide and benzammonium (3-methylpropionamyl) peroxide and benzhydryl peroxide . The photosensitive resin composition according to claim 6, wherein the hydrogen peroxide compound is selected from the group consisting of decane hydrogen peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl group. At least one of the group consisting of hydrogen peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. The photosensitive resin composition of claim 1, wherein the alkali-soluble resin (A) is used in an amount of 100 parts by weight, and the first alkali-soluble resin (A-1) having the structure represented by the formula (1) The amount used is 20 to 100 parts by weight; the compound (B) having an ethylenically unsaturated group is used in an amount of 20 to 180 parts by weight; and the photoinitiator (C) is used in an amount of 10 to 80 parts by weight; The ketoxime compound (C-1) is used in an amount of 10 to 70 parts by weight; the solvent (D) is used in an amount of 1000 to 8000 parts by weight; and the black pigment (E) is used in an amount of 140 to 1200 parts by weight. Share. The photosensitive resin composition of claim 6, wherein the hot start agent (F) is used in an amount of 4 to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). A black matrix formed of the photosensitive resin composition according to any one of claims 1 to 11. A color filter comprising a black matrix according to claim 12. A liquid crystal display element comprising a color filter according to claim 13.