CN112147842A - Black photosensitive resin composition, black pattern and liquid crystal display device - Google Patents

Abstract

The invention provides a black photosensitive resin composition, a black pattern and a liquid crystal display device. The above-mentioned black photosensitive resin composition includes an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment (E). The present invention also provides a black pattern formed using the above black photosensitive resin composition. The present invention further provides a liquid crystal display device including the above black pattern. The black pattern i formed by the black photosensitive resin composition of the present invention has the advantages of good taper angle and drying property.

Description

Black photosensitive resin composition, black pattern and liquid crystal display device

technical field

The present invention relates to a black photosensitive resin composition, a black pattern formed by using the black photosensitive resin composition, and a liquid crystal display device including the black pattern; in particular, a black photosensitive resin composition is provided, the black photosensitive resin composition is The black pattern formed by the flexible resin composition has the advantages of good taper angle and good drying properties.

Background technique

In recent years, with the vigorous development of various technologies of liquid crystal display devices, and in order to improve the contrast ratio and display quality of liquid crystal display devices, stripes and dots of color filters in liquid crystal display devices are usually used. A black pattern, such as a black matrix, is set between the gaps. The black matrix can prevent defects such as a decrease in contrast ratio and a decrease in color purity caused by light leakage between pixels.

Japanese Patent Laid-Open No. 2008-268854 provides a photosensitive resin composition for a black matrix. The photosensitive resin composition includes an alkali-soluble resin having a carboxylic acid group and an unsaturated group for polymerization, an ethylenically unsaturated group-containing photopolymerizable monomer, a photopolymerization initiator, and a black pigment. This patent improves the pattern resolution of a black matrix formed by a photosensitive resin composition with a high content of black pigment by using a specific alkali-soluble resin. In addition, Japanese Patent Laid-Open No. 2009-145432 provides a photosensitive resin composition for a black matrix. The photosensitive resin composition contains an ethylenically unsaturated group-containing monomer, a photopolymerization initiator, a black pigment, and a resin. The resin is selected from thermosetting resin, photosensitive resin, thermoplastic resin, or a combination thereof. This patent improves the problems of low sensitivity and poor developability of photosensitive resin compositions with high content of black pigments in the photolithography process by regulating the content of black pigments in the solid content of the photosensitive resin compositions.

However, due to the increasing demand for the light-shielding properties of black matrices in the industry, the solution is to increase the content of black pigments to improve the light-shielding properties of the black matrix. The taper angle and dryness of the pattern are poor. When the taper angle is not good, the shape control of the color photoresist in the subsequent process is easy to be difficult; when the dryness is not good, it is easy to generate foreign matter, resulting in defects.

To sum up, how to make the black pattern prepared by the black photosensitive resin composition, such as the black matrix, have good taper angle and dryness, so as to meet the requirements of the current industry, which is a diligent research in the technical field of the present invention. Target.

SUMMARY OF THE INVENTION

The present invention provides a black photosensitive resin composition containing a special combination of components, a black pattern formed by the black photosensitive resin composition with good taper angle and dryness, and a liquid crystal display device including the black pattern.

Therefore, the present invention provides a black photosensitive resin composition, comprising:

Alkali-soluble resin (A);

A compound (B) having an ethylenically unsaturated group;

photoinitiator (C);

solvent (D); and

black pigment (E);

Wherein, the alkali-soluble resin (A) includes a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture, and the first mixture includes A diol compound (a-1-1) represented by the formula (1), a tetracarboxylic acid or its acid dianhydride (a-1-2), and a dicarboxylic acid or its acid anhydride (a-1-3);

In formula (1), A ₁ and A ₁ ′ are each R _a SR _b , and R _a is a single bond, a C ₁ -C ₁₀ alkylene group (Alkylene) or a C ₆ -C ₁₅ aryl group (Arylene) , the R _b is a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₁₅ aryl group; n is an integer from 1 to 6; A ₂ , A ₂ ' are each hydrogen, hydroxyl, thiol, amino, nitro or halogen substituent;

The solvent (D) comprises the first solvent (D-1) represented by the formula (2);

In formula (2), D ₁ is a linear or branched C ₁ -C ₈ alkylene, D ₂ is a linear or branched C ₁ -C ₈ alkyl; a is an integer of 2 to 4 , and multiple D ₁ are the same or different.

The present invention also provides a black pattern, which is formed by subjecting the above black photosensitive resin composition to a pre-baking treatment, an exposure treatment, a developing treatment and a post-baking treatment.

The present invention further provides a liquid crystal display device including the above-mentioned black pattern.

Description of drawings

FIG. 1 is a schematic cross-sectional view of the taper angle θ of the black matrix observed by the evaluation method of the taper angle according to an embodiment of the present invention.

Symbol Description

701 glass substrate; 703 black matrix; θ taper angle.

Detailed ways

In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solutions of the present invention are now described in detail below, but should not be construed as limiting the scope of implementation of the present invention.

Therefore, the present invention provides a black photosensitive resin composition, comprising:

Alkali-soluble resin (A);

A compound (B) having an ethylenically unsaturated group;

photoinitiator (C);

solvent (D); and

black pigment (E);

Wherein, the alkali-soluble resin (A) includes a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture, and the first mixture includes A diol compound (a-1-1) represented by the formula (1), a tetracarboxylic acid or its acid dianhydride (a-1-2), and a dicarboxylic acid or its acid anhydride (a-1-3);

In formula (1), A ₁ and A ₁ ' are each R _a SR _b , the R _a is a single bond, a C ₁ -C ₁₀ alkylene group or a C ₆ -C ₁₅ aryl group, and the R _b is C ₁ -C ₁₀ alkyl or C ₆ -C ₁₅ aryl; n is an integer from 1 to 6; A ₂ , A ₂ ' are each hydrogen, hydroxyl, thiol, amino, nitro or halogen substituents;

The solvent (D) comprises the first solvent (D-1) represented by the formula (2);

In formula (2), D ₁ is a linear or branched C ₁ -C ₈ alkylene, D ₂ is a linear or branched C ₁ -C ₈ alkyl; a is an integer of 2 to 4 , and a plurality of D ₁ can be the same or different.

The alkali-soluble resin (A) according to the present invention contains the first alkali-soluble resin (A-1) obtained by polymerizing the first mixture. The first mixture may contain a diol compound (a-1-1) represented by formula (1), a tetracarboxylic acid or its acid dianhydride (a-1-2), and a dicarboxylic acid or its acid anhydride (a- 1-3);

In formula (1), A ₁ and A ₁ ' are each R _a SR _b , the R _a is a single bond, a C ₁ -C ₁₀ alkylene group or a C ₆ -C ₁₅ aryl group, and the R _b is C ₁ -C ₁₀ alkyl or C ₆ -C ₁₅ aryl; n is an integer from 1 to 6; A ₂ , A ₂ ′ are each hydrogen, hydroxyl, thiol, amino, nitro or halogen substituents.

C ₁ -C ₁₀ alkyl is straight-chain or branched, examples of which can be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl aryl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl and decyl; C ₆ -C ₁₅ aryl can be, for example, phenyl, naphthyl, Anthracenyl, phenanthrene, etc. The C ₁ -C ₁₀ alkylene group and the C ₆ -C ₁₅ aryl group may be the alkylene group and the aryl group corresponding to the above-mentioned C ₁ -C ₁₀ alkyl group and C ₆ -C ₁₅ aryl group, respectively.

The tetracarboxylic acid or its acid dianhydride (a-1-2) of the present invention includes a tetracarboxylic acid containing a fluorine atom, a linear hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, or the above-mentioned tetracarboxylic acid A dianhydride compound of a carboxylic acid, or a combination thereof.

Specific examples of the fluorine atom-containing tetracarboxylic acid or its acid dianhydride include 4,4'-hexafluoroisopropylidene diphthalic acid, 1,4-difluoropyromellitic acid, 1-monofluoro Pyromellitic acid, 1,4-bis(trifluoromethyl)pymellitic acid, 3,3'-hexafluoroisopropylidene diphthalic acid, 5,5'-[2,2,2- Trifluoro-1-[3-(trifluoromethyl)phenyl]ethylene]diphthalic acid, 5,5'-[2,2,3,3,3-pentafluoro-1-(trifluoro Fluoromethyl) propylene] diphthalic acid, 5,5'-oxybis[4,6,7-trifluoro-pyromellitic acid], 3,6-bis(trifluoromethyl) Fluorine-containing tetracarboxylic acids such as pyromellitic acid, 4-(trifluoromethyl)pyromellitic acid, 1,4-bis(3,4-dicarboxylate trifluorophenoxy)tetrafluorobenzene, or the above A dianhydride compound of a carboxylic acid, or a combination of the foregoing.

The straight-chain hydrocarbon tetracarboxylic acid may be a saturated straight-chain hydrocarbon tetracarboxylic acid. Specific examples of the saturated linear hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or a combination of the above compounds. The saturated straight-chain 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 combinations thereof. Alicyclic tetracarboxylic acid may have a substituent.

Specific examples of the dianhydride compound of the alicyclic tetracarboxylic acid include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride or 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, or a combination of the foregoing.

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

Specific examples of the dianhydride compound of the aromatic tetracarboxylic acid include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'- Biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2' ,3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, bis(3,4- Dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4 -Dicarboxyphenoxy)phenyl}fluorinated dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9, 10-Perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or a combination of the foregoing.

The dicarboxylic acid or its anhydride (a-1-3) of the present invention includes dicarboxylic acids containing fluorine atoms, saturated linear hydrocarbon dicarboxylic acids, saturated cyclic hydrocarbon dicarboxylic acids, unsaturated dicarboxylic acids, and other dicarboxylic acids Acids or anhydrides of the above dicarboxylic acid compounds, or a combination of the above compounds.

Specific examples of the fluorine atom-containing dicarboxylic acid or its anhydride include 3-fluorophthalic acid, 4-fluorophthalic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, Tetrafluorosuccinic acid, or an anhydride compound of the above-mentioned dicarboxylic acids, or a combination of the above-mentioned compounds.

Specific examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxo Glutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or a combination of the foregoing. The hydrocarbon group in the saturated straight-chain 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, hexahydro trimellitic acid, or the above combination of 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, methyl-methylenetetrahydrophthalic acid, chlorendic acid, trimene Triacids, or combinations of the above compounds.

Specific examples of the other dicarboxylic acids or their anhydrides include trimethoxysilylpropylsuccinic anhydride, triethoxysilylpropylsuccinic anhydride, methyldimethoxysilylpropylsuccinic anhydride, Methyldiethoxysilylpropylsuccinic anhydride, trimethoxysilylbutylsuccinic anhydride, triethoxysilylbutylsuccinic anhydride, methyldiethoxysilylbutylsuccinic anhydride , p-(trimethoxysilyl) phenylsuccinic anhydride, p-(triethoxysilyl) phenylsuccinic anhydride, p-(methyldimethoxysilyl) phenylsuccinic anhydride, p-(methyl dimethoxysilyl) phenylsuccinic anhydride Diethoxysilyl)phenylsuccinic anhydride, m-(trimethoxysilyl)phenylsuccinic anhydride, m-(triethoxysilyl)phenylsuccinic anhydride, m-(methyldiethoxy) dicarboxylic acid anhydrides such as silyl)phenylsuccinic anhydride, or dicarboxylic acid compounds of the above dicarboxylic acid anhydrides, or a combination of the above compounds.

The method for synthesizing the first alkali-soluble resin (A-1) is not particularly limited, as long as the diol compound (a-1-1) represented by the formula (1), the tetracarboxylic acid or an acid thereof is combined The dianhydride (a-1-2) and the dicarboxylic acid or its acid anhydride (a-1-3) can be obtained by reacting.

However, it is preferable to first carry out a polymerization reaction between the diol compound (a-1-1) represented by the formula (1) and the tetracarboxylic acid or its acid dianhydride (a-1-2), for example, in 100°C to 130°C, preferably 110°C to 120°C for 2 hours to 24 hours, preferably 4 hours to 12 hours.

Based on 100 parts by weight of the diol compound (a-1-1) represented by the formula (1), the tetracarboxylic acid or its acid dianhydride (a-1-2) is used in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, and more preferably 10 to 20 parts by weight.

After the above-mentioned polymerization reaction starts, add the dicarboxylic acid or its anhydride (a-1-3), for example, at 100°C to 130°C, preferably at 110°C to 120°C for 30 minutes to 4 hours, preferably The optimal reaction time is 1 hour to 3 hours.

The dicarboxylic acid or its anhydride (a-1-3) is used in an amount of 2 to 10 parts by weight based on 100 parts by weight of the diol compound (a-1-1) represented by the formula (1). The weight part is preferably 2 to 5 parts by weight, and more preferably 3 to 5 parts by weight.

The weight-average molecular weight of the first alkali-soluble resin (A-1) measured by Gel Permeation Chromatography (GPC) can be 1,000g/mol to 100,000g/mol, preferably 2,000g/mol to 50,000g /mol, more preferably 3,000 g/mol to 10,000 g/mol. In addition, the dispersion degree of the above-mentioned first alkali-soluble resin (A-1) measured by GPC may be in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0.

The first alkali-soluble resin (A-1) is used in an amount of 30 to 100 parts by weight, preferably 40 to 90 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). , and more preferably 50 to 90 parts by weight. When the first alkali-soluble resin (A-1) is not used, the black pattern obtained from the black photosensitive resin composition of the present invention has a problem of poor taper angle.

The alkali-soluble resin (A) of the present invention may further comprise a second alkali-soluble resin (A-2), the second alkali-soluble resin (A-2) is obtained by polymerizing the second mixture, and the second alkali-soluble resin (A-2) is The two mixtures include a polymerizable unsaturated group-containing diol compound (a-2-1), a tetracarboxylic acid or its acid dianhydride (a-2-2), and a dicarboxylic acid or its acid anhydride (a-2-3) .

The polymerizable unsaturated group-containing diol compound (a-2-1) of the present invention is composed of an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group response.

The epoxy compound having at least two epoxy groups includes the structure represented by formula (a-2-1-1), the structure represented by formula (a-2-1-2), and the structure represented by formula (a-2- The structure shown in 1-3), or the above three structures. The structure represented by formula (a-2-1-1), the structure represented by formula (a-2-1-2), and the structure represented by formula (a-2-1-3) will be specifically described below.

Specifically, the structure represented by the formula (a-2-1-1) is as follows:

In formula (a-2-1-1), W ¹ , W ² , W ³ and W ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkane having 1 to 5 carbon atoms. An oxy group, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 12 carbon atoms.

The epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-2-1-1) may include an epoxy compound having an epoxy group obtained by reacting a bisphenol-indene compound with a halogenated propylene oxide. of bisphenol-indene compounds.

In detail, specific examples of the bisphenol fluoride compound include: 9,9-bis(4-hydroxyphenyl) fluoride, 9,9-bis(4-hydroxy-3-methylphenyl) fluoride, 9,9-bis(4-hydroxy-3-methylphenyl) fluoride ,9-bis(4-hydroxy-3-chlorophenyl) fluoride, 9,9-bis(4-hydroxy-3-bromophenyl) fluoride, 9,9-bis(4-hydroxy-3-fluorophenyl) ) fluoride, 9,9-bis(4-hydroxy-3-methoxyphenyl) fluoride, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) fluoride, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluoride, 9,9-bis(4-hydroxy-3,5-dibromophenyl) fluoride or an analog thereof, or a combination of the foregoing compounds.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxypropane or 3-bromo-1,2-epoxypropane or the like, or a combination of the above compounds.

Specific examples of the epoxy group-containing bisphenol fentanyl compound include (1) products manufactured by Nippon Steel Chemicals: such as ESF-300 or the like; (2) products manufactured by Osaka Gas: such as PG-100, EG-210 or its analogues; (3) commercial products manufactured by S.M.S Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or its analogues.

In addition, specifically, the structure represented by the formula (a-2-1-2) is as follows:

In formula (a-2-1-2), W ⁵ to W ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms, and s represents 0 to An integer of 10.

The epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-2-1-2) may be included in the presence of an alkali metal hydroxide to have the following formula (a-2-1-2 The compound of -I) structure is obtained by reacting with halogenated propylene oxide.

In the above formula (a-2-1-2-1), the definitions of W ⁵ to W ¹⁸ and s are the same as the definitions of W ⁵ to W ¹⁸ and s in the formula (a-2-1-2), respectively , which will not be repeated here.

For the synthesis method of the epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-2-1-2), reference may be made to the patent of Taiwan Publication No. TW201508418.

Specific examples of the epoxy compound having at least two epoxy groups having the structure represented by the above formula (a-2-1-2) include trade names NC-3000, NC-3000H, NC-3000S, and NC-3000P and other products manufactured by Nippon Kayaku.

In addition, specifically, the structure represented by the formula (a-2-1-3) is as follows:

In formula (a-2-1-3), Ar ₃ represents a naphthalene ring, W ¹⁹ represents a cyano group, halogen or hydrocarbon group, and W ²⁰ represents a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkoxy group , alkylthio, cycloalkylthio, arylthio, aralkylthio, acyl, halogen, nitro, cyano or substituted amino, W ²¹ represents alkylene, a represents an integer from 0 to 4, b and c represent an integer of 0 or more.

Specific examples of the above-mentioned epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-2-1-3) include 9,9-bis(glycidoxynaphthyl)fluorene, and for example It is a similar compound such as 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene or 9,9-bis(5-glycidyloxy-1-naphthyl)fluorene.

The compound having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from one of the following groups (1) to (3):

(1) Acrylic acid, methacrylic acid, 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxybutylsuccinic acid, 2-methacryloyloxyethyladipic acid, 2- Methacryloyloxybutyladipic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxypropylmaleic acid Lactic acid, 2-methacryloyloxybutylmaleic acid, 2-methacryloyloxypropylsuccinic acid, 2-methacryloyloxypropyladipic acid, 2-methacryloyloxypropyl tetrahydrophthalic acid, 2-methacryloyloxypropylphthalic acid, 2-methacryloyloxybutylphthalic acid, 2-methacryloyloxybutylhydrophthalic acid or the like ;

(2) A compound obtained by reacting a (meth)acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein specific examples of the dicarboxylic acid compound include adipic acid, succinic acid, maleic acid, phthalic acid Formic acid or its analogs; and

(3) A half-ester compound obtained by reacting a (meth)acrylate having a hydroxyl group with a carboxylic acid anhydride compound, and specific examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethylacrylate, 2-hydroxyl Ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate or the like thing.

In addition, the carboxylic acid anhydride compound described here is the same as the tetracarboxylic dianhydride or dicarboxylic acid anhydride described above, and will not be repeated here.

The types of the tetracarboxylic acid or its acid dianhydride (a-2-2) and the dicarboxylic acid or its acid anhydride (a-2-3) used in the second alkali-soluble resin (A-2) may be the same as those of the above-mentioned No. The tetracarboxylic acid or its acid dianhydride (a-1-2) and the dicarboxylic acid or its acid anhydride (a-1-3) used in the alkali-soluble resin (A-1) are the same, so they will not be repeated here.

The synthesis method of the second alkali-soluble resin (A-2) is not particularly limited, as long as the polymerizable unsaturated group-containing diol compound (a-2-1), the tetracarboxylic acid or its acid are combined The dianhydride (a-2-2) and the dicarboxylic acid or its anhydride (a-2-3) can be obtained by reacting, and can be synthesized with reference to the patent of Taiwan Publication No. TW201508418.

The number average molecular weight of the second alkali-soluble resin (A-2) in terms of polystyrene measured by GPC is preferably 800 to 8,000, more preferably 1,000 to 6,000.

Based on the total usage of the alkali-soluble resin (A) as 100 parts by weight, the usage of the second alkali-soluble resin (A-2) is 0 to 70 parts by weight, for example, 10 to 70 parts by weight, preferably It is 10 to 60 parts by weight, and more preferably 10 to 50 parts by weight. When the second alkali-soluble resin (A-2) is used, the taper angle of the black pattern obtained from the black photosensitive resin composition of the present invention can be further improved.

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

The above-mentioned compounds with one ethylenically unsaturated group may include but are not limited to (meth)acrylamide, (meth)acryloyl morpholine, (meth)acrylic acid-7-amino-3,7-dimethyloctane ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl Diethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, (meth)acrylic acid Dodecyl ester, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, (meth)acrylic acid Tetrachlorophenyl, (meth)acrylate-2-tetrachlorophenoxyethyl, (meth)acrylate tetrahydrofurfuryl, (meth)acrylate tetrabromophenyl, (meth)acrylate-2-tetra Bromophenoxyethyl ester, (meth)acrylic acid-2-trichlorophenoxyethyl ester, (meth)acrylic acid tribromophenyl ester, (meth)acrylic acid-2-tribromophenoxyethyl ester, 2 -Hydroxy-ethyl (meth)acrylate, 2-hydroxy-propyl (meth)acrylate, vinyl caprolactam, N-vinylpyrrolidone, phenoxyethyl (meth)acrylate, penta(meth)acrylate Compounds such as chlorophenyl ester, pentabromophenyl (meth)acrylate, polyethylene mono(meth)acrylate, polytrimethylene mono(meth)acrylate or bornyl (meth)acrylate. The compound having one ethylenically unsaturated group may be used alone or in combination.

The above-mentioned compounds with two or more (including two) ethylenically unsaturated groups may include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate (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, trimethylolpropyl tri(meth)acrylate, ethylene oxide ( Referred to as EO) modified trimethylol propyl tri(meth)acrylate, propylene oxide modified (referred to as PO) trimethylol propyl tri(meth)acrylate, tripropylene glycol di(meth)acrylic acid ester, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyester di(meth)acrylate ) acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified Quality dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ditrimethylolpropyl tetra(meth)acrylate, ethylene oxide modified Bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, ethylene oxide modified hydrogenated bisphenol A di(meth)acrylate, Propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate or novolac polyglycidyl ether (meth)acrylate, etc. compound of. The compound having two or more (including two) ethylenically unsaturated groups may be used alone or in combination of two or more.

Specific examples of the compound (B) having an ethylenically unsaturated group may include, but are not limited to: trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified by ethylene oxide, cyclic triacrylate Oxypropane-modified trimethylolpropyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol Hexacrylate, ditrimethylolpropyl tetraacrylate, propylene oxide modified glycerol triacrylate, or any combination of the foregoing.

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

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the compound (B) having an ethylenically unsaturated group is 10 to 100 parts by weight, preferably 15 to 90 parts by weight parts by weight, more preferably 20 parts by weight to 80 parts by weight.

The photoinitiator (C) of the present invention contains the photoinitiator (C-1) represented by the formula (3):

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, COR ₁₆ , or

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together

provided that at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with _one or more of _the following groups: halogen , phenyl;

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen;

X represents CO or direct bond;

R ₁₃ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ ;

or R ₁₃ represents a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O or CO, wherein the mixed C ₂ -C ₂₀ alkyl group is unsubstituted or substituted with one or more halogens;

or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl;

R ₁₄ represents hydrogen, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl;

R ₁₅ is C ₆ -C ₂₀ aryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , C ₂ interspersed with one or more O -C ₂₀ alkyl; or each substituted with C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with _one or more of _the following: halogen, COOR ₁₇ , phenyl , OR ₁₇ ;

or R ₁₅ represents hydrogen, C ₃ -C ₈ cycloalkyl; or R ₁₅ is C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following: halogen, C ₃ -C ₈ cycloalkyl;

R ₁₆ represents C ₆ -C ₂₀ aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ ; or each of which is substituted with one or more C ₁ - _C20 alkyl substituted, the _C1 - _C20 alkyl is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ ;

R ₁₇ represents hydrogen, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O;

Or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O;

or R ₁₇ represents phenyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy;

provided that there is at least one

The photoinitiator (C-1) of formula (3) is characterized in that its phenyl ring is fused with a carbazole moiety to form a "naphthyl" ring, that is, it contains one or more on the carbazole moiety Annelated unsaturated rings. In other words, at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

C ₁ -C ₂₀ alkyl is straight-chain or branched, examples of which can be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl base, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, Eighteen bases and twenty bases.

C ₁ -C ₄ haloalkyl may be C ₁ -C ₄ alkyl as defined above and substituted with halogen as defined below. Alkyl groups can be mono- or polyhalogenated, or all hydrogen atoms can be replaced with halogens. It can be, for example, _CzHxHaly , where _x + _y =2z+1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

A C2 _{- C20} alkyl group interspersed with one or more Os may be interspersed with O, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times, or 1 or 2 times. The two O atoms are separated by at least one methyl group, preferably at least two methyl groups (ie, ethyl groups). These alkyl groups can be straight or branched. For example, the following structural units can be: _-CH2 - _{CH2 -} O- _CH2CH3 , -[ _CH2CH2O ] _y - _{CH3 (} where y= ₁ to 9), -(CH2- CH ₂ O) ₇ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ ), -O-CH ₂ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ .

C ₁ -C ₁₂ alkoxy is C ₁ -C ₁₂ alkyl substituted with one O atom.

基、并四苯基、联伸三苯基等，尤其为苯基或萘基，较佳为苯基。萘基是1-萘基或2-萘基。C ₆ -C ₂₀ aryl can be, for example, phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl,

phenyl, naphthyl, triphenyl, etc., especially phenyl or naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

Substituted aryl groups (phenyl, naphthyl, _C6 - _C20 aryl) can be substituted 1 to 7 times, 1 to 6 times or 1 to 4 times, in particular 1, 2 or 3 times, respectively. Obviously, the aryl group here cannot have more substituents than the number of free positions on its aryl ring.

Substituents on the phenyl ring are preferably in position 4 on the phenyl ring, or in groups 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6- state.

The intervened group can be intervened, for example, 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times, or 1 or 2 times. Obviously, the number of atoms of the meta-hetero group depends on the number of C atoms of the pseudo-inter-hetero group. A substituted group may have, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.

则形成例如以下式(Ia)至式(Ii)所示的结构：A substituted group may have one substituent, or a plurality of the same or different substituents. The halogen can be fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ independently of each other and together are

Then, for example, the structures shown in the following formulas (Ia) to (Ii) are formed:

Among them, formula (Ia), formula (Ib), and formula (Ic) are preferred, and formula (Ia) or formula (Ic), or formula (Ia), formula (Ic), or formula (Id) are more preferred. of formula (Ia).

In one example, R ₁₅ represents hydrogen, phenyl, naphthyl, each of which is unsubstituted or substituted with C ₁ -C ₈ alkyl, OR ₁₇ ; or R ₁₅ represents C ₁ -C ₂₀ alkyl; or R ₁₅ Represents a C ₂ -C ₂₀ alkyl group mixed with one or more O.

In one example, R ₁₆ represents C ₆ -C ₂₀ aryl (preferably phenyl or naphthyl, more preferably phenyl), each of which is unsubstituted or substituted with one or more of the following groups: halogen, or each substituted with _one or _{more C1 - C20} alkyl groups that are unsubstituted or substituted with _one or more of _the following: Halogen, OR ₁₇ . Alternatively, R ₁₆ is preferably phenyl or naphthyl, more preferably phenyl or carbazole, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ or C ₁ -C ₂₀ alkyl. Alternatively, R ₁₆ is preferably phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ or C ₁ -C ₂₀ alkyl. Alternatively, R ₁₆ is more preferably phenyl, unsubstituted or substituted with one or more of the following groups: OR ₁₇ or C ₁ -C ₂₀ alkyl. R ₁₆ is especially preferably phenyl substituted with one or more C ₁ -C ₂₀ alkyl groups.

In one example, R ₁₇ represents hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O ; or R ₁₇ represents phenyl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy.

Examples of the photoinitiator (C-1) represented by the formula (3) include the following compounds represented by the formula (3-1) to the formula (3-22):

Based on the total usage amount of the photoinitiator (C) being 100 parts by weight, the usage amount of the photoinitiator (C-1) represented by the formula (3) is 5 to 50 parts by weight, preferably 7 parts by weight to 45 parts by weight, and more preferably 10 parts by weight to 40 parts by weight. When the photoinitiator (C-1) represented by the formula (3) is used, the taper angle of the black pattern obtained from the black photosensitive resin composition of the present invention can be further improved.

Other photoinitiators (C-2) may be optionally added to the black photosensitive resin composition of the present invention.

Specific examples of the other photoinitiators (C-2) include other oxy-acyloxime-based compounds (O-acyloxime) or non-oxy-acyloxime-based photoinitiators.

Specific examples of the other oxy-acyl oxime compounds include 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzoyl oxime ), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyl oxime), 1-[4-(phenylthio)phenyl] -Octane-1,2-dione-2-(O-benzoyl oxime), or a combination of the above. 1-[4-(Phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyl oxime) can be manufactured by Ciba Specialty Chemicals Co., Ltd., type It is a product of IRGACURE OXE-01.

In addition, specific examples of the other oxy-acyl oxime compounds include 1-[4-(benzoyl)phenyl]-heptane-1,2-dione-2-(O-benzoyloxime), 1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone-1-(O-acetyloxime), 1-[9-ethyl- 6-(3-Methylbenzoyl)-9H-carbazole-3-substituent]-ethanone-1-(O-acetyloxime), 1-[9-ethyl-6-benzoyl-9H -carbazole-3-substituted]-ethanone-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl) )-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyl) Benzoyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzene) Acyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyran) benzoyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl Methoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4- Tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2- Methyl-5-tetrahydrofurylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-( 2-Methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-[9-ethyl base-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolane)benzoyl}-9H-carbazole-3-substituent]-1-( O-acetyl oxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolane)methane Oxybenzoyl}-9H-carbazole-3-substituent]-1-(O-acetyloxime), or a combination of the foregoing. 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone-1-(O-acetyloxime) can be refined by Ciba Manufactured by Co., Ltd. with the model number IRGACURE OXE-02.

The other oxy-acyl oxime compounds can be used alone or in combination.

Specific examples of the non-oxy-acyl oxime-based photoinitiators include triazabenzene-based compounds, acetophenone-based compounds, diimidazole-based compounds, benzophenone-based compounds, α-diketone-based compounds, alcohols Ketone compounds, alcohol ketone ether compounds, acylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, or a combination of the above compounds.

Specific examples of the triazabenzene compounds include vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituent)-4,6-bis(halomethyl) )-s-triazabenzene compound, 4-(p-aminophenyl)-2,6-bis(halomethyl)-s-triazabenzene compound, or a combination of the foregoing.

Specific examples of the vinyl-halomethyl-s-triazabenzene compound include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene , 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloromethane yl-3-amino-6-p-methoxystyryl-s-triazabenzene, or a combination of the foregoing.

Specific examples of the 2-(naphtho-1-substituent)-4,6-bis(halomethyl)-s-triazabenzene compound include 2-(naphtho-1-substituent)-4 ,6-bis(trichloromethyl)-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituent)-4,6-bis(trichloromethyl)-s- Triazepine, 2-(4-ethoxy-naphtho-1-substituent)-4,6-bis(trichloromethyl)-s-trazine, 2-(4-butoxy -naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-substituted base]-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphtho-1-substituent]-4,6- Bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1-substituent]-4,6-bis(trichloromethyl) -s-triazabenzene, 2-(2-methoxy-naphtho-1-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(6- Methoxy-5-methyl-naphtho-2-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(6-methoxy-naphtho-2 - Substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(5-methoxy-naphtho-1-substituent)-4,6-bis(trichloro Methyl)-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene , 2-(6-ethoxy-naphtho-2-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4,5-dimethoxy- naphtho-1-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, or a combination of the foregoing.

Specific examples of the 4-(p-aminophenyl)-2,6-bis(halomethyl)-s-triazabenzene compound include 4-[p-N,N-bis(ethoxy) Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl) base)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-bis(triazine) Chloromethyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-( p-N-Ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(phenyl)amine phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl) base)-s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triaza Benzene, 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m- Bromo-para-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-para -N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N, N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-di (Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxy ylcarbonylmethyl)aminophenyl-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl) )aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl] -2,6-bis(trichloromethyl)-s-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-bis(trichloromethyl) -s-triazabenzene, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triaza Benzene, 4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m -Fluoro-p-N,N-bis(chloroethyl)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-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N -Ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6 -Bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl) -s-triazabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-( m-Chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethyl Aminophenyl)-2,6-bis(trichloromethyl)-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-triaza Heterobenzene, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 2,4-bis(trichlorophenyl) Methyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene, or a combination of the above . The triazabenzene compounds can be used alone or in combination.

The triazabenzene compounds preferably include 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl) )-s-triazabenzene, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, or a combination of the foregoing.

Specific examples of the acetophenone compounds include p-dimethylamine acetophenone, α,α'-dimethoxy azo acetophenone, 2,2'-dimethyl-2-benzene Ethyl acetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2 -N,N-Dimethylamine-1-(4-morpholinophenyl)-1-butanone, or a combination of the above compounds.

The acetophenone compounds can be used alone or in combination.

The 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone can be a commodity of IRGACURE 907 manufactured by Ciba Refinery Co., Ltd. 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone may be a commercial product of IRGACURE 369 manufactured by Ciba Refinery Co., Ltd.

The acetophenone compounds preferably include 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N - Dimethylamine-1-(4-morpholinophenyl)-1-butanone, or a combination of the above.

Specific examples of the diimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl) Phenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole , 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4, 4',5,5'-tetraphenyldiimidazole, 2,2'-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, or a combination of the above compounds.

The diimidazole compounds can be used alone or in combination.

The diimidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

Specific examples of the benzophenone compounds include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamine) ) benzophenone, 4,4'-bis(diethylamine)benzophenone, or a combination of the foregoing. The benzophenone compounds can be used alone or in combination. The benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone.

Specific examples of the α-diketone compounds include benzil, diacetyl, or a combination of the above compounds. The α-diketone compounds may be used alone or in combination.

Specific examples of the ketol-based compound include benzophenone. The ketone alcohol compounds can be used alone or in combination.

Specific examples of the ketol ether compounds include benzophenone methyl ether, benzophenone ethyl ether, benzophenone isopropyl ether, or a combination of the above compounds. The ketol ether compounds can be used alone or in combination.

Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4- Trimethylphenylphosphine oxide, or a combination of the above. The acylphosphine oxide compounds can be used alone or in combination.

Specific examples of the quinone compound include anthraquinone, 1,4-naphthoquinone, or a combination of the above compounds. The quinone compounds can be used alone or in combination.

Specific examples of the halogen-containing compound include benzoyl methyl chloride, tribromomethyl phenyl sulfone, tris(trichloromethyl)-s-triazabenzene, or a combination of the above compounds. The halogen-containing compounds can be used alone or in combination.

Specific examples of the peroxide include di-tert-butyl peroxide and the like. The peroxides may be used alone or in combination.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the photoinitiator (C) used is 5 to 80 parts by weight, preferably 7 to 75 parts by weight, and more preferably 10 to 70 parts by weight.

The solvent (D) of the present invention contains the first solvent (D-1) represented by the formula (2):

In formula (2), D ₁ is a linear or branched C ₁ -C ₈ alkylene, D ₂ is a linear or branched C ₁ -C ₈ alkyl; a is an integer of 2 to 4 , and a plurality of D ₁ can be the same or different.

Examples of the first solvent (D-1) include, but are not limited to, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol n-butyl ether ethyl acetate acid ester, diethylene glycol tert-butyl ether acetate, diethylene glycol n-amyl ether acetate, diethylene glycol isoamyl ether acetate, diethylene glycol n-hexyl ether acetate, diethylene glycol n-heptyl ether Ether acetate, diethylene glycol n-octyl ether acetate, diethylene glycol-1,1,3,3-tetramethyl butyl ether acetate, dipropylene glycol methyl ether acetate, di-1,2 - Propylene glycol tert-butyl ether acetate, di-1,3-butanediol ethyl ether acetate, di-2-methyl-1,3-propanediol ethyl ether acetate, dipeopentyl glycol ethyl ether acetate, Di-2,4-hexanediol ethyl ether acetate, di-1,7-heptanediol ethyl ether acetate, di-1,2-octanediol ethyl ether acetate, bis-2,5-dimethyl ether Ethyl-2,5-hexanediol ethyl ether acetate, triethylene glycol ethyl ether acetate, tetraethylene glycol ethyl ether acetate, tetra-1,7-octanediol n-octyl ether acetate, ethylene glycol Propylene glycol n-butyl glycol neopentyl glycol tert-butyl ether acetate, diethylene glycol dipropylene glycol n-hexyl ether acetate, di-3-methyl-1,4-pentanediol isoamyl ether acetate, etc.

Based on the total usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount of the first solvent (D-1) is 150 to 1500 parts by weight, preferably 200 parts by weight to 1400 parts by weight, and More preferably, it is 250 to 1300 parts by weight. When the first solvent (D-1) is not used, the black pattern obtained from the black photosensitive resin composition of the present invention has a problem of poor drying properties.

The solvent (D) of the present invention may further comprise the second solvent (D-2) represented by the formula (4):

Wherein, D ₃ is a linear or branched C ₁ -C ₃ alkyl group, and D ₄ is a linear or branched C ₁ -C ₄ alkyl group.

Examples of the second solvent (D-2) include, but are not limited to, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate ester, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, sec-butyl propionate, tert-butyl propionate, n-butyl propionate Methyl n-butyrate, ethyl n-butyrate, n-propyl n-butyrate, isopropyl n-butyrate, n-butyl n-butyrate, isobutyl n-butyrate, sec-butyl n-butyrate, tert-butyl n-butyrate ester, methyl isobutyrate, ethyl isobutyrate, n-propyl isobutyrate, isopropyl isobutyrate, n-butyl isobutyrate, isobutyl isobutyrate, sec-butyl isobutyrate, isobutyrate tert-butyl butyrate, methyl 2-methyl propionate, ethyl 2-methyl propionate, n-propyl 2-methyl propionate, isopropyl 2-methyl propionate, 2-methyl propionic acid n-Butyl, isobutyl 2-methylpropionate, sec-butyl 2-methylpropionate, tert-butyl 2-methylpropionate, etc.

Based on the total usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount of the second solvent (D-2) is 100 to 1300 parts by weight, preferably 150 parts by weight to 1200 parts by weight, and More preferably, it is 200 to 1100 parts by weight. When the second solvent (D-2) is used, the drying properties of the black pattern obtained from the black photosensitive resin composition of the present invention can be further improved.

When the usage ratio of the first solvent (D-1) and the second solvent (D-2) (which is defined as the usage amount of the first solvent (D-1) divided by the second solvent (D-2) When it is 0.5 to 3, preferably 0.8 to 2.5, more preferably 1.0 to 2.0, the drying property of the black pattern obtained from the black photosensitive resin composition of the present invention can be further improved.

The black photosensitive resin composition of the present invention may optionally add another solvent (D-3).

Examples of other solvents (D-3) include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether , triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether or the like; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate or the like; diethylene glycol diethyl ether Methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or its analogues; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or its analogues; 2-hydroxy-2 -Methyl methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate , ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate , 3-methyl-3-methoxybutyl propionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate Esters or analogues thereof; toluene, xylene or analogues thereof; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or analogues thereof.

The solvent (D) is used in an amount of 250 to 5000 parts by weight, preferably 350 to 4800 parts by weight, and more preferably 450 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A) in total. parts by weight to 4600 parts by weight.

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

Specific examples of the above-mentioned black pigment (E) are: black organic pigments such as perylene black, cyanine black, and aniline black; Among the pigments such as cyanine and magenta, two or more kinds of pigments are selected and mixed to form a nearly black color mixing organic pigment; carbon black (carbon black), chromium oxide, iron oxide, titanium Black (titanium black), graphite and other light-shielding materials, wherein the above-mentioned carbon black can include but not limited to C.I.pigment black 7 etc. 970, #1000, #2350, #2650). The above-mentioned black pigments (E) are generally used alone or in combination of two or more.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the black pigment (E) used is 50 to 600 parts by weight, preferably 60 to 550 parts by weight, more preferably 70 to 500 parts by weight share.

On the premise of not affecting the efficacy of the present invention, the black photosensitive resin composition of the present invention may further selectively add an additive (F). Specific examples of the additive (F) may include surfactants, fillers, adhesion promoters, antioxidants, anti-aggregation agents, or other substances other than the above-mentioned alkali-soluble resin (A) that can increase various properties such as mechanical properties. polymer.

Specific examples of the above-mentioned surfactants may include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants or the above-mentioned surfactants any combination of agents.

Specific examples of the surfactant may include, but are not limited to, polyethoxyalkyl ethers such as polyethoxylauryl ether, polyethoxystearyl ether or polyethoxyoleyl ether; polyethoxylated alkyl ethers; Polyethoxyalkyl phenyl ethers such as ethoxyoctyl phenyl ether or polyethoxy nonyl phenyl ether; polyethylene glycol dilaurate or polyethylene glycol distearate, etc. Polyethylene glycol diesters; sorbitan fatty acid ester compounds; fatty acid-modified polyester compounds; tertiary amine-modified polyurethane compounds; or commercial products. Wherein, the commercially available commodity may be a product manufactured by Shin-Etsu Chemical Industry Co., Ltd., and its model is KP; a product manufactured by Dow Corning Toray Co., Ltd., and its model is SF-8427 ; Products manufactured by Kyoeisha Oil Chemical Industry, and its model is Polyflow; products manufactured by Tochem Products Co., Ltd., and its model is F-Top; Dai Nippon Ink Chemical Industry products manufactured by Sumitomo 3M and have the model number Fluorade; or products manufactured by Asahi Glass and have the model number Asahi Guard or Surflon. The surfactants may be used alone or in combination.

Specific examples of the above-mentioned filler can include glass, aluminum, or the like.

Specific examples of the above-mentioned adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ring Oxypropoxypropyltrimethoxysilane (product of Shin-Etsu Chemical Co., Ltd., and its model is KBM-403), EPPN501H (manufactured by Nippon Kayaku Co., Ltd.), EPIKOTE152 (manufactured by Shell Chemical Co., Ltd.), 3-glycidoxy Propylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane Silane, compounds such as 3-methylpropionyloxypropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane, or any combination of the foregoing.

Specific examples of the aforementioned antioxidants may include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or any combination of the aforementioned compounds.

Specific examples of the above-mentioned anti-aggregation agent may include compounds such as sodium polyacrylate.

Based on 100 parts by weight of the alkali-soluble resin (A), fillers, adhesion promoters, antioxidants, anti-aggregation agents, or polymers other than the alkali-soluble resin (A) in the additive (F) are used in amounts Not more than 10 parts by weight, and preferably not more than 6 parts by weight.

The black photosensitive resin composition of the present invention generally comprises the above-mentioned alkali-soluble resin (A), compound (B) having an ethylenically unsaturated group, photoinitiator (C), solvent (D), black pigment (E) ) placed in a stirrer and stirred to make it evenly mixed into a solution state. If necessary, additives (F) such as surfactants, fillers, adhesion promoters, bridging agents, antioxidants, and anti-aggregation agents can be added to uniformly After mixing, a black photosensitive resin composition in a solution state can be prepared.

Secondly, the preparation method of the black photosensitive resin composition of the present invention is not particularly limited. For example, the black pigment (E) can be directly added to the black photosensitive resin composition and dispersed, or a part of the black pigment can be dispersed in advance. (E) After dispersing in a medium containing a part of alkali-soluble resin (A) and solvent (D) to form a pigment dispersion liquid, the compound (B) having an ethylenically unsaturated group and a photoinitiator (C) are mixed. , alkali-soluble resin (A) and the rest of solvent (D) are obtained. The dispersing step of the above-mentioned black pigment (E) can be carried out by mixing the above-mentioned components with a mixer such as a bead mill or a roll mill.

The present invention also provides a black pattern (eg, a black matrix) formed from the above-mentioned black photosensitive resin composition.

The black pattern is obtained by sequentially applying pre-baking, exposure, development and post-exposure baking treatment to the black photosensitive resin composition as described above, wherein, when the film thickness is 1 μm, the optical The density range is above 3.0. Preferably, when the film thickness is 1 μm, the optical density of the black pattern ranges from 3.2 to 5.5; more preferably, when the film thickness is 1 μm, the optical density of the black pattern ranges from 3.5 to 5.5.

For the black pattern of the present invention, the above-mentioned black photosensitive resin composition can be coated on the substrate by a coating method such as spin coating or casting coating, and the solvent therein can be removed by drying under reduced pressure and pre-baking treatment. Further, a pre-baked coating film is formed on the substrate. Among them, the above-mentioned conditions of drying under reduced pressure and pre-baking vary according to the type and mixing ratio of each component. Generally, drying under reduced pressure is performed at a pressure of less than 200 mmHg for 1 second to 20 seconds, while the pre-baking treatment is performed at a pressure of less than 200 mmHg. 70°C to 110°C for 1 minute to 15 minutes. After pre-baking, the above-mentioned coating film is exposed under a designated mask, and then immersed in a developer at a temperature of 23±2°C for 15 seconds to 5 minutes to remove the unnecessary parts and form a specific pattern. . The light used for exposure is preferably ultraviolet rays such as g-line, h-line or i-line, and the ultraviolet irradiation device can be (ultra) high pressure mercury lamp and metal halide lamp.

Specific examples of the above-mentioned suitable developer are: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine, Dimethylethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene, etc. Basic compounds, etc. The concentration of the developing solution is generally 0.001 wt % (wt %) to 10 wt %, preferably 0.005 wt % to 5 wt %, and more preferably 0.01 wt % to 1 wt %.

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

Specific examples of the above-mentioned substrates are: alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz glass, and transparent conductive films attached to these glasses for liquid crystal display devices; or for solid-state photography Photoelectric conversion device substrates (eg, silicon substrates) of devices and the like.

The present invention further provides a color filter comprising the above-mentioned black pattern.

In the method for forming a color filter of the present invention, the photosensitive composition for a color filter mixed in a solution state can be coated on a substrate by a coating method such as spin coating, casting coating, or roll coating. , wherein the substrate has previously formed a black pattern separating each pixel coloring layer by using the above-mentioned black photosensitive resin composition. After coating, most of the solvent is removed by drying under reduced pressure, and then the solvent is removed by a pre-bake method to form a pre-bake coating film. Among them, the conditions of vacuum drying and pre-baking vary according to the types of ingredients and the mixing ratio. Generally, vacuum drying is carried out under the pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and pre-baking is performed at 70 mmHg. °C to 110 °C temperature for 1 minute to 15 minutes. After pre-baking, the pre-baking coating film is exposed between the designated masks, immersed in the above-mentioned developing solution at a temperature of 23±2° C. for 15 seconds to 5 minutes for development, and the unnecessary parts are removed to form Has a pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, i-line, etc., and the ultraviolet device can be (ultra) high pressure mercury lamp and metal halide lamp.

After the above development, wash with water, and dry the pattern with compressed air or compressed nitrogen, and then perform post-baking treatment with a heating device such as a hot plate or an oven.

The above steps are repeated for each color (mainly including red, green and blue) to obtain the pixel layer of the color filter. Next, an indium tin oxide (ITO) vapor deposition film is formed on the pixel layer in a vacuum environment at a temperature of 220°C to 250°C. If necessary, after etching and wiring the ITO coating film, the polyimide for liquid crystal alignment film is then coated. The amine is further fired, and it can be used as a color filter for liquid crystal display elements.

The present invention further provides a liquid crystal display element comprising the above-mentioned color filter and a black pattern therein.

The liquid crystal display element of the present invention includes a color filter substrate formed by the above-mentioned method for producing a color filter, and a driving substrate provided with a thin film transistor (TFT), with a gap interposed between the two substrates (cell gap) are arranged oppositely, and the surrounding parts of the two substrates are bonded together with a sealing agent, and the liquid crystal is filled and injected into the gap between the surface of the substrate and the sealing agent, and the injection hole is sealed to form a liquid crystal unit cell. Then, on the outer surface of the liquid crystal cell, that is, the other side surfaces of the respective substrates constituting the liquid crystal cell, a polarizing plate is attached to obtain a liquid crystal display element.

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

In addition, the liquid crystal alignment film used above is used to restrict the alignment of liquid crystal molecules, which is not particularly limited here, and any inorganic material or organic material may be used. The technology for forming the liquid crystal alignment film is well known to those skilled in the art to which the present invention pertains, and is not the focus of the present invention, so it will not be described in detail.

The following examples are given to illustrate the present invention in detail, but it is not intended that the present invention is limited to the contents provided by these examples.

Preparation example of diol compound (a-1-1) represented by formula (1)

Step A: Set a reflux condenser and a thermometer in the three-necked flask, add 42.5 g of 9,9-bisphenol fluorene, and quantitatively inject 220 mL of 2-(chloromethyl)ethylene oxide. After adding 100 mg of tetrabutylammonium bromide, it was stirred and the temperature was raised to 90°C. After confirming that the content of the unreacted material was less than 0.3%, distillation under reduced pressure was carried out.

Step B: After the temperature was lowered to 30°C, dichloromethane was injected and NaOH was slowly added. The yield was confirmed to be more than 96% by high performance liquid chromatography (HPLC), and then 5% HCl was added dropwise to terminate the reaction. The reactant was extracted by liquid separation, and the organic phase was washed with water until neutral. Then, the organic layer was dried with MgSO ₄ , and then concentrated under reduced pressure with a cyclone concentrator. Dichloromethane was added to the concentrated product, and while the temperature was raised to 40°C, methanol was added with stirring, and the solution was cooled and stirred. The solid produced by filtration was dried under vacuum at room temperature to obtain 52.7 g of white solid powder (recovery rate 94%), the structure of which was confirmed by 1H NMR, as shown in the following formula (1a):

1H NMR of _CDCl3 : 7.75(2H), 7.36 to 7.25(6H), 7.09(4H), 6.74(4H), 4.13(2H), 3.89(2H), 3.30(2H), 2.87(2H), 2.71( 2H).

Step C: set a reflux condenser and a thermometer in the three-necked flask, add 1000 g of the compound of formula (1a) obtained by the above synthesis, 524 g of thiophenol and 617 g of ethanol and stir, and continue to add 328 g of triethylamine dropwise to the reaction solution. After confirming the disappearance of the reactant by HPLC, the reaction was terminated. After the reaction was completed, ethanol was distilled off under reduced pressure. The organic matter was dissolved in dichloromethane, followed by washing with water, and the dichloromethane was distilled off under reduced pressure. The concentrated organic matter was dissolved in ethyl acetate, ether solvent was added dropwise, and the mixture was stirred for 30 minutes. Then, the compound was distilled under reduced pressure to obtain 945 g (yield 64%) of a pale yellow oil whose structure was confirmed by 1H NMR, as shown in the following formula (1b):

1H NMR of _CDCl3 : 7.82 (2H), 7.38 to 6.72 (20H), 6.51 (4H), 4.00 (2H), 3.97 (2H), 3.89 (2H), 3.20 (2H), 3.01 (2H), 2.64 ( 2H).

Preparation example of the first alkali-soluble resin (A-1)

Synthesis Example A-1-1

A reflux condenser and a thermometer were set in the three-necked flask, and 200 g of the compound of formula (1b) synthesized above was dissolved in 50% propylene glycol methyl ether acetate (PGMEA) and heated to 115°C. After 31.1 g of 3,3',4,4'-biphenyltetracarboxylicdianhydride was added dropwise at 115°C, stirring was continued at 115°C for 6 hours. 7.35 g of phthalic anhydride (Phthalicanhydride) was added and the reaction was terminated after stirring was continued for 2 hours. After cooling, the first alkali-soluble resin A-1-1 with a weight average molecular weight of 3,500 g/mol was obtained, and its structure was shown in the following formula (a-1-a):

Synthesis Example A-1-2

Replace 31.1 g of 3,3',4,4'-biphenyltetracarboxylic anhydride in Preparation Example 1 with 28.4 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (Benzophenonetetracarboxylic dianhydride) ), the remaining components and conditions are the same as above, to obtain the first alkali-soluble resin A-1-2 with a weight-average molecular weight of 5,000 g/mol, whose structure is shown in the following formula (a-1-b):

Synthesis Example A-1-3

Substitute 31.1 g of 3,3',4,4'-biphenyltetracarboxylic anhydride in Preparation Example 1 with 21.1 g of pyromellitic dianhydride, the rest of the ingredients and conditions are the same as above, and the weight is obtained. The first alkali-soluble resin A-1-3 with an average molecular weight of 4,500 g/mol has a structure as shown in the following formula (a-1-c):

Synthesis Example A-1-4

Substitute 31.1 g of 3,3',4,4'-biphenyltetracarboxylic anhydride in Preparation Example 1 with 21.7 g of Cyclohexyl dianhydride, and the other components and conditions are the same as above to obtain the weight average molecular weight It is the first alkali-soluble resin A-1-4 of 4,200 g/mol, and its structure is shown in the following formula (a-1-d):

Synthesis Example A-1-5

31.1 g of 3,3',4,4'-biphenyltetracarboxylic anhydride in Preparation Example 1 was replaced with 18.7 g of cyclobutyl dianhydride, and the rest of the ingredients and conditions were the same as above, and the weight average was obtained. The first alkali-soluble resin A-1-5 with a molecular weight of 4,200 g/mol has a structure as shown in the following formula (a-1-e):

Preparation example of polymerizable unsaturated group-containing diol compound (a-2-1)

Preparation Example 1

First, 100 parts by weight of a perylene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight of Parts of 2,6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were added to a 500-mL four-necked flask in a continuous manner. The feeding rate was controlled at 25 parts by weight/min, and the temperature during the reaction was maintained at 100°C to 110°C. After 15 hours of reaction, a pale yellow transparent mixed solution with a solid concentration of 50% by weight was obtained. Next, the above-mentioned light yellow transparent mixed solution was subjected to the steps of extraction, filtration and heating and drying to obtain the polymerizable unsaturated group-containing diol compound (a-2- 1-a).

Preparation Example 2

First, 100 parts by weight of a perylene epoxy compound (type 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 parts by weight of Parts of 2,6-di-tert-butyl-p-cresol and 135 parts by weight of propylene glycol methyl ether acetate were added to a 500-mL four-necked flask in a continuous addition manner. The feeding rate was controlled at 25 parts by weight per minute, and the temperature during the reaction was maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed solution with a solid content of 50% by weight was obtained. The above-mentioned light yellow transparent mixed solution is subjected to the steps of extraction, filtration and heating and drying to obtain the polymerizable unsaturated group-containing diol compound (a-2-1- b).

Preparation Example 3

100 parts by weight of a perylene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 100 parts by weight of 2-methacryloyl ethoxysuccinate, 0.3 parts by weight of chlorine Benzyltriethylammonium, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol, and 200 parts by weight of propylene glycol methyl ether acetate were added to a 500-mL four-necked flask in a continuous manner. The feeding rate was controlled at 25 parts by weight per minute, and the temperature during the reaction was maintained at 100°C to 110°C. After 15 hours of reaction, a pale yellow transparent mixed solution with a solid content of 50% by weight was obtained. The above-mentioned light yellow transparent mixed solution is subjected to the steps of extraction, filtration and heating and drying to obtain the polymerizable unsaturated group-containing diol compound (a-2-1-c of Preparation Example 3 with a solid content of 99.9% by weight) ).

Preparation example of the second alkali-soluble resin (A-2)

Synthesis Example A-2-1

First, 1.0 mol of the diol compound (a-2-1-a) having a polymerizable unsaturated group of Preparation Example 1, 0.3 mol of biphenyltetracarboxylic acid (a-2-2-b), 1.4 mol of Succinic acid (a-2-3-d), 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2,6-di-tert-butyl-p-cresol, 700 g of propylene glycol methyl ether acetate and 100 g of ethyl 3-ethoxypropionate was added simultaneously to a 500-mL four-necked flask to form a reaction solution. Here, the "simultaneous addition" means that the tetracarboxylic acid or its acid dianhydride (a-2-2) and the dicarboxylic acid or its acid anhydride (a-2-3) are added at the same reaction time. Next, the above-mentioned reaction solution was heated to 110° C. and reacted for 2 hours to obtain the second alkali-soluble resin A-2-1.

Synthesis Example A-2-2

1.0 mol of the diol compound (a-2-1-b) having a polymerizable unsaturated group of Preparation Example 2, 2.9 g of benzyltriethylammonium chloride and 950 g of propylene glycol methyl ether acetate were added to 500 ml in a four-necked flask to form a reaction solution. Next, 0.6 mol of benzophenone tetracarboxylic dianhydride (a-2-2-c) was added, and it was made to react at 90 degreeC for 2 hours. Then, 0.8 mol of maleic acid (a-2-3-b) was added and reacted at 90°C for 4 hours. Here, "adding in stages" means adding tetracarboxylic acid or its acid dianhydride (a-2-2) and dicarboxylic acid or its acid anhydride (a-2-3) respectively at different reaction times, that is, first A tetracarboxylic acid or its acid dianhydride (a-2-2) is added, and a dicarboxylic acid or its acid anhydride (a-2-3) is added after that. Through the above synthesis steps, the resin A-2-2 having an unsaturated group can be obtained.

Synthesis Example A-2-3, Synthesis Example A-2-5, and Synthesis Example A-2-6

The unsaturated group-containing resins of Synthesis Example A-2-3, Synthesis Example A-2-5, and Synthesis Example A-2-6 were prepared in the same procedure as Synthesis Example A-2-2, with the exception of The point is to change the types of components of the resin having an unsaturated group and its usage amount, reaction time, reaction temperature and reactant addition time (as shown in Tables 1-1 and 1-2).

Synthesis Example A-2-4

The resin having an unsaturated group of Synthesis Example A-2-4 was prepared in the same procedure as that of Synthesis Example A-2-1, and the difference was that the kinds of components of the resin having an unsaturated group and the amount used were changed. , reaction time, reaction temperature and reactant addition time (as shown in Table 1-1 and Table 1-2).

Table 1-1

Table 1-2

In Table 1-1 and Table 1-2:

a-2-1-a is the polymerizable unsaturated group-containing diol compound (a-2-1-a) of Preparation Example 1;

a-2-1-b is the polymerizable unsaturated group-containing diol compound (a-2-1-b) of Preparation Example 2;

a-2-1-c is the polymerizable unsaturated group-containing diol compound (a-2-1-c) of Preparation Example 3;

a-2-2-a is 4,4'-hexafluoroisopropylidene diphthalic dianhydride (4,4'-hexafluoroisopropylidene diphthalic dianhydride; 6FDA);

a-2-2-b is Biphenyl tetracarboxylic acid;

a-2-2-c is Benzophenone tetracarboxylicdianhydride;

a-2-2-d is pyromellitic dianhydride;

a-2-3-a is 3-fluorophthalic anhydride;

a-2-3-b is maleic acid (Maleic acid);

a-2-3-c is Tetrahydrophthalic anhydride;

a-2-3-d is Succinic acid;

PGMEA is propylene glycol monomethyl ether acetate (PGMEA);

EEP is Ethyl 3-ethoxypropionate (EEP).

Examples and Comparative Examples of Black Photosensitive Resin Compositions

Example 1

100 parts by weight of the first alkali-soluble resin (A-1-1), 10 parts by weight of ethylene glycol dimethacrylate (abbreviated as B-1), and 10 parts by weight of the The compound shown (abbreviated as C-1-1), 5 parts by weight of IRGACUREOXE-02 (abbreviated as C-2-1), 100 parts by weight of black pigment MA100 (abbreviated as E-1) were added with 150 parts by weight of two In ethylene glycol ethyl ether acetate (referred to as D-1-1) and 100 parts by weight of propylene glycol methyl ether acetate (referred to as D-3), and after stirring with a rocking stirrer, it can be prepared. The black photosensitive resin composition of Example 1.

Examples 2 to 12 and Comparative Examples 1 to 3

The black photosensitive resin compositions of Examples 2 to 12 and Comparative Examples 1 to 3 were prepared in the same steps as in Example 1, and the difference was that the types of components and their usage amounts of the black photosensitive resin compositions were changed. (as shown in Table 2-1 and Table 2-2), and will not be repeated here.

Evaluation method

black matrix

The negative photosensitive resin compositions for black matrices prepared in the above examples and comparative examples were coated on the length and width of the matrix by a coating machine (model MS-A150, purchased from Shin Kong Trading) by spin coating. All on a 100 millimeter (mm) glass substrate. Then, the above-mentioned glass substrate was pre-baked at 100° C. for 2 minutes to form a pre-baked coating film with a film thickness of 1.2 micrometers (μm). Then, the above-mentioned pre-baked coating film was placed under a specific mask, and exposed with ultraviolet light of 50 mJ/cm ² (exposure machine model AG500-4N; manufactured by M&R Nano Technology). Next, develop with a 0.045% potassium hydroxide aqueous solution at 23°C for 1 minute to remove the unexposed part of the coating film on the substrate, then wash with water and post-bake the pre-bake coating film at 230°C for 30 minutes, that is, A black matrix with a film thickness of about 1.0 μm and a specific pattern can be formed on a glass substrate.

taper angle

The taper angle was evaluated by observing the black matrix with a specific pattern by a scanning electron microscope (manufactured by Hitachi High-Technologies, and its model is S-4800), and measuring the taper angle. Please refer to FIG. 1 , which is a schematic cross-sectional view of the taper angle θ of the black matrix observed by the evaluation method of the taper angle according to an embodiment of the present invention. Among them, 701 is a glass substrate, and 703 is a black matrix. Based on the measured taper angle θ, the evaluation is performed on the following criteria:

◎: 30 degrees ≦ taper angle ≦ 40 degrees

○: 40 degrees < taper angle ≦ 60 degrees

△: 60 degrees < taper angle ≦ 80 degrees

╳: Taper angle > 80 degrees, or taper angle < 30 degrees

dryness

After the glass sheet was immersed in the negative photosensitive resin composition for black matrix for 5 seconds, the glass sheet was taken out and air-dried for 55 seconds. The glass sheet was immersed and taken out again, and the operation was repeated 120 times. Next, the black photoresist surface of the immersed area was observed with an optical microscope, and the following criteria were evaluated:

◎: No foreign matter remains on the dry surface

○: A very small amount of foreign matter remains on the dry surface

△: Conspicuous foreign matter agglomerates and remains on the dry surface

X: A large amount of foreign matter remains on the dry surface

table 2-1

Table 2-2

In Table 2-1 and Table 2-2:

The above-mentioned embodiments are only to illustrate the principle and effect of the present invention, but not to limit the present invention. Modifications and changes made to the above embodiments by those skilled in the art still do not violate the spirit of the present invention. The scope of the rights of the present invention should be set forth in the claims.

Claims (11)

1. A black photosensitive resin composition, comprising: Alkali-soluble resin (A); A compound (B) having an ethylenically unsaturated group; photoinitiator (C); solvent (D); and black pigment (E); Wherein, the alkali-soluble resin (A) includes a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture, and the first mixture includes A diol compound (a-1-1) represented by the formula (1), a tetracarboxylic acid or its acid dianhydride (a-1-2), and a dicarboxylic acid or its acid anhydride (a-1-3);

In formula (1), A ₁ and A ₁ ' are each R _a SR _b , the R _a is a single bond, a C ₁ -C ₁₀ alkylene group or a C ₆ -C ₁₅ aryl group, and the R _b is C ₁ -C ₁₀ alkyl or C ₆ -C ₁₅ aryl; n is an integer from 1 to 6; A ₂ , A ₂ ' are each hydrogen, hydroxyl, thiol, amino, nitro or halogen substituents; The solvent (D) comprises the first solvent (D-1) represented by the formula (2);

In formula (2), D ₁ is a linear or branched C ₁ -C ₈ alkylene, D ₂ is a linear or branched C ₁ -C ₈ alkyl; a is an integer of 2 to 4 , and multiple D ₁ are the same or different. 2 . The black photosensitive resin composition according to claim 1 , wherein the alkali-soluble resin (A) contains a second alkali-soluble resin (A-2), the second alkali-soluble resin (A-2) is obtained by polymerizing a second mixture comprising a diol compound (a-2-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or its acid dianhydride (a-2-2), and Dicarboxylic acid or its anhydride (a-2-3). 3. The black photosensitive resin composition according to claim 1, wherein the photoinitiator (C) comprises a photoinitiator (C-1) represented by the formula (3):

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, COR ₁₆ , or

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together

provided that at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with _one or more of _the following groups: halogen , phenyl; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen; X represents CO or direct bond; R ₁₃ represents C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ ; or R ₁₃ represents a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O or CO, wherein the mixed C ₂ -C ₂₀ alkyl group is unsubstituted or substituted with one or more halogens; or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl; R ₁₄ represents hydrogen, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl; R ₁₅ is C ₆ -C ₂₀ aryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , C ₂ interspersed with one or more O -C ₂₀ alkyl; or each substituted with C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with _one or more of _the following: halogen, COOR ₁₇ , phenyl , OR ₁₇ ; or R ₁₅ represents hydrogen, C ₃ -C ₈ cycloalkyl; or R ₁₅ is C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following: halogen, C ₃ -C ₈ cycloalkyl; R ₁₆ represents C ₆ -C ₂₀ aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ ; or each of which is substituted with one or more C ₁ - _C20 alkyl substituted, the _C1 - _C20 alkyl is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ ; R ₁₇ represents hydrogen, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O; Or R ₁₇ represents a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O; or R ₁₇ represents phenyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy; provided that there is at least one

4. The black photosensitive resin composition according to claim 1, wherein the solvent (D) further comprises a second solvent (D-2) represented by the formula (4):

Wherein, D ₃ is a linear or branched C ₁ -C ₃ alkyl group, and D ₄ is a linear or branched C ₁ -C ₄ alkyl group. 5 . The black photosensitive resin composition according to claim 1 , wherein the use of the first alkali-soluble resin (A-1) is 100 parts by weight based on the total usage of the alkali-soluble resin (A). 6 . The amount is 30 to 100 parts by weight, the amount of the compound (B) with an ethylenically unsaturated group is 10 to 100 parts by weight, and the amount of the photoinitiator (C) is 5 by weight parts to 80 parts by weight, the total usage amount of the solvent (D) is 250 parts by weight to 5000 parts by weight, the usage amount of the first solvent (D-1) is 150 parts by weight to 1500 parts by weight, and the The black pigment (E) is used in an amount of 50 to 600 parts by weight. 6. The black photosensitive resin composition according to claim 2, wherein the use of the second alkali-soluble resin (A-2) is 100 parts by weight based on the total usage of the alkali-soluble resin (A) The amount is 10 parts by weight to 70 parts by weight. 7. The black photosensitive resin composition according to claim 3, wherein the photoinitiator ( The usage amount of C-1) is 5 parts by weight to 50 parts by weight. 8. The black photosensitive resin composition according to claim 4, wherein based on the total usage of the alkali-soluble resin (A) is 100 parts by weight, the usage of the second solvent (D-2) is 100 parts by weight. 100 to 1300 parts by weight. 9 . The black photosensitive resin composition according to claim 4 , wherein the use ratio of the first solvent (D-1) and the second solvent (D-2) is 0.5 to 3. 10 . 10. A black pattern formed by the black photosensitive resin composition according to any one of claims 1 to 9 undergoing a pre-baking treatment, an exposure treatment, a developing treatment and a post-baking treatment. 11. A liquid crystal display device comprising the black pattern of claim 10.

Images