TW202100569A - Black photosensitive resin composition and uses thereof - Google Patents

Abstract

The invention relates to a black photosensitive resin composition, a black pattern formed by the black photosensitive resin composition, and a liquid crystal display element including the black pattern. The black photosensitive resin composition includes an alkali-soluble resin (A), a compound having an unsaturated ethylenically group (B), a photoinitiator (C), a solvent (D) and a black pigment (E). The black pattern formed by the black photosensitive resin composition has the advantages of improved taper angle and dryness.

Description

Black photosensitive resin composition and its application

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 element containing the black pattern; in particular, a black photosensitive resin composition is provided, the black photosensitive resin composition The black pattern formed by the resin composition has the advantages of a taper angle and good drying properties.

In recent years, with the vigorous development of various technologies of liquid crystal display devices, and in order to improve the contrast and display quality of the liquid crystal display device, the stripes and dots of the color filter in the liquid crystal display device are usually used. A black pattern, such as a black matrix, is arranged 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.

JP 2008-268854 discloses a photosensitive resin composition for 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 uses a specific alkali-soluble resin to improve the pattern resolution of the black matrix formed by a photosensitive resin composition with a high content of black pigments. In addition, Japanese Patent Application Publication No. 2009-145432 discloses 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. The patent improves the low sensitivity and poor developability of the photosensitive resin composition with high content of black pigment during the photolithography process by adjusting the black pigment content in the solid content of the photosensitive resin composition.

However, as the industry has increasingly higher requirements for the light-shielding properties of the black matrix, the solution is to increase the content of black pigments to improve the light-shielding properties of the black matrix. However, the black color produced by the aforementioned black photosensitive resin composition The taper angle and dryness of the pattern are poor. When the taper angle is not good, it is easy to control the shape of the color photoresist in the subsequent manufacturing process; and when the drying property is not good, it is easy to generate foreign matter and cause defects.

In summary, how to make the black pattern made of the black photosensitive resin composition, such as the black matrix, have a good taper angle and dryness, so as to meet the current industry requirements, is the subject of hard work in the technical field of the present invention. the goal.

The present invention provides a black photosensitive resin composition containing a special combination of components, thereby obtaining a black pattern with good taper angle and drying properties formed by the black photosensitive resin composition.

式(1) 式(1)中，A₁ 、A₁ ’各自為R_a SR_b ，所述R_a 為單鍵、C₁ -C₁₀ 伸烷基(Alkylene)或C₆ -C₁₅ 伸芳基(Arylene)，所述R_b 為C₁ -C₁₀ 烷基或C₆ -C₁₅ 芳基；n為1至6的整數；A₂ 、A₂ ’各自為氫、羥基、硫醇基、氨基、硝基或鹵素取代基； 該溶劑(D)包含式(2)所示之第一溶劑(D-1)；

式(2) 式(2)中，D₁ 為具直鏈或支鏈之C₁ -C₈ 伸烷基，D₂ 為具直鏈或支鏈之C₁ -C₈ 烷基；a為2至4的整數，且複數個D₁ 可相同或不同。Therefore, the present invention provides a black photosensitive resin composition comprising: an alkali-soluble resin (A); a compound having an ethylenically unsaturated group (B); a photoinitiator (C); a solvent (D); and a black pigment (E); Wherein, the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture, and the first mixture Comprising the diol compound (a-1-1) represented by formula (1), tetracarboxylic acid or its acid dianhydride (a-1-2) and dicarboxylic acid or its acid anhydride (a-1-3);

Formula (1) In formula (1), A ₁ and A ₁ 'are each _Ra SR _b , and the Ra is _a single bond, C ₁ -C ₁₀ Alkylene or C ₆ -C ₁₅ Arylene 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 and A ₂ 'are each hydrogen, hydroxyl, thiol, Amino group, nitro group or halogen substituent; The solvent (D) contains the first solvent (D-1) represented by formula (2);

Formula (2) In the 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 2 An integer from to 4, and plural D ₁ may be the same or different.

The present invention also provides a black pattern, which is formed by the aforementioned black photosensitive resin composition undergoing a pre-baking treatment, an exposure treatment, a development treatment and a post-baking treatment.

The present invention also provides a liquid crystal display device including the aforementioned black pattern.

式(1) 式(1)中，A₁ 、A₁ ’各自為R_a SR_b ，所述R_a 為單鍵、C₁ -C₁₀ 伸烷基或C₆ -C₁₅ 伸芳基，所述R_b 為C₁ -C₁₀ 烷基或C₆ -C₁₅ 芳基；n為1至6的整數；A₂ 、A₂ ’各自為氫、羥基、硫醇基、氨基、硝基或鹵素取代基； 該溶劑(D)包含式(2)所示之第一溶劑(D-1)；

式(2) 式(2)中，D₁ 為具直鏈或支鏈之C₁ -C₈ 伸烷基，D₂ 為具直鏈或支鏈之C₁ -C₈ 烷基；a為2至4的整數，且複數個D₁ 可相同或不同。Therefore, the present invention provides a black photosensitive resin composition comprising: an alkali-soluble resin (A); a compound having an ethylenically unsaturated group (B); a photoinitiator (C); a solvent (D); and a black pigment (E); Wherein, the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture, and the first mixture Comprising the diol compound (a-1-1) represented by formula (1), tetracarboxylic acid or its acid dianhydride (a-1-2) and dicarboxylic acid or its acid anhydride (a-1-3);

Formula (1) In the formula (1), A ₁ and A ₁ 'are each _Ra SR _b , and the Ra is _a single bond, C ₁ -C ₁₀ alkylene or C ₆ -C ₁₅ arylene, so Said 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 and A ₂ 'are each hydrogen, hydroxyl, thiol, amino, nitro or halogen Substituents; The solvent (D) includes the first solvent (D-1) represented by formula (2);

Formula (2) In the 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 2 An integer from to 4, and plural D ₁ may be the same or different.

式(1) 式(1)中，A₁ 、A₁ ’各自為R_a SR_b ，所述R_a 為單鍵、C₁ -C₁₀ 伸烷基或C₆ -C₁₅ 伸芳基，所述R_b 為C₁ -C₁₀ 烷基或C₆ -C₁₅ 芳基；n為1至6的整數；A₂ 、A₂ ’各自為氫、羥基、硫醇基、氨基、硝基或鹵素取代基。The alkali-soluble resin (A) according to the present invention includes the first alkali-soluble resin (A-1), which is obtained by polymerizing the first mixture. The first mixture may comprise the diol compound (a-1-1) represented by formula (1), tetracarboxylic acid or its acid dianhydride (a-1-2) and dicarboxylic acid or its acid anhydride (a-1 -3);

Formula (1) In the formula (1), A ₁ and A ₁ 'are each _Ra SR _b , and the Ra is _a single bond, C ₁ -C ₁₀ alkylene or C ₆ -C ₁₅ arylene, so Said 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 and A ₂ 'are each hydrogen, hydroxyl, thiol, amino, nitro or halogen Substituents.

The C ₁ -C ₁₀ alkyl group is linear or branched, and examples thereof can be methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, pentyl Yl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl and decyl; C ₆ -C ₁₅ aryl may be, for example, phenyl, naphthyl, Anthryl, phenanthryl, etc. The C ₁ -C ₁₀ alkylene group and the C ₆ -C ₁₅ arylene group may be the alkylene group and the arylene group corresponding to the aforementioned 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 tetracarboxylic acid containing fluorine atom, linear hydrocarbon tetracarboxylic acid, alicyclic tetracarboxylic acid, aromatic tetracarboxylic acid, or the above-mentioned tetracarboxylic acid The dianhydride compound of 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)pyromellitic acid, 3,3'-hexafluoroisopropylidene diphthalic acid, 5,5'-[2,2,2-tris Fluoro-1-[3-(trifluoromethyl)phenyl]ethylene]diphthalic acid, 5,5'-[2,2,3,3,3-pentafluoro-1-(trifluoro (Methyl)propylene]diphthalic acid, 5,5'-oxybis[4,6,7-trifluoro-pyromellitic acid], 3,6-bis(trifluoromethyl) benzene Fluorine-containing tetracarboxylic acids such as tetracarboxylic acid, 4-(trifluoromethyl)pyromellitic acid, 1,4-bis(3,4-dicarboxylic acid trifluorophenoxy)tetrafluorobenzene, or the above-mentioned tetracarboxylic acids An acid dianhydride compound, or a combination of the above compounds.

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

Specific examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, norbornane tetracarboxylic acid, or a combination of the foregoing compounds. The alicyclic tetracarboxylic acid may have a substituent.

Specific examples of the dianhydride compound of the alicyclic tetracarboxylic acid include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1 , 2,3,4-cyclohexanetetracarboxylic dianhydride or 3,3',4,4'-diphenyl tetracarboxylic dianhydride, or a combination of the above compounds.

Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl 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 aromatic tetracarboxylic dianhydride compound include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'- Phenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic 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)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-di Carboxyphenyl) methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) dianhydride, bis(3,4-dicarboxyphenyl) ether Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic 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 above compounds.

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 Acid or anhydride of the aforementioned dicarboxylic acid compound, or a combination of the aforementioned 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, tetrafluorophthalic acid, Fluorosuccinic acid, or anhydride compounds of the above dicarboxylic acids, or a combination of the above compounds.

Specific examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetosuccinic 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 compounds. The hydrocarbon group in the saturated linear hydrocarbon dicarboxylic acid may also be substituted.

Specific examples of the saturated cyclic hydrocarbon dicarboxylic acid include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, hexahydrotrimellitic acid, or the aforementioned compounds The combination. The saturated cyclic hydrocarbon dicarboxylic acid may also be alicyclic dicarboxylic acid substituted with saturated hydrocarbon.

Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl bridge methylene tetrahydrophthalic acid, chlorendic acid, trimellitium Acid, or a combination of the above compounds.

Specific examples of the other dicarboxylic acid or its anhydride include trimethoxysilyl propyl succinic anhydride, triethoxy silyl propyl succinic anhydride, methyl dimethoxy silyl propyl succinic anhydride, methane Diethoxysilyl propyl succinic anhydride, trimethoxysilyl butyl succinic anhydride, triethoxy silyl butyl succinic anhydride, methyl diethoxy silyl butyl succinic anhydride, P-(trimethoxysilyl)phenyl succinic anhydride, p(triethoxysilyl)phenyl succinic anhydride, p(methyldimethoxysilyl)phenyl succinic anhydride, p(methyl Diethoxysilyl) phenyl succinic anhydride, m (trimethoxysilyl) phenyl succinic anhydride, m (triethoxy silyl) phenyl succinic anhydride, m (methyl diethoxy) Dicarboxylic acid anhydrides such as silyl)phenyl succinic anhydride, or dicarboxylic acid compounds of the above-mentioned dicarboxylic acid anhydrides, or a combination of the above-mentioned compounds.

The synthesis method of 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 its acid dianhydride ( a-1-2) and the dicarboxylic acid or its anhydride (a-1-3) can be obtained.

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

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

After the aforementioned polymerization reaction starts, the dicarboxylic acid or its anhydride (a-1-3) is added, for example, at 100°C to 130°C, preferably at 110°C to 120°C, for 30 minutes to 4 hours, preferably React for 1 hour to 3 hours.

Based on the usage amount of the diol compound (a-1-1) represented by the formula (1) being 100 parts by weight, the usage amount of the dicarboxylic acid or its anhydride (a-1-3) is 2 to 10 parts by weight , Preferably 2 parts by weight to 5 parts by weight, and more preferably 3 parts by weight 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 1,000 g/mol to 100,000 g/mol, preferably 2,000 g/mol to 50,000 g/mol, more preferably 3,000 g/mol to 10,000 g/mol. In addition, the dispersion degree of the 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.

Based on the total usage amount of the alkali soluble resin (A) being 100 parts by weight, the usage amount of the first alkali soluble resin (A-1) is 30 to 100 parts by weight, preferably 40 to 90 parts by weight, and More preferably, it is 50 parts by weight to 90 parts by weight. When the first alkali-soluble resin (A-1) is not used, the black pattern produced by 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 include a second alkali-soluble resin (A-2), the second alkali-soluble resin (A-2) is obtained by polymerizing a second mixture, and the second mixture includes Polymerizable unsaturated group-containing diol compound (a-2-1), tetracarboxylic acid or its acid dianhydride (a-2-2), and dicarboxylic acid or its acid anhydride (a-2-3).

The diol compound (a-2-1) containing a polymerizable unsaturated group 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 From the reaction.

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 formula (a-2-1 -3) The structure shown, or the above three structures. The structure represented by the formula (a-2-1-1), the structure represented by the formula (a-2-1-2), and the structure represented by the formula (a-2-1-3) are specifically described below.

式(a-2-1-1) 式(a-2-1-1)中，W¹ 、W² 、W³ 以及W⁴ 各自獨立表示氫原子、鹵素原子、碳數為1至5的烷基、碳數為1至5的烷氧基、碳數為6至12的芳基或碳數為6至12的芳烷基。Specifically, the structure represented by the formula (a-2-1-1) is as follows:

Formula (a-2-1-1) 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 alkane having 1 to 5 carbon atoms Group, alkoxy group having 1 to 5 carbons, aryl group having 6 to 12 carbons, or aralkyl group having 6 to 12 carbons.

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 obtained by reacting a bisphenol phenolic compound with a halogenated propylene oxide Bisphenolic compound.

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

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

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

式(a-2-1-2) 式(a-2-1-2)中，W⁵ 至W¹⁸ 各自獨立表示氫原子、鹵素原子、碳數為1至8的烷基或碳數為6至15的芳香基，s表示0至10的整數。In addition, specifically, the structure represented by formula (a-2-1-2) is as follows:

Formula (a-2-1-2) In formula (a-2-1-2), W ⁵ to W ¹⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbons, or a carbon number 6 To 15 aromatic groups, s represents an integer of 0-10.

式(a-2-1-2-I) 在上式(a-2-1-2-I)中，W⁵ 至W¹⁸ 以及s的定義是分別與式(a-2-1-2)中的W⁵ 至W¹⁸ 以及s的定義相同，在此不另贅述。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 -I) The compound of the structure is obtained by reacting with halogenated propylene oxide.

Formula (a-2-1-2-I) In the above formula (a-2-1-2-I), W ⁵ to W ¹⁸ and s are defined respectively with the formula (a-2-1-2) The definitions of W ⁵ to W ¹⁸ and s are the same, and will not be repeated here.

The synthesis method of the epoxy compound with at least two epoxy groups containing the structure represented by formula (a-2-1-2) can refer to the patent of Taiwan Publication No. TW201508418.

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

式(a-2-1-3) 式(a-2-1-3)中，Ar₃ 表示萘環，W¹⁹ 表示氰基、鹵素或烴基，W²⁰ 表示烴基、烷氧基、環烷氧基、芳氧基、芳烷氧基、烷硫基、環烷硫基、芳硫基、芳烷硫基、醯基、鹵素、硝基、氰基或是經取代的氨基，W²¹ 表示伸烷基，a表示0至4的整數，b以及c表示0或0以上的整數。In addition, specifically, the structure represented by the formula (a-2-1-3) is as follows:

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

Specific examples of the epoxy compound having at least two epoxy groups and containing the structure represented by the formula (a-2-1-3) include: 9,9-bis(glycidyloxynaphthyl)fluorene, and for example It is 9,9-bis(6-glycidoxy-2-naphthyl)fluorene or 9,9-bis(5-glycidoxy-1-naphthyl)fluorene and similar compounds.

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-methacryloxyethyl succinic acid, 2-methacryloxybutyl succinic acid, 2-methacryloxyethyl adipic acid, 2- Methacryloxybutyl adipic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl maleic acid, 2-methacryloxypropyl horse Acid, 2-methacryloxybutyl maleic acid, 2-methacryloxypropyl succinic acid, 2-methacryloxypropyl adipic acid, 2-methacryloxypropyl Tetrahydrophthalic acid, 2-methacryloxypropyl phthalic acid, 2-methacryloxybutyl phthalic acid, 2-methacryloxybutylhydrophthalic acid Or its analogues; (2) A compound obtained by reacting a (meth)acrylate having a hydroxyl group with a dicarboxylic acid compound. Specific examples of the dicarboxylic acid compound include adipic acid, succinic acid, maleic acid, and phthalic acid. Formic acid or its analogues; and (3) A half-ester compound obtained by reacting a (meth)acrylate having a hydroxyl group with a carboxylic acid anhydride compound. Specific examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxyl Ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate or the like Things.

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

The types of tetracarboxylic acid or its acid dianhydride (a-2-2) and dicarboxylic acid or its acid anhydride (a-2-3) used in the second alkali-soluble resin (A-2) can be the same as those of the aforementioned first 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 dianhydride ( a-2-2) and the dicarboxylic acid or its anhydride (a-2-3) can be obtained by reaction, 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) measured by GPC in terms of polystyrene is preferably 800 to 8,000, more preferably 1,000 to 6,000.

Based on the total usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount of the second alkali-soluble resin (A-2) is 0 to 70 parts by weight, preferably 10 to 60 parts by weight, and More preferably, it is 10 to 50 parts by weight. When the first alkali-soluble resin (A-2) is used, the taper angle of the black pattern produced by the black photosensitive resin composition of the present invention can be further improved.

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

The aforementioned compound having an ethylenically unsaturated group may include, but is not limited to, (meth)acrylamide, (meth)acrylamide, (meth)acrylic acid-7-amino-3,7-dimethyl Octyl ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , Ethyl diethylene glycol (meth)acrylate, the third octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, ( Lauryl meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, Tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, (meth) Acrylic acid-2-tetrabromophenoxyethyl, (meth)acrylic acid-2-trichlorophenoxyethyl, (meth)acrylic acid tribromophenyl ester, (meth)acrylic acid-2-tribromophenoxyethyl Ethyl ester, 2-hydroxy-(meth)ethyl acrylate, 2-hydroxy-(meth) propyl acrylate, vinyl caprolactam, N-vinyl pyrrolidone, (meth) phenoxy ethyl acrylate Ester, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, poly(ethylene mono(meth)acrylate), poly(propylene mono(meth)acrylate or borneol (meth)acrylate) Compounds such as esters. The compound having one ethylenically unsaturated group can be used alone or in combination of plural kinds.

The aforementioned compounds having 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 two (Meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate (Meth) acrylate, caprolactone modification three (2-hydroxyethyl) isocyanate tri(meth)acrylate, tri(meth)acrylate trimethylol propyl ester, ethylene oxide ( (Referred to as EO) modified three (meth)acrylic acid trimethylol propyl ester, propylene oxide modification (abbreviated as PO) three (meth)acrylic acid trimethylol propyl ester, tripropylene glycol di(meth)acrylic acid Esters, 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 Dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate modified by caprolactone, ditrimethylol propyl tetra(meth)acrylate, modified with ethylene oxide Bisphenol A di(meth)acrylate, bisphenol A di(meth)acrylate modified with propylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with ethylene oxide, Hydrogenated bisphenol A di(meth)acrylate modified by propylene oxide, bisphenol F di(meth)acrylate modified by ethylene oxide, or novolac polyglycidyl ether (meth)acrylate, etc. The compound. The compound having two or more (including two) ethylenic unsaturated groups can be used alone or in a mixture of plural kinds.

Specific examples of the compound (B) having an ethylenically unsaturated group may include but are not limited to: trimethylol propyl triacrylate, trimethylol propyl triacrylate modified with ethylene oxide, epoxy Propane modified trimethylol propyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexa Acrylate, ditrimethylolpropyl tetraacrylate, glycerol triacrylate modified by propylene oxide, or any combination of the above compounds.

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

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

式(3) 其中R₁ 、R₂ 、R₃ 、R₄ 、R₅ 、R₆ 、R₇ 及R₈ 彼此獨立地為氫、C₁ -C₂₀ 烷基、COR₁₆ 、或

； 或R₁ 及R₂ 、R₂ 及R₃ 、R₃ 及R₄ 、R₅ 及R₆ 、R₆ 及R₇ 或R₇ 及R₈ 彼此獨立地共同為

； 但條件為R₁ 及R₂ 、R₂ 及R₃ 、R₃ 及R₄ 、R₅ 及R₆ 、R₆ 及R₇ 或R₇ 及R₈ 中之至少一對為

； R₉ 、R₁₀ 、R₁₁ 及R₁₂ 彼此獨立地為氫、C₁ -C₂₀ 烷基，該C₁ -C₂₀ 烷基是未經取代或經一或多個以下基團取代：鹵素、苯基； 或R₉ 、R₁₀ 、R₁₁ 及R₁₂ 彼此獨立地為未經取代之苯基或經一或多個以下基團取代之苯基：C₁ -C₆ 烷基、鹵素； X表示CO或直接鍵； R₁₃ 表示C₁ -C₂₀ 烷基，其未經取代或經一或多個以下基團取代：鹵素、R₁₇ 、COOR₁₇ 、OR₁₇ ； 或R₁₃ 表示C₂ -C₂₀ 烷基，其間雜有一或多個O或CO，其中該經間雜之C₂ -C₂₀ 烷基是未經取代或經一或多個鹵素取代； 或R₁₃ 表示苯基或萘基，其各為未經取代或經一或多個以下基團取代：C₁ -C₂₀ 烷基、C₁ -C₄ 鹵代烷基； R₁₄ 表示氫、C₁ -C₂₀ 烷氧基或C₁ -C₂₀ 烷基； R₁₅ 是C₆ -C₂₀ 芳基，其各是未經取代或經一或多個以下基團取代：鹵素、C₁ -C₄ 鹵代烷基、OR₁₇ 、間雜有一或多個O之C₂ -C₂₀ 烷基；或其各經C₁ -C₂₀ 烷基取代，該C₁ -C₂₀ 烷基是未經取代或經一或多個以下基團取代：鹵素、COOR₁₇ 、苯基、OR₁₇ ； 或R₁₅ 表示氫、C₃ -C₈ 環烷基；或R₁₅ 是C₁ -C₂₀ 烷基，其是未經取代或經一或多個以下基團取代：鹵素、C₃ -C₈ 環烷基； R₁₆ 表示C₆ -C₂₀ 芳基，其各是未經取代或經一或多個以下基團取代：鹵素、C₁ -C₄ 鹵代烷基、OR₁₇ ；或其各經一或多個C₁ -C₂₀ 烷基取代，該C₁ -C₂₀ 烷基是未經取代或經一或多個以下基團取代：鹵素、OR₁₇ ； R₁₇ 表示氫、C₁ -C₂₀ 烷基，其是未經取代或經一或多個以下基團取代：鹵素或間雜有一或多個O之C₃ -C₂₀ 環烷基； 或R₁₇ 表示C₂ -C₂₀ 烷基，其間雜有一或多個O； 或R₁₇ 表示苯基，其各是未經取代或經一或多個以下基團取代：鹵素、C₁ -C₁₂ 烷基、C₁ -C₁₂ 烷氧基； 但條件為在式(3)中存在至少一個

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

Formula (3) wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently 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 are independently of each other and collectively are

; But the condition is that at least one 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, and the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen , Phenyl; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen; X represents CO or a 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 C ₂ -C ₂₀ alkyl group with one or more O or CO interposed therebetween, wherein the intervening 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 groups: halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , or A plurality of O C ₂ -C ₂₀ alkyl groups; or each of them is substituted by a C ₁ -C ₂₀ alkyl group, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: 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 has one or more of the following groups Substitution: 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 is substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group 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 with one or more O interspersed; or R ₁₇ represents C ₂ -C ₂₀ alkyl group, with one or more O interposed therebetween; or R ₁₇ represents a phenyl group, 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; but the condition is that there is at least one in formula (3)

.

。The photoinitiator (C-1) represented by formula (3) is characterized in that its phenyl ring is fused with the carbazole moiety to form a "naphthyl" ring, that is, it contains one or more on the carbazole moiety Annealed unsaturated ring. In other words, at least one 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

.

The C ₁ -C ₂₀ alkyl group is linear or branched, and examples thereof can be methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, pentyl Base, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, Eighteen base and twenty base.

The C ₁ -C ₄ haloalkyl group may be a C ₁ -C ₄ alkyl group as defined above, and it is 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, C _z H _x Hal _y , where x+y=2z+1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

The C ₂ -C ₂₀ alkyl group interspersed with one or more O can be interspersed with O 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 methylidene group, preferably at least two methylidene groups (ie, ethylidene groups). These alkyl groups can be straight or branched. For example, it can be the following structural units: -CH ₂ -CH ₂ -O-CH ₂ CH ₃ , -[CH ₂ CH ₂ O] _y -CH ₃ (where y=1 to 9), -(CH _2- 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 substituted by O atom of a C ₁ -C ₁₂ alkyl.

The C ₆ -C ₂₀ aryl group may be, for example, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, eryl, naphthyl, triphenylene, etc., especially phenyl or naphthyl, preferably Phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

The substituted aryl groups (phenyl, naphthyl, C ₆ -C ₂₀ aryl) can be substituted 1 to 7, 1 to 6 or 1 to 4 times, especially 1, 2 or 3 times, respectively. Obviously, the number of substituents of the aryl group here cannot be more than the number of free positions on the aryl ring.

The substituents on the phenyl ring are preferably in position 4 on the phenyl ring, or in the group 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6- state.

The group of interspersed can be, for example, interspersed 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 time or 2 times. Obviously, the number of heteroatoms depends on the number of C atoms of the pseudoheterogroup. The substituted group may have, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3, or 1 or 2 substituents which are the same or different.

，則形成例如以下(Ia)至(Ii)所示之結構：

(Ia) (Ib) (Ic)

(Id) (Ie) (If)

(Ig) (Ih) (Ii) ，其中較佳為式(Ia)、(Ib)、(Ic)，更佳為式(Ia)或(Ic)、或式(Ia)、(Ic)或(Id)、尤佳為式(Ia)。The substituted group may have one substituent, or multiple substituents that are the same or different. The halogen may 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 are independently of each other and jointly are

, For example, the following structures (Ia) to (Ii) are formed:

(Ia) (Ib) (Ic)

(Id) (Ie) (If)

(Ig) (Ih) (Ii) , Wherein the formula (Ia), (Ib), (Ic) is preferred, the formula (Ia) or (Ic), or the formula (Ia), (Ic) or (Id) is more preferred, and the formula (Ia) is more preferred. ).

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

In an example, R ₁₆ represents a C ₆ -C ₂₀ aryl group (preferably phenyl or naphthyl, more preferably phenyl), 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 them is substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: 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 groups: 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 a phenyl group, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ or C ₁ -C ₂₀ alkyl. R _{16 is} particularly preferably phenyl, which is substituted with one or more C ₁ -C ₂₀ alkyl groups.

In one example, 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 with one or more O interspersed 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.

(3-1) (3-2)

(3-3) (3-4)

(3-5) (3-6)

(3-7) (3-8)

(3-9) (3-10)

(3-11) (3-12)

(3-13) (3-14)

(3-15) (3-16)

(3-17) (3-18)

(3-19) (3-20)

(3-21) (3-22) Examples of the photoinitiator (C-1) represented by formula (3) include the following compounds represented by formula (3-1) to formula (3-22):

(3-1) (3-2)

(3-3) (3-4)

(3-5) (3-6)

(3-7) (3-8)

(3-9) (3-10)

(3-11) (3-12)

(3-13) (3-14)

(3-15) (3-16)

(3-17) (3-18)

(3-19) (3-20)

(3-21) (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 Parts to 45 parts by weight, and more preferably 10 parts to 40 parts by weight. When the photoinitiator (C-1) represented by the formula (3) is used, the taper angle of the black pattern produced by the black photosensitive resin composition of the present invention can be further improved.

In the black photosensitive resin composition of the present invention, another photoinitiator (C-2) can be optionally added.

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

Specific examples of the other oxy-acetoxime compounds include specific examples including 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O- Phenanyl oxime), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenanyl oxime), 1-[4-(phenylsulfide) (O) phenyl]-octane-1,2-dione-2-(O-phenacyl oxime), or a combination of the above compounds. 1-[4-(Phenylthio)phenyl]-octane-1,2-dione-2-(O-phenyloxime) can be manufactured by Ciba Specialty Chemicals Co., Ltd. , The product model is IRGACURE OXE-01.

In addition, specific examples of the other oxy-phenyloxime compounds include 1-[4-(phenanyl)phenyl]-heptane-1,2-dione-2-(O-phenanyl oxime), 1-[9-Ethyl-6-(2-Methylphenanyl)-9H-carbazole-3-substituent]-Ethanone-1-(O-Acetyloxime), 1-[9 -Ethyl-6-(3-Methylphenanyl)-9H-carbazole-3-substituent]-Ethanone-1-(O-Acetyloxime), 1-[9-Ethyl- 6-Phenyl-9H-carbazole-3-substituent]-ethane ketone-1-(O-acetoxime), ethane ketone-1-[9-ethyl-6-(2-methyl -4-tetrahydrofuranylphenyl)-9H-carbazole-3-substituent)-1-(O-acetoxime), ethaneketone-1-[9-ethyl-6-(2- Methyl-4-tetrahydropyranylphenyl)-9H-carbazole-3-substituent)-1-(O-acetoxyoxime), ethyl ketone-1-[9-ethyl-6 -(2-Methyl-5-tetrahydrofuranylphenyl)-9H-carbazole-3-substituent)-1-(O-acetoxyoxime), ethaneketone-1-[9-ethyl- 6-(2-Methyl-5-tetrahydropyranylphenanyl)-9H-carbazole-3-substituent)-1-(O-acetyloxime), ethaneketone-1-[9 -Ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxyphenanyl)-9H-carbazole-3-substituent)-1-(O-acetyloxime), ethane ketone- 1-[9-Ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenanyl)-9H-carbazole-3-substituent]-1-(O-acetinyl Oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxyphenanyl)-9H-carbazole-3-substituent)-1-(O -Acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenacyl)-9H-carbazole-3-substituted Yl]-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-di Oxolane) phenanyl}-9H-carbazole-3-substituent]-1-(O-acetoxyoxime), ethaneketone-1-[9-ethyl-6-{2- Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxyphenacyl)-9H-carbazole-3-substituent)-1-(O-ethyl Oxime), or a combination of the above compounds. 1-[9-Ethyl-6-(2-Methylphenanyl)-9H-carbazole-3-substituent]-Ethanone-1-(O-Acetyloxime) can be made from Ciba A product manufactured by Jinghua Co., Ltd., with model number IRGACURE OXE-02.

The other oxy-oxime compounds can be used alone or in combination of multiple types.

Specific examples of the non-oxygen-oxime photoinitiator include triazabenzene compounds, acetophenone compounds, diimidazole compounds, benzophenone compounds, α-diketone compounds, alcohol ketones Compounds, alcohol ketone ether compounds, phosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, or a combination of the foregoing compounds.

Specific examples of the triazabenzene compound include vinyl-halomethyl-s-triazabenzene compound, 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 compounds.

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-trichloromethyl -3-amino-6-p-methoxystyryl-s-triazabenzene, or a combination of the above compounds.

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-tri Azabenzene, 2-(4-ethoxy-naphtho-1-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4-butoxy- Naphtho-1-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-substituent ]-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphtho-1-substituent]-4,6-di (Trichloromethyl)-s-Triazine, 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-methyl Oxy-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(trichloromethyl) Group)-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-naphthalene -1-Substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, or a combination of the above compounds.

Specific examples of the 4-(p-aminophenyl)-2,6-bis(halomethyl)-s-triazabenzene compound include 4-[p-N,N-bis(ethoxycarbonyl Methyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl) )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(trichloro Methyl)-s-triazine, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(p- -N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(phenyl)amino Phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl) )-s-Triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene , 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo -P-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p- N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N -Bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis( Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxy) Carbonylmethyl)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-bis( 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-triazabenzene , 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-ethoxycarbonylmethylamino) 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-chloroethylamine Phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis( Trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene Benzene, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 2,4-bis(trichloromethyl) Yl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene, or a combination of the above compounds. The triazine compound can be used alone or in combination of multiple types.

The triazine compound preferably includes 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 compounds.

Specific examples of the acetophenone compound include p-dimethylamine acetophenone, α,α'-dimethoxyazoacetophenone, 2,2'-dimethyl-2-phenyl 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 compound can be used alone or in combination of multiple types.

The 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone can be manufactured by Ciba Fine Chemicals Co., Ltd. with a model number of IRGACURE 907. 2-Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone can be manufactured by Ciba Fine Chemicals Co., Ltd., and the model is IRGACURE 369.

The acetophenone compound preferably includes 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.

Specific examples of the diimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorobenzene) Group)-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 Combinations of the above compounds.

The diimidazole compound can be used alone or in combination of multiple types.

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

Specific examples of the benzophenone compound include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfur, benzophenone, 4,4'-bis(dimethylamine) Benzophenone, 4,4'-bis(diethylamine)benzophenone, or a combination of the above compounds. 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 compound include benzil, diacetyl, or a combination of the foregoing compounds. The α-diketone compound can be used alone or in combination of multiple types.

Specific examples of the ketone alcohol compound include benzophenone. The ketone alcohol compound can be used alone or in combination of multiple types.

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

Specific examples of the phosphine oxide compound include 2,4,6-trimethylphenydiphenylphosphine oxide, bis(2,6-dimethoxyphenylate)-2,4,4- Trimethylphenylphosphine oxide, or a combination of the above compounds. Phosphine oxide compounds can be used alone or in combination of multiple types.

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

Specific examples of the halogen-containing compound include phenacyl chloride, tribromomethyl benzene, tris(trichloromethyl)-s-triazabenzene, or a combination of the foregoing compounds. The halogen-containing compounds can be used alone or in combination of multiple types.

Specific examples of this peroxide include di-tertiary butyl peroxide and the like. Peroxide can be used individually or in combination of multiple types.

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

式(2) 式(2)中，D₁ 為具直鏈或支鏈之C₁ -C₈ 伸烷基，D₂ 為具直鏈或支鏈之C₁ -C₈ 烷基；a為2至4的整數，且複數個D₁ 可相同或不同。The solvent (D) of the present invention includes the first solvent (D-1) represented by formula (2):

Formula (2) In the 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 2 An integer from to 4, and plural D ₁ may 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 Ester, diethylene glycol tert-butyl ether acetate, diethylene glycol n-pentyl ether acetate, diethylene glycol isoamyl ether acetate, diethylene glycol n-hexyl ether acetate, diethylene glycol n-heptane 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, dineopentyl 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, di-2,5-dimethyl Base-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-butanediol neopentyl glycol tert-butyl ether acetate, diethylene glycol dipropylene glycol n-hexyl ether acetate, bis-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 parts by weight to 1300 parts by weight. When the first solvent (D-1) is not used, the black pattern produced by the black photosensitive resin composition of the present invention has a problem of poor drying properties.

式(4) 其中，D₃ 為具直鏈或支鏈的C₁ -C₃ 烷基，D₄ 為具直鏈或支鏈的C₁ -C₄ 烷基。The solvent (D) of the present invention may further include a second solvent (D-2) represented by formula (4):

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 Methyl acid, 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-methylpropionate, ethyl 2-methylpropionate, n-propyl 2-methylpropionate, isopropyl 2-methylpropionate, 2-methylpropionic acid N-butyl ester, 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 parts by weight to 1100 parts by weight. When the second solvent (D-2) is used, the dryness of the black pattern produced 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 of the first solvent (D-1) divided by the usage of the second solvent (D-2) When the amount) is 0.5 to 3, preferably 0.8 to 2.5, and more preferably 1.0 to 2.0, the dryness of the black pattern produced by the black photosensitive resin composition of the present invention can be further improved.

In the black photosensitive resin composition of the present invention, other solvents (D-3) can be optionally added.

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 its analogues; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate or its analogues; diethylene glycol two Methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or their analogs; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or their analogs; 2-hydroxy-2 -Methyl methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 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 acetyl acetate, ethyl acetyl acetate, 2-oxybutan Ethyl acid or its analogue; toluene, xylene or its analogue; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or its analogue.

Based on the total usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount of the solvent (D) is 250 to 5000 parts by weight, preferably 350 parts by weight to 4800 parts by weight, and more preferably 450 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 aforementioned black pigment (E) are black organic pigments such as perylene black, cyanine black, and aniline black; consisting of red, blue, green, purple, and yellow Among the pigments such as cyanine, magenta, etc., select two or more pigments to mix to make them into a nearly black mixed color organic pigment; carbon black, chromium oxide, iron oxide , Titanium black (titanium black), graphite and other light-shielding materials, wherein the aforementioned carbon black may include but is not limited to CIpigment black 7, etc., and specific examples of the aforementioned carbon black are commercially available products manufactured by Mitsubishi Chemical (trade names MA100, MA230) , MA8, #970, #1000, #2350, #2650). The aforementioned black pigment (F) can generally be used singly or as a mixture of multiple types.

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

Without affecting the efficacy of the present invention, the black photosensitive resin composition of the present invention may further optionally add an additive (F). Specific examples of the additive (F) may include surfactants, fillers, adhesion promoters, antioxidants, anti-agglomeration agents, or polymerization that can increase various properties (such as mechanical properties) other than the aforementioned alkali-soluble resin (A) Things.

Specific examples of the aforementioned surfactants may include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants, or the aforementioned surfactants. Any combination of agents.

Specific examples of the surfactant may include, but are not limited to, polyethoxyalkyl ethers such as polyethoxylauryl ether, polyethoxy stearyl ether or polyethoxy oleyl ether; polyethylene Polyethoxy alkyl phenyl ethers such as oxyoctyl phenyl ether or polyethoxy nonyl phenyl ether; polyethylene glycol dilaurate or polyethylene glycol distearate, etc. Ethylene glycol diesters; sorbitan fatty acid ester compounds; fatty acid modified polyester compounds; tertiary amine modified polyurethane compounds; or commercially available products. Among them, the commercially available product can be a product manufactured by Shin-Etsu Chemical Industry Co., and its model is KP; a product manufactured by Dow Corning Toray Co., Ltd. and its model is SF-8427; A product manufactured by Kyoeisha’s oleochemical industry, and its model is Polyflow; a product manufactured by Tochem Products Co., Ltd., and its model is F-Top; manufactured by Dainippon Ink Chemical Industry The product, and its model is Megafac; the product manufactured by Sumitomo 3M, and its model is Fluorade; or the product manufactured by Asahi Glass Company, and its model is Asahi Guard or Surflon. The surfactant can be used singly or in combination.

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

Specific examples of the aforementioned adhesion promoter may include vinyl trimethoxysilane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, and N-(2-aminoethyl) -3-aminopropylmethyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidoxypropyl trimethoxysilane (product manufactured by Shin-Etsu Chemical, and its model number is KBM-403), EPPN501H (manufactured by Nippon Kayaku Co.), EPIKOTE 152 (manufactured by Shell Chemical Co.), 3-epoxypropylene Oxyoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Compounds such as oxysilane, 3-methylpropoxypropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane, or any combination of the above compounds.

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

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

Based on the usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount of the filler, adhesion promoter, antioxidant, anti-coagulant or polymer other than the alkali-soluble resin (A) in the additive (F) It does not exceed 10 parts by weight, and preferably does not exceed 6 parts by weight.

The black photosensitive resin composition of the present invention is generally composed of the above-mentioned alkali-soluble resin (A), compound having ethylenic unsaturated group (B), photoinitiator (C), solvent (D), black pigment (E) ) Place in a stirrer and stir to make it evenly mixed into a solution state. If necessary, add surfactants, fillers, adhesion promoters, bridging agents, antioxidants, anti-coagulants and other additives (F) for uniformity 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 to be dispersed, or a part of the black pigment (E) Disperse in a part of a medium containing alkali-soluble resin (A) and solvent (D) to form a pigment dispersion, and then mix the compound (B) with ethylenic unsaturated group and the photoinitiator (C) , Alkali-soluble resin (A) and the rest of the solvent (D). The dispersing step of the above-mentioned black pigment (E) can be performed 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 (such as a black matrix), which is formed by the aforementioned black photosensitive resin composition.

The black pattern is made by sequentially applying pre-bake, exposure, development, and post-exposure baking treatments to the black photosensitive resin composition as described above. When the film thickness is 1 μm, the optical density of the black pattern The range is 3.0 or more. Preferably, when the film thickness is 1 μm, the optical density of the black pattern is in the range of 3.2 to 5.5; more preferably, when the film thickness is 1 μm, the optical density of the black pattern is in the range of 3.5 to 5.5.

The black pattern of the present invention can be coated with the aforementioned black photosensitive resin composition on a substrate by a coating method such as spin coating or cast coating, and the solvent can be removed by drying under reduced pressure and pre-baking. , And then form a pre-baked coating film on the substrate. Among them, the aforementioned vacuum drying and pre-baking conditions vary according to the types and mixing ratios of the ingredients. Generally, the vacuum drying is performed at a pressure of less than 200 mmHg for 1 to 20 seconds, while the pre-baking treatment is Perform 1 minute to 15 minutes at a temperature of 70°C to 110°C. After pre-baking, expose the aforementioned coating film under a specified mask, and then immerse it in a developer at a temperature of 23±2°C for 15 seconds to 5 minutes to remove unnecessary parts to 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 aforementioned applicable developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, diethylamine, One of 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 developer is generally 0.001 wt% (wt%) to 10 wt%, preferably 0.005 wt% to 5 wt%, more preferably 0.01 wt% to 1 wt%.

When these developers are used, they are generally washed with water after development, then the pattern is dried with compressed air or compressed nitrogen, and then post-baked with heating devices such as hot plates or ovens. 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 film attached to these glasses for liquid crystal display devices; or for solid-state photography Photoelectric conversion device substrates (such as silicon substrates) for devices, etc.

The present invention also provides a color filter, which contains the aforementioned black pattern.

The method of forming the color filter of the present invention can be applied to the substrate by coating the photosensitive composition for the color filter mixed into a solution state by coating methods such as spin coating, casting coating, or roll coating. Above, the substrate has previously used the aforementioned black photosensitive resin composition to form a black pattern separating the colored layers of each pixel. After coating, first remove most of the solvent by drying under reduced pressure, and then remove the solvent by pre-bake to form a pre-baked coating film. Among them, the conditions of reduced-pressure drying and pre-baking vary according to the types of ingredients and the mixing ratio. Generally, the reduced-pressure drying is carried out at a pressure of 0mmHg to 200mmHg for 1 to 60 seconds, and the pre-baking is at 70 ℃ to 110 ℃ temperature for 1 minute to 15 minutes. After pre-baking, the pre-baked coating film is exposed between the designated masks, and immersed in the aforementioned developer solution at a temperature of 23±2°C for 15 seconds to 5 minutes for development. Unnecessary parts are removed to form a pattern. The light used for exposure is preferably g-line, h-line, i-line and other ultraviolet rays, and the ultraviolet device can be (ultra) high pressure mercury lamps and metal halide lamps.

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

Repeating the above steps for each color (mainly including red, green and blue) can produce the pixel layer of the color filter. Secondly, form an indium tin oxide (ITO) vapor-deposited film on the pixel layer at a temperature of 220°C to 250°C in a vacuum environment. If necessary, after etching and wiring the ITO coating, apply the polyamide for the liquid crystal alignment film. Imine, and then fired, can be used as a color filter for liquid crystal display elements.

The present invention further provides a liquid crystal display element, which includes the aforementioned color filter and the black pattern therein.

The liquid crystal display element of the present invention is a color filter substrate formed by the above-mentioned color filter manufacturing method, and a drive substrate provided with thin film transistors (TFT), between the two substrates The intervening gap (cell gap) is arranged to face each other, and the surrounding parts of the two substrates are bonded with a sealant, and liquid crystal is filled in the gap between the surface of the substrate and the sealant, and the injection hole is sealed. It forms a liquid crystal cell (cell). Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, that is, the other side surfaces of each substrate constituting the liquid crystal cell, and a liquid crystal display element is manufactured.

As for the liquid crystal used above, that is, the liquid crystal compound or the liquid crystal composition, there is no particular limitation here, but any liquid crystal compound and liquid crystal composition can be used.

Furthermore, the aforementioned liquid crystal alignment film is used to restrict the alignment of liquid crystal molecules, and is not particularly limited here, and any inorganic or organic substance may be used. As for the technology of forming the liquid crystal alignment film, it is well known by anyone with ordinary knowledge in the technical field to which the present invention belongs, and is not the focus of the present invention, so it will not be repeated.

The following examples are used to illustrate the present invention in detail, but it does not mean that the present invention is limited to the content disclosed in these examples. <Production example of the diol compound (a-1-1) represented by formula (1)>

Step A: Set up a reflux condenser and thermometer in a three-necked flask, add 42.5 g of 9,9-bisphenol fluorene, and quantitatively inject 220 mL of 2-(chloromethyl)oxirane. After adding 100 mg of tetrabutylammonium bromide, stir and raise the temperature to 90°C. It was confirmed that the content of unreacted materials was less than 0.3%, and then vacuum distillation was performed.

式(1a)Step B: After cooling down to 30°C, inject dichloromethane and slowly add NaOH. High performance liquid chromatography (HPLC) confirmed that the yield was over 96%, and then 5% HCl was added dropwise to stop the reaction. The reactants were separated and extracted, and the organic phase was washed with water to neutrality. Then, after the organic layer was dried with MgSO ₄ , it was distilled under reduced pressure with a cyclotron and concentrated. Dichloromethane was added to the concentrated product, and while heating to 40°C, methanol was stirred and added, and then the solution was cooled and stirred. The filtered solid was vacuum dried at room temperature to obtain 52.7 g of white solid powder (recovery rate of 94%), the structure of which was confirmed by 1 H NMR, as shown in the following formula (1a):

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) ).

式(1b)Step C: Set up a reflux condenser and a thermometer in a three-necked flask, add 1000 g of the compound of formula (1a) obtained in the above synthesis, 524 g of thiophenol and 617 g of ethanol and stir, then add 328 g of triethylamine dropwise to the reaction In 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, washed with water, and distilled under reduced pressure to remove dichloromethane. The concentrated organic matter was dissolved in ethyl acetate, ether solvent was added dropwise and stirred for 30 minutes. Then, the compound was distilled under reduced pressure to obtain 945 g (yield: 64%) of a light yellow oil whose structure was confirmed by 1H NMR, as shown in the following formula (1b):

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＞

式(a-1-a) ＜合成例A-1-2＞A reflux condenser and a thermometer were set in a three-necked flask, and 200 g of the compound of formula (1b) obtained by the aforementioned synthesis was dissolved in 50% propylene glycol methyl ether acetate (PGMEA) and heated to 115°C. After dripping 31.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride at 115°C, keep the temperature at 115°C and continue stirring for 6 hours. After adding 7.35 g of phthalic anhydride (Phthalic anhydride) and continuing to stir for 2 hours, the reaction was terminated. After cooling, the first alkali-soluble resin A-1-1 with a weight average molecular weight of 3,500 g/mol is obtained, and its structure is shown in the following formula (a-1-a):

Formula (a-1-a) <Synthesis Example A-1-2>

式(a-1-b) ＜合成例A-1-3＞31.1 g of 3,3',4,4'-biphenyltetracarboxylic anhydride in Preparation Example 1 was replaced with 28.4 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (Benzophenonetetracarboxylic dianhydride) ), the rest of the components and conditions are the same as above, and the first alkali-soluble resin A-1-2 with a weight average molecular weight of 5,000 g/mol is obtained, and its structure is shown in the following formula (a-1-b):

Formula (a-1-b) <Synthesis Example A-1-3>

式(a-1-c) ＜合成例A-1-4＞Replace 31.1 g of 3,3',4,4'-biphenyltetracarboxylic anhydride in Preparation Example 1 with 21.1 g of Pyromellitic dianhydride, and the rest of the ingredients and conditions are the same as the 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 the structure shown in the following formula (a-1-c):

Formula (a-1-c) <Synthesis Example A-1-4>

式(a-1-d) ＜合成例A-1-5＞Replace 31.1 g of 3,3',4,4'-biphenyltetracarboxylic acid anhydride in Preparation Example 1 with 21.7 g of Cyclohexyl dianhydride, and the rest of the ingredients and conditions are the same as above, to obtain the weight average molecular weight The first alkali-soluble resin A-1-4 is 4,200 g/mol, and its structure is shown in the following formula (a-1-d):

Formula (a-1-d) <Synthesis Example A-1-5>

式(a-1-e) ＜含有聚合性不飽和基的二醇化合物(a-2-1)的製備例＞ ＜製備例1＞Replace 31.1 g of 3,3',4,4'-biphenyltetracarboxylic anhydride in Preparation Example 1 with 18.7 g of Cyclobutyl dianhydride. The rest of the ingredients and conditions are the same as the above, and the weight average is obtained. The first alkali-soluble resin A-1-5 with a molecular weight of 4,200 g/mol has the structure shown in the following formula (a-1-e):

Formula (a-1-e) <Production example of polymerizable unsaturated group-containing diol compound (a-2-1)><Production example 1>

First, 100 parts by weight of 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 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 addition manner. The feeding rate is controlled at 25 parts by weight/minute, and the temperature during the reaction process is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. Then, the light yellow transparent mixed liquid was subjected to the steps of extraction, filtration, and heating and drying to obtain the polymerizable unsaturated group-containing diol compound (a-2-) of Preparation Example 1 with a solid content of 99.9% by weight. 1-a). <Preparation Example 2>

First, 100 parts by weight of the epoxy compound (model PG-100, manufactured by Osaka Gas; epoxy equivalent 259), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight 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 is controlled at 25 parts by weight/minute, and the temperature during the reaction process is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heating and drying to obtain the polymerizable unsaturated group-containing diol compound (a-2-1-) of Preparation Example 2 with a solid content of 99.9% by weight. b). <Preparation Example 3>

100 parts by weight of epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 100 parts by weight of 2-methacrylic acid ethoxy succinate, and 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 addition manner. The feeding rate is controlled at 25 parts by weight/minute, and the temperature during the reaction process is maintained at 100°C to 110°C. After 15 hours of reaction, a light yellow transparent mixed liquid with a solid content of 50% by weight can be obtained. The light yellow transparent mixed liquid was 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 Mole of succinic acid (a-2-3-d), 1.9 g of benzyl triethylammonium 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 were added to a 500-ml four-necked flask by simultaneous addition to form a reaction solution. Here, "simultaneous addition" means adding tetracarboxylic acid or its acid dianhydride (a-2-2) and dicarboxylic acid or its acid anhydride (a-2-3) at the same reaction time. Then, the above reaction solution is 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 four-necked flask to form the reaction solution. Next, 0.6 mol of benzophenone tetracarboxylic dianhydride (a-2-2-c) was added and reacted at 90°C 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, "addition in stages" refers to adding tetracarboxylic acid or its dianhydride (a-2-2) and dicarboxylic acid or its anhydride (a-2-3) at different reaction times, that is, first Add tetracarboxylic acid or its acid dianhydride (a-2-2), and then add dicarboxylic acid or its acid anhydride (a-2-3). Through the above synthesis steps, resin A-2-2 with unsaturated groups can be obtained. <Synthesis Example A-2-3, Synthesis Example A-2-5, and Synthesis Example A-2-6>

Synthesis Example A-2-3, Synthesis Example A-2-5, and Synthesis Example A-2-6 are prepared by the same procedure as Synthesis Example A-2-2, and their differences It lies in: changing the type of the components of the resin with unsaturated groups and their usage, reaction time, reaction temperature and reactant addition time (as shown in Table 1). ＜Synthesis example A-2-4＞

The unsaturated group-containing resin of Synthesis Example A-2-4 was prepared by the same procedure as Synthesis Example A-2-1, and the difference was: the type of the unsaturated group-containing resin and the amount used , Reaction time, reaction temperature and reactant addition time (as shown in Table 1-1, Table 1-2). Table 1-1: ingredient Synthesis example A-2-1 A-2-2 A-2-3 Polymeric components Diol compound containing polymerizable unsaturated group (a-2-1) (mole) a-2-1-a 1.0 - - a-2-1-b - 1.0 0.5 a-2-1-c - - 0.5 Tetracarboxylic acid or its acid dianhydride (a-2-2) (mole) a-2-2-a - - - a-2-2-b 0.3 - - a-2-2-c - 0.6 - a-2-2-d - - 0.5 Dicarboxylic acid or its anhydride (a-2-3) (mole) a-2-3-a - - - a-2-3-b - 0.8 - a-2-3-c - - 1.0 a-2-3-d 1.4 - - Monomer feeding method Also add Add by section Add by section catalyst Benzyltriethylammonium chloride (g) 1.9 2.9 2.5 Polymerization inhibitor 2,6-Di-tert-butyl p-cresol (g) 0.6 - - Solvent PGMEA (g) 700 950 900 EEP (g) 100 - - Reaction temperature (℃) 110 90 90 Reaction time (hours) 2 2 2 4 4 Table 1-2: ingredient Synthesis example A-2-4 A-2-5 A-2-6 Polymeric components Diol compound containing polymerizable unsaturated group (a-2-1) (mole) a-2-1-a 1.0 - - a-2-1-b - 1.0 - a-2-1-c - - 1.0 Tetracarboxylic acid or its acid dianhydride (a-2-2) (mole) a-2-2-a 0.2 - - a-2-2-b 0.1 - - a-2-2-c - - 0.3 a-2-2-d - 0.1 0.5 Dicarboxylic acid or its anhydride (a-2-3) (mole) a-2-3-a - 0.6 - a-2-3-b 0.4 1.0 - a-2-3-c 1.0 - 0.2 a-2-3-d 0.2 0.2 Monomer feeding method Also add Add by section Add by section catalyst Benzyltriethylammonium chloride (g) 1.9 1.1 2.4 Polymerization inhibitor 2,6-Di-tert-butyl p-cresol (g) 0.6 0.4 0.8 Solvent PGMEA (g) 750 600 100 EEP (g) - - 900 Reaction temperature (℃) 110 90 90 Reaction time (hours) 2 2 2 3.5 4 In Table 1-1 and Table 1-2: a-2-1-a The polymerizable unsaturated group-containing diol compound (a-2-1-a) of Preparation Example 1 a-2-1-b The polymerizable unsaturated group-containing diol compound (a-2-1-b) of Preparation Example 2 a-2-1-c The polymerizable unsaturated group-containing diol compound (a-2-1-c) of Preparation Example 3 a-2-2-a 4,4'-hexafluoro isopropylidene diphthalic dianhydride (4,4'-hexafluoro isopropylidene diphthalic dianhydride; 6FDA) a-2-2-b Biphenyl tetracarboxylic acid a-2-2-c Benzophenone tetracarboxylic dianhydride (Benzophenone tetracarboxylic dianhydride) a-2-2-d Pyromellitic dianhydride (Pyromellitic dianhydride) a-2-3-a 3-fluorophthalic anhydride a-2-3-b Maleic acid a-2-3-c Tetrahydrophthalic anhydride a-2-3-d Succinic acid PGMEA Propylene glycol monomethyl ether acetate (PGMEA) EEP Ethyl 3-ethoxypropionate (Ethyl 3-ethoxypropionate, EEP) <Examples and comparative examples of black photosensitive resin composition><Example1>

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 formula (3-1) The compound shown (referred to as C-1-1), 5 parts by weight of IRGACURE OXE-02 (referred to as C-2-1), 100 parts by weight of black pigment MA100 (referred to as E-1) are added to 150 parts by weight Diethylene 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 stirred evenly with a shaking stirrer, 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 lies in: changing the types of black photosensitive resin compositions and their usage amount (As shown in Table 2-1 and Table 2-2), I will not repeat them here. <Evaluation method> Black matrix

The negative photosensitive resin composition for black matrix prepared in the above-mentioned Examples and Comparative Examples was applied on the length and width by spin coating using a coater (model: MS-A150, purchased from Shinko Trading) All are on a 100 mm (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 50 mJ/cm ² ultraviolet light (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 rinse with water and post-bake the pre-baked 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 is formed on the glass substrate. Taper angle

The taper angle is evaluated by observing the aforementioned black matrix with a specific pattern with a scanning electron microscope (made by Hitachi High-Technologies, and its model is S-4800), and measuring its taper angle. Please refer to FIG. 1, which is a schematic cross-sectional view of the taper angle θ of the black matrix observed according to the taper angle evaluation method of an embodiment of the present invention. Among them, the 701 series is a glass substrate, and the 703 series is a black matrix. Based on the measured taper angle θ, the evaluation is based 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 the taper angle <30 degrees dry

表2-2：

表1-1、表1-2中： B-1 乙二醇二甲基丙烯酸酯 B-2 三丙烯酸三羥甲基丙酯 B-3 二季戊四醇六丙烯酸酯 C-1-1 式(3-1)之化合物 C-1-2 式(3-4)之化合物 C-1-3 式(3-9)之化合物 C-1-4 式(3-11)之化合物 C-1-5 式(3-14)之化合物 C-1-6 式(3-22)之化合物 C-2-1 1-[9-乙基-6-(2-甲基苯醯基)-9H-咔唑-3-取代基]-乙烷酮-1-(O-乙醯基肟) (商品名IRGACURE OXE-02；汽巴精化有限公司製造) C-2-2 2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮 (商品名IRGACURE 907；汽巴精化有限公司製造) D-1-1 二乙二醇乙醚乙酸酯 D-1-2 二乙二醇正丁醚乙酸酯 D-1-3 二丙二醇甲醚乙酸酯 D-1-4 三乙二醇乙醚乙酸酯 D-1-5 四乙二醇乙醚乙酸酯 D-1-6 二新戊二醇乙醚乙酸酯 D-2-1 乙酸乙酯 D-2-2 乙酸異丁酯 D-2-3 丙酸正丙酯 D-2-4 丙酸正丁酯 D-2-5 正丁酸甲酯 D-2-6 2-甲基丙酸正丁酯 D-3 丙二醇甲醚醋酸酯 E-1 商品名MA100；三菱化學製造 E-2 商品名MA230；三菱化學製造 After the glass piece was immersed in the negative photosensitive resin composition for black matrix for 5 seconds, the glass piece was taken out and air-dried for 55 seconds. The glass slide was immersed again and taken out, and the operation was repeated 120 times in total. Then, the black photoresist surface of the immersed area was observed with an optical microscope and evaluated based on the following criteria: ◎: No foreign matter remained on the dry surface at all ○: Extremely A small amount of foreign matter remains on the dry surface △: Obviously 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 1-1 and Table 1-2: B-1 Ethylene glycol dimethacrylate B-2 Trimethylol Propyl Triacrylate B-3 Dipentaerythritol hexaacrylate C-1-1 Compound of formula (3-1) C-1-2 Compound of formula (3-4) C-1-3 Compound of formula (3-9) C-1-4 Compound of formula (3-11) C-1-5 Compound of formula (3-14) C-1-6 Compound of formula (3-22) C-2-1 1-[9-Ethyl-6-(2-Methylphenanyl)-9H-carbazole-3-substituent]-Ethanone-1-(O-Acetyloxime) (trade name IRGACURE OXE -02; manufactured by Ciba Fine Chemical Co., Ltd.) C-2-2 2-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-acetone (trade name IRGACURE 907; manufactured by Ciba Fine Chemical Co., Ltd.) D-1-1 Diethylene glycol ethyl ether acetate D-1-2 Diethylene glycol n-butyl ether acetate D-1-3 Dipropylene glycol methyl ether acetate D-1-4 Triethylene glycol ethyl ether acetate D-1-5 Tetraethylene glycol ethyl ether acetate D-1-6 Dineopentyl glycol ethyl ether acetate D-2-1 Ethyl acetate D-2-2 Isobutyl acetate D-2-3 N-propyl propionate D-2-4 N-butyl propionate D-2-5 Methyl Butyrate D-2-6 N-Butyl 2-methylpropionate D-3 Propylene Glycol Methyl Ether Acetate E-1 Trade name MA100; manufactured by Mitsubishi Chemical E-2 Trade name MA230; manufactured by Mitsubishi Chemical

The above-mentioned embodiments only illustrate the principles and effects of the present invention, but do not limit the present invention. Modifications and changes made by those skilled in this technology to the above-mentioned embodiments still do not violate the spirit of the present invention. The scope of rights of the present invention should be listed in the scope of patent application described later.

701: glass substrate 703: black matrix θ: Taper angle

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

701: glass substrate

703: black matrix

θ: Taper angle

Claims (11)

A black photosensitive resin composition comprising: 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 alkali-soluble resin (A) includes a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture, and the first mixture includes formula (1) The indicated diol compound (a-1-1), tetracarboxylic acid or its acid dianhydride (a-1-2) and dicarboxylic acid or its acid anhydride (a-1-3);

Formula (1) In the formula (1), A ₁ and A ₁ 'are each _Ra SR _b , and the Ra is _a single bond, C ₁ -C ₁₀ alkylene or C ₆ -C ₁₅ arylene, so Said 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 and A ₂ 'are each hydrogen, hydroxyl, thiol, amino, nitro or halogen Substituents; The solvent (D) includes the first solvent (D-1) represented by formula (2);

Formula (2) In the 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 2 An integer from to 4, and plural D ₁ may be the same or different. The black photosensitive resin composition of claim 1, wherein the alkali-soluble resin (A) comprises a second alkali-soluble resin (A-2), and the second alkali-soluble resin (A-2) is polymerized from the second mixture And the second mixture includes a diol compound containing a polymerizable unsaturated group (a-2-1), a tetracarboxylic acid or its acid dianhydride (a-2-2), and a dicarboxylic acid or its anhydride (a -2-3). The black photosensitive resin composition of claim 1, wherein the photoinitiator (C) comprises a photoinitiator (C-1) represented by formula (3):

Formula (3) wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently 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 are independently of each other and collectively are

; But the condition is that at least one 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, and the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen , Phenyl; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen; X represents CO or a 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 C ₂ -C ₂₀ alkyl group with one or more O or CO interposed therebetween, wherein the intervening 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 groups: halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , or A plurality of O C ₂ -C ₂₀ alkyl groups; or each of them is substituted by a C ₁ -C ₂₀ alkyl group, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more of the following groups: 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 has one or more of the following groups Substitution: 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 is substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group 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 with one or more O interspersed; or R ₁₇ represents C ₂ -C ₂₀ alkyl group, with one or more O interposed therebetween; or R ₁₇ represents a phenyl group, 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; but the condition is that there is at least one in formula (3)

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

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. The black photosensitive resin composition of claim 1, wherein the total usage amount based on the alkali-soluble resin (A) is 100 parts by weight, and the usage amount of the alkali-soluble resin (A-1) is 30 to 100 parts by weight , The usage amount of the compound (B) with ethylenic unsaturated group is 10 parts by weight to 100 parts by weight, the usage amount of the photoinitiator (C) is 5 parts by weight to 80 parts by weight, the solvent (D) The total usage amount 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 usage amount of the black pigment (E) is 50 parts by weight to 600 parts by weight. Parts by weight. The black photosensitive resin composition of claim 2, wherein the total usage amount based on the alkali soluble resin (A) is 100 parts by weight, and the usage amount of the alkali soluble resin (A-2) is 10 parts by weight to 70 parts by weight . The black photosensitive resin composition of claim 3, wherein the total usage amount based on the alkali-soluble resin (A) is 100 parts by weight, and the usage amount of the photoinitiator (C-1) represented by the formula (3) It is 5 parts by weight to 50 parts by weight. The black photosensitive resin composition of claim 4, wherein the total usage amount based on the alkali-soluble resin (A) is 100 parts by weight, and the usage amount of the second solvent (D-2) is 100 parts by weight to 1300 parts by weight . The black photosensitive resin composition of claim 4, wherein the use ratio of the first solvent (D-1) and the second solvent (D-2) is 0.5 to 3. A black pattern is formed by the black photosensitive resin composition of any one of claims 1 to 9 through a pre-baking treatment, an exposure treatment, a development treatment and a post-baking treatment. A liquid crystal display device comprising the black pattern of claim 10.

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