KR101973253B1 - Black Photosensitive Resin Composition - Google Patents

Abstract

The present invention provides a black photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent, wherein the colorant comprises a bisbenzofuranone derivative or a cis-trans isomer thereof. The black photosensitive resin composition according to the present invention is excellent in optical characteristics and reliability.

Description

[0001] The present invention relates to a black photosensitive resin composition,

The present invention relates to a black photosensitive resin composition, and more particularly to a black photosensitive resin composition excellent in optical characteristics and reliability.

The liquid crystal display device comprises a top plate provided with a color filter, a bottom plate provided with a thin film transistor (TFT), and a liquid crystal injected therebetween.

The color filter is composed of a black matrix that implements various colors on the screen through RGB patterns, a black matrix that is positioned between each RGB pattern and blocks light leakage between pixels, an overcoat (OC) that improves the flatness of the upper part of the pigment, And a column spacer (CS) for adjusting the gap between the electrodes.

Among them, the black matrix and the column spacer are formed by a photolithography process using a photosensitive resin composition for a fine pattern.

Recently, a black column spacer (BCS) has been studied in which a black matrix and a column spacer are simultaneously realized as a single material in a single process. The black column spacer has a pattern of a black matrix and a column spacer Can be implemented.

Korean Patent Publication No. 2015-0062889 discloses a photosensitive resin composition for a black column spacer comprising an alkali-soluble binder resin, a polyfunctional monomer, a colorant, a solvent, and a oxime-based photoinitiator having a long- It is said that it is excellent.

However, the conventional black column spacer has a problem that the optical characteristics and reliability are not sufficient.

Korean Patent Publication No. 2015-0062889

An object of the present invention is to provide a black photosensitive resin composition excellent in optical properties and reliability.

Another object of the present invention is to provide a black column spacer formed using the black photosensitive resin composition.

It is still another object of the present invention to provide a liquid crystal display device having the black column spacer.

On the other hand, the present invention provides a black photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent, wherein the colorant comprises a bisbenzofuranone derivative represented by the following formula (I) or a cis- Lt; / RTI >

(I)

In this formula,

X is OR ¹ or SR ^1,

R ¹ is hydrogen; Or a C ₁ -C ₁₀ alkyl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of -Cl, -CN and -Si (R ² ) ₃ ,

R ² is a C ₁ -C ₁₀ alkyl group.

On the other hand, the present invention provides a black column spacer formed using the black photosensitive resin composition.

On the other hand, the present invention provides a liquid crystal display provided with the black column spacer.

The black photosensitive resin composition according to the present invention is excellent in optical characteristics and reliability and can be effectively used in the production of a high-resolution black column spacer.

Hereinafter, the present invention will be described in more detail.

An embodiment of the present invention includes a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) and a solvent (E) The present invention relates to a black photosensitive resin composition comprising a furanone derivative or a cis-trans isomer thereof,

(I)

In this formula,

X is OR ¹ or SR ^1,

R ¹ is hydrogen; Or a C ₁ -C ₁₀ alkyl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of -Cl, -CN and -Si (R ² ) ₃ ,

R ² is a C ₁ -C ₁₀ alkyl group.

As used herein, a C ₁ -C ₁₀ alkyl group means a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, -Butyl, t-butyl, n-pentyl, n-hexyl, and the like.

In one embodiment of the invention, X is OR ¹ or SR ^1, R ¹ is hydrogen; Or a C ₁ -C ₁₀ alkyl group substituted by at least one substituent selected from the group consisting of -Cl, -CN and -Si (R ² ) ₃ , and R ² may be a C ₁ -C ₁₀ alkyl group.

The cis-trans isomers of the bisbenzofuranone derivatives of formula (I) have the following structure, and these isomers alone or a mixture of these isomers.

트랜스-트랜스

Trans-transformer

트랜스-시스

Trans-cis

시스-시스

Cis-cis

The bisbenzofuranone derivatives of the above formula (I) or their cis-trans isomers are commercially available or can be easily prepared by methods known in the art.

The bisbenzofuranone derivative of the above formula (I) or its cis-trans isomer is excellent in optical characteristics and reliability and can be usefully used as a coloring agent for a black photosensitive resin composition for a black matrix or a black column spacer.

The colorant (A)

In one embodiment of the present invention, the colorant (A) is at least one kind selected from pigments (a1) and dyes (a2) commonly used in the related art in addition to the bisbenzofuranone derivative of the formula (I) or a cis- Or more.

Pigment ( a1 )

As the pigment (a1), an organic pigment or an inorganic pigment generally used in the related art can be used. The above-mentioned pigments include various pigments used in printing ink, ink-jet ink and the like, and specifically include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments , Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments (for example, pyranthrone pigments, perynone pigments, perynone pigments, perynone pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, Oxide, carbon black and the like.

Particularly, the organic pigments and inorganic pigments include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and more specifically, those having the following color index (CI) numbers Pigments, but are not limited thereto.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63;

C.I. Pigment Brown 28;

C.I. Pigment Black 1 and 7 and the like.

The above-exemplified pigments may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment selected from Pigment Green 58 can be preferably used.

The pigment is preferably used as a pigment dispersion in which the particle size is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method in which the pigment dispersant (a3) is contained and dispersed. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained .

Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used alone or in combination of two or more.

Pigment dispersant ( a3 )

The pigment dispersant (a3) is added to maintain deactivation and stability of the pigment. Those commonly used in the art can be used without limitation. An acrylate-based dispersant (hereinafter also referred to as an " acrylic dispersant ") containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) is preferably used. DISCLOSURE OF THE INVENTION The acrylic dispersant used in the present invention is preferably prepared by a living control method as disclosed in Korean Patent Publication No. 2004-0014311. DISPER BYK-2000 , DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used. Examples of the other resin type pigment dispersants include polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, polycarboxylic acids An alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, or a polyester having a free carboxyl group and a poly An amide formed by the reaction of an alkyleneimine) or a salt thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, DISPER BYK-160, , DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The amount of the pigment dispersant (a3) to be used is preferably 5 to 60 parts by weight, more preferably 15 to 50 parts by weight based on 100 parts by weight of the solid content of the pigment (a1). If the content of the pigment dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

dyes( a2 )

The dye (a2) may be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and securing reliability such as solubility in an alkali developing solution, heat resistance, solvent resistance and the like can be used.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and their derivatives can also be used.

Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colourists) or a dye described in a dyeing note (coloring yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70;

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.

The exemplified C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent Orange 45, 62 is more preferred.

Also, C.I. As the acid dye,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, Yellow dyes such as 1,190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243,

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Orange dyes such as Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 1, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 335, and 340;

C.I. Violet dyes such as Acid Violet 6B, 7, 9, 17, 19, 66 and the like;

C.I. Green dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

In the exemplified acid dyes described above, C.I. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

C.I. As a direct dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138 and 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Orange dyes such as Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 164, 166, 167, 170, 171, 172, 173, 188, 189, 169, 169, 160, 161, 162, 163, 164, 248, 242, 243, 244, 245, 247, 248, 228, 229, 238, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

C.I. Violet dyes such as Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

C.I. Green dyes such as Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.

Also, C.I. As modatto dyes,

C.I. Yellow dyes such as Modan Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Orange dyes such as Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, ;

C.I. 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C.I. Violet colored dyes such as Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Green dyes such as Modan green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

The above-exemplified dyes may be used alone or in combination of two or more.

The content of the colorant (A) is preferably in the range of 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total weight of the solid components of the black photosensitive resin composition of the present invention. When the content of the colorant is less than 10% by weight, the optical density is not sufficient. When the content of the colorant is more than 70% by weight, pattern formation may be difficult.

The binder resin (B)

In one embodiment of the present invention, the binder resin (B) is not limited, and preferably a copolymer of a compound having an unsaturated carboxyl group and another monomer copolymerizable therewith can be used.

The compound having an unsaturated carboxyl group can be used without limitation as long as it is a carboxylic acid compound having an unsaturated double bond capable of being polymerized. Specifically, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Anhydrides of the dicarboxylic acids; And mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -Carboxypolycaprolactone mono (meth) acrylate, monomethyl maleate, 5-norbornene-2-carboxylic acid, 2 - ((meth) acryloyloxy) ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate and the like. The above-exemplified compounds having an unsaturated carboxyl group may be used alone or in combination of two or more. Among the compounds having an unsaturated carboxyl group, acrylic acid and methacrylic acid are preferable because they have excellent copolymerization reactivity and solubility in a developing solution.

The other monomer copolymerizable with the unsaturated carboxyl group-containing compound may be any monomer as long as it has a carbon-carbon unsaturated bond. Specifically, aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinylcyanide compounds such as acrylonitrile, methacrylonitrile and? -Chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, And unsaturated oxetane carboxylate compounds such as 3-methyl-3-acryloxyethyl oxetane and 3-methyl-3-methacryloxyethyl oxetane. The above-exemplified monomers copolymerizable with the compounds having an unsaturated carboxyl group may be used alone or in combination of two or more thereof.

In addition, the binder resin may be a carded resin commonly used in the art.

Specific examples of the cation resin include bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane and bis Bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane and bis Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- Propane and 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy- (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9- 3,5-dibromophenyl) fluorene, and the like, but the present invention is not limited thereto.

The content of the binder resin (B) is preferably in the range of 10 to 80% by weight, and more preferably 10 to 70% by weight, based on the total solid content of the black photosensitive resin composition of the present invention. When the content of the binder resin is 10 to 80% by weight, the solubility of the developing solution is sufficient, the pattern formation is easy, and the reduction of the film of the pixel portion of the exposed portion is prevented at the time of development.

Photopolymerization  The monomer (C)

In one embodiment of the present invention, the photopolymerizable monomer (C) is a monomer that can be polymerized by an active radical or the like generated from a photopolymerization initiator by light irradiation.

Specific examples of the photopolymerizable monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, Acrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 2-butanediol dimethacrylate, 1, 2-butanediol dimethacrylate, , 4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like. . The above-mentioned photopolymerizable monomers may be used singly or in combination of two or more thereof.

The content of the photopolymerizable monomer (C) is preferably in the range of 5 to 45% by weight, more preferably 10 to 35% by weight, based on the total weight of the solid components of the black photosensitive resin composition of the present invention. When the content of the photopolymerizable monomer (C) is in the range of 5 to 45% by weight, pattern characteristics are preferably formed, which is preferable.

Light curing Initiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) can be used without any particular limitation as long as it can polymerize the binder resin (B) and the photopolymerizable monomer (C). Specifically, at least one compound selected from the group consisting of an oxime ester compound, a triazine compound, an acetophenone compound, and a nonimidazole compound may be used.

In particular, the use of an oxime ester compound is effective in producing a black photosensitive resin composition having a small color change and a small decrease in film thickness.

Specific examples of the oxime ester compound include o-ethoxycarbonyl-? -Oxyimino-1-phenylpropan-1-one, compounds represented by the following formulas (II) to (IV), and the like.

≪ RTI ID = 0.0 &

(III)

(IV)

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2,6-dichlorophenyl) - 4,4 ', 5,5'-tetra (trialkoxyphenyl) 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or imidazole compounds in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group have. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Is used.

Further, in addition to the above-mentioned photopolymerization initiator, other photopolymerization initiators conventionally used in the art may be further used insofar as the effect of the present invention is not impaired. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds, and these may be used alone or in combination of two or more.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-diethoxyanthracene. have.

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylchloroxylate, Titanocene compounds and the like can be mentioned as other photopolymerization initiators.

The photopolymerization initiator (D) may be used in combination with a photopolymerization initiator (D-1). When the photopolymerization initiator (D) is used in combination with the photopolymerization initiator (D-1), the photosensitive resin composition containing the photopolymerization initiator (D)

As the photopolymerization initiation auxiliary (D-1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl aminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- Ethylamino) benzophenone, and the like. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) Triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). .

The amount of the photopolymerization initiator (D) to be used is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight based on the total amount of the binder resin (B) and the photopolymerizable monomer (C) . When the photopolymerization initiator is in the range of 0.1 to 40% by weight, the black photosensitive resin composition of the present invention has high sensitivity and shortens the exposure time, thereby improving productivity and maintaining high resolution. The strength of the pixel portion and the smoothness on the surface of the pixel portion become favorable.

When the photopolymerization initiator (D-1) is used, the amount of the photopolymerization initiator (D-1) to be used is preferably in the range of 0.1 to 10 parts by weight based on the solids of the total amount of the binder resin (B) Preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight. When the amount of the photopolymerization initiator is within the range of 0.1 to 50% by weight, the sensitivity of the black photosensitive resin composition of the present invention is higher and the productivity of the black column spacer formed using the composition is improved.

Solvent (E)

In one embodiment of the present invention, the solvent (E) can be used without particular limitation insofar as it is effective in dispersing or dissolving the other components contained in the black photosensitive resin composition of the present invention. In particular, ethers, aromatic hydrocarbons Ketones, alcohols, esters, amides and the like are preferable.

Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol mono Alkylene glycol alkyl ether acetates such as methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene , Methyl ethyl ketone , Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, 3- Esters such as methyl methoxypropionate, and cyclic esters such as? -Butyrolactone.

In view of the coating property and the dryness of the solvent, it is preferable to use an organic solvent having a boiling point of 100 to 200 DEG C, and examples thereof include alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, 3- It is more preferable to use esters such as methyl methoxypropionate and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate Is more preferable. These solvents may be used alone or in combination of two or more.

The content of the solvent (E) is preferably 60 to 90% by weight, more preferably 60 to 85% by weight based on the total amount of the black photosensitive resin composition of the present invention. When the content of the solvent is in the range of 60 to 90% by weight, the coating property tends to be improved when the coating composition is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater) Therefore, it is preferable.

Additive (F)

The black photosensitive resin composition according to one embodiment of the present invention may further contain additives (F), if necessary, in addition to the above components.

As the additive (F), at least one selected from other polymer compounds, a curing agent, a pigment dispersant, a silane coupling agent, an antioxidant, an ultraviolet absorber, an anti-

Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .

The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than glycidyl ester resins, glycidyl amine resins or brominated derivatives of such epoxy resins, epoxy resins and their brominated derivatives ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators.

The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.).

The curing agents exemplified above may be used alone or in combination of two or more.

As the pigment dispersing agent, a surfactant may be used to improve the coating property. As the surfactant, a silicone surfactant, a fluorine surfactant, an ester surfactant, or the like may be preferably used.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimine (Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Mega (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kagaku Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (Manufactured by Lubrisol), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and Disperbyk-series (manufactured by BYK-chemi).

The above-exemplified surfactants may be used alone or in combination of two or more.

The silane coupling agent has a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof for enhancing adhesion to a substrate.

Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, Trimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The silane coupling agents exemplified above may be used alone or in combination of two or more.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The black photosensitive resin composition according to one embodiment of the present invention can be produced, for example, by the following method.

The colorant (A) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes about 0.2 탆 or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin (B) may be blended. After adding the remainder of the binder resin (B), the photopolymerizable monomer (C) and the photopolymerization initiator (D) and, if necessary, the additive (F) to the obtained dispersion (hereinafter also referred to as a mill base) The desired black photosensitive resin composition can be obtained by further adding an additional solvent so as to have a predetermined concentration.

The black photosensitive resin composition according to the present invention can be used for producing black matrix, black column spacer and the like. In particular, the black photosensitive resin composition according to the present invention is excellent in optical characteristics and reliability, and can be effectively used in the production of high resolution black column spacers.

Therefore, one embodiment of the present invention relates to a black column spacer formed using the above-mentioned black photosensitive resin composition.

A method for forming a pattern of a black column spacer using the black photosensitive resin composition according to the present invention includes the steps of applying the above-mentioned black photosensitive resin composition on a substrate, selectively exposing a part of the black photosensitive resin composition And a developing step of removing the exposed area or the non-exposed area of the black photosensitive resin composition.

In the application step, the black photosensitive composition of the present invention is coated on a substrate and pre-dried to remove volatile components such as solvents to obtain a smooth coating film. At this time, the thickness of the coating film is usually about 0.5 to 5 mu m.

The exposure step irradiates a specific region with ultraviolet rays through a mask to obtain a desired pattern on the coating film obtained above. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel rays, and the mask and the substrate are accurately positioned.

In the developing step, the coated film, which has been cured by irradiation of ultraviolet rays, is contacted with an alkali aqueous solution, which is a developer, to dissolve and expose the non-exposed region, thereby producing a desired pattern. After development, if necessary, post-drying may be performed at about 150 to 230 DEG C for about 10 to 60 minutes.

The developing solution used in the developing step is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound in the developer may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, , Potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The preferable concentration of the alkaline compound in the developer is 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

As the surfactant in the developing solution, at least one of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used. Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, poly Oxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium naphthalenesulfonate. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more. The content of the surfactant is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, and even more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the developer.

Through the above process, a black column spacer having a predetermined pattern shape is obtained on the substrate.

One embodiment of the present invention relates to a liquid crystal display provided with the above-described black column spacer.

The liquid crystal display of the present invention includes a structure known in the art, except that it has the above-described black column spacer. That is, all the liquid crystal display devices to which the black column spacer of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer are faced at predetermined intervals and a liquid crystal material is injected into the gap portion to form a liquid crystal layer . There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer. As another example, a thin film transistor (TFT) substrate integrated on a transparent electrode of a color filter and a liquid crystal display device including a backlight fixed to a position where a TFT substrate overlaps a color filter can be given.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples. It should be apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Comparative Manufacturing Example  One: Bisbenzofuranone  Preparation of derivatives

A mixture of 8.5 g of 2,5-dihydroxy-1,4-benzene diacetic acid (0.37 mol), 11 g of isatin (0.74 mol) and 14 g of p-toluenesulfonic acid monohydrate in 800 ml of glacial acetic acid was added to 105 Lt; 0 > C for 14 hours. The reaction mixture was cooled to room temperature and the suspension was filtered through a paper filter and then washed with 250 ml of acetic acid, 200 ml of methanol and 500 ml of water. The black powder was dried at 70 [deg.] C in a vacuum oven to obtain a bisbenzofuranone derivative of the formula (a). Elemental analysis showed C, 69.65; H, 2.70; N, 6.25; O, 21.41. The molecular weight of the product was confirmed to be 448.

(A)

Manufacturing example  One: Bisbenzofuranone  Preparation of derivatives

를 사용하는 것을 제외하고는, 비교제조예 1과 동일한 방법으로 X가 OR¹이고, R¹은 수소인 화학식 I의 비스벤조퓨란 유도체를 제조하였다. 원소분석 결과 C, 65.01; H, 2.52; N, 5.83, O, 26.64임을 확인하였다. 또한, 생성물의 분자량을 확인한 결과 480임을 확인하였다.
Instead of Isin Tin

A and in the same manner as in Comparative Preparation Example 1, except that X is OR ^1, R ¹ is prepared the bis-benzofuran derivatives of general formula I are hydrogen. Elemental analysis result C, 65.01; H, 2.52; N, 5.83, O, 26.64. The molecular weight of the product was confirmed to be 480.

Manufacturing example  2: Bisbenzofuranone  Preparation of derivatives

를 사용하는 것을 제외하고는, 비교제조예 1과 동일한 방법으로 X가 OR¹이고, R¹은 수소인 화학식 I의 비스벤조퓨란 유도체를 제조하였다. 원소분석 결과 C, 65.03; H, 2.51; N, 5.85, O, 26.61임을 확인하였다. 또한, 생성물의 분자량을 확인한 결과 480임을 확인하였다.
Instead of Isin Tin

A and in the same manner as in Comparative Preparation Example 1, except that X is OR ^1, R ¹ is prepared the bis-benzofuran derivatives of general formula I are hydrogen. Elemental analysis result C, 65.03; H, 2.51; N, 5.85, O, 26.61. The molecular weight of the product was confirmed to be 480.

Manufacturing example  3: Bisbenzofuranone  Preparation of derivatives

를 사용하는 것을 제외하고는, 비교제조예 1과 동일한 방법으로 X가 SR¹이고, R¹은 수소인 화학식 I의 비스벤조퓨란 유도체를 제조하였다. 원소분석 결과 C, 60.93; H, 2.36; N, 5.47, O, 18.73; S, 12.51임을 확인하였다. 또한, 생성물의 분자량을 확인한 결과 512임을 확인하였다.
Instead of Isin Tin

, Bisbenzofuran derivatives of formula (I) wherein X is SR ¹ and R ¹ is hydrogen were prepared in the same manner as in comparative preparation example 1. Elemental analysis showed C, 60.93; H, 2.36; N, 5.47, 0. 18.73; S, 12.51. The molecular weight of the product was confirmed to be 512.

Manufacturing example  4: Bisbenzofuranone  Preparation of derivatives

를 사용하는 것을 제외하고는, 비교제조예 1과 동일한 방법으로 X가 OR¹이고, R¹은 CN으로 치환된 메틸인 비스벤조퓨란 유도체를 제조하였다. 원소분석 결과 C, 64.52; H, 2.53; N, 10.03; O, 22.92임을 확인하였다. 또한, 생성물의 분자량을 확인한 결과 558임을 확인하였다.
Instead of Isin Tin

, A bisbenzofuran derivative in which X is OR ¹ and R ¹ is methyl substituted with CN was prepared in the same manner as in Comparative Preparation Example 1. Elemental analysis result C, 64.52; H, 2.53; N, 10.03; O, 22.92. The molecular weight of the product was confirmed to be 558.

Manufacturing example  5: Bisbenzofuranone  Preparation of derivatives

를 사용하는 것을 제외하고는, 비교제조예 1과 동일한 방법으로 X가 OR¹이고, R¹은 Si(R²)₃로 치환된 메틸이며, R²가 메틸인 비스벤조퓨란 유도체를 제조하였다. 원소분석 결과 C, 62.56; H, 4.94; N, 4.29; O, 19.61; Si, 8.60임을 확인하였다. 또한, 생성물의 분자량을 확인한 결과 653임을 확인하였다.
Instead of Isin Tin

, A bisbenzofuran derivative in which X is OR ¹ , R ¹ is methyl substituted with Si (R ² ) ₃ , and R ² is methyl was prepared in the same manner as in Comparative Preparation Example 1. Elemental analysis showed C, 62.56; H, 4.94; N, 4.29; O, 19.61; Si, 8.60. The molecular weight of the product was confirmed to be 653.

Manufacturing example  6: Bisbenzofuranone  Preparation of derivatives

를 사용하는 것을 제외하고는, 비교제조예 1과 동일한 방법으로 X가 OR¹이고, R¹은 Cl로 치환된 프로필인 비스벤조퓨란 유도체를 제조하였다. 원소분석 결과 C, 60.68; H, 3.50; Cl, 11.19; N, 4.42; O, 20.21임을 확인하였다. 또한, 생성물의 분자량을 확인한 결과 633임을 확인하였다.
Instead of Isin Tin

, A bisbenzofuran derivative in which X is OR ¹ and R ¹ is Cl is substituted with Cl was prepared in the same manner as in Comparative Preparation Example 1. Elemental analysis showed C, 60.68; H, 3.50; Cl, 11.19; N, 4.42; O, 20.21. The molecular weight of the product was confirmed to be 633.

Example  1 to 6 and Comparative Example  1: Preparation of black photosensitive resin composition

Each component was mixed at a ratio (unit: wt%) as shown in Table 1 below to prepare a black photosensitive resin composition.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 coloring agent Production Example 1 8.00 Production Example 2 8.00 Production Example 3 8.00 Production Example 4 8.00 Production Example 5 8.00 Production Example 6 8.00 Comparative Preparation Example 1 8.00 The binder resin (B) 6.50 6.50 6.50 6.50 6.50 6.50 6.50 The photopolymerizable monomer (C) 2.79 2.79 2.79 2.79 2.79 2.79 2.79 Photopolymerization initiator (PI) 0.56 0.56 0.56 0.56 0.56 0.56 0.56 Additive 1 (A1) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Additive 2 (A2) 2.13 2.13 2.13 2.13 2.13 2.13 2.13 Solvent 1 (S1) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Solvent 2 (S2) 77.00 77.00 77.00 77.00 77.00 77.00 77.00

Binder resin (B): Cathode resin (WR-101, manufactured by Adeka)

Photopolymerizable monomer (C): dipentaerythritol hexaacrylate (Kayarad DPHA: Nippon Kayaku Co., Ltd.))

Photopolymerization initiator (PI): 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone- 1- (O- acetyloxime) (Irgacure OXE- four)

Additive 1 (A1): Sol Spurs 5000 (manufactured by Lubrisol)

Additive 2 (A2): DisperBYK-163 (BYK)

Solvent 1 (S1): n-butanol

Solvent 2 (S2): Propylene glycol monomethyl ether acetate

Experimental Example : Evaluation of Physical Properties of Colored Patterned Substrate

A 5 cm x 5 cm glass substrate (Corning Inc.) was cleaned with a neutral detergent and water and dried. Each of the black photosensitive resin compositions prepared in Examples and Comparative Examples was spin-coated on the glass substrate to a final film thickness of 3.0 탆, prebaked at 80 to 120 캜 and dried for 1 to 2 minutes to remove the solvent Respectively. Then, exposure was performed at an exposure amount of 40 to 100 mJ / cm ² to form a pattern, and an unexposed area was removed using an aqueous alkaline solution. Followed by baking at 200 to 230 ° C for 10 to 30 minutes to prepare a colored substrate.

Optical characteristics and reliability of the fabricated color pattern substrate were evaluated by the following methods, and the results are shown in Table 2 below.

(1) Optical density ( optical density ) Measure

The optical density of the fabricated color pattern substrate was measured using an optical density (OD) meter (X-rite 301 Densitometer), and the results at 3 μm of the final film thickness are shown in Table 2.

(2) Evaluation of heat resistance

The fabricated color pattern substrate was further placed in a post-baking step (200 to 230 ° C) for 2 hours, and color change was measured before and after 2 hours. The color change (ΔE · ab) was measured using a colorimeter OSP-SP2000 (Olympus), and the results are shown in Table 2.

(3) Solvent resistance  evaluation

The solvent resistance of the resulting colored patterned substrate film was evaluated, and the results are shown in Table 2 below. The solvent resistance was evaluated by UV-vis spectrometer (UV-2550, manufactured by Mitsubishi Rayon Co., Ltd.) after removing the membrane in a size of 3 x 3 cm and putting it in 15 g of N-methyl-2-pyrrolidone (NMP) Shimatzu), and the absorbance was evaluated according to the following criteria.

<Evaluation Criteria>

Good: Max absorbance less than 0.5

Defect: Max absorbance 0.5 or more

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Optical density 4.01 3.98 3.95 3.97 4.0 3.99 3.71 Heat resistance 0.9 0.8 1.2 0.9 0.9 1.0 2.3 Solvent resistance Good Good Good Good Good Good Bad

As shown in Table 2, the black photosensitive resin compositions of Examples 1 to 6 containing the bisbenzofuranone derivatives of Production Examples 1 to 6 as colorants exhibited excellent optical properties, excellent heat resistance and solvent resistance, . In comparison with Comparative Example 1, Comparative Example 1 containing the compound of Comparative Preparation Example 1 as a coloring agent had poor optical properties and heat resistance as compared with Examples, and it was confirmed that the solvent resistance was poor such as the edge of the film was expelled or decomposed by NMP Respectively.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims (5)

A black photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent, wherein the colorant comprises a bisbenzofuranone derivative represented by the following formula (I) or a cis-trans isomer thereof:
(I)

In this formula,
X is OR ¹ or SR ^1,
R ¹ is a C ₁ -C ₁₀ alkyl group substituted by at least one substituent selected from the group consisting of -Cl, -CN, and -Si (R ² ) ₃ ,
R ² is a C ₁ -C ₁₀ alkyl group. delete The black photosensitive resin composition according to claim 1, wherein the coloring agent further comprises at least one of a pigment and a dye. A black column spacer formed using the black photosensitive resin composition according to claim 1 or 3. A liquid crystal display device comprising the black column spacer according to claim 4.