KR101953936B1 - Black photosensitive resin composition, black matrix and image display device having the same - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition, a black matrix using the black photosensitive resin composition, and an image display device having the black matrix. The black photosensitive resin composition according to the present invention has excellent adhesion to a substrate and can form a fine pattern for realizing a high resolution.

Description

TECHNICAL FIELD [0001] The present invention relates to a black photosensitive resin composition, a black matrix using the black photosensitive resin composition, and an image display device having the black matrix.

The present invention relates to a black photosensitive resin composition, a black matrix using the black photosensitive resin composition, and an image display device having the black matrix.

The quality of the display depends on the color filter. A black pattern on the lattice called a black matrix is disposed between the color pixels of the color filter. In order to realize a large screen area and high contrast, the black matrix of the color filter is required to be patterned with high light resolution and high resolution.

In the conventional black matrix, chromium has been used. This process deposits chromium on the entire glass substrate and forms a pattern by etching treatment. Therefore, high cost is required in the process, and high reflection of chrome, environmental pollution . For this reason, studies of a resin black matrix by a pigment dispersion method capable of micromachining are actively conducted.

In addition, studies have been made to prepare black compositions using color pigments other than carbon black. However, color pigments other than carbon black are required to have a very large blending amount because of low light shielding property. As a result, viscosity of the composition increases, There is a problem that the strength of the formed film or the adhesion to the substrate is considerably lowered. Currently, various studies are under way in response to the demand for continuous improvement of the industry.

In addition, according to the slimness of the display and the requirement for a wider screen, a technique for increasing the screen size even by one inch is applied by using a minimum area even in the upper and lower plate joint portions of the module. Particularly, in order to maximize the characteristics of the mobile as the mobile market gradually grows, besides the slimming of the module itself, there are also plans to reduce the number of devices and maximize the display.

As one of the methods, a new type of cementation method is used instead of the existing cementation method. In the conventional bonding method, the method of attaching the glass and the black matrices at the same time has been performed, but the display efficiency on the panel is lowered by using a larger glass than the actual visible region. On the other hand, in the new joining method, in order to increase the display efficiency, the joining is performed only in the black matrix portion without using the glass during joining, thereby maximizing the display efficiency in the panel. In this method, Characteristics can be secured.

However, in the conventional method, since adhesion was carried out using glass and black matrix at the same time, there was no big problem in adhesion of sealant in reliability and pressure applied at the time of adhesion, but adhesion with only black matrix portion was carried out using cadmium binder In one case, the pressure applied during bonding and the adhesion of the black matrix to the substrate in the reliability process became a problem, resulting in cracking and film breakage. Both the OD (Optical Density) characteristics and the substrate adhesion were satisfied There was a problem.

Korean Patent No. 1068622 discloses a high-order black matrix composition with improved substrate adhesion, which solves the problem of high OD (Optical Density) characteristics and substrate adhesion, but the problem is that high resolution can not be achieved with the composition have.

Korea Patent No. 1068622

An object of the present invention is to provide a black photosensitive resin composition excellent in adhesion to a substrate and capable of forming a fine pattern for realizing a high resolution.

It is another object of the present invention to provide a black matrix formed using the black photosensitive resin composition.

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

(A), a photopolymerizable compound (B), a photopolymerization initiator (C), a black pigment (D) and a solvent (E), wherein the alkali soluble resin ) Comprises a cationic binder resin (A) having at least one repeating unit of the following general formula (1) and (2), wherein the photopolymerization initiator (C) comprises a compound represented by the following general formula to provide.

[Chemical Formula 1]

(2)

,

,

,

,

,

,

,

,

,

,

, 또는

이고,In Formula 1 or 2, X and X 'each independently represents a single bond, -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ - _{-C (CH 3) 2 -,} -O-,

,

,

,

,

,

,

,

,

,

,

, or

ego,

Y is an acid anhydride residue,

Z is an acid dianhydride residue,

R 'is a hydrogen atom, an ethyl group, a phenyl _{group, -C 2 H 4 Cl, -C} 2 H 4 OH, or -CH ₂ CH = CH _2,

R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ', R ₆ and R ₆ ' are each independently a hydrogen atom or a methyl group ,

R ₇ , R ₇ ', R ₈ and R ₈ ' are each independently a straight or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, Or an arylene group having 1 to 14 carbon atoms,

R ₉ , R ₉ ', R ₁₀ , R ₁₀ ', R ₁₁ , R ₁₁ ', R ₁₂ and R ₁₂ ' are each independently a hydrogen atom, a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms ,

m and n are integers satisfying 0? m? 30 and 0? n? 30, respectively.

(3)

In Formula 3, R ₁₃ is an aryl group having 6 to 10 carbon atoms and substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, -OR ₁₅ , and a halogen group, or -OR ₁₅ and a halogen group Gt; is an arylalkyl group having 7 to 24 carbon atoms and substituted with at least one substituent selected from the group consisting of < RTI ID = 0.0 >

R ₁₄ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms,

R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms.

An embodiment of the present invention relates to a photosensitive resin composition comprising 1 to 40 parts by weight of an alkali-soluble binder resin (A), 1 to 20 parts by weight of a photopolymerizable compound (B), 0.1 to 10 parts by weight of a photopolymerization initiator (C) 5 to 20 parts by weight of the black pigment (D) and 20 to 85 parts by weight of the solvent (E).

The present invention also provides a black matrix formed using a black photosensitive resin composition.

Further, the present invention provides an image display apparatus provided with a black matrix.

The black photosensitive resin composition according to the present invention has excellent adhesion to a substrate and can form a fine pattern for realizing a high resolution.

Fig. 1 shows the results of the evaluation of adhesion in the experimental example.
Fig. 2 shows a minimum pattern according to the evaluation of developing adhesion in the experimental example.

The present invention relates to a photosensitive resin composition comprising an alkali soluble binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a black pigment (D) and a solvent (E) (A) having at least one repeating unit of formula (2), wherein the photopolymerization initiator (C) is a black photosensitive resin composition comprising a compound represented by formula (3) And a compound represented by the general formula (3), the adhesion to the substrate is excellent, and a fine pattern can be formed for realizing a high resolution.

Hereinafter, the present invention will be described in detail.

The black photosensitive resin composition of the present invention comprises an alkali-soluble binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a black pigment (D) and a solvent (E).

≪ Alkali-soluble binder resin (A) >

The cationic binder resin (A) according to the present invention includes at least one repeating unit represented by the following formulas (1) and (2) to improve the adhesion to a substrate and to provide a fine pattern for high resolution do.

[Chemical Formula 1]

(2)

,

,

,

,

,

,

,

,

,

,

, 또는

이고,Expression in, X and X 'is a single bond, -CO-, -SO ₂ each independently _{-, -C (CF 3) 2} -, -Si (CH 3) 2 -, -CH 2 -, -C (CH ₃ ) _2- , -O-,

,

,

,

,

,

,

,

,

,

,

, or

ego,

Y is an acid anhydride residue,

Z is an acid dianhydride residue,

R 'is a hydrogen atom, an ethyl group, a phenyl _{group, -C 2 H 4 Cl, -C} 2 H 4 OH, or -CH ₂ CH = CH _2,

_{R 1, R 1 `, R</sub> 2, R 2`, R 3, R 3 `, R 4, R 4`, R 5, R 5 `, R 6 and R <sub>6`} are each independently a hydrogen atom or a methyl group ,

,

,

, 또는

인 것이 좋다.R ₇ , R ₇ , R ₈ and R ₈ 'are each independently a straight or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, An arylene group having 1 to 14 carbon atoms, preferably an ethylene group,

,

,

, or

.

R ₉ , R ₉ , R ₁₀ , R ₁₀ , R ₁₁ , R ₁₁ , R ₁₂ and R ₁₂ 'each independently represents a hydrogen atom, a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms ,

m and n are integers satisfying 0? m? 30 and 0? n? 30, respectively.

When the cationic binder resin (A) of the present invention contains all the repeating units of the above formulas (1) and (2), the molar ratio is not particularly limited, but m / n may be, for example, 1/99 to 90/10 , More preferably 5/95 to 80/20.

When the ratio m / n satisfies the above range, the content of the carboxyl group of the binder resin is appropriately maintained to maintain the excellent alkali resistance, the developing solution does not dissolve in the exposed portion, .

Y in the formula (1) can be obtained by reacting a bisphenol epoxy acrylate compound, which is a synthetic intermediate of the cationic binder resin (A) of the present invention, with an acid anhydride compound as a residue of an acid anhydride. The acid anhydride compound capable of introducing the residue Y is not particularly limited and includes, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic anhydride, methylenedomethylene tetrahydrophthalic anhydride , Anhydrous chlorinated acid, and anhydrous methyl tetrahydrophthalic acid.

Z in the above formula (2) can be obtained by reacting a bisphenol epoxy acrylate compound, which is a synthetic intermediate of the cationic binder resin (A) of the present invention, with an acid dianhydride compound as a residue of an acid anhydride. The acid dianhydride compound capable of introducing the residue Z is not particularly limited and includes, for example, an aromatic acid such as anhydrous pyromellitic acid, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride and butenyl ether tetracarboxylic acid dianhydride And polybasic carboxylic acid anhydrides.

In the present invention, 'single bond' means a structure directly connected without any other functional group. For example, in the above formula (1), it means that an oxyphenyl group is directly connected without X and X '.

In the present invention, "acid dianhydride" means a compound containing two acid anhydride groups in the molecule.

The cationic binder resin (A) of the present invention can be prepared by the following method.

First, a bisphenol epoxy compound is synthesized by reacting a bisphenol compound with an epoxy compound, and then the synthesized bisphenol epoxy compound is reacted with an acrylate compound to synthesize a bisphenol epoxy acrylate compound.

Thereafter, the cationic binder resin (A) of the present invention can be synthesized by reacting the synthesized bisphenol epoxy acrylate compound with an acid anhydride, an acid anhydride or a mixture thereof.

The bisphenol compound is not particularly limited and includes, for example, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy- (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis 2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy- Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- Bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Fluorene) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, , 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis -3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, And the like.

The type of the acrylate compound is not particularly limited and may be, for example, a compound represented by the following general formula (4).

[Chemical Formula 4]

In the formula, R ₁₆ , R ₁₇ and R ₁₈ are each independently a hydrogen atom or a methyl group,

R ₁₉ is a straight or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group may be interrupted by at least one of an ester bond, a cycloalkylene group having 6 to 14 carbon atoms, and an arylene group having 6 to 14 carbon atoms.

The kinds of the acid anhydride and the acid dianhydride are not particularly limited, and the same compounds as those used for introducing Y and Z described above can be used.

The acid value of the cationic binder resin (A) may be 20 to 200 mgKOH / g, preferably 50 to 150 mgKOH / g. When the acid value is in the range of 20 to 200 mgKOH / g, a sufficient developing rate can be ensured and a black matrix of high resolution can be realized.

The weight average molecular weight of the cationic binder resin (A) may be 2,000 to 100,000, preferably 3,000 to 40,000. When it has a weight average molecular weight of 2,000 to 100,000, adhesion and developability can be improved.

The content of the cadmium binder resin (A) is not particularly limited, but may be 1 to 40 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of the colored photosensitive resin composition. When the content of the binder resin is within the above range, solubility in a developing solution is sufficient and pattern formation is easy.

&Lt; Photopolymerizable compound (B) >

The photopolymerizable compound (B) according to the present invention may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer as a component for enhancing the strength of a pattern, and preferably a monomer having two or more functionalities is preferably used.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate N-vinylpyrrolidone, and the like.

The type of the bifunctional monomer is not particularly limited and examples thereof include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The type of the polyfunctional monomer is not particularly limited and includes, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The content of the photopolymerizable compound (B) is not particularly limited, but may be 1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the black photosensitive resin composition. If the content of the photopolymerizable compound is less than 1 part by weight, the photosensitivity may be lowered. If the content of the photopolymerizable compound is more than 20 parts by weight, the photosensitive resin layer may be excessively tacky and the strength of the film may be insufficient.

&Lt; Photopolymerization initiator (C) >

The photopolymerization initiator of the present invention is characterized by containing an oxime ester compound in which NO ₂ is substituted for the ethyl carbazole structure represented by the following formula (3). The photopolymerization initiator of the present invention is characterized in that the absorbance of the solution containing the photopolymerization initiator at a concentration of 0.01% or more is 0.5 or more at 405 nm. The solvent for dissolving the photopolymerization initiator should be one which can dissolve the photopolymerization initiator more effectively. Examples of the solvent include propylene glycol methyl ether acetate, 1,2-propylene glycol diacetate, 3-methoxybutyl acetate, propylene glycol methyl ether, 3-ethoxypropionate, and dipropylene glycol monomethyl ether acetate. It is preferable to use propylene glycol methyl ether acetate.

(3)

In Formula 3, R ₁₃ is an aryl group having 6 to 10 carbon atoms and substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, -OR ₁₅ , and a halogen group, or -OR ₁₅ and a halogen group and an arylalkyl group having 7 to 24 substituted with one or more substituents selected from the group, R ₁₄ is an arylalkenyl kalgi C 1 -C 8 alkyl group, a C6 - C10 aryl group or C7 to 24, R ₁₅ Is an alkyl group having 1 to 20 carbon atoms substituted with hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

When the absorbance of the solution containing the photopolymerization initiator (Formula 3) at a concentration of 0.01% is 0.5 or more at 405 nm, when the color filter pattern is formed by exposure with a 405 nm single wavelength exposing device, the initiation efficiency is increased, Excellent sensitivity and reliability of the colored photosensitive resin composition can be obtained without using an initiator.

Further, other photopolymerization initiators than those described above may be further used within the scope of not impairing the effects of the present invention. The photopolymerization initiator that can be further used includes, for example, at least one compound selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a nonimidazole compound, and a thioxanone compound .

The acetophenone-based compounds include, for example, 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.

The benzophenone compound may be, for example, benzophenone, methyl 0-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 triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

The non-imidazole compound may be, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Bis (2,6-dichlorophenyl) -4, 5,5'-tetra (trialkoxyphenyl) bimidazole, 2,2- , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and imidazole compounds wherein the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group . Among the imidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole Is preferably used.

The thioxanthone compound may be, for example, 2-isopropylthioxanecone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4- .

The photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the colored photosensitive resin composition of the present invention. Since the colored photosensitive resin composition according to the present invention contains a photopolymerization initiator auxiliary agent, the sensitivity can be further improved and the productivity can be increased.

As the photopolymerization initiation auxiliary, 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.

The amine compounds include, for example, aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4- Aromatic amine compounds such as bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, and aromatic amine compounds are used as the amine compounds .

The carboxylic acid compound is, for example, selected from the group consisting of phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, , And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The organic sulfur compounds having thiol groups include, for example, 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like can be used. .

The content of the photopolymerization initiator (C) is not particularly limited, but may be 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the black photosensitive resin composition. If it is contained in an amount of less than 0.1 part by weight, the sensitivity may be lowered and the pattern may be detached during the developing process. If the amount exceeds 10 parts by weight, wrinkles may occur.

&Lt; Black pigment (D) >

Examples of the black pigment (D) used in the present invention include carbon black, organic black pigment, titanium black and pigments obtained by mixing red, blue and green.

More specifically, the black pigment may be prepared by mixing a carbon black and two or more colored pigments to prepare a milled colored dispersion. Examples of usable carbon black include CHBK-17 from Mikuni Color; HS, SISO 3HHAF-HS, Sisato NH, Sisato 3M, Sisso 300HAF-LS, Sisso 116HMMAF-HS, Sisato 116MAF, Sisito FMFEF- HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX-55, PRINTEX-85, PRINTEX-75, PRINTEX- SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; RAVEN-1080 ULTRA, RAVEN-1060ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, 420, RAVEN-410, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN- RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170.

Examples of color pigments usable in combination with the carbon black include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), Mitsubishi carbon black MA100, perylene black (BASF K0084. K0086) , Linol Yellow (CI 21090), Linol Yellow GRO (CI 21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI42595) PIGMENT RED97, 122, 149, 168, 177, 180, 192, 215, C.I. PIGMENT GREEN 7, 36, C.I. PIGMENT 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. PIGMENT 83, 139 C.I. PIGMENT VIOLET 23, etc. In addition, white pigments, fluorescent pigments, etc. may be used.

The carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon black can be used. Specific examples of the carbon black that is the black pigment include channel black, furnace black, thermal black, lamp black, and the like.

The carbon black, which is the black pigment, may be a resin-coated carbon black. Since the carbon black coated with the resin has a lower conductivity than that of the carbon black not coated with the resin, excellent electrical insulation can be imparted to the black matrix or black column spacer when the spacer is formed.

The black pigment may be used as a pigment dispersion in which the particle size of the black pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (d1) by containing the pigment dispersant (d1), and a method of obtaining a pigment dispersion in which the pigment is uniformly dispersed in a solution have.

( d1 ) Pigment Dispersant

Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. These surfactants may be used singly or in combination of two or more.

It is also preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

The pigment dispersant (d1) may be a pigment dispersant of a resin type other than the above acrylic dispersant. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts 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, BYK (trade name) 164, 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 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 black pigment (D) of the present invention may be contained in an amount of 5 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the black photosensitive resin composition.

&Lt; Solvent (E) >

The solvent (E) according to the present invention is used for dissolving other components of the black photosensitive resin composition of the present invention, and can be used without any particular limitation as long as it is a solvent used in a commonly used black photosensitive resin composition. , 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;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol 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;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl 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;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. The solvents (E) exemplified above may be used alone or in combination of two or more.

The content of the solvent (E) is not particularly limited, but may be 20 to 85 parts by weight based on 100 parts by weight of the black photosensitive resin composition. When the content is within the above range, the coating ability can be improved.

Further, the photosensitive resin composition of the present invention may further include at least one additive selected from an adhesion promoter, a surfactant, a dispersant, an antioxidant, an ultraviolet absorber, a thermal polymerization inhibitor, and a leveling agent.

Examples of the adhesion promoter include methacrylate such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyldimethoxysilane, methacryloyloxypropyltriethoxysilane, and methacryloyloxypropyldimethoxysilane. At least one member selected from the group consisting of octyltrimethoxysilane, dodecyltrimethoxysilane, and octadecyltrimethoxysilane may be used as the alkyltrimethoxysilane. Species can be used.

Examples of the surfactant include MCF 350SF, F-475, F-488 and F-552 (hereinafter referred to as DIC), but the present invention is not limited thereto.

As the dispersant and leveling agent, any of those commonly used in the art can be used.

Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol, t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, alkoxybenzophenone and the like. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- butylcatechol, benzoquinone, 4,4-thiobis t-butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole and the like.

The photosensitive resin composition of the present invention may further comprise at least one secondary additive selected from a carbon black dispersion, a functional resin binder, a monomer, a radiation-sensitive compound, and other additives.

The present invention also provides a black mattress made of the black photosensitive resin composition and an image display device having the black mattress.

The image display apparatus of the present invention includes the above-described black matrix, and specific examples thereof include a liquid crystal display, an OLED, and a flexible display. However, the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.

Synthetic example  One: Carometer  Synthesis of binder resin (A-1)

(1) A reactor was charged with 138 g of bisphenol epoxy compound 9,9'-bis (4-glycyloxyphenyl) fluorene (Hear chem), 54 g of 2-carboxyethyl acrylate, 1 g of triphenylphosphine (Aldrich), 128 g of propylglycolmethylethylacetate (Daicel Chemical Co.), and 0.5 g of hydroquinone were charged, and the mixture was heated to 120 캜 and maintained at that temperature for 12 hours. A compound represented by the general formula (5) was synthesized.

(2) In the reactor, 60 g of the compound represented by the formula 5, 11 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas), 3 g of tetrahydrophthalic anhydride (Aldrich), 20 g of propylglycolmethylethylacetate (Daicel Chemical Co.) And 0.1 g of N, N'-tetramethylammonium chlorite were charged, heated to 120 ° C and maintained at this temperature for 2 hours to synthesize a compound represented by the following formula (6). The weight average molecular weight of the compound represented by the formula (6) was 5,400 g / mol.

[Chemical Formula 5]

[Chemical Formula 6]

Synthetic example  2: Carometer  Synthesis of binder resin (A-2)

(1) 138 g of bisphenol epoxy compound 9,9'-bis (4-glycyloxyphenyl) fluorene (Hear chem), 54 g of mono-2-acryloyloxyethyl succinate, benzyltriethylammonium chloride 1 g of triphenylphosphine (Aldrich), 128 g of propylglycolmethylethylacetate (Daicel Chemical Co.) and 0.5 g of hydroquinone were charged, and the mixture was heated to 120 DEG C and maintained at that temperature for 12 hours to obtain a compound Were synthesized.

(2) In the reactor, 60 g of the compound represented by the formula (7), 11 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas), 3 g of tetrahydrophthalic anhydride (Aldrich), 20 g of propylglycolmethylethylacetate , And 0.1 g of N, N'-tetramethylammonium chlorite were charged, and the mixture was heated to 120 ° C and maintained at this temperature for 2 hours to synthesize a compound represented by the following formula (8). The weight average molecular weight of the compound represented by the formula (8) was 5,400 g / mol.

 (7)

[Chemical Formula 8]

Comparative Synthetic Example : Binder resin (A-3) Synthesis

200 g of a THF (tetrahydrofuran) solution as a reaction solvent was charged into a 500 ml four-necked flask and maintained at 50 캜. 89 g of the compound represented by the formula (9) was introduced and 44.5 g of the epiklohydrin solution represented by the formula (10) was introduced at a rate of 5.25 g per minute using a dropping funnel, and the reaction was conducted for 1 hour and 30 minutes. 348 g of the bisphenol-based fluorene-type epoxy resin compound obtained by the reaction was charged into a 1000-mL reactor, 140.52 g of an acrylic acid solution was added, and the temperature was raised to 80 ° C to conduct the reaction. Thereafter, 13.5 g of tetraethylammonium bromide was slowly added thereto, and the reaction was allowed to proceed for 60 hours. 150 g of the above reaction product was placed in a reactor, and 180.5 g of anhydride (phthalic anhydride) and 348.8 g of anhydride (anhydrous pyromellitic acid) were added thereto and maintained at 120 ° C. At this time, 0.718 g of Fascat 4101 as a catalyst was slowly added thereto and reacted for 5 hours to prepare a binder resin.

[Chemical Formula 9]

[Chemical formula 10]

Synthetic example  3: Light curing Initiator  synthesis

3.1

37.3 g of AlCl ₃ and 112.0 g of dichloroethane were charged into a reactor having a nitrogen atmosphere, and the mixture was stirred at a temperature of 5 ° C. 240.3 g of dichloroethane and 48.1 g of nitrocarbazole were dissolved in 17.27 g of acetyl chloride solution, and the dissolved solution was added dropwise to the reactor for 1 hour. The temperature was then raised to 15 ° C and stirring was continued for another 2 hours. Distilled water was added to the reaction solution, washed and separated, and then the solvent was dried to obtain a reactant 1 having a purity of 94%.

3.2

35.0 g of the above reaction product 1, 11.1 g of hydrochloric acid hydroxylamine, 15.1 g of sodium acetate, 90 g of ethanol and 30 g of distilled water were put into a reactor having a nitrogen atmosphere, and the mixture was stirred at the temperature of 80 캜 for 5 hours. Thereafter, distilled water was added to separate the precipitate and dried to obtain a reactant 2 having a purity of 92%.

3.3

26.0 g of Reactant 2 and 78 g of dichloromethane were charged into a reactor having a nitrogen atmosphere and stirred at room temperature. Then, a mixed solution obtained by diluting 15.0 g of acetic anhydride with 15.0 g of dichloroethane was added dropwise to the reactor for 1 hour, followed by stirring for 1 hour. After stirring, distilled water was added thereto, washed several times, and dichloromethane was evaporated to obtain a compound of formula 11 having a purity of 90%. Formula 11 is a structure in which R ₁₃ and R ₁₄ in Formula 3 are methyl groups, and can be represented as follows.

(11)

Example  1 to 10 and Comparative Example  1 to 6

The photosensitive resin composition was prepared using the components and the content (unit: parts by weight, based on 100 parts by weight of the photosensitive resin composition) shown in Table 1 below.

division The binder resin (A) The photopolymerizable compound (B) The photopolymerization initiator (C) The black pigment (D) menstruum
(E) A-1 A-2 A-3 A-4 C-1 C-2 C-3 Example 1 15 10 0.3 0.3 8 66.3 Example 2 15 10 0.5 8 66.4 Example 3 7 5 0.3 0.3 8 79.3 Example 4 25 10 0.3 0.3 8 56.3 Example 5 7 5 6 6 8 67.9 Example 6 15 10 0.3 0.3 8 66.3 Example 7 15 10 0.5 8 66.4 Example 8 7 5 0.3 0.3 8 79.3 Example 9 25 10 0.3 0.3 8 56.3 Example 10 7 5 6 6 8 67.9 Comparative Example 1 15 10 0.3 0.3 8 66.3 Comparative Example 2 15 10 0.3 0.3 8 66.3 Comparative Example 3 15 10 0.5 8 66.4 Comparative Example 4 15 10 0.5 8 66.4 Comparative Example 5 15 10 0.5 8 66.4 Comparative Example 6 15 10 0.3 0.3 8 66.3 [Binder resin (A)]
A-1: Cathode binder resin of Synthesis Example 1 (Cathode binder resin of the present invention)
A-2: Cathode binder resin of Synthesis Example 2 (Cathode binder resin of the present invention)
A-3: Binder resin of Comparative Synthesis Example
A-4: Acrylic binder (benzylmethacrylate / N-phenylmaleimide / styrene / methacrylic acid)
(Molar ratio: 55/9/11/25, Mw = 20,000, acid value: 100 mgKOH / g)
[Photopolymerizable Compound (B)]: Dipentaerythritol triacrylate
[Photopolymerization initiator (C)]
C-1: A photopolymerization initiator of Synthesis Example 3
C-2: N-1919 (Adeka)
C-3: Triazine-EB (Tronly)
[Black pigment (D)]: CHBK-17 (Mikuni Color Company)
[Solvent (E)]: Propylene glycol monomethyl ether acetate
[Adhesion promoter (F)]: 3-methacryloyloxypropyltrimethoxysilane (Shin-Etsu)

Experimental Example

[Evaluation of adhesion strength]

The photosensitive resin compositions of Examples and Comparative Examples were applied and dried on a hot plate at 100 占 폚 for 1 minute to obtain a coated film. Thereafter, the exposure process was carried out using a high-pressure mercury lamp having a wavelength of 365 nm by using a mask having a pattern thickness of 1 to 20 mu m and engraved in a unit of 1 mu m on the coating film. After performing the post-bake for 100 minutes in a convection oven at 230 ° C without performing development for the exposure process, PCT (Pressure-cookertest) was performed, and then the glass and coating pieces were peeled off by a cross- (See FIG. 1). The results are shown in Table 2 below (PCT process condition: 2 atmospheres, humidity 120% 4hr / 1 cycle).

[Evaluation of developing adhesion]

The photosensitive resin compositions of Examples and Comparative Examples were applied to a glass substrate having a thickness of 1 mm at a thickness of 1 占 퐉 and dried on a hot plate at 100 占 폚 for 1 minute to obtain a coated film. Thereafter, using a mask engraved in a unit of 1 mu m in width from 1 to 20 mu m in pattern width on the coating film, the resist film was exposed using a high-pressure mercury lamp having a wavelength of 365 nm, and then developed with a 1% KOH aqueous solution at 30 DEG C, The development was carried out for a certain period of time. The minimum pattern was measured based on the mask size in which the pattern remained (see FIG. 2), and the results are shown in Table 2 below.

division Minimum pattern (탆) Substrate adhesion 1 cycle 2cycle 3cycle Example 1 4 Peeling off Peeling off Peeling off Example 2 4 Peeling off Peeling off Peeling off Example 3 3 Peeling off Peeling off Peeling off Example 4 5 Peeling off Peeling off Peeling off Example 5 6 Peeling off Peeling off Peeling off Example 6 4 Peeling off Peeling off Peeling off Example 7 4 Peeling off Peeling off Peeling off Example 8 3 Peeling off Peeling off Peeling off Example 9 5 Peeling off Peeling off Peeling off Example 10 6 Peeling off Peeling off Peeling off Comparative Example 1 6 Peeling off Exfoliation Exfoliation Comparative Example 2 8 Peeling off Peeling off Peeling off Comparative Example 3 8 Peeling off Exfoliation Exfoliation Comparative Example 4 8 Peeling off Exfoliation Exfoliation Comparative Example 5 8 Peeling off Exfoliation Exfoliation Comparative Example 6 8 Peeling off Peeling off Exfoliation

As shown in Table 2, in Examples 1 to 10, a color filter having a high resolution can be realized because the developing adhesion is excellent and the minimum pattern size that can be formed without loss of the pattern is remarkably small, and the adhesion to the substrate is excellent, In particular, Examples 1 to 3 and 6 to 8 were small in the minimum pattern size and excellent in substrate adhesion.

In the case of Comparative Example 1 using the binder resin polymerized from a compound having a structure different from the formulas 5 and 7, it was confirmed that the developing adhesion was decreased, the minimum pattern size was large, the substrate strength under the anti- Respectively. In the case of Comparative Example 2 using the acrylic binder resin, the adhesion to the substrate was somewhat superior, but it was confirmed that the durability was weak. In the case of Comparative Examples 3 and 4 in which a triazine-based photoinitiator was used in place of the oxime ester-based photoinitiator, The adhesiveness to the substrate was all lowered.

Claims (4)

(A), a photopolymerizable compound (B), a photopolymerization initiator (C), a black pigment (D) and a solvent (E)
The alkali-soluble resin (A) comprises a cationic binder resin (A) having a repeating unit represented by the following formula (1)
Wherein the photopolymerization initiator (C) comprises a compound represented by the following general formula (3):
[Chemical Formula 1]

(In Formula 1, X is a single _{bond, -CO-, -SO 2 -, -C} (CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-,

,

,

,

,

,

,

,

,

,

,

, or

ego,
Y is an acid anhydride residue,
R 'is a hydrogen atom, an ethyl group, a phenyl _{group, -C 2 H 4 Cl, -C} 2 H 4 OH, or -CH ₂ CH = CH _2,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a methyl group,
R ₇ and R ₈ are each independently a straight or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group may have at least one of an ester bond, a cycloalkylene group having 6 to 14 carbon atoms and an arylene group having 6 to 14 carbon atoms May include,
R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom, a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms,
and m is an integer satisfying 0? m? 30)
(3)

(3)
R ₁₃ is an aryl group having 6 to 10 carbon atoms substituted with at least one substituent selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, -OR ₁₅ , and a halogen group, or a group selected from the group consisting of -OR ₁₅ and a halogen group An arylalkyl group having 7 to 24 carbon atoms substituted with at least one substituent,
R ₁₄ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms,
R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms. The positive photosensitive resin composition according to claim 1, which comprises 1 to 40 parts by weight of an alkali-soluble binder resin (A), 1 to 20 parts by weight of a photopolymerizable compound (B), 0.1 to 10 parts by weight of a photopolymerization initiator (C) , 5 to 20 parts by weight of a black pigment (D) and 20 to 85 parts by weight of a solvent (E). A black matrix formed by using the black photosensitive resin composition according to claim 1 or 2. An image display apparatus comprising a black matrix according to claim 3.

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