KR102361573B1 - A black photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display device comprising the color filter - Google Patents

Abstract

(상기 화학식 1에서, R¹은 수소 원자 또는 메틸기이고, n은 1 내지 10의 정수이다.)
[화학식 2]

(상기 화학식 2에서, R¹은 수소 원자 또는 메틸기이고, X는 탄소수 1내지 6의 알킬렌기이며, n은 1 내지 30의 정수이다.)The present invention relates to a black photosensitive resin composition comprising a fluorine-based surfactant obtained by copolymerizing a monomer represented by the following formula (1) and a monomer represented by the following formula (2), a black matrix prepared using the black photosensitive resin composition, a column spacer, black A color filter including a column spacer or a black bank, and a display device including the color filter.
[Formula 1]

(In Formula 1, R ¹ is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.)
[Formula 2]

(In Formula 2, R ¹ is a hydrogen atom or a methyl group, X is an alkylene group having 1 to 6 carbon atoms, and n is an integer of 1 to 30.)

Description

A black photosensitive resin composition, a black matrix manufactured using the same, a color filter including a column spacer or a black column spacer, and a display device including the color filter a column spacer or black column spacer prepared by using the composition, and a display device comprising the color filter}

The present invention relates to a black photosensitive resin composition, a black matrix manufactured using the same, a color filter including a column spacer or a black column spacer, and a display device including the color filter.

A color filter is widely used in various display devices such as an imaging device and a liquid crystal display (LCD), and its application range is rapidly expanding. The color filter used in the image pickup device, liquid crystal display device, etc. is made of a coloring pattern of three colors of red, green, and blue, or yellow, magenta and cyan ( It consists of a coloring pattern of 3 colors of Cyan).

The color pattern of each color filter is generally formed using a black photosensitive resin composition including a colorant such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the black photosensitive resin composition is generally performed by a lithography process.

The black photosensitive resin is an essential material for color filters, liquid crystal display materials, organic light emitting devices, displays, and the like. For example, in the case of a color filter used in a liquid crystal display, a pixel composed of each color of red, green, and blue is included, and it is important to prevent mixing of each of these pixels. very important. Accordingly, various methods for preventing color mixing in the manufacture of color filters have been proposed.

In addition, in order to reduce cost and improve productivity, the color matrix forming material requires high sensitivity for patterning with a small exposure dose, and the price of the material used for manufacturing the pixel is sharply increased due to the advancement of the material used in the pixel. There is a need to curb unnecessary wasted material. For this purpose, a property of repelling water, organic solvents, etc., so-called liquid repellency, is required.

In this regard, Korean Patent Application Laid-Open No. 10-2010-0016089 and Korean Patent Application Laid-Open No. 10-2016-0057877 disclose a black photosensitive resin composition including a fluorine-containing surfactant. However, it does not seem to be sufficient in improving the liquid repellency.

Republic of Korea Patent Publication No. 10-2010-0016089 Republic of Korea Patent Publication No. 10-2016-0057877

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a black photosensitive resin composition having excellent light-shielding properties, and in particular, providing a black photosensitive resin composition having excellent liquid repellency to water or organic solvents aim to do

Another object of the present invention is to provide a color filter including a pattern layer made of the black photosensitive resin composition, and a display device including the color filter.

It provides a black photosensitive resin composition comprising a fluorine-based surfactant obtained by copolymerizing a monomer represented by the following formula (1) and a monomer represented by the following formula (2).

[Formula 1]

(In Formula 1, R ¹ is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.)

[Formula 2]

(In Formula 2, R ¹ is a hydrogen atom or a methyl group, X is an alkylene group having 1 to 6 carbon atoms, and n is an integer of 1 to 30.)

In addition, the present invention provides a patterned layer made of the black photosensitive resin composition of the present invention.

In addition, the present invention provides a color filter comprising the pattern layer of the present invention.

In addition, the present invention provides a display device including the color filter of the present invention.

The black photosensitive resin composition of the present invention can form a cured film having a contact angle with respect to water and an organic solvent equal to or greater than a certain standard by introducing a fluorine-based surfactant obtained by copolymerizing the monomers represented by Chemical Formulas 1 and 2, and at the same time, optical density, etc. It is also possible to provide a black matrix excellent in liquid repellency and light blocking properties by satisfying the characteristics of . Therefore, the black photosensitive resin composition of the present invention can be usefully used in the manufacture of color filters and display devices.

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

The present invention relates to a black photosensitive resin composition comprising a fluorine-based surfactant obtained by copolymerizing a monomer represented by the following formula (1) and a monomer represented by the following formula (2).

[Formula 1]

(In Formula 1, R ¹ is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.)

[Formula 2]

(In Formula 2, R ¹ is a hydrogen atom or a methyl group, X is an alkylene group having 1 to 6 carbon atoms, and n is an integer of 1 to 30.)

In the present invention, when a fluorine-based surfactant obtained by copolymerizing a monomer represented by Formula 1 and a monomer represented by Formula 2 as a surfactant is introduced into a black photosensitive resin composition, water and propylene glycol methyl ether of a cured film formed using the surfactant The present invention was completed by experimentally confirming that excellent liquid repellency properties can be obtained at each contact angle with respect to acetate (PGMEA) above a certain standard.

The black photosensitive resin composition may be characterized in that a contact angle of a cured film formed using the same to water is 100° or more, and a contact angle to propylene glycol methyl ether acetate (PGMEA) is 50° or more.

In addition, the black photosensitive resin composition may be characterized in that the contact angle with respect to water of the cured film formed using the same is 100˚ to 130˚, and the contact angle with respect to propylene glycol methyl ether acetate is 50˚ to 100˚ can be done with When the contact angle of the cured film with respect to water and propylene glycol methyl ether acetate satisfies the above range, it is preferable to exhibit excellent liquid repellency.

The black photosensitive resin composition may include a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent together with the fluorine-based surfactant.

Hereinafter, the black photosensitive resin composition of the present invention will be described in detail for each component.

Fluorine surfactant

The fluorine-based surfactant serves to uniformly disperse the pigment component in the solvent and to improve the leveling property to improve the coating property and prevent the formation of defects.

The surfactant according to the present invention contains a fluorine (F) component to improve the contact angle, a radically polymerizable monomer having one fluorinated alkyl group having 6 carbon atoms directly bonded to the fluorine atom, an oxyalkylene group, and a polymerizable unsaturated group It is characterized in that it is a copolymer obtained by copolymerizing a polymerizable monomer.

Examples of the radically polymerizable monomer having one fluorinated alkyl group having 6 carbon atoms to which the fluorine atom is directly bonded may include a compound represented by the following formula (1), and examples of the polymerizable monomer having the oxyalkylene group and the polymerizable unsaturated group A compound represented by the following formula (2) may be mentioned.

[Formula 1]

(In Formula 1, R ¹ is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.)

[Formula 2]

(In Formula 2, R ¹ is a hydrogen atom or a methyl group, X is an alkylene group having 1 to 6 carbon atoms, and n is an integer of 1 to 30.)

The content of the fluorine-based surfactant is not particularly limited as long as the contact angle of the cured film formed using the black photosensitive resin composition according to the present invention and the contact angle with respect to propylene glycol methyl ether acetate can satisfy the above range. Preferably, it may be included in an amount of 0.1 to 10.0 wt%, more preferably 0.2 to 7.0 wt%, based on the total weight of the black photosensitive resin composition. When included below the above range, the contact angle improvement effect may be insignificant, and when included above the above range, there is a problem in that process characteristics are improperly affected.

coloring agent

The colorant is used to implement black, and provides light blocking properties to the column spacer, the black matrix, and the black column spacer prepared using the black photosensitive resin composition according to the present invention.

As long as the colorant has light-shielding properties against visible light, all colorants known in the field of black photosensitive resin compositions such as black pigments, organic pigments, dyes and the like can be used, but it is preferable to use a black pigment.

The black pigment includes both organic black pigments and inorganic black pigments, and any known black pigment may be used without particular limitation. Specifically, the black pigment may include lactam black, aniline black, perylene black, titanium black and carbon black, and the carbon black may include channel black, furnace black, thermal black, lamp black, and the like. These black pigments can be used individually or in mixture of 2 or more types.

As the carbon black, if necessary, carbon black coated with a resin on the surface for electrical insulation may be used. Since the resin-coated carbon black has a lower conductivity than the non-resin-coated carbon black, excellent electrical insulation can be imparted when forming a black matrix, column spacer, or black column spacer (black matrix integrated spacer).

The colorant may include at least one organic black pigment selected from the group consisting of lactam black, aniline black and phenylene black; at least one inorganic black pigment selected from the group consisting of titanium black and carbon black; and blue pigments.

The organic black pigment preferably uses lactam black (eg, Irgaphor® Black S 0100 CF from BASF) in terms of optical density, dielectric constant, transmittance, etc., and the inorganic black pigment is carbon in terms of pattern characteristics and chemical resistance. It is preferable to use black, and it is preferable to use CI Pigment Blue 15:6 for the blue pigment to prevent light leakage.

The colorant may optionally further include a color correcting agent, if necessary. As the color correcting agent, condensed polycyclic pigments such as anthraquinone pigments or perylene pigments, organic pigments such as phthalocyanine pigments or azo pigments may be used, preferably anthraquinone pigments or phthalocyanine pigments, more preferably phthalocyanine pigments can be used

Examples of the anthraquinone-based pigment include C.I Pigment Blue 60.

Examples of the phthalocyanine pigment include C.I Pigment Blue 15:6, C.I Pigment Blue 15:4 and C.I Pigment Blue 16, preferably C.I Pigment Blue 15:6.

The colorant is included in an amount of 5 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of the black photosensitive resin composition of the present invention. included as When the colorant is included in the above range, it is possible to form a pattern having sufficient color density and mechanical strength when manufactured as a color filter.

In addition, as the colorant, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the particle size of the pigment include a method of dispersing treatment by containing a pigment dispersant, and according to the method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

pigment dispersant

The pigment dispersant is added to deagglomerate and maintain stability of the pigment, and specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine surfactants, etc. and these can be used individually or in combination of 2 or more types, respectively.

Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines are mentioned. have.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter, acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). It is preferable to use the acrylate-based dispersant prepared by the living control method, and commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, and the acrylic The rate-based dispersant may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants may be used in addition to the acrylate-based dispersant. As the pigment dispersant of the other resin type, a pigment dispersant of a known resin type, particularly polyurethane, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly(lower alkyleneimine); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylates; adducts of ethylene oxide/propylene oxide; and phosphate esters.

As a commercial product of the above-mentioned other resin type pigment dispersant, as a cationic resin dispersant, for example, BYK (Big) Chemi Corporation's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned.

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

The pigment dispersant is included in an amount of more than 0 and 1 part by weight or less, preferably 0.01 to 0.5 parts by weight, based on 1 part by weight of the colorant. When the pigment dispersant is included in the above range, it is preferable to obtain a uniformly dispersed pigment.

alkali-soluble resin

The alkali-soluble resin has reactivity and alkali solubility under the action of light or heat, acts as a dispersion medium for solid content including a colorant, and performs the function of a binder resin. A resin known in the field of black photosensitive resin composition is selected without particular limitation. so it can be used The alkali-soluble resin is preferably a cardo-based resin to ensure a low dielectric constant.

Specifically, as the cardo-based resin, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, Bis(4-hydroxyphenyl)hexafluoropropane, 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-dichlorophenyl)dimethylsilane, bis(4- Hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichloroethyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxy Phenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5- Dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3- Methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis( 4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethyl Phenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc. may be used, and these may be used alone or in combination of two or more.

In addition, the alkali-soluble resin having an acid value of 20 to 200 (KOH mg / g) may be preferably used. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer and is related to the solubility of the resin. When the acid value of the resin falls within the above range, solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased. As a result, the pattern of the exposed portion remains at the time of development, thereby improving the film remaining ratio.

In addition, the alkali-soluble resin may consider limitation of molecular weight and molecular weight distribution (MW/MN) in order to improve surface hardness, and in the case of a weight average molecular weight, 3,000 to 200,000, preferably 5,000 to 100,000, more preferably 5,000 to 30,000 can be used. In the case of molecular weight distribution, a range of 1.5 to 6.0, preferably 1.8 to 4.0, may be used. When the alkali-soluble resin has a molecular weight and molecular weight distribution within the above ranges, it is preferable because the hardness is improved, the residual film prevention effect is excellent, and the solubility of the non-exposed part in the developer is excellent and the resolution can be improved.

The alkali-soluble resin may be used in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, based on the total weight of the black photosensitive resin composition of the present invention. The content range of the alkali-soluble resin is selected in consideration of solubility in a developer and pattern formation, etc., and when used within the content range, solubility in a developer is sufficient to form a pattern, and exposure during development Film reduction of the negative pixel portion is prevented, and the omission property of the non-pixel portion is improved.

photopolymerizable compound

The photopolymerizable compound is a component for reinforcing the strength of the pattern, and may include monofunctional, bifunctional or polyfunctional monomers, and may preferably be bifunctional or more functional monomers.

The photopolymerizable compound is, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate or N-vinyl p monofunctional monomers such as rolidone; 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyl of bisphenol A) bifunctional monomers such as oxyethyl) ether or 3-methylpentanediol di(meth)acrylate; Trimethylol propane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaeryth Ritol tetra (meth) acrylate, dipentaeryth ritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, di Polyfunctional monomers, such as pentaerythritol hexa (meth)acrylate, are mentioned. These can be used individually or in mixture of 2 or more types.

In the present invention, the "(meth)acrylate" means "acrylate" or "methacrylate".

The photopolymerizable compound is included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content in the black photosensitive resin composition of the present invention. When the photopolymerizable compound is included in the above range, the strength and flatness of the pixel portion can be improved.

photopolymerization initiator

The photopolymerization initiator is a compound for initiating polymerization of the photopolymerizable compound, and may be used without limitation as long as it can polymerize the photopolymerizable compound, but is preferably acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, Oxime-based, benzoin-based, anthraquinone-based and biimidazole-based compounds may be used, and these may be used alone or in combination of two or more.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-1-[4-(2-hydroxyethane). Toxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- oligomers of benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc. Among them, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one may be preferably used.

Examples of the benzophenone-based compound include benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4'- Bis(diethylamino)benzophenone etc. are mentioned.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, and 2-(3',4'-dime oxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-triyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -Biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl (piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, etc. are mentioned.

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

Examples of the oxime-based compound include o-ethoxycarbonyl-*j oxyimino-1-phenylpropan-1-one, and commercially available products include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF.

As the benzoin-based compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, and the like can be used.

Examples of the anthraquinone-based compound include 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benzanthraquinone, and 2,3-diphenyl anthraquinone.

As the biimidazole-based compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) )-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole and the phenyl group at the 4,4',5,5' position and imidazole compounds substituted by

The photopolymerization initiator is included in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 5.0% by weight, based on the total weight of the black photosensitive resin composition. When the photopolymerization initiator is included in the above range, the black photosensitive resin composition may be highly sensitive, and the strength of the pixel portion formed using the photopolymerization initiator and the straightness of the pattern may be improved.

In addition, in the present invention, a photopolymerization initiator auxiliary may be used in addition to the photopolymerization initiator. When a photopolymerization initiation auxiliary is used in combination with the photoinitiator, the black photosensitive resin composition containing them becomes more sensitive, and productivity is improved when using the photopolymerization initiator to form a support spacer for maintaining a cell gap, so it is preferable.

The photopolymerization initiation adjuvant is used to increase the polymerization efficiency of the photopolymerizable compound, the polymerization of which is initiated by the photoinitiator, and examples thereof include an amine-based compound, an alkoxyanthracene-based compound, and a thioxanthone-based compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-Dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethylamino) Benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. can

As the thioxanthone-based compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-pro Foxy oxanthone etc. are mentioned.

Moreover, a commercially available thing can be used as a photoinitiation adjuvant, As a commercially available photoinitiation adjuvant, the brand name "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) etc. are mentioned.

In the case of using the photopolymerization initiation aid, it may be used in an amount of more than 0 and 10 moles or less, preferably 0.01 to 5 moles, based on 1 mole of the photopolymerization initiator. When the photopolymerization initiation adjuvant is included in the above range, the effect of improving the productivity can be expected by increasing the polymerization efficiency.

solvent

As long as the solvent can dissolve or disperse other components included in the black photosensitive resin composition, the solvent used in the general black photosensitive resin composition may be used without particular limitation, and in terms of coatability and dryness, a boiling point of 100 - It is preferable to use the organic solvent of 200 degreeC*.

Examples of the solvent include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower alcohols, higher alcohols, and cyclic esters.

More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene 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; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; 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 *j butyrolactone.

Among the solvents, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate may be used, and more preferably, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate and 3-methoxy methyl propionate may be used. These solvents can be used individually or in mixture of 2 or more types.

The solvent may be included in the remaining amount to satisfy 100% by weight of the black photosensitive resin composition. This content is a range selected in consideration of dispersion stability of the composition and ease of processing (eg, coatability) in the manufacturing process.

additive

The black photosensitive resin composition of the present invention includes, in addition to the above components, other additives according to various needs of those skilled in the art within a range that does not impair the object of the present invention.

Specifically, for example, the additive may be at least one selected from the group consisting of a dispersant, a dispersing aid, a filler, another high molecular compound, an ultraviolet absorber, and an anti-aggregation agent.

As the dispersant, a commercially available dispersing agent may be used, and specifically, BYK's Disper BYK-163 (DISPER BYK-163), Disper BYK-170 (DISPER BYK-170) and Disper BYK-2000 (DISPER) BYK-2000); and Ciba Specialties Chemicals Corp.'s EFKA-1101 (EFKA-1101) and EFKA-4310 (EFKA-4310) may be used.

As the dispersing aid, a commercially available dispersing aid may be used, and preferably, there are Solsperse 5000, Solsperse 12000, Solsperse 22000, etc. manufactured by Lubrisol. The dispersing aid is a copper phthalocyanine-based pigment derivative that imparts affinity with carbon black, thereby helping electrical and chemical adsorption between the carbon black surface and the dispersing agent, and improving dispersibility and dispersion stability compared to the case of using the dispersing agent alone. can

As the filler, glass, silica and alumina may be used.

Curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane may be used as the other polymer compound. have.

As the ultraviolet absorber, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like may be used.

As the aggregation inhibitor, sodium polyacrylate may be used.

The additive may be included in an amount of 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the black photosensitive resin composition.

The preparation of the black photosensitive composition of the present invention is not particularly limited, and a known method for preparing the black photosensitive composition is followed. For example, after adding the colorant to the solvent, the remaining composition and other additives may be added and obtained through stirring. In this case, the colorant may be added in the form of a mill base in which a pigment or the like is dissolved or dispersed in a solvent or alkali-soluble resin in advance. The additive may be previously added to the solvent together with the colorant when in solution form.

The black photosensitive resin composition thus prepared can be preferably used for manufacturing a black matrix of a display device, preferably a liquid crystal display device, a column spacer for maintaining a cell gap, or a black column spacer.

The column spacer, the black matrix, and/or the black column spacer according to the present invention has advantages of high optical density, excellent reliability, and excellent shielding properties.

In particular, the black photosensitive resin composition of the present invention may be preferably used for manufacturing a black column spacer (black matrix-integrated spacer), wherein the black column spacer does not form a black matrix and a column spacer, respectively, but is black in one pattern. It means that the matrix and the column spacer are integrally formed.

In addition, the present invention provides a pixel defining film prepared by using the black photosensitive resin composition. In one embodiment of the present invention, the black photosensitive resin composition may be used for forming a pixel defining layer of an organic light emitting device, or the black photosensitive resin composition may be used for a black bank or a light blocking layer. That is, in the present invention, the "pixel defining film" may be used interchangeably with "black bank" or "light blocking film".

In general, when an organic light emitting diode is driven, especially in a mobile device used outdoors, scattering by light reduces visibility. When a separate black matrix is introduced for absorption of the scattered light, visibility in the outdoors can be improved, but since a process for introducing the black matrix must be added, the process becomes complicated, and the cost and time increase, and consequently the efficiency of the process is reduced. can be lowered

Since the pixel defining film prepared using the black photosensitive resin composition according to the present invention can serve not only as a black bank of the organic light emitting device but also as a black matrix, light scattering of the organic light emitting device without additional process There is an advantage in that visibility can be improved.

In addition, the present invention provides an organic light emitting device including the pixel defining layer, and a display device including the organic light emitting device.

The present invention also relates to a color filter including a pattern layer prepared using the black photosensitive resin composition.

The color filter according to the present invention has advantages of high optical density, excellent reliability, and excellent shielding properties. The color filter includes a substrate and a pattern layer formed on the substrate.

The pattern layer is a layer including a cured product of the black photosensitive resin composition of the present invention, and may include a column spacer, a black matrix, a black column spacer, and/or a black bank.

The pattern layer may be a layer formed by applying the above-described black photosensitive resin composition and exposing, developing, and thermosetting in a predetermined pattern, and the pattern layer may be formed by performing a method commonly known in the art.

The color filter including the substrate and the pattern layer as described above may further include a barrier rib formed between each pattern, and may further include a black matrix, but is not limited thereto.

The present invention also relates to a display device including the color filter. In other words, the liquid crystal display according to the present invention may include a color filter including a pattern layer including a cured product of the aforementioned black photosensitive resin composition.

The color filter of the present invention can be applied to various image display devices, such as an electroluminescence display, a plasma display, and a field emission display, as well as a general liquid crystal display.

A typical patterning process for forming a black matrix, a column spacer, or a black column spacer according to a photolithography method is

a) applying a black photosensitive resin composition to the substrate;

b) a prebaking step of drying the solvent;

c) applying a photomask on the obtained film and irradiating actinic light to cure the exposed portion;

d) performing a developing process for dissolving the unexposed part using an aqueous alkali solution; and

e) drying and post-baking.

The substrate is a glass substrate or a polymer plate is used. As a glass substrate, especially soda-lime glass, barium or strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. can be used preferably. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide or polysulfone.

In this case, the application may be performed by a wet coating method using an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate, etc. At this time, the heating temperature and heating time in a prebaking are suitably selected according to the solvent to be used, and are performed at the temperature of 80-150 degreeC for 1 to 30 minutes, for example.

Moreover, exposure performed after a prebaking is performed by an exposure machine, and only the part corresponding to a pattern is exposed by exposing through a photomask. In this case, the irradiated light may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure It is performed for the purpose of removing the black photosensitive resin composition of the non-removed part of an unexposed part, and a desired pattern is formed by this development. As a developing solution suitable for this alkali development, the aqueous solution of the carbonate of an alkali metal or alkaline-earth metal, etc. can be used, for example. In particular, using an aqueous alkali solution containing less than 1 to 3 wt% of carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, etc., using a developer or ultrasonic cleaner within a temperature of 10 to 50 ° C, preferably 20 to 40 ° C. to do it

Post-baking is performed to increase adhesion between the patterned film and the substrate, and is performed through heat treatment at 80 to 250° C. for 10 to 120 minutes. Post-bake, like pre-bake, is performed using an oven, a hot plate, or the like.

At this time, as a film thickness of a black matrix, 0.2 micrometer - 10 micrometers are preferable, 0.5 micrometer - 7.0 micrometers are more preferable, and 1.0 micrometer - 5.0 micrometers are especially preferable.

Moreover, as a film thickness of a column spacer and a black column spacer, 0.5 micrometer - 8.0 micrometers are preferable, 1.0 micrometer - 6.0 micrometers are more preferable, and 1.0 micrometer - 4.0 micrometers are especially preferable.

The black matrix, column spacer or black column spacer prepared from the black photosensitive resin composition of the present invention has excellent physical properties such as optical density, adhesion, electrical insulation, and light blocking, as well as excellent contact angle with water or organic solvents. It can exhibit liquid repellency.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Synthesis Example 1: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared. As a monomer dropping lot, a mixture 40 of 3,4-epoxytricyclodecan-8-yl (meth)acrylate and 3,4-epoxytricyclodecan-9-yl (meth)acrylate in a molar ratio of 50:50 Parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added to prepare for stirring. In addition, 6 parts by weight of n-dodecanthiol and 24 parts by weight of PGMEA were added to a chain transfer agent dropping tank to prepare stirring.

Thereafter, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. After that, dripping of a monomer and a chain transfer agent was started. The dropping was carried out for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH/g.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin were measured by GPC method, and HLC-8120GPC (manufactured by Toso Corporation) was used.

For measurement conditions, TSK-GELG4000HXL and TSK-GELG2000HXL columns were connected in series, and the temperature of the column was set to 40°C. Tetrahydrofuran was used as a mobile phase solvent, and it was measured while flowing at a flow rate of 1.0 mL/min. The concentration of the measurement sample was 0.6% by weight, and the injection amount was 50 μl, and it was analyzed using an RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as a calibration standard, and the weight average molecular weight and number of alkali-soluble resins obtained under the above conditions The average molecular weight was measured.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthesis Example 2: Synthesis of fluorine-based surfactant (A1)

47.5 g of 2-propanol and 25.6 g of dicyclopentanyl methacrylate were thrown into the flask which carried out nitrogen substitution as a solvent, and it heated up at 40 degreeC, stirring under nitrogen stream. Next, 5.3 g of 2,2'-bipyridyl and 1.9 g of cuprous chloride were added, and the flask was stirred for 30 minutes while maintaining the temperature at 40°C. Then, 3.3 g of ethyl 2-bromoisobutyrate was added, and the reaction was carried out at 40° C. under a nitrogen stream for 2 hours, and then 25.6 g of dicyclopentanyl methacrylate was added and reacted at 40° C. for 2 hours to crosslinked hydrocarbons. A polymer segment containing a skeleton of Next, 45.9 g of 2-(tridecafluorohexyl)ethyl methacrylate was added to the reaction system containing the obtained polymer segment, and it was made to react at 40 degreeC for 5 hours, and the reaction material was obtained. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorine-containing surfactant (A1) of the present invention. As a result of measuring the molecular weight of the obtained said fluorochemical surfactant (A1) by GPC, it was 3,300 weight average molecular weights (Mw), and 2,900 number average molecular weights (Mn). In addition, the fluorine atom content was 14.5 mass %.

Synthesis Example 3: Synthesis of fluorine-based surfactant (A2)

65 g of methyl ethyl ketone and 31 g of isoboronyl methacrylate were thrown into the flask which carried out nitrogen substitution as a solvent, and it heated up at 60 degreeC, stirring under nitrogen stream. Next, 3.1 g of 2,2'-bipyridyl and 1.1 g of cuprous chloride were thrown in, and it stirred for 30 minutes, maintaining the inside of a flask at 60 degreeC. Then, 2.0 g of ethyl 2-bromoisobutyrate was added, and it was made to react at 60 degreeC under nitrogen stream for 3 hours, and the polymer segment containing the skeleton of a cross-linked hydrocarbon was obtained. Next, 10.5 g of 2-(tridecafluorohexyl)ethyl methacrylate was added to the reaction system containing the obtained polymer segment, and it was made to react at 60 degreeC for 8 hours, and the reaction material was obtained. Then, 30 g of activated alumina was added to the obtained reactant and stirred. After filtering activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorine-containing surfactant (A2) of the present invention. As a result of measuring the molecular weight of the obtained fluorine-based surfactant (A2) by GPC, the weight average molecular weight (Mw) was 4,200 and the number average molecular weight (Mn) was 3,600. In addition, the fluorine atom content was 14.5 mass %.

Examples 1 to 3 and Comparative Examples 1 to 8

A black photosensitive resin composition was prepared by mixing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an additive, and a solvent in a mixer, and the contents thereof are shown in Table 1 below.

[Table 1]

(Unit: % by weight)

Colorant: OBP (BASF)

Fluorine-based surfactants

A1: Fluorine-based surfactant prepared in Synthesis Example 2

A2: Fluorine-based surfactant prepared in Synthesis Example 3

(옴노바 社)A3:

(Omnova)

A4: HO(CH ₂ CH ₂ O)nCH ₂ CF ₂ O(CF ₂ CF ₂ O)p(CF ₂ O)qCF ₂ CH ₂ (OCH ₂ CH ₂ )nOH (Solvay)

(다우코팅 社)Silane-based surfactants:

(Dow Coating)

Alkali-soluble resin: dispersion resin prepared in Synthesis Example 1

Photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

Photoinitiator: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime) (Ciba Corporation)

Solvent: propylene glycol monomethyl ether acetate (PGMEA)

<Experimental example>

1. Substrate Fabrication

A 5 cm X 5 cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the black photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 8 was spin-coated on the glass substrate to have a final film thickness of 1.5 μm, and the solvent was removed by holding at 100° C. for 3 minutes. Then, using an ultra-high pressure mercury lamp (trade name: USH-250D: Ushio Denki Co., Ltd.), it was irradiated with light at an exposure dose of 70 mJ/cm2 in an atmospheric atmosphere, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed in a developing solution of a KOH aqueous solution having a pH of 12.5 for 90 seconds using a spray developer, and then heated in a heating oven at 230° C. for 30 minutes to prepare a colored substrate.

2. Contact angle measurement

DSA 100 of KRUSS was used as the measuring equipment, and 0.3 ml of DI water was dropped on the coating film of the prepared colored substrate, the contact angle was measured for 30 seconds, and the above process was repeated 3 times to obtain the average value. In addition, after 0.3 ml of PGMEA was dropped, the above process was repeated to obtain a contact angle.

The contact angle was measured in an atmosphere of atmospheric pressure, a temperature of 26° C. and a humidity of 30%, and the measurement results are shown in Table 2 below.

[Table 2]

Referring to Table 2, in the case of the black photosensitive resin compositions of Examples 1 to 4 containing the fluorine-based surfactant according to the present invention, it was confirmed that both the contact angles to DI water and PGMEA exhibited excellent liquid repellency beyond the standard value. . On the other hand, in the case of the black photosensitive resin compositions of Comparative Examples 1 to 8 using other surfactants, it was confirmed that the contact angles for DI water and PGMEA were less than the standard value, so that the liquid repellency was not sufficient.

Claims (12)

A fluorine-based surfactant obtained by copolymerizing a monomer represented by the following Chemical Formula 1, and at least one monomer selected from the group consisting of dicyclopentanyl methacrylate and isoboronyl methacrylate; and
containing an alkali-soluble resin,
The alkali-soluble resin is a black photosensitive resin comprising a repeating unit derived from 3,4-epoxytricyclodecan-8-yl (meth)acrylate and 3,4-epoxytricyclodecan-9-yl (meth)acrylate. resin composition.
[Formula 1]

(In Formula 1, R ¹ is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.) The black photosensitive resin composition according to claim 1, wherein the cured film formed using the black photosensitive resin composition has a contact angle of 100° or more with respect to water and a contact angle of 50° or more with respect to propylene glycol methyl ether acetate (PGMEA). The black photosensitive resin composition according to claim 2, wherein the cured film formed using the black photosensitive resin composition has a contact angle with respect to water of 100° to 130°. The black photosensitive resin composition according to claim 2, wherein a contact angle of the cured film formed using the black photosensitive resin composition with respect to propylene glycol methyl ether acetate is 50° to 100°. The black photosensitive resin composition of claim 1, wherein the black photosensitive resin composition comprises a colorant, a photopolymerizable compound, a photoinitiator, and a solvent. The method according to claim 5, 0.1 to 10% by weight of a fluorine-based surfactant, 5 to 20% by weight of a colorant, 1 to 30% by weight of an alkali-soluble resin, 1 to 20% by weight of a photopolymerizable compound, and a photopolymerization initiator based on the total weight of the black photosensitive resin composition A black photosensitive resin composition comprising 0.1 to 5% by weight and the remaining amount of the solvent. The black photosensitive resin composition according to claim 5, wherein the colorant comprises at least one selected from the group consisting of an organic black pigment, aniline black, phenylene black, titanium black, and carbon black. The black photosensitive resin composition according to claim 5, wherein the black photosensitive resin composition further comprises at least one additive selected from the group consisting of a dispersant, a filler, another polymer compound, an ultraviolet absorber, and an aggregation inhibitor. A pattern layer made of the black photosensitive resin composition of any one of claims 1 to 8. The pattern layer of claim 9 , wherein the pattern layer is at least one selected from the group consisting of column spacers, black matrixes, black column spacers, and black banks. A color filter comprising the pattern layer of claim 10 . A display device comprising the color filter of claim 11 .