KR20130060036A

KR20130060036A - Photosensitive resin composition for color filter comprising the same and color filter using the same

Info

Publication number: KR20130060036A
Application number: KR1020110126317A
Authority: KR
Inventors: 이창민; 김광섭; 백호정; 최현무; 전환승
Original assignee: 제일모직주식회사
Priority date: 2011-11-29
Filing date: 2011-11-29
Publication date: 2013-06-07

Abstract

PURPOSE: A photo-sensitive resin composition for a color filter and a color filter using the same are provided to form a black matrix with superior optical density in addition to high aperture ratio and contrast ratio in the process of manufacturing a color filter. CONSTITUTION: A photo-sensitive resin composition includes an alkali solution resin, a photopolymerizable monomer, a photopolymerization initiator, a coloring agent, and a solvent. The photopolymerizable monomer is represented by chemical formula 1. In the chemical formula 1, W1 to W6 are respectively -NR1, in which R1 is hydrogen or a substituted or non-substituted C1-C20 alkyl group, sulfur, or oxygen; Q1 to Q6 are hydrogen or function groups represented by chemical formula 2 or 3; and at least one of W1 to W6 and Q1 to Q6 is not a hydroxyl group or an amino group.

Description

PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER COMPRISING THE SAME AND COLOR FILTER USING THE SAME}

A color filter, and a color filter using the same.

A color filter is used for a liquid crystal display (LCD), an optical filter of a camera, and the like, and is manufactured by coating a fine area colored with three or more colors onto a solid-state image sensor or a transparent substrate. Such a colored thin film is usually formed by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like.

The manufacturing process of the color filter includes many chemical treatment steps. In order to maintain the pattern formed under these conditions, there is a demand for a photosensitive resin for a color filter which can improve the yield of a color filter with excellent chemical resistance while ensuring a developing margin.

In particular, conventional color LCDs usually produce color filter substrates for displaying color images differently from the driving substrates on which TFTs are arranged, and fabricate the color filter substrates by bonding them with the driving substrates. However, in this method, the junction accuracy was low and the width of the light shielding layer had to be made large. For this reason, it was difficult to raise an aperture ratio (ratio of the opening which light transmits). In addition, in recent years, as the glass substrate and the LCD screen of the LCD are enlarged, a long time is required that the liquid crystal composition is disposed on the front surface of the substrate when the liquid crystal is vacuum injected. For this reason, as a new technique, a manufacturing method for significantly shortening the bonding time by printing a seal material and dropping liquid crystals has been proposed. However, when such a method is adopted, there is a problem that the alignment accuracy is lowered.

On the contrary, a method of forming a color filter on a TFT array substrate for driving a TFT-type color LCD has been proposed. As a result, a color filter substrate on the surface is not required, and a transparent electrode is formed by simple sputtering , It is advantageous in that alignment can be facilitated and aperture ratio can be increased by manufacturing two substrates by bonding. However, when forming a color filter on a TFT array substrate, since a pixel electrode is formed on a color filter by the photolithographic method using the normal positive photosensitive resin composition, it is necessary to peel a photosensitive resin film after electrode formation. That is, a transparent electrode film is formed on the colored pixel of a color filter, a positive photosensitive resin composition is apply | coated on this transparent electrode film, and a pattern, exposure, and image development process are performed on it, and a pixel electrode is formed. After the pixel electrode is formed, the photosensitive resin film remaining on the pixel electrode is removed with a stripping solution, so that the photosensitive resin composition needs resistance to the stripping solution. Conventional photosensitive resin compositions for color filters have such stripping solution resistance. There was a problem of this weakness.

Therefore, conventionally, a transparent film (pixel protective film) having a peeling liquid resistance is formed on a color filter, and a pixel electrode is formed. In addition, in the method which did not apply a pixel protective film, in order to reduce the influence which a peeling solution has on the color filter, the peeling solution was processed for a long time under low temperature conditions. However, such a conventional method has a problem that the number of processes or time is increased and the mass production rate is lowered or the production efficiency is lowered.

In order to solve this problem, a color filter using a radiation-sensitive composition having an expansion ratio of 5% or less with respect to a peeling solution of a cured film forming a color layer on a color filter on array (COA) method has been proposed. Moreover, the color filter which improved the thermal-polymerization crosslinking effect using the polyfunctional alicyclic epoxy compound as a thermal-polymerization crosslinking agent, and the benzophenone peroxide as a thermal-polymerization initiator was proposed. According to this, it is possible to cure at a low temperature and a short time, so that a color filter having excellent durability and good adhesion can be obtained. However, in recent years, since the demand for high quality large screens has increased, there is a demand for the development of color filters having a high aperture ratio and high performance.

One embodiment of the present invention, to provide a photosensitive resin composition for color filters excellent in sensitivity and adhesion.

Another embodiment of the present invention is to provide a color filter having a high opening ratio and high contrast ratio, and implements a high optical density black matrix.

According to one embodiment of the present invention, a color filter comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer represented by the following formula (1), (C) a photopolymerization initiator, (D) a colorant, and (E) a solvent It provides a photosensitive resin composition.

[Formula 1]

In Formula 1, W ¹ to W ⁶ are each independently-(NR ¹ )-, -S-, or -O-, wherein R ¹ in-(NR ¹ )-is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Q ¹ To Q ⁶ are each independently any one of a hydrogen atom, a functional group represented by the formula (2) or formula (3),

However, -W ¹ Q ¹ to -W ⁶ Q ⁶ At least one of is not -OH and -NH ₂ ,

[Formula 2]

In Formula 2,

R ² is a hydrogen atom or a substituted or unsubstituted C 1 to C 20 alkyl group,

(3)

In Formula 3,

R ³ is a hydrogen atom or a substituted or unsubstituted C 1 to C 20 alkyl group,

X ₁ is a C1 to C30 alkyl group,

Y ₁ and Y ₂ are Each independently is -N (H)-, -S-, or -O-, n is an integer of 1 to 30;

The said photosensitive resin composition for color filters may contain (A) alkali-soluble resin # 1-50 weight%; (B) 0.5 to 20% by weight of the photopolymerizable monomer represented by Formula 1; (C) 0.1 to 10% by weight of the photopolymerization initiator; (D) 0.1 to 40% by weight of the colorant; And (E) the solvent residue.

The acrylic photopolymerizable monomer is Q ¹ To Q ⁶ may be one selected from the group consisting of a monomer represented by Formula 2, a monomer represented by Formula 3, and a combination thereof.

The alkali-soluble resin may include one or more selected from acrylic resins and cardo-based resins.

The photosensitive resin composition for color filters is a dispersant; Epoxy compounds; Malonic acid; 3-amino-1,2-propanediol; Silane coupling agents having an epoxy group, an isocyanate group, an amine group, a vinyl group, or a (meth) acryloxy group; Leveling agents; Silicone surfactants; Fluorine surfactants; A radical polymerization initiator, and a mixture thereof.

According to another embodiment of the present invention, a color filter manufactured by using the photosensitive resin composition for color filters is provided.

The photosensitive resin composition for the color filter is very excellent in sensitivity and adhesion, while realizing a high opening ratio and a high contrast ratio when manufacturing the color filter, it is possible to form a high optical density black matrix.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise defined herein, "alkyl group" means C1 to C30 "alkyl group," aryl group "means C6 to C30" aryl group, "arylalkyl group" means C7 to C30 arylalkyl group, " Alkylene group "means a C1 to C20 alkylene group and" alkoxy group "means a C1 to C20 alkoxylene group.

In the present specification, "substituted" means, unless otherwise defined, at least one hydrogen atom of the functional group of the present invention is halogen atom (F, Cl, Br, or I), hydroxy group, nitro group, cyano group, imino group ( = NH, = NR, and R are C7 to C10 alkyl groups, amino groups (-NH ₂ , -NH (R '), -N (R ") (R"'), R 'to R "' are each independently C7 to C10 alkyl group), amidino group, hydrazine or hydrazone group, carboxyl group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 cycloalkyl group, It means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted C3 to C30 heteroaryl group and a substituted or unsubstituted C2 to C30 heterocycloalkyl group.

In addition, in the present specification, unless otherwise defined, hetero means a carbon atom substituted with any one atom selected from the group consisting of N, O, S and P.

In addition, in this specification, "*" means the part connected with the same or different atom or formula.

According to one embodiment of the present invention, provides a photosensitive resin composition for a color filter comprising a photopolymerizable monomer represented by the following formula (1).

[Formula 1]

However, -W ¹ Q ¹ to -W ⁶ Q ⁶ At least one of is not -OH and -NH ₂ ,

[Formula 2]

In Formula 2,

(3)

In Formula 3,

X ₁ is a C1 to C30 alkyl group,

The acrylic photopolymerizable monomer represented by Formula 1 may obtain high crosslinking, substrate adhesion, and patternability when reacted with a photosynthetic initiator in the photosensitive resin composition for color filters .

According to another embodiment of the invention, (A) alkali-soluble resin; (B) a photopolymerizable monomer represented by Formula 1; (C) photoinitiator; (D) a coloring agent; And (E) a solvent. The present invention also provides a photosensitive resin composition for a color filter. Hereinafter, each component included in the photosensitive resin composition for color filters according to the present invention will be described in detail.

(A) Alkali-soluble resin

The acrylic resin may include an ethylenic copolymer of an ethylenically unsaturated first monomer having one or more carboxyl groups and an ethylenically unsaturated second monomer copolymerizable therewith. Here, the ethylenically unsaturated first monomer having a carboxyl group is 1 to 50% by weight, for example, 3 to 40% by weight, for example 5 to 30% by weight, based on the total weight of the monomers forming the copolymer. It may be included in the amount of%.

Examples of the first monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and the like, and include one or more of them. However, the present invention is not limited thereto.

Examples of the second monomers include alkenyl aromatic compounds such as styrene, α-methyl styrene, vinyl toluene and vinyl benzyl methyl ether; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylic Unsaturated carboxylic ester compounds such as latex, 2-hydroxy butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate and phenyl methacrylate; 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate, 'N-phenylmaleimide, N-benzylmaleimide, N-alkylmaleimide, methacrylic acid, 2-dimethyl amino ethyl Unsaturated carboxylic acid amino alkyl ester compounds such as methacrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amide compounds, such as acryl amide and methacryl amide, are mentioned, but it is not limited to this. The ethylenic copolymers used in the present invention include one or more other monomers of these.

Specific examples of the ethylenic copolymer composed of the above monomers include methacrylic acid / methyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene air Copolymers, methacrylic acid / benzyl methacrylate / 2-hydroxy ethyl methacrylate copolymers, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymers, and the like. It is not limited.

The weight average molecular weight (Mw) of the acrylic resin may be in the range of 3,000 to 500,000, for example, 5,000 to 50,000. In addition, the acid value of the acrylic resin may be in the range of 20 to 200 mgKOH / g, for example, 40 to 200 mgKOH / g. When the weight average molecular weight and the acid value of the acrylic resin are in the above range, excellent developability can be obtained.

[Formula 4]

-[A] _m- [B] _n-

In Formula 4, m and n are each independently an integer of 1 to 100, A is represented by the following formula (5), B is represented by the following formula (6).

[Chemical Formula 5]

In Formula 4, R ⁴ To R ⁷ are each independently a hydrogen atom, an alkyl group or a halogen atom of C1 to C30, R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group,

X ₂ is

,

(Wherein R ¹⁰ is a hydrogen atom, an ethyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, -CH ₂ CH = CH ₂ or -Ph),

,

or

Is,

Y ₃ and Y ₄ are each independently -O-, -NR ^11- (wherein R ¹¹ is a hydrogen atom, a methyl group, an ethyl group, -CH ₂ OH, -C ₂ H ₄ OH or -CH ₂ CH = CH ₂ ) or -C (= O) O-,

Z ₁ is an acid monoanhydride derivative or a derivative of an acid dianhydride.

[Formula 6]

In Chemical Formula 6, R ¹² To R ¹⁵ are each independently a hydrogen atom, an alkyl group or a halogen atom, and R ¹⁶ And R ¹⁷ are each independently a hydrogen atom or a methyl group,

X ₃ is

,

(Wherein R ¹⁸ is a hydrogen atom, an ethyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, -CH ₂ CH = CH ₂ or -Ph),

,

or

Is,

Y ₅ and Y ₆ are each independently -O-, -NR ^19- (wherein R ¹⁹ is a hydrogen atom, a methyl group, an ethyl group, -CH ₂ OH, -C ₂ H ₄ OH or -CH ₂ CH = CH ₂ ) or -C (= O) O-,

Z ₂ is an acid monoanhydride derivative or a derivative of an acid dianhydride.

The weight average molecular weight (Mw) of the cardo-based resin may be 500 to 30,000.

The amount of the alkali-soluble resin (A) may be 1 to 50% by weight based on the total amount of the photosensitive resin composition for all color filters, for example, 2 to 30% by weight. When the content of the alkali-soluble resin is in the above range, the developability to the alkaline developer is excellent, the crosslinkability is good, the surface roughness is reduced, the chemical resistance is good, the pattern does not occur, and the color does not change even when contained in the organic solvent. .

(B) Photopolymerization Monomer

The photopolymerizable monomer may include a compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1, W ¹ to W ⁶ are each independently-(NR ¹ )-, -S-, or -O-, wherein R ¹ in-(NR ¹ )-is H or a substituted or unsubstituted C1. To C20 alkyl group,

However, -W ¹ Q ¹ to -W ⁶ Q ⁶ At least one of is not -OH and -NH ₂ ,

[Formula 2]

In Formula 2,

(3)

In Formula 3,

X ₁ is a C1 to C30 alkyl group,

Y ₁ and Y ₂ are each independently -N (H)-, -S-, or -O-, and n is an integer of 1 to 30.

In the acrylic photopolymerizable monomer included in the photosensitive composition for color filters, the content of functional groups represented by Formulas 2 ′ and 3 may be appropriately adjusted according to desired physical properties. The functional group represented by Chemical Formula 2 may contribute to the improvement of the taper property, and the functional group represented by Chemical Formula 3 may contribute to the property for improving adhesion.

The photosensitive resin composition for color filters, in addition to the photopolymerizable monomer represented by the formula (1), ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate Neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexa Acrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethyl dimethacryl Rate, 1,4-butanediol dimethacrylate, 1,6-hexane All dimethacrylate may further include a photopolymerizable monomer such as methacrylate.

It is preferable that the usage-amount of the said photopolymerizable monomer is 0.5-20 weight% with respect to the total amount of the photosensitive resin composition for color filters. When the amount of K content of the photopolymerizable monomer is in the above range, the corners of the pattern are formed cleanly, and developability in the alkaline developer is good.

(C) Light curing Initiator

As an example of the photoinitiator used for this invention, a triazine type compound, an acetophenone type compound, a benzophenone type compound, a thioxanthone type compound, a benzoin type compound, an oxime type compound, etc. can be used.

Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (3 ', 4'-dimeth Methoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -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 (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho-1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2,4-trichloro Methyl (piperonyl) -6-triazine, 2,4- (trichloromethyl (4'-methoxy styryl) -6-triazine, and the like.

Examples of the acetophenone compounds include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methyl propiophenone, pt-butyl trichloro acetophenone and pt- Butyl dichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propane-1- On, 2-benzyl-2-dimethyl amino-1- (4-morpholino phenyl) -butan-1-one, and the like.

Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, and 4,4'- Dichloro benzophenone, 3,3'-dimethyl-2-methoxy benzophenone, and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- And Oakstone.

The benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is a photopolymerization initiator.

In the present invention, in addition to the photopolymerization initiator, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, and the like can also be used as the photopolymerization initiator.

The photopolymerization initiator may be used in an amount of 0.1 to 10 wt% based on the total amount of the photosensitive resin composition for color filters. When the content of the photopolymerization initiator is in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and does not cause a decrease in transmittance due to the unreacted initiator remaining after the photopolymerization.

(D) Colorant

As the colorant, one or more selected from organic pigments, inorganic pigments and dyes may be used.

As the organic pigments and dyes, compounds having colors such as red, green, blue, yellow, violet, black, and the like may be used. These are condensed polycyclic pigments, such as an anthraquinone pigment and a perylene pigment, a phthalocyanine pigment, an azo pigment, etc., Any one of these can be used individually, or can mix and use 2 or more types. Two or more kinds can be mixed and used for the adjustment of the maximum absorption wavelength and the adjustment of the cross point and cross talk.

The inorganic pigments include all organic-inorganic pigments such as carbon black, titanium oxide, zirconium oxide, and halogen as titanium (TiOx) black, perylene-based black, and aniline-based black pigment. May be used alone or in combination.

The said coloring agent may be manufactured in the liquid state disperse | distributed or dissolved in the solvent, and may be contained in the photosensitive resin composition for color filters.

In addition, a dispersant may be used as necessary to uniformly disperse the colorant in the disperse solution. For this purpose, a nonionic, anionic or cationic dispersant may be used, for example, polyalkylene glycol and esters thereof, poly Oxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines and the like can be used. These dispersants may be used singly or in combination of two or more.

In addition, by using the first acrylic resin containing the above carboxyl group together with the dispersant, not only can the stability of the pigment dispersion be improved, but also the pattern of the pixel can be improved.

The amount of the colorant used may be 0.1 to 40% by weight based on the total amount of the photosensitive resin composition for color filters. When the content is in the above range, the coloring effect and developing performance are appropriate.

(E) Solvent

The solvents include ethylene glycol acetate, ethyl cellosolve, ethyl ethoxy propionate , ethyl lactate, polyethylene glycol, and the like, and the solvents include ethylene glycol compounds such as ethylene glycol and diethylene glycol; Glycol ether compounds such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; Glycol ether acetate compounds such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate; Propylene glycols such as propylene glycol; Propylene such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether Glycol ether compounds; Propylene glycol ether acetate compounds such as propylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; Amide compounds such as N-methyl pyrrolidone, dimethyl formamide, and dimethyl acetamide; Ketone compounds such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; Petroleum compounds such as toluene, xylene, and solvent naphtha; Ester compounds, such as ethyl acetate, butyl acetate, and an ethyl lactate, etc. are mentioned. As the solvent of the present invention, any one of these species may be used alone, or two or more thereof may be mixed and used.

The amount of the solvent used is used in the amount of the balance, for example, in an amount of 20 to 90% by weight. The content of the solvent is preferred within the above range because the coating property of the photosensitive resin composition is excellent and the flatness can be maintained in a film having a thickness of 1 μm or more.

(F) Other additives

The photosensitive resin composition for color filters of this invention may further contain the dispersing agent mentioned above so that a coloring agent (D) component may be disperse | distributed uniformly in a solvent (E) other than the component of said (A)-(E).

Examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkyls Amide alkylene oxide adducts, alkylamines and the like may be added alone or in combination of two or more thereof.

The dispersant may be included in an amount of 10 to 20 parts by weight based on 100 parts by weight of the pigment.

In addition, in order to improve the coating property and the anti-foaming property, an adhesion improving agent or the like may be further included in order to improve the adhesion with a substrate or a coating improving agent such as silicone or fluorine.

The coating improver and the adhesion improving agent may be included in an amount of 0.01 to 1 wt% based on the total amount of the photosensitive resin composition.

In addition, in order to prevent spots and spots upon application and to prevent the generation of residues due to leveling characteristics or undeveloped, epoxy compounds; Malonic acid; 3-amino-1,2-propanediol; Silane coupling agents having an epoxy group, an isocyanate group, an amine group, a vinyl group, or a (meth) acryloxy group; Leveling agents; Silicone surfactants; Fluorine surfactants; It may further include other additives such as radical polymerization initiators. The amount of these additives to be used can be easily controlled depending on the desired physical properties.

As said epoxy compound, a phenol novolak epoxy resin, a tetramethyl bi-phenyl epoxy resin, a bisphenol A epoxy resin, an alicyclic epoxy resin, an ortho-cresol novolak resin, etc. are mentioned. The epoxy compound may be present in an amount of 0.01 to 10% by weight based on the total amount of the photosensitive resin composition for a color filter protective film. When the content of the epoxy compound is within the above range, storage stability and process margin are excellent.

Specific examples of the silane coupling agent include vinyl trimethoxysilane, vinyl tris (2-methoxyethoxysilane), 3-glycidoxypropyl trimethoxysilane, and 2- (3,4-epoxy cyclohexyl). Ethyl trimethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, and the like.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. As a specific brand name, Toray Silicone Co., Ltd. DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA; SH8400 from Toray Silicone, a polyester modified silicone oil; Shin-Etsu Silicone KP321, KP322, KP323, KP324, KP326, KP340, GF; Toshiba Silicon TSF4445, TSF4446, TSF4452, TSF4460; And the like.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. As a specific brand name, Floroid FC430 and Floroid FC431 by Sumitomo 3M Corporation; Mega Pack F142D, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack F183, Mega Pack F470, Mega Pack F475, Mega Pack R30 from Dainiphon Ink Chemical Co., Ltd .; F-top EF301, F-top EF303, F-top EF351, F-top EF352 from Shin-Akida Hwaseong Co., Ltd .; Saffron S381, Saffron S382, Saffron SC101, Saffron SC105 from Asahi Glass Co., Ltd .; E5844 from Daikin Fine Chemical Research Institute; And the like.

Said silicone type surfactant and fluorine type surfactant can also be used individually or in combination of 2 or more types.

A color filter according to another embodiment of the present invention is manufactured using the blue photosensitive resin composition for color filters.

The photosensitive resin composition for color filters is 3.1 to 3.4 mu m using a suitable method such as spin coating or slit coating on a glass substrate on which nothing is applied and a glass substrate on which a SiNx (protective film) is applied to a thickness of 500 to 1500 kPa. It is applied to the thickness of. After the application, light is irradiated to form a pattern necessary for the color filter. After the light is irradiated and the coating layer is treated with an alkali developing solution, the unexposed portions of the coating layer are dissolved and a pattern necessary for the color filter is formed. By repeating this process according to the required number of colors such as red, green, blue, and black, a color filter having a desired pattern can be obtained. Further, in the above process, the image pattern obtained by the development can be further heated, cured by actinic ray irradiation or the like to further improve crack resistance, solvent resistance, and the like.

In general, the negative photosensitive resin is not easily stripped in the organic solvent, so that the lower layer may be contaminated by the residue. In addition, as compared with the positive photosensitive resin, the adhesion to the lower layer is weak, and thus the undercut may be increased. The photosensitive resin composition for color filters of this invention is excellent in the resistance to the peeling liquid of such a negative photosensitive resin, prevents contamination of a lower film, and improves adhesiveness with a lower film.

Hereinafter, the present invention will be described in more detail with reference to preferred examples and comparative examples. However, the following examples are for illustrative purposes only and do not limit the invention.

Synthetic example 1 to 2

Acrylic system Photopolymerization Synthesis of Monomers

Nitrogen was added to a 300 ml three-necked flask equipped with a cooling tube and a stirrer, and the compounds shown in Table 1 were added, followed by reaction under the following conditions to obtain a photopolymerizable monomer represented by Formulas 7 to 8.

Mannitol
(Aldrich) Acryloyl
Chloride
(Aldrich) 2-isocyanoethyl
Methacrylate
(Showa Precision) PGMEA Reaction time Reaction temperature Synthesis Example 1
(Formula 7) 30 89 - 119 8 20 Synthesis Example 2
(Formula 8) 30 - 153 183 8 60

[Formula 7]

[Formula 8]

Preparation of the photosensitive resin composition for color filters

Example 1 to 3

The photosensitive resin compositions of Examples 1 to 3 were prepared using the components listed in Table 2. First, the photopolymerization initiator (C) (IGACURE OXE02 (Ciba Fine Chemical Co., Ltd.)) was dissolved in solvents (PGMEA and ethylethoxy propionate), followed by stirring at room temperature for 2 hours. Subsequently, the acrylic photopolymerizable monomer (B) synthesized in Synthesis Examples 1 to 3 and the acrylic resin binder resin (A) (NPR3300, Miwon Corporation) were added and stirred at room temperature for 2 hours. After the pigment (D) dispersion was added thereto, the mixture was stirred at room temperature for 1 hour to prepare a photosensitive resin composition for color filters according to the present invention. The solution was filtered three times to remove impurities.

Composition (content [g]) Example 1 Example 2 Example 3 Comparative Example 1 (A) Acrylic Binder Resin
(NPR3300, Miwon Corporation) 6.0 6.0 6.0 6.0 (B) an acrylic photopolymerizable monomer
Monomer represented by the formula (7)
Monomer represented by the formula (8)
Dipentaerythritol hexaacrylate
4.2
2.1
-
- - 2.1 4.2 - - - - 4.2 (C) photopolymerization initiator
IGACURE OXE02 (Ciba Fine Chemicals)
0.2
0.2
0.2
0.2 (D) Pigment Dispersion
TDB-1 (DNS, Blue Pigment)
RL-01 (Clariant, purple pigment)
BYK 6919 (BYK, Dispersant)
Acrylic binder resin of the said (A)
PGMEA (solvent) 46.8 46.8 46.8 46.8 (9.2) (9.2) (9.2) (9.2) (0.8) (0.8) (0.8) (0.8) (2.4) (2.4) (2.4) (2.4) (5.4) (5.4) (5.4) (5.4) (30.0) (30.0) (30.0) (30.0) (E) Solvent
PGMEA
Ethylethoxy propionate 24.0 24.0 24.0 24.0 11.4 11.4 11.4 11.4 (F) additive
F-475 (DIC, fluorine-based surfactant)
0.1
0.1
0.1
0.1

Comparative example One

A photosensitive resin composition for color filters was manufactured in the same manner as in Examples 1 to 3, except that dipentaerythritol hexaacrylate (DPHA) was used for the acrylic photopolymerizable monomer (A).

Pattern manufacturing and pattern evaluation for color filter

Using the photosensitive resin composition prepared in Examples 1 to 3 and Comparative Example 1, the pattern was formed as follows, and the taper angle evaluation was performed as follows.

Using a spin-coater (K-Spin8 from KDNS), a glass substrate coated with a transparent bare glass and silicon nitride (SiNx) coated with nothing at a thickness of 500 mm3 On the above, the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were applied to a thickness of 3 μm. After soft-baking at 80 ° C. for 150 seconds using a hot-plate, and exposing at a power of 60 mJ using an exposure machine (I10C manufactured by Nikon), the developer The developing temperature was 25 ° C., a developing time of 60 seconds, a washing time of 60 seconds, and spin-drying for 25 seconds. At this time, a 1 wt% aqueous solution of potassium hydroxide was used as the developing solution.

Thereafter, the wafer was hard-baked for 30 minutes in an oven at 230 ° C., and the taper angle was measured for the pattern formed by the 10 μm mask using an optical microscope. The taper angle means an angle formed by the pattern slope with respect to the glass substrate, and the measured results are shown in Table 3 below.

Example 1 Example 2 Example 3 Comparative Example 1 10㎛ pattern
Taper angle 77 ° 55 ° 34 ° 30 °

As shown in Table 3, Examples 1 to 3 according to the present invention can confirm that the taper angle of the pattern formed compared to Comparative Example 1. In particular, when an acrylic photopolymerizable monomer containing a compound represented by the formula (7) was used, the taper angle was very high. From this, it can be seen that a highly precise pattern can be realized by the photosensitive resin compound for color filters using the acrylic photopolymerizable monomer represented by Formula 1.

Adhesion evaluation

Adhesive evaluation was performed using the photosensitive resin composition prepared in Examples 1 to 3 and Comparative Example 1 as follows.

A photosensitive resin prepared in Examples 1 to 3 and Comparative Example 1 on a transparent round glass glass coated with nothing using a spin-coater (K-Spin8 manufactured by KDNS). The composition was applied to a thickness of 3 μm. After soft-baking at 80 ° C. for 150 seconds using a hot-plate, and exposing at a power of 60 mJ using an exposure machine (I10C manufactured by Nikon), the developer The developing temperature was 25 ° C., a developing time of 60 seconds, a washing time of 60 seconds, and spin-drying for 25 seconds. At this time, a 1 wt% aqueous solution of potassium hydroxide was used as the developing solution.

Thereafter, the mixture was hard-baked for 30 minutes in an oven at 230 ° C., and then immersed in a 70 ° C. stripping solution (PRS-2000, JTBaker) for 40 minutes, followed by deionized water (DIW). warer) and dried.

The peeling state of the photosensitive resin composition coating film manufactured by the above method was observed using the optical microscope, and the result is shown in Table 4.

Optical image Example 1

Example 2

Example 3

Comparative Example 1

As shown in Table 4, Examples 1 to 3 is excellent in peel resistance compared to Comparative Example 1, it can be confirmed that the adhesion to the substrate is very excellent. In particular, in the case of Example 3 including the formula (8), the adhesion was more excellent than in the case of Examples 1 and 2. Therefore, it can be seen that the inclusion of the compound of formula 8 in a greater amount can improve the adhesion of the photosensitive resin composition to the substrate.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims

(A) alkali-soluble resins;
(B) a photopolymerizable monomer represented by Formula 1 below;
(C) photoinitiator;
(D) a colorant; And
(E) Photosensitive resin composition for color filters containing a solvent:
[Formula 1]

In Formula 1, W ¹ to W ⁶ are each independently -NR ^1- , -S- or -O-, wherein R ¹ in -NR ¹ -is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. ,
Q ¹ To Q ⁶ are each independently any one of a hydrogen atom, a functional group represented by the formula (2) or formula (3),
However, -W ¹ Q ¹ to -W ⁶ Q ⁶ At least one of is not -OH and -NH ₂ ,
(2)

In Formula 2,
R ² is a hydrogen atom or a substituted or unsubstituted C 1 to C 20 alkyl group,
(3)

In Chemical Formula 3,
R ³ is a hydrogen atom or a substituted or unsubstituted C 1 to C 20 alkyl group,
X ₁ is a C1 to C30 alkyl group,
Y ₁ and Y ₂ are Each independently is -N (H)-, -S-, or -O-, n is an integer of 1 to 30;

The method of claim 1,
The photosensitive resin composition for color filters,
(A) 1 to 50% by weight of alkali-soluble resin;
(B) 0.5 to 20% by weight photopolymerizable monomer;
(C) 0.1 to 10% by weight of the photopolymerization initiator;
(D) 0.1 to 40 wt% colorant; And
(E) Solvent Residue
Wherein the photosensitive resin composition is a photosensitive resin composition for a color filter.

The method of claim 1,
The acrylic photopolymerizable monomer is Q ¹ To Q ⁶ is a photosensitive resin composition for a color filter is one selected from the group consisting of a monomer represented by the formula (2), a monomer represented by the formula (3), and combinations thereof.

The method of claim 1,
The alkali-soluble resin is a photosensitive resin composition for color filters comprising at least one selected from acrylic resins and cardo resins.

The method of claim 1,
The photosensitive resin composition is a dispersant; Epoxy compounds; Malonic acid; 3-amino-1,2-propanediol; Silane coupling agents having an epoxy group, an isocyanate group, an amine group, a vinyl group, or a (meth) acryloxy group; Leveling agents; Silicone surfactants; Fluorine surfactants; A photosensitive resin composition for color filters, further comprising an additive selected from the group consisting of a radical polymerization initiator and mixtures thereof.

The color filter manufactured using the photosensitive resin composition for color filters of any one of Claims 1-5.