KR101225952B1 - Photosensitive resin composition for color filter - Google Patents

Abstract

Acrylic resins containing repeating units represented by the following Chemical Formulas 1 to 3; Photopolymerization monomers; Photopolymerization initiator; Pigments; And it provides the photosensitive resin composition for color filters containing a solvent.

[Formula 1]

[Formula 2]

(3)

In Chemical Formulas 1 to 3,

R ₁ to R ₆ and n ₁ are as defined in the specification.

Acrylic resin, color filter, photosensitive resin composition, developability

Description

Photosensitive resin composition for color filters {PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER}

This substrate relates to the photosensitive resin composition for color filters.

The liquid crystal display device has advantages such as light weight, thinness, low cost, low power consumption, and excellent integration with the integrated circuit, and thus its use range is expanding for notebooks, PDAs, mobile phones, and color TVs. Such a liquid crystal display device includes an active circuit unit including a light blocking layer, for example, a black filter matrix, a color filter, and an ITO pixel electrode, and an active circuit part including a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer, and an ITO pixel electrode. It comprises a substrate (TFT array). Among them, as a manufacturing method of the color filter, a method of forming red, green, and blue pixels and a light shielding layer in which colored pigment fine particles are dispersed in the photosensitive resin composition is used on a glass substrate.

The light shielding layer serves to block uncontrolled light transmitted through the transparent pixel electrode of the substrate in order to prevent a decrease in contrast due to light transmitted through the thin film transistor, and the colored layers of red, green, and blue are white light. The main role is to transmit light of a specific wavelength to express colors.

In general, the substrate of the color filter is manufactured by a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method, an inkjet printing method.

Among them, the pigment dispersion method is a method of coating a color filter by coating a photopolymerizable composition containing a colorant on a transparent substrate, exposing the pattern of the form to be formed, and then removing a non-exposed portion with a solvent and thermally curing the color filter by repeating a series of steps. It is a method of manufacturing. The pigment dispersion method has the advantage of improving the heat resistance and durability, which is the most important property of the color filter, and maintaining the thickness of the film uniformly, and thus is widely used in the manufacture of light shielding layers. For example, Korean Patent Publication No. 92-7002502, Republic of Korea Patent Publication No. 94-5617, Republic of Korea Patent Publication No. 95-11163, Republic of Korea Patent Publication No. 95-700359 and the like have been proposed for producing a color resist using pigment dispersion. have.

The light shielding layer manufactured by the pigment dispersion method is composed of two components, a polymer compound that largely serves as a support and maintains a constant thickness, that is, a binder resin and a photopolymerization monomer which reacts with light upon exposure to form a photoresist image. In addition to one component, it is prepared by a photosensitive resin composition comprising a pigment dispersion, a polymerization initiator, an epoxy resin, a solvent and other additives and the like. As a binder resin used for the pigment dispersion method, the photosensitive resin which consists of the polyimide resin disclosed by Unexamined-Japanese-Patent No. 60-237403, the acrylic polymer of Unexamined-Japanese-Patent No. 1-200353, 4-7373, and 4-91173, etc. , Radically polymerizable photosensitive resin comprising an acrylate monomer, an organic polymer binder and a photopolymerization initiator as described in Japanese Patent Application Laid-Open No. Hei 15244949, a phenolic resin disclosed in Japanese Patent Application Laid-Open No. Hei 4-163552 and Korean Patent No. 92-5780, Various kinds of photosensitive resins including a crosslinking agent having an N-methylol structure and a photoacid generator have been proposed.

However, the use of photosensitive polyimide or phenolic resins as binder resins according to the pigment dispersion method has disadvantages such as high heat resistance but low sensitivity and development with an organic solvent. Conventional systems using azide compounds as photosensitizers have problems of low sensitivity, poor heat resistance, or effects of oxygen upon exposure.

In addition, in the case of using a conventional acrylic resin, it is excellent in heat resistance, shrinkage resistance, chemical resistance and the like, but tends to be inferior in sensitivity, developability and adhesion. Further, in the case of the light shielding layer, since the content of the black pigment is much higher than that of other colored photosensitive resin compositions in order to match the required optical density, there is a problem in that the sensitivity, developability and adhesion deterioration are more severe.

In recent years, in order to achieve high color purity, the density | concentration of the pigment in the coloring photosensitive resin composition used for manufacture of a color filter is increasing. However, when the pixel is formed using a conventional composition, the colored layer formed on the background has a low development speed due to a high concentration of pigment, develops a residual residue, and can not maintain a pattern at a low exposure amount, resulting in surface defects. Has the disadvantage that occurs.

Therefore, in order to improve process productivity and yield, research on the photosensitive resin composition which can have the outstanding sensitivity and reliability even at a fast developing speed and a small exposure amount is performed.

One aspect of the present invention provides a photosensitive resin composition for color filters that is excellent in developability and can improve thickness uniformity, surface roughness and adhesion.

Another aspect of the present invention provides a light shielding layer manufactured using the photosensitive resin composition.

Another aspect of the present invention provides a color filter including the light blocking layer.

According to an aspect of the invention the acrylic resin comprising a repeating unit represented by the following formula 1 to 3; Photopolymerization monomers; Photopolymerization initiator; Pigments; And it provides the photosensitive resin composition for color filters containing a solvent.

[Formula 1]

[Formula 2]

(3)

In Chemical Formulas 1 to 3,

R ₁ , R ₂ and R ₄ are the same or different from each other and are each independently hydrogen or a methyl group,

R ₃ is the same or different at each repeating unit, and is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group,

R ₅ is the same or different at each repeating unit, and each independently a substituted or unsubstituted alkylene group,

R ₆ is the same or different at each repeating unit, and is each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₁ is an integer of 1 to 20.

The photosensitive resin composition for the color filter is 1 to 40% by weight of the acrylic resin containing a repeating unit represented by the formula 1 to 3, 1 to 30% by weight of the photopolymerization monomer, 0.1 to 10% by weight of the photopolymerization initiator, The pigment may comprise 1 to # 40 wt% of the pigment and the solvent in the amount of the balance.

The acrylic resin is 5 to 60% by weight of the repeating unit represented by the formula (1) relative to the total amount of the acrylic resin, 5 to 70% by weight of the repeating unit represented by the formula (2), and the repeating unit represented by the formula (3) To 50% by weight.

Acrylic resin containing a repeating unit represented by the formula 1 to 3 may have a weight average molecular weight of 3,000 to 50,000, and may have an acid value of 30 mg / KOH to 200 mg / KOH.

The photopolymerization monomer may be ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate Latex, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacryl Latex, triethylene glycol dimethac It may be selected from the group consisting of relate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and combinations thereof.

The photopolymerization initiator is a triazine compound, acetophenone compound, benzophenone compound, thioxanthone compound, benzoin compound, oxime compound, carbazole compound, diketone compound, sulfonium borate compound, diazo type, already It may be selected from the group consisting of a dazole compound, a biimidazole compound and a combination thereof.

According to another aspect of the invention provides a light shielding layer for a color filter manufactured using the photosensitive resin composition for color filters.

According to another aspect of the invention provides a color filter comprising the light shielding layer for the color filter.

Other specific details of embodiments of the present invention are included in the following detailed description.

The photosensitive resin composition according to an embodiment of the present invention is excellent in developability, and may improve thickness uniformity, surface roughness and adhesion, and thus may be usefully used for manufacturing color filters of electronic display devices such as liquid crystal display devices.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, "substituted" to "substituted" means that at least one hydrogen of the functional group of the present invention is halogen (F, Br, Cl or I), hydroxy group, nitro group, cyano group, amino group (NH ₂ , NH (R ₁₀₀ ) or N (R ₁₀₁ ) (R ₁₀₂ ), wherein R ₁₀₀ , R ₁₀₁ and R ₁₀₂ are the same or different from each other, and are each independently C 1 to C 10 alkyl groups, amidino groups , Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group It means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocycloalkyl group.

Unless stated otherwise in the present specification, "alkyl group" means a C1 to C30 alkyl group, specifically means a C1 to C15 alkyl group, and "cycloalkyl group" means a C3 to C30 cycloalkyl group, specifically C3 To C15 cycloalkyl group, "alkoxy group" means C1 to C30 alkoxy group, specifically C1 to C15 alkoxy group, "alkoxyalkyl group" means C2 to C30 alkoxyalkyl group, specifically C2 To C15 alkoxyalkyl group, "ether group" means C2 to C30 ether group, specifically C2 to C15 ether group, "aryl group" means C6 to C30 aryl group, specifically C6 to It means a C18 aryl group, "alkylene group" means a C1 to C30 alkylene group, and specifically means a C1 to C15 alkylene group.

Unless stated otherwise in the specification, a heterocycloalkyl group and a heteroaryl group each independently contain 1 to 3 heteroatoms of N, O, S, Si or P in one ring, and the rest are carbon cycloalkyl groups And an aryl group.

Also, unless specified otherwise in this specification, "alicyclic" means C3 to C30 cycloalkyl, C3 to C30 cycloalkenyl, C3 to C30 cycloalkynyl, C3 to C30 cycloalkylene, C3 to C30 cycloalkenylene, or Meaning C3 to C30 cycloalkynylene, specifically C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C3 to C20 cycloalkylene, C3 to C20 cycloalkenylene, or C3 to C20 C20 cycloalkynylene.

Unless otherwise defined herein, “combination” generally means mixing or copolymerizing. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymerization.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

Photosensitive resin composition for a color filter according to an embodiment of the present invention is a acrylic resin containing a repeating unit represented by the formula 1 to 3; Photopolymerization monomers; Photopolymerization initiator; Pigments; And solvents.

[Formula 1]

[Formula 2]

(3)

In Chemical Formulas 1 to 3,

R ₁ , R ₂ and R ₄ are the same or different from each other and are each independently hydrogen or a methyl group. The R ₁ may be the same or different from each repeating unit, and likewise, R ₂ and R ₄ may be the same or different from each other.

R ₃ is the same as or different from each other at each repeating unit, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group, and the alkyl group may be C1 to C15 alkyl group. The cycloalkyl group may be a C3 to C15 cycloalkyl group, and the aryl group may be a C6 to C18 aryl group.

R ₅ is the same or different in each repeating unit, each independently represent a substituted or unsubstituted alkylene group, the alkylene group may be a C1 to C15 alkylene group, n ₁ is an integer of 1 to 20, specifically May be 1 to 15. When n ₁ is an integer of 2 or more, R ₅ may be the same or different from each other within one repeating unit.

R ₆ is the same or different in each repeating unit, and each independently hydrogen or a substituted or unsubstituted alkyl group, and the alkyl group may be a C1 to C15 alkyl group.

In the acrylic resin, the repeating units represented by Formulas 1 to 3 may exist by copolymerization.

The photosensitive resin composition for color filters may improve developability, thickness uniformity, surface roughness, and adhesion by including a acrylic resin including a repeating unit represented by Chemical Formulas 1 to 3. Therefore, in the color filter manufactured using the photosensitive resin composition for color filters, surface defects may not occur in the pixel portion, and development residues may not remain.

Specifically, the photosensitive resin composition for color filters may include 1 to 40% by weight of an acrylic resin containing a repeating unit represented by Formulas 1 to 3, 1 to 30% by weight of the photopolymerization monomer, and 0.1 to 10 of the photopolymerization initiator. % By weight, 1 to 40% by weight of the pigment and the solvent in the amount of the balance.

Hereinafter, each component of the present invention will be described in detail.

Acrylic resin

The acrylic resin includes a repeating unit represented by Chemical Formulas 1 to 3. In the photosensitive resin composition for color filters according to the embodiment of the present invention, the acrylic resin may be used as a binder.

The repeating unit represented by Chemical Formula 1 may be derived from an ethylenically unsaturated compound having at least one carboxyl group, and examples of the ethylenically unsaturated compound having the carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and the like. It may be selected from the group consisting of a combination of these, but is not limited thereto.

The repeating unit represented by Chemical Formula 1 may be included in an amount of 5 to 60 wt% based on the total amount of the acrylic resin. When the content of the repeating unit represented by the formula (1) is within the above range, the acrylic resin has an appropriate acid value, thereby effectively improving the developability with respect to the alkaline developer and effectively stabilizing the pigment dispersion. Specifically, the repeating unit represented by Chemical Formula 1 may be included in an amount of 10 to 40 wt% based on the total amount of the acrylic resin.

The repeating unit represented by Formula 2 may be derived from an ethylenically unsaturated compound except for a carboxyl group-containing ethylenically unsaturated compound, and examples of the ethylenically unsaturated compound include styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate Unsaturated carboxylic ester compounds including latex, 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate; Unsaturated carboxylic acid amino alkyl ester compounds including 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, and 2-dimethylaminoethyl methacrylate; Carboxylic acid vinyl ester compounds containing vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds including glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds including acrylonitrile and methacrylonitrile; Unsaturated amide compounds such as acrylamide and methacrylamide; And combinations thereof, but is not limited thereto.

The repeating unit represented by Formula 2 may be included in 5 to 70% by weight based on the total amount of the acrylic resin. When the content of the repeating unit represented by the formula (2) is within the above range, it may have excellent pattern formation and can effectively improve the mechanical strength of the film. Specifically, the repeating unit represented by Formula 2 may be included in an amount of 10 to 50 wt% based on the total amount of the acrylic resin.

The repeating unit represented by Formula 3 may be derived from an ethylenically unsaturated compound containing an alkoxyalkyl group, an alkoxy group, an ether group or a combination thereof, and contains the alkoxyalkyl group, an alkoxy group, an ether group or a combination thereof. Examples of the ethylenically unsaturated compound include 2- (2-ethoxyethoxy) ethyl acrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, and the like, but are not limited thereto.

The repeating unit represented by Chemical Formula 3 may be included in an amount of 5 to 50 wt% based on the total amount of the acrylic resin. When the content of the repeating unit represented by the formula (3) is in the above range, it is possible to effectively improve the developability for the alkaline developer, and to improve the thickness uniformity, surface roughness, adhesion and thermal properties effectively. Specifically, the repeating unit represented by Chemical Formula 3 may be included in an amount of 5 to 30 wt% based on the total amount of the acrylic resin. 　　

Specific examples of the acrylic resins include copolymers of methacrylic acid / benzyl methacrylate / 2- (2-ethoxyethoxy) ethyl acrylate and methacrylic acid / benzyl methacrylate / 2- (2-ethoxy. And copolymers of methoxy) propyl acrylate, but are not limited thereto.

The acrylic resin may have a weight average molecular weight (Mw) of 3,000 to 50,000. When the weight average molecular weight of acrylic resin is in the said range, developability by alkaline developing solution can be improved and a pigment dispersion liquid can be stabilized. Specifically, the acrylic resin may have a weight average molecular weight (Mw) of 5,000 to 35,000. 　

In addition, the acrylic resin may have an acid value of 30 mg / KOH to 200 mg / KOH. When the acid value of acrylic resin is in the said range, it is excellent in developability with respect to alkaline developing solution, and the pattern of a color filter can be formed easily.

In addition, the acrylic resin may be any one of random, block or alternating copolymer.

The acrylic resin may be included in 1 to 40% by weight relative to the total weight of the photosensitive resin composition for color filters. When the content of the acrylic resin is within the above range, the developability, thickness uniformity, surface roughness and adhesion to the alkaline developer can be improved. Specifically, the acrylic resin may be included in 5 to 30% by weight based on the total weight of the photosensitive resin composition for color filters.

Light curing  Monomer

The photopolymerization monomer is an acrylic photopolymerization monomer generally used in the photosensitive resin composition for color filters, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexane Diol diacrylate, neopentylglycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, dipentaerytate Lithol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, Novolac epoxy acrylate, Tylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Etc. can be used.

The photopolymerization monomer may be included in an amount of 1 to 30 wt% based on the total weight of the photosensitive resin composition for color filters. When the photopolymerization monomer is included in the above range, the photopolymerization occurs sufficiently during exposure in the pattern forming process to obtain excellent reliability, can effectively improve the heat resistance, light resistance and chemical resistance of the pattern, and can also effectively improve the resolution and adhesion have. Specifically, the photopolymerization monomer may be included in an amount of 5 to 20 wt% based on the total weight of the photosensitive resin composition for color filters.

Light curing Initiator

The photopolymerization initiator is a photopolymerization initiator generally used in the photosensitive resin composition for color filters. Examples of the photopolymerization initiator include triazine compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, oxime compounds, and carba. A sol compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or a combination thereof may be used, but is not limited thereto.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl-4,6-bis (trichloromethyl) -s-triazine, 2 -Biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (bichlorochloromethyl) -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-trichloro Romethyl (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt- Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1- Warm and so on.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4 ' -Bis (diethylamino) benzophenone, 4,4'- dimethylamino benzophenone, 4,4'- dichloro benzophenone, 3,3'- dimethyl- 2-methoxy benzophenone, etc. are mentioned.

Examples of the thioxanthone compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl Thioxanthone, 2-chloro thioxanthone, etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

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

The photopolymerization initiator may be included in an amount of 0.1 kPa to 10 kPa, based on the total weight of the photosensitive resin composition for color filters. When the content of the photopolymerization initiator is within the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, thereby obtaining excellent reliability, effectively improving heat resistance, light resistance, and chemical resistance of the pattern, and effectively improving resolution and adhesion. . Moreover, the fall of the transmittance by the unreacted initiator remaining after photopolymerization can be prevented or suppressed. Specifically, the photopolymerization initiator may be included in an amount of about 1 wt% to about 5 wt% based on the total weight of the photosensitive resin composition for color filters.

Pigment

The photosensitive resin composition for color filters includes a pigment, and the pigment may have a color of red, green, blue, yellow, black, and violet. Pigments may be used, and both organic and inorganic pigments may be used.

Specific examples include organic pigments such as condensed polycyclic pigments such as anthraquinone pigments and perylenes, phthalocyanine pigments and azo pigments; Alternatively, inorganic pigments such as carbon black may be used, and these pigments may be used alone, but two or more kinds may be mixed to adjust maximum absorption wavelength, cross point and cross talk. Good to do.

Examples of red pigments among the pigments include C.I. Dipyrrolopyrrole pigments such as red pigments 254, 255, 264, 270, 272, and C.I. Pigments such as red pigments 177 and 89, and examples of green pigments include C.I. Halogen-substituted copper phthalocyanine pigments such as green pigments 36 and 7; and examples of blue pigments include C.I. Copper phthalocyanine pigments such as blue pigments 15: 6, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 16, and C.I. Isoindolin pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, and C.I. Nickel complex pigments such as yellow pigment 150 may be cited, and examples of the black pigment include, but are not limited to, aniline black, perylene black, titanium black, and carbon black. The pigments may be used alone or in combination of two or more.

The pigment may be included in 1 to 40% by weight based on the total weight of the photosensitive resin composition for the color filter. When the pigment is included in the above range, it is possible to effectively improve the color reproduction rate, it is possible to effectively improve the developability, curing characteristics and adhesion of the pattern. Specifically, the pigment may be included in 5 to 30% by weight based on the total weight of the photosensitive resin composition for the color filter.

The pigment may be included in the photosensitive resin composition for color filters as a dispersion, wherein the pigment dispersion solvent is ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, Propylene glycol methyl ether and the like can be used. A dispersant may be used to uniformly disperse the pigment in the pigment dispersion. The pigment may be used by surface treatment with a dispersant in advance, or a dispersant may be added together with the pigment in preparing the pigment dispersion.

In addition, a dispersant may be used to uniformly disperse the pigment in the photosensitive resin composition for color filters according to an embodiment of the present invention. That is, the pigment may be used by surface treatment with a dispersant in advance, or a dispersant may be added together with the pigment in preparing the photosensitive resin composition for color filters.

As such dispersants, nonionic, anionic or cationic dispersants may be used. Specific examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acids. Ester, sulfonate, carboxylic acid ester, carboxylate, alkylamide alkylene oxide adduct, alkylamine and the like can be used. These may be added alone or in combination of two or more thereof.

In addition, the pigment may have an average particle diameter of 5 nm to 150 nm. When the average particle diameter of the pigment is within the above range, it is possible to effectively implement the contrast ratio while having excellent heat resistance and light resistance.

menstruum

Examples of the solvent include ethylene glycol compounds such as ethylene glycol and diethylene glycol; Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; Propylene glycol compounds 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 acetates such as propylene glycol methyl ether acetate and dipropylene glycol ethyl ether acetate; Amide compounds such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide; 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 ethyl lactate; And these may be selected from the group consisting of a combination, but is not limited thereto. The said solvent can be used individually or in mixture of 2 or more types.

In the photosensitive resin composition for color filters, the solvent is used as the remainder except for the acrylic resin, the photopolymerization monomer, the photopolymerization initiator, and the pigment, and the content thereof is different depending on the photosensitive resin composition for color filters. Although not possible, it is preferable to use so that the photosensitive resin composition for color filters may have a viscosity which can be apply | coated to a board | substrate.

Epoxy compound

The photosensitive resin composition for color filters according to the embodiment of the present invention may further include an epoxy compound as necessary to improve physical properties such as adhesion. As the epoxy compound, at least one selected from the group consisting of phenol novolac epoxy resins, tetramethyl bi-phenyl epoxy resins, bisphenol A type epoxy resins, and alicyclic epoxy resins may be used. The epoxy compound may be included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition for color filters. When the epoxy compound is included in the above range, it is possible to effectively improve physical properties such as storage properties, adhesion.

Silane Coupling agent

The photosensitive resin composition for a color filter according to an embodiment of the present invention may be a silane coupling agent having a vinyl group or a (meth) acryloxy group as necessary to improve the adhesion between the pattern and the color filter substrate. It may further comprise in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the composition.

Other additives

In addition, additives such as surfactants, antioxidants, stabilizers, etc. may be added to the photosensitive resin composition for color filters according to the embodiment of the present invention within a range that does not impair the physical properties of the composition.

The photosensitive resin composition for color filters according to the embodiment of the present invention is an alkali developing type that is curable by irradiation of light and develops with an alkaline aqueous solution. When the photosensitive resin composition is laminated on a substrate and irradiated with actinic rays to form a pattern required for a color filter, the reaction is caused by light. It can be selectively dissolved. The solution for removing the unexposed portions is called a developer, and there are two types of such developers, organic solvent type and alkali developing type. Of these, the organic solvent type is not preferable because it causes air pollution and is harmful to the human body, and the alkali developing type is more preferable in terms of environment. Since the photosensitive resin composition for color filters which concerns on one Embodiment of this invention can use alkali developing type | mold developer, it is preferable from an environmental point of view.

The photosensitive resin composition for color filters according to the embodiment of the present invention may be usefully used for manufacturing a light shielding layer for a color filter. An example of a method of manufacturing a light blocking layer of a color filter of a display device, such as a liquid crystal display device, according to another embodiment of the present invention is as follows.

Using a suitable method such as spin coating, roller coating, spray coating, or the like on a glass substrate, a photosensitive resin composition is applied to a thickness of, for example, 0.5 µm to 10 µm to form a resin composition layer.

Next, the hardening process for forming the pattern which a color filter requires on the board | substrate with which the said resin composition layer was formed is performed. The curing process is carried out by irradiating active rays, UV, electron beams or X-rays may be used as the light source used for irradiation, for example, 190 nm to 450 nm, specifically 200 nm to 400 nm UV can be irradiated. The photoresist mask may be further used in the step of irradiating the active line. After performing the process of irradiating an active line in this way, the resin composition layer to which the said light source was irradiated is processed with a developing solution. At this time, the non-exposed part in the resin composition layer is dissolved to form a light shielding layer pattern, for example, a matrix pattern. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained.

In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic ray irradiation or the like, crack resistance, solvent resistance and the like can be improved.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples and Comparative Examples are for illustrative purposes only and are not intended to limit the present invention.

Example

Synthetic example  1: Synthesis of Acrylic Resin

In a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, propylene glycol methyl ether acetate as a solvent 200 g, 15 g of methacrylic acid, 60 g of benzyl methacrylate, and 25 g of 2- (2-ethoxyethoxy) ethyl acrylate were added as a monomer, followed by stirring by passing nitrogen. Subsequently, the temperature was raised to 80 ° C. and maintained for 8 hours to prepare a solution including an acrylic resin represented by Formula 4 below. Solid content of the solution containing the acrylic resin represented by Formula 4 was 45% by weight, the weight average molecular weight of the acrylic resin was 18,000. In this case, the weight average molecular weight is a value obtained by converting a value measured using gel permeation chromatography (GPC) using a polystyrene standard. In addition, the acid value was 70 mg / KOH.

[Chemical Formula 4] 　

In Chemical Formula 4,

The weight ratio l: m: n of each repeating unit is 15:60:25.

Synthetic example  2: Synthesis of Acrylic Resin

Except for using 45 g of methacrylic acid, 35 g of benzyl methacrylate and 20 g of 2- (2-ethoxyethoxy) ethyl acrylate, Acrylic resin was prepared. The weight average molecular weight of the acrylic resin represented by Formula 5 was 15,000, and the acid value was 150 mg / KOH.

[Chemical Formula 5]

In Formula 5,

The weight ratio l: m: n of each repeating unit is 40:35:25.

Synthetic example  3: Synthesis of Acrylic Resin

In a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector and a cooler, 15 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, propylene glycol methyl ether acetate as a solvent After 200 g and 25 g of methacrylic acid and 75 g of benzyl methacrylate were added as monomers, the mixture was stirred while passing nitrogen. Subsequently, the temperature was raised to 80 ° C. and maintained for 8 hours to prepare a solution including an acrylic resin represented by the following Formula 6. Solid content of the solution containing the acrylic resin represented by Formula 6 was 35% by weight, the weight average molecular weight of the acrylic resin was 17,000. In addition, the acid value was 100 mg / KOH.

[Formula 6]

In Formula 6,

The weight ratio l: m of each repeating unit is 25:75.

Manufacturing example  1: Preparation of Red Pigment Dispersion

CIRed254 / CIRed177 (weight ratio = 80/20), Disperbyk-163, benzyl methacrylate acrylic acid, and propylene glycol methyl ether acetate were added to the reactor in the following amounts, followed by mixing and painting with a paint shaker (Asada). Company), and dispersed for 12 hours to prepare a red pigment dispersion.

* C.I.Red254 (product of Ciba) /C.I.Red254 (product of Ciba) (weight ratio = 80/20) 15 g

* Disperbyk-163 (manufactured by BYK Corporation) 4 g

* Benzyl methacrylate copolymer (NPR8000, manufactured by Miwon Corporation) 3 g

* Propylene glycol methyl ether acetate 78 g

Example  One, Example  2 and Comparative example  1: Preparation of photosensitive resin composition for color filters

After dissolving the photopolymerization initiator in the solvent, the mixture was stirred at room temperature for 2 hours, and then, each of the acrylic resin and the photopolymerization monomer prepared from Synthesis Examples 1 to 3 was added thereto, followed by stirring at room temperature for 2 hours. Subsequently, the red pigment dispersion prepared in Preparation Example 1 and the silane coupling agent were added to the obtained reactant, followed by stirring at room temperature for 1 hour. Subsequently, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition for a color filter. The component content in the photosensitive resin composition for color filters prepared above is shown in Table 1 below.

ingredient Example 1 Example 2 Comparative Example 1 Binder resin Resin prepared from Synthesis Example 1 9.4 - - Resin Prepared from Synthesis Example 2 - 9.4 - Resin prepared from Synthesis Example 3 - - 9.4 Photopolymerization monomer Dipentaerythritol hexaacrylate 7 7 7 Photopolymerization initiator IRGACURE OXE02 (product of Shiba Gai Corporation) 1.5 1.5 1.5 menstruum Propylene Glycol Methyl Ether Acetate 32 32 32 Pigment Dispersion Red pigment dispersion prepared in Preparation Example 1
(15% of pigment solids) 50
(7.5) 50
(7.5) 50
(7.5) Silane coupling agent γ-glycidoxy propyltrimethoxysilane
(S-510, Chisso Corporation) 0.1 0.1 0.1

(Unit: wt%)

Property evaluation

Test Example  1: Pattern Property Evaluation

2.1 μm using a spin coater (K-Spin8, manufactured by KDNS) on a glass substrate having a thickness of 1 mm obtained by degreasing the color filter-sensitive photosensitive resin composition prepared according to Examples 1, 2 and Comparative Example 1. After coating in thickness, it was dried at 80 ° C. for 150 seconds on a hot plate to obtain a coating film. Subsequently, a photomask was placed on each coating film, and the exposure amount was changed by using a high pressure mercury lamp having a wavelength of 365 nm. Subsequently, the solution was developed at 30 ° C. under atmospheric pressure for 150 seconds using a 1.33 wt% potassium hydroxide (KOH) -based aqueous solution, followed by washing with water and drying. Subsequently, a post bake process was performed at 235 ° C. for 25 minutes in a hot air circulation drying oven to prepare a pattern. The physical properties of the produced pattern were observed and measured by an optical microscope, and those having good line width and straightness of the pattern were selected, and the pattern properties were evaluated by measuring the exposure amount. The results are shown in Table 2 below.

<Evaluation Criteria for Pattern Properties>

○: When the line width and straightness of the pattern are good at an exposure dose of 30 mJ / cm ² to 80 mJ / cm ²

△: When the line width and the straightness of the pattern in an exposure amount less than 80 mJ / cm ² greater than 130 mJ / cm ² good

X: When the line width and straightness of a pattern are favorable at an exposure dose of 130 mJ / cm ² or more

Test Example  2: development speed evaluation

2.1 μm using a spin coater (K-Spin8, manufactured by KDNS) on a glass substrate having a thickness of 1 mm obtained by degreasing the color filter-sensitive photosensitive resin composition prepared according to Examples 1, 2 and Comparative Example 1. After coating in thickness, it was dried at 80 ° C. for 150 seconds on a hot plate to obtain a coating film. Subsequently, a photomask was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm. Then, using a 1.33 wt% potassium hydroxide (KOH) -based aqueous solution as a developer, the development speed was evaluated by measuring the time taken for the non-exposure portion to be completely dissolved in the developer at 150 ° C. for 150 seconds. The results are shown in Table 2 below.

<Evaluation Criteria for Development Speed>

○: 30 seconds or less

△: more than 30 seconds less than 45 seconds

×: 45 seconds or more

Test Example  3: Residue  evaluation

The photosensitive resin composition for color filters prepared in Examples 1, 2 and Comparative Example 1 was coated on a glass substrate having a thickness of 1 mm degreased and washed, and a hot plate of 80 ° C. was used. Drying in the phase for 150 seconds gave a thin film. Subsequently, using 1% potassium hydroxide (KOH) aqueous solution, it developed and wash | cleaned for 150 second at 150 degreeC under normal pressure (KOH), without going through an exposure process. After removing the water, it was visually confirmed whether the microfibers were scraped by partially scratching the developed part using microfibers. The results are shown in Table 2 below.

<Evaluation Criteria for Residual Characteristics>

(Circle): When there is nothing buried in microfiber

X: When there is something which gets on microfiber

Test Example  4: surface roughness (roughness) evaluation

Using a spin coater (K-Spin 8, manufactured by KDNS) on a glass substrate having a thickness of 1 mm obtained by degreasing and washing the color filter-sensitive photosensitive resin composition prepared according to Examples 1, 2 and Comparative Example 1 above, After coating in thickness, it was dried at 80 ° C. for 150 seconds on a hot plate to obtain a coating film. Subsequently, a photomask was placed on each coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm. Subsequently, the solution was developed at 30 ° C. under atmospheric pressure for 150 seconds using a 1.33 wt% potassium hydroxide (KOH) -based aqueous solution, followed by washing with water and drying. Subsequently, a post bake process was performed at 235 ° C. for 25 minutes in a hot air circulation drying oven to prepare a pattern. The produced pattern was subjected to a UV-ashing process to remove impurities remaining on the substrate. The surface roughness of the pattern was then evaluated by observing with an atomic force microscope (AFM). The results are shown in Table 2 below.

<Evaluation Criteria for Surface Roughness>

○: surface roughness 2 nm to 6 nm

(Triangle | delta): More than 6 nm of surface roughness less than 10 nm

X: surface roughness 10 nm or more

Photosensitive resin composition Pattern properties Developing speed
(Seconds) Phenomenon residue Surface roughness Example # 1 ○ ○ (30) ○ ○ Example 2 ○ ○ (20) ○ ○ Comparative Example 1 ○ × (45) × ○

As shown in Table 2, when using the photosensitive resin composition for color filters prepared in Examples 1 and 2 it can be confirmed that the pattern properties, development speed, development residue and surface roughness properties are all excellent. On the other hand, when the photosensitive resin composition for color filters manufactured in Comparative Example 1 is used, the pattern properties and surface roughness characteristics are excellent, but the development speed and development residue characteristics are poor.

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, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (9)

Acrylic resins containing repeating units represented by the following Chemical Formulas 1 to 3; Photopolymerization monomers; Photopolymerization initiator; Pigments; And menstruum Photosensitive resin composition for color filters comprising a. [Formula 1]

[Formula 2]

(3)

In Chemical Formulas 1 to 3, R ₁ , R ₂ and R ₄ are the same or different from each other and are each independently hydrogen or a methyl group, R ₃ is the same or different at each repeating unit, and is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group, R ₅ is the same or different at each repeating unit, and each independently a substituted or unsubstituted alkylene group, R ₆ is the same or different at each repeating unit, and is each independently hydrogen or a substituted or unsubstituted alkyl group, n ₁ is an integer of 1 to 20. The method of claim 1, The photosensitive resin composition for color filters 1 to 40% by weight of the acrylic resin; 1 to 30% by weight of the photopolymerization monomer ;; 0.1 to 10% by weight of the photopolymerization initiator; 1 to 40% by weight of the pigment; And The photosensitive resin composition for color filters containing the said solvent in the quantity of remainder. The method of claim 1, The acrylic resin is 5 to 60% by weight of the repeating unit represented by the formula (1) relative to the total amount of the acrylic resin, 5 to 70% by weight of the repeating unit represented by the formula (2), and the repeating unit represented by the formula (3) Photosensitive resin composition for a color filter comprising from 50% by weight. The method of claim 1, The acrylic resin is a photosensitive resin composition for color filters having a weight average molecular weight of 3,000 kPa to 50,000. The method of claim 1, The acrylic resin is a photosensitive resin composition for a color filter having an acid value of 30 mg / KOH to 200 mg / KOH. The method of claim 1, The photopolymerization monomer may be ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate Latex, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacryl Latex, triethylene glycol dimethac Photosensitive resin composition for color filters selected from the group consisting of a relate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and a combination thereof. The method of claim 1, The photopolymerization initiator may be a triazine compound, acetophenone compound, benzophenone compound, thioxanthone compound, benzoin compound, oxime compound, carbazole compound, diketone compound, sulfonium borate compound, diazo or already The photosensitive resin composition for color filters selected from the group which consists of a diazole type compound, a biimidazole type compound, and a combination thereof. The light shielding layer for color filters manufactured using the photosensitive resin composition for color filters of any one of Claims 1-7. A color filter comprising the light shielding layer of claim 8.