KR102243166B1 - A photo sensitive resin composition, a pattern layer prepared by using the composition, a color filter comprising the pattern layer, and a display device comprising the color filter - Google Patents

Abstract

The present invention is a colored photosensitive resin composition comprising an organic black pigment, a colorant including a blue pigment and a violet pigment, an alkali-soluble resin including two or more copolymers having different epoxy equivalents, a photopolymerizable compound, a photopolymerization initiator, and a solvent, It relates to a pattern layer manufactured using the colored photosensitive resin composition, a color filter including the pattern layer, and a display device including the color filter.

Description

A colored photosensitive resin composition, a pattern layer prepared using the resin composition, a color filter including the pattern layer, and a display device including the color filter {A photo sensitive resin composition, a pattern layer prepared by using the composition, a color filter comprising the pattern layer, and a display device comprising the color filter}

The present invention relates to a colored photosensitive resin composition, a pattern layer manufactured using the resin composition, a color filter including the pattern layer, and a display device including the color filter.

Color filters are widely used in various display devices such as image pickup devices and liquid crystal displays (LCDs), and their application range is rapidly expanding. The color filters used in the image pickup device and liquid crystal display device are composed of three colored patterns of red, green, and blue, or are yellow, magenta, and cyan ( Cyan) consists of three colored colored patterns.

The colored pattern of each of the color filters is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The colored pattern processing using the colored photosensitive resin composition is generally performed by a lithography process.

Colored photosensitive resins are essential materials such as color filters, liquid crystal display materials, organic light emitting devices, and displays. 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 mixing of these pixels is prevented or an electrode In order to hide the pattern of, a black matrix is formed at the boundary between the colored layers of each color. In addition, the black column spacer (BCS) is a part that directly contacts the liquid crystal and is required to have excellent solvent resistance and properties that do not leave any residue on the organic film.

Korean Patent Registration No. 10-1658374 relates to a black column spacer in which a column spacer and a black matrix are integrated into one module. A colored photosensitive resin composition and a black column spacer are disclosed. However, it seems to be insufficient in improving the solvent resistance and storage stability.

Korean Patent Registration No. 10-1658374

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 colored photosensitive resin composition having excellent solvent resistance, storage stability, residual film rate, and elastic recovery rate.

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

To achieve the above object,

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin comprising a copolymer represented by the following formula (1), a photopolymerizable compound, a photoinitiator, and a solvent,

The colorant includes an organic black pigment, a blue pigment and a violet pigment,

The alkali-soluble resin provides a colored photosensitive resin composition comprising two or more kinds of copolymers having different epoxy equivalents.

[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and a and b are each independently an integer of 1 to 20.)

In addition, the present invention provides a pattern layer made of the colored photosensitive resin composition of the present invention.

In addition, the present invention provides a color filter including 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 colored photosensitive resin composition of the present invention uses an alkali-soluble resin containing a copolymer represented by the general formula (1), thereby exhibiting excellent effects such as solvent resistance and storage stability, and excellent film residual rate.

In addition, the colored photosensitive resin composition of the present invention exhibits an effect of having an excellent elastic recovery rate of a coating film prepared by using two or more copolymers having different epoxy equivalents by mixing.

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

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin comprising a copolymer represented by the following formula (1), a photopolymerizable compound, a photoinitiator, and a solvent,

The colorant includes an organic black pigment, a blue pigment and a violet pigment,

The alkali-soluble resin relates to a colored photosensitive resin composition comprising two or more kinds of copolymers having different epoxy equivalents.

[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and the molar ratio of the a monomer and the b monomer is 1:20 to 20:1.)

The colored photosensitive resin composition of the present invention can improve the dispersibility and storage stability of the pigment by using an alkali-soluble resin containing the copolymer of Formula 1, and further, the solvent resistance and storage stability of the colored photosensitive resin composition to which it is applied. Such reliability can be improved.

When a colored dispersion is prepared using a dispersion resin containing the copolymer of Formula 1, a colored dispersion in which the dispersion resin is evenly coated on the surface of the pigment can be obtained. Therefore, the colored photosensitive resin composition containing such a colored dispersion contains pigment particles coated with the dispersion resin, so that solvent resistance can be improved by preventing the pigment from dissolving in a solvent, and agglomeration between the pigment particles is suppressed, resulting in a colored photosensitive resin. Storage stability can be improved by preventing the viscosity of the resin composition from increasing.

In addition, the colored photosensitive resin composition of the present invention uses an alkali-soluble resin containing two or more copolymers having different epoxy equivalents as the copolymer represented by Formula 1, thereby improving the elastic recovery rate of the coated film prepared using the same. I can make it.

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

<Colored photosensitive resin composition>

coloring agent

In the present invention, a colorant having light-shielding property to visible light is used, and the colorant of the present invention includes an organic black pigment, a violet pigment, and a blue pigment, whereby the optical density of the colored photosensitive resin composition can be improved.

The organic black pigment includes at least one selected from the group consisting of lactam black, aniline black, and perylene black, and preferably includes lactam black. By including the organic black pigment, it is possible to improve the optical density and not affect the infrared region, and to improve the dielectric constant and transmittance.

The violet pigment serves to improve optical density (O.D) by reducing transmittance in the region of 400 to 600 nm. In addition, the content of the organic black pigment can be reduced through the use of the violet pigment, thereby improving the reliability of the colored photosensitive resin composition. The violet pigment is not particularly limited in its kind, but C.I. It is preferable to use at least one selected from the group consisting of pigment violet 19, 23, 29, 31 and 37, and C.I. It is most preferable to use including pigment violet 29.

The blue pigment is a compound that does not contain a central metal, and if the central metal is present, it may have an effect on driving the liquid crystal. However, in the present invention, a compound that does not contain a central metal is used as a blue pigment to secure an advantage in driving equipment. can do. In the present invention, if the blue pigment is a compound that does not contain a central metal, its kind is not particularly limited, but C.I. It is preferable to use at least one selected from the group consisting of Pigment Blue 16, 60, 63 and 66, and C.I. It is most preferable to use including Pigment Blue 60.

In addition, the colored photosensitive resin composition of the present invention may contain a black pigment as an additional colorant. The type of the black pigment is not particularly limited as long as it has light-shielding properties from visible light, but it is preferable to use at least one selected from the group consisting of titanium black and carbon black, including carbon black. It is more preferable to do it. The carbon black is not particularly limited as long as it is a light-shielding pigment, and a known carbon black may be used. Specific examples of carbon black as the black pigment include channel black, furnace black, thermal black, and lamp black. The carbon black may be resin-coated, and the carbon black coated with the resin has low conductivity compared to the non-coated carbon black, so that excellent electrical insulation may be provided when a black matrix or column spacer is formed.

In the present invention, the colorant is included in an amount of 13 to 60% by weight, preferably 25 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the colorant is included in an amount of 13 to 60% by weight, optical density and reliability are excellent.

More specifically, the colorant may include an organic black pigment, a violet pigment, a blue pigment, and a black pigment in a weight ratio of 1:0.08 to 2.5:0.2 to 3.3:0.12 to 1.7. In addition, it may be preferably mixed in a weight ratio of 1:0.27 to 1:0.47 to 1.88:0.27 to 0.87. When the organic black pigment, violet pigment, blue pigment, and black pigment are included in the weight ratio, a colored photosensitive resin composition having excellent optical density and reliability can be obtained.

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

Dispersion resin

The dispersion resin serves to prevent dissolution in a solvent by coating the pigment particles present in the colored dispersion with a dispersion resin, and inhibit aggregation between pigment particles to prevent an increase in viscosity due to aggregation between pigment particles.

The dispersion resin is not particularly limited, but may include a copolymer represented by the following formula (1).

[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and the molar ratio of the a monomer and the b monomer is 1:20 to 20:1.)

By including the copolymer of Formula 1 containing an epoxy group as the dispersion resin in the present invention, it is possible to improve the solvent resistance, storage stability, and film residual rate.

The weight average molecular weight of the dispersion resin is not particularly limited, but may be 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 50,000.

The acid value of the dispersion resin is 50 to 200 mgKOH/g based on solid content. It is possible to improve the dispersion stability of the pigment within the above range.

The dispersion resin may be a copolymer of the copolymer represented by Formula 1 and another monomer copolymerizable.

Specific examples of monomers copolymerizable with Formula 1 of the dispersion resin include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- Aromatic vinyl compounds such as vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether ; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, 2- Alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; (meth)acrylamide, Unsaturated amide compounds such as N,N-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

Each of the compounds exemplified above may be used alone or in combination of two or more.

The dispersion resin of the present invention may be used by further mixing various other known alkali-soluble resins generally used in the art, if necessary.

The dispersion resin is contained in an amount of 1 to 20% by weight based on the total weight of solids in the colored dispersion, and is preferably contained in an amount of 7 to 12% by weight. When the content of the dispersion resin is within the above range, the pigment particles are evenly dispersed, and aggregation between the pigment particles can be prevented, so that solvent resistance and storage stability are improved.

Dispersant

The dispersant is added to deaggregate and maintain stability of the pigment. Specific examples of the dispersant include surfactants such as cationic, anionic, nonionic, polyester, polyamine, and the like, respectively, or It can be used in combination of two or more.

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

Specific examples of the anionic surfactant include higher alcohol sulfate ester 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 sulfonic acid salts, 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 copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

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 listed. have.

In addition, the dispersant preferably includes an acrylate-based dispersant (hereinafter, an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). It is preferable to use the acrylate-based dispersant manufactured 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 like, the acrylic Each of the rate-based dispersants may be used alone or in combination of two or more.

In addition to the acrylate-based dispersant, the dispersant may use other resin type pigment dispersants. As the dispersant of the other resin type, a known dispersant of a resin type, in particular, a polycarboxylic acid ester typified by polyurethane and polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a (partial) amine salt of a polycarboxylic acid , Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free carboxyl groups An oily dispersant such as an amide or a salt thereof formed by reaction of a polyester having a 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 polyacrylate; Adducts of ethylene oxide/propylene oxide; And phosphate esters.

Commercially available products of the above other resin type dispersants include cationic resin dispersants, such as BYK (Big) Chemie's brand 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, DISPER BYK-2000; BASF's 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 of Lubrizol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemicals' brand name: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, and the like.

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

The dispersant is contained in an amount greater than 0 and 1 part by weight or less, and preferably in an amount of 0.05 to 0.5 parts by weight, based on 1 part by weight of the colorant. If the dispersant is contained in an amount of more than 0 and 1 part by weight or less of the above, it is preferable because a uniformly dispersed pigment can be obtained.

Alkali-soluble resin

The alkali-soluble resin is a component that imparts solubility to the alkali developer used in the developing process.

The alkali-soluble resin of the present invention includes a copolymer represented by the following formula (1), and may be characterized in that it includes two or more copolymers having different epoxy equivalents.

[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and the molar ratio of the a monomer and the b monomer is 1:20 to 20:1.)

By including the copolymer of Formula 1 containing an epoxy group as the alkali-soluble resin in the present invention, it is possible to improve the solvent resistance, storage stability and film residual rate.

In addition, the alkali-soluble resin in the present invention may be used by mixing two or more types of copolymers having different epoxy equivalents as the copolymer of Formula 1, preferably by mixing a copolymer (a1) and a copolymer (a2) Can be used.

The copolymer (a1) may have an epoxy equivalent of 500 to 800, preferably 600 to 700. In addition, the copolymer (a2) may have an epoxy equivalent of 1,000 to 1,300, preferably 1,100 to 1,200.

In addition, the copolymers (a1) and (a2) are included in a weight ratio of 1: 0.1 to 5, and are preferably included in a weight ratio of 1: 0.25 to 3. When the copolymers (a1) and (a2) satisfy the range of the epoxy equivalent and the range of the weight ratio, they are preferable in that they can exhibit a better elastic recovery rate.

The weight average molecular weight of the alkali-soluble resin is not particularly limited, but may be 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 50,000.

The acid value of the alkali-soluble resin is 50 to 200 mgKOH/g based on solid content. It is possible to improve the dispersion stability of the pigment within the above range.

The alkali-soluble resin may be a copolymer of the copolymer represented by Formula 1 and another monomer copolymerizable.

Specific examples of monomers copolymerizable with Formula 1 of the alkali-soluble resin include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o -Aromatic vinyls such as vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether compound; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, 2- Alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; (meth)acrylamide, Unsaturated amide compounds such as N,N-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

Each of the compounds exemplified above may be used alone or in combination of two or more.

The alkali-soluble resin of the present invention may be used by further mixing various other known alkali-soluble resins generally used in the art, if necessary.

The alkali-soluble resin is contained in an amount of 5 to 60% by weight, and preferably contained in an amount of 20 to 50% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. If the content of the alkali-soluble resin is within the above-described range, pattern formation is facilitated, and resolution and residual film rate are improved, so it is preferable.

Further, the alkali-soluble resin of the present invention is mixed in an amount of 30 to 95 parts by weight, preferably 40 to 85 parts by weight, based on a total of 100 parts by weight of the alkali-soluble resin and the photopolymerizable compound. When the alkali-soluble resin is mixed within the above range, it has sufficient solubility to facilitate pattern formation, and film reduction in the exposed pixel portion during development is prevented, thereby providing a colored photosensitive resin composition having good omission of non-pixel portions. have.

Photopolymerizable compound

The photopolymerizable compound contains an unsaturated bond, forms a colored photosensitive resin layer by performing a photoreaction with a photopolymerization initiator, and must be a compound capable of polymerization by the action of a photopolymerization initiator described later.

In the present invention, the functional group of the photopolymerizable compound may be a commonly used (meth)acrylate.

The photopolymerizable compound contains 3 to 10 functional groups, preferably 4 to 8 functional groups.

Specific examples of the trifunctional monomer among the polyfunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylic Rate, pentaerythritol tri(meth)acrylate, and the like.

Specific examples of the tetrafunctional monomers among the polyfunctional monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethyrolpropane tetraacrylate, ditrimethyrolpropane tetramethacrylate, dipentaeryth Lithol tetraacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerin tetraacrylate, glycerin tetramethacrylate, etc. are mentioned.

Specific examples of the 5-functional monomers among the polyfunctional monomers include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate. And acrylate.

Specific examples of the 6-functional monomer among the polyfunctional monomers include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

Specific examples of 7 to 10 functional monomers among the polyfunctional monomers include tripentaerythritol octamethacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol heptamethacrylate, and tetrapentaerythritol heptaacrylate. Can be lifted.

The photopolymerizable compound is contained in an amount of 5 to 50% by weight, and is preferably contained in an amount of 7 to 45% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention. The photopolymerizable compound may improve the strength or flatness of the pixel portion in the range of 5 to 50% by weight.

Photopolymerization initiator

The photopolymerization initiator may be used without limitation as long as it can polymerize the photopolymerizable compound, but preferably, in consideration of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price, acetophenone-based compound, benzoin-based compound, benzophene It may be one or more compounds selected from the group consisting of non-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4- (2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl ]Propan-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzo isobutyl ether.

Specifically, as the benzophenone-based compound, for example, benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4' -Tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone, etc. are mentioned.

Specifically, as the triazine-based compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, Romethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3, 5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis( Trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-di Ethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1 , 3,5-triazine, etc. are mentioned.

Specifically, as the biimidazole compound, for example, 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, 2,2-bis(2,6-dichlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group, etc. Can be mentioned.

More preferably, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4 ,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole Etc. are mentioned.

Specifically, examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products may be BASF's OXE01 or OXE02.

Specifically, the thioxanthone compound is, for example, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxythioc Santon, etc. are mentioned.

The photopolymerization initiator may be used alone or in combination of two or more.

In the present invention, the photopolymerization initiator is contained in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

The colored photosensitive resin composition is highly sensitive within the range of 0.1 to 20% by weight, so that the strength of the pixel portion formed using the colored photosensitive resin composition and smoothness on the surface of the pixel portion may be improved.

In addition, in the present invention, a photopolymerization initiator auxiliary agent may be used in addition to the photopolymerization initiator.

The photopolymerization initiation aid is a compound used to promote polymerization of a photopolymerizable compound in which polymerization was initiated by a photoinitiator, and examples of the photopolymerization initiation aid include amine-based compounds or alkoxyanthracene-based compounds.

Specifically, as the amine compound, for example, triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid 2 -Dimethylaminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Mihilers' ketone), 4,4'-bis (Diethylamino)benzophenone and 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned. Among these, 4,4'-bis(diethylamino)benzophenone is preferable.

As the alkoxyanthracene-based compound, specifically, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10- Diethoxyanthracene and the like.

Moreover, what is marketed can be used as a photopolymerization initiation auxiliary agent, and a brand name "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) etc. are mentioned as a commercially available photoinitiation auxiliary agent.

In the case of using the photopolymerization initiation aid, it is preferable to use in an amount of usually more than 0 and 10 moles or less and 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiation aid is used in the range of more than 0 and 10 moles or less, the sensitivity of the colored photosensitive resin composition may be higher, and the productivity of the color filter formed using the colored photosensitive resin composition may be improved.

solvent

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, but does not react, the solvent used in the usual colored photosensitive resin composition may be used without particular limitation, and in particular, ethers, acetates, and aromatics Hydrocarbons, ketones, alcohols, esters, and the like are preferable.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, etc. are mentioned.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 -Methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, and propylene carbonate.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

Each of the above solvents may be used alone or in combination of two or more.

The solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of applicability and drying properties, and, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- Ethyl ethoxypropionate and methyl 3-methoxypropionate.

The solvent is contained in an amount of 60 to 90% by weight, preferably 65 to 85% by weight, based on the total weight of the colored photosensitive resin composition. If the solvent is included in the range of 60 to 90% by weight, the coating property is good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), and an inkjet. Can be set.

additive

In addition to the above-described components, the colored photosensitive resin composition of the present invention contains other additives according to the needs of a person skilled in the art within a range that does not impair the object of the present invention.

The additive may further include one or more additives selected from the group consisting of, for example, a filler, another polymer compound, a thermal initiator, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent. .

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

The thermal initiator serves to maximize the initiation efficiency by causing a curing reaction by heat. The thermal initiator may be a peroxide-based compound.

The specific type of the thermal initiator is not particularly limited, but tetramethylbutylperoxy neodecanoate (ex. Perocta ND, NOF company (manufactured by)), bis (4-butylcyclohexyl) peroxydicarbonate (ex. Peroyl TCP) , NOF (manufactured by)), di(2-ethylhexyl) peroxy carbonate, butyl peroxy neodecanoate (ex. Perbutyl ND, NOF (manufactured)), dipropyl peroxy dicarbonate (ex. Peroyl NPP) , NOF (manufactured by)), diisopropyl peroxydicarbonate (ex. Peroyl IPP, NOF (manufactured by)), diethoxyethyl peroxy dicarbonate (ex. Peroyl EEP, NOF (manufactured by)), diethoxy Hexyl peroxy dicarbonate (ex. Peroyl OEP, NOF Corporation (manufactured)), hexyl peroxy dicarbonate (ex. Perhexyl ND, NOF Corporation (manufactured)), dimethoxybutyl peroxy dicarbonate (ex. Peroyl MBP, NOF) (Manufacturer)), bis(3-methoxy-3-methoxybutyl) peroxy dicarbonate (ex.Peroyl SOP, NOF Corporation (manufactured)), dibutyl peroxy dicarbonate, dicetyl peroxy Dicarbonate, dimyristyl peroxy dicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, hexyl peroxy pivalate (ex. Perhexyl PV, NOF Corporation (manufactured)) , Butyl peroxy pivalate (ex. Perbutyl, NOF company (manufactured)), trimethyl hexanoyl peroxide (ex. Peroyl 355, NOF company (manufactured)), dimethyl hydroxybutyl peroxyneodecanoate (ex. Luperox) 610M75, Atofina (manufactured by)), amyl peroxyneodecanoate (ex. Luperox 546M75, Atofina (manufactured)), butyl peroxyneodecanoate (ex. Oxy neoheptanoate, amylperoxy pivalate (ex.Luperox 546M75, Alofina (manufactured)), t-butylperoxy pivalate, t-amylperoxy-2-ethylhexanoate, t-butyl Peroxy- 2-ethylhexanoate, lauryl peroxide, dilauroyl peroxide, didecanoyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 2,2-bis(tert-butylperoxy)butane , 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-1-methyl Ethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxybenzoate, tert- Butylperoxy isopropyl carbonate, cumene hydroxyperoxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, tert-butyl peracetate, peracetic acid (peracetic acid), and potassium persulfate (potassium persulfate) may be one or more selected from the group consisting of.

With respect to the content of the thermal initiator, it is preferably included in an amount of 1 to 10% by weight, and more preferably included in an amount of 1 to 5% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When it is included in the above amount, it is more preferable for fairness and undercut.

The curing agent is used to increase deep curing and mechanical strength, and specific examples include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins. , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxidation products, isoprene ( Co) polymer epoxidation product, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

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

The curing agent may be used in combination with a curing agent and a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyhydric carboxylic anhydrides may be commercially available as an epoxy resin curing agent. Specific examples of the epoxy resin curing agent are commercial products such as a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries, Ltd.), a brand name (Rika Shiddo HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) ( Shin Nippon Ewha Co., Ltd.) and the like. The curing agent exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation property of the photosensitive resin composition, and for example, surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic and amphoteric can be used. , A silicone-based surfactant or a fluorine-based surfactant, etc. may be preferably used.

The silicone surfactants are commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 of Dow Corning Toray Silicone, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4460 and TSF-4452. The fluorine-based surfactants are commercially available products, for example, Megapieces F554, F-470, F-471, F-475, F-482 and F-489 (Dainibon Ink Chemical Co., Ltd.), BM-1000, BM-1100. (BM Chemie), Prolide FC-135/FC-170C/FC-430 (Sumitomo 3M), and the like.

As another example of the surfactant, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, polyethylene In addition to immortals, commercial products include KP (Shin-Etsu Chemical Industries, Ltd.), Polyflow (Kyoei Chemicals, Inc.), Ftop (Tochem Products), Megapak (Dai Nippon Ink Chemicals, Inc.), and Florade (Sumitomo 3M). Co., Ltd.), Asahi Guard, Saffron (above, Asahi Glass Co., Ltd.), Sor Spas (Zeneca Co., Ltd.), EFKA (EFKACHEMICALS Co., Ltd.), and PB821 (Ajinomoto Co., Ltd.).

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

The adhesion promoter is an additive used to improve coatability and adhesion with a substrate, and includes a silane coupling agent including a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof. Can include. The silane coupling agent is specifically, for example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Mercaptopropyl trimethoxysilane, trimethoxysilyl benzoic acid, vinyltriacetoxysilane, γ-isocyanate propyl triethoxysilane, and the like.

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

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

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

The additive is included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

<Pattern layer, color filter and display device>

The colored photosensitive resin composition thus prepared can be preferably used in the production of a display device, preferably a black matrix of 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 have high optical density, high reliability, and excellent shielding properties.

In particular, the colored photosensitive resin composition of the present invention may be preferably used in the manufacture of a black column spacer (a black matrix integrated spacer), and the black column spacer does not form a black matrix and a column spacer, respectively, but black as a single pattern. It means that the matrix and the column spacer are integrally formed.

The present invention also relates to a color filter including a black matrix, a column spacer, or a black column spacer prepared by using the colored photosensitive resin composition.

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

The substrate may be a substrate of the color filter itself, or may be a portion in which the color filter is located in a display device, etc., and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

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

The pattern layer may be a layer formed by applying the above-described colored 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 partition wall 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 short, the liquid crystal display device according to the present invention may include a color filter including a pattern layer including a cured product of the above-described colored photosensitive resin composition.

The color filter of the present invention can be applied not only to an ordinary liquid crystal display device, but also to various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device.

When the liquid crystal display device includes a color filter including a pattern layer according to the present invention, there is an advantage in that shielding properties and reliability are excellent.

<patterning process>

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

a) applying a colored photosensitive resin composition to a substrate;

b) a prebaking step of drying the solvent;

c) placing a photo mask on the obtained film and irradiating active light to cure the exposed portion;

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

e) It includes drying and post-baking.

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Moreover, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, etc. are mentioned as a polymer plate.

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

Pre-baking is performed by heating with an oven, a hot plate, or the like. At this time, the heating temperature and heating time in the pre-baking are appropriately selected depending on the solvent to be used, and are performed at a temperature of, for example, 80 to 150°C for 1 to 30 minutes.

Further, the exposure performed after the prebaking is performed by an exposure machine and exposed through a photomask, thereby sensitizing only the portion corresponding to the pattern. The irradiated light at this time may be, for example, visible light, ultraviolet light, X-ray, and electron beam.

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

Post-baking is performed to increase the adhesion between the patterned film and the substrate, and is performed through heat treatment at 80 to 220°C for 10 to 120 minutes. Post-baking is performed using an oven, a hot plate, or the like, similar to pre-baking.

At this time, the thickness of the black matrix is preferably 0.2 µm to 20 µm, more preferably 0.5 µm to 10 µm, and particularly preferably 0.8 µm to 5 µm.

Further, the film thickness of the column spacer and the black column spacer is preferably 0.1 µm to 8 µm, more preferably 0.1 µm to 6 µm, and particularly preferably 0.1 µm to 4 µm.

The black matrix, column spacer or black column spacer made of the colored photosensitive resin composition of the present invention not only has excellent physical properties such as optical density, adhesion, electrical insulation, and light-shielding properties, but also has excellent heat resistance and solvent resistance. Can improve the reliability of

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by a person skilled in the art within the scope of the present invention.

Preparation Example 1. Preparation of alkali-soluble resin A1

277 g of methoxybutyl acetate was added to a 1 L separate flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, and heated to 80°C. Subsequently, 3,4-epoxytricyclo[5.2.1.0,2,6]decane-9-ylacrylate and 3,4-epoxytricyclo[5.2.1.0,2,6]decane-8-ylacrylate were prepared. A mixed solution in which 301 g of a mixture, 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile mixed at a molar ratio of 50:50 was dissolved in 350 g of methoxybutyl acetate was prepared. The mixed solution was added dropwise to the flask over 5 hours using a dropping funnel, and then reacted for 3 hours to prepare a dispersion resin A1 [solid content (NV) 35.0 wt%]. The acid value (dry) of the prepared alkali-soluble resin A1 was 69.8 mgKOH/g, the weight average molecular weight (Mw) was 12,300, the dispersion degree (Mw/Mn) was 2.1, and the epoxy equivalent was 1,130.

Preparation Example 2. Preparation of alkali-soluble resin A2

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared. As a monomer dropping lot, acrylic acid 14.4 parts by weight (0.2 moles), benzyl methacrylate 140.8 parts by weight (0.8 moles), t-butylperoxy-2-ethylhexanoate 2.0 parts by weight, propylene glycol monomethyl ether acetate (PGMEA ) Prepared by mixing 40.0 parts by weight. As a chain transfer agent dropping tank, 3.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA were mixed and prepared. Thereafter, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Subsequently, the monomer and the chain transfer agent were dripped from the dropping lot. Dropping was carried out for 4 hours while maintaining 70°C, and after 1 hour, the temperature was raised to 90°C and the reaction was proceeded for 8 hours to prepare a dispersion resin A2 [solid content (NV) 35.0% by weight]. The acid value (dry) of the prepared alkali-soluble resin A2 was 80.0 mgKOH/g, the weight average molecular weight (Mw) was 45,200, and the dispersion degree (Mw/Mn) was 2.8.

Preparation Example 3. Preparation of alkali-soluble resin A3

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared. As a monomer dropping lot, 2-phenylthioethyl acrylate 52.1 parts by weight (0.25 moles), benzyl methacrylate 44.0 parts by weight (0.25 moles), methacrylic acid 12.9 parts by weight (0.15 moles), vinyl toluene 41.3 parts by weight (0.35 moles) Mol), 4.0 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40.0 parts by weight of PGMEA were mixed and prepared. As a chain transfer agent dropping tank, 6.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA were mixed and prepared. Thereafter, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Subsequently, a monomer and a chain transfer agent were dripped from the dropping lot. The dropping was carried out for 2 hours while maintaining 90°C, and after 1 hour, the temperature was raised to 110°C and the reaction was proceeded for 8 hours to prepare a dispersion resin A3 [solid content (NV) 35.0% by weight]. The acid value (dry) of the prepared alkali-soluble resin A3 was 70.0 mgKOH/g, the weight average molecular weight (Mw) was 23,000, and the dispersion degree (Mw/Mn) was 2.4.

Preparation Example 4. Preparation of alkali-soluble resin A4

277 g of methoxybutyl acetate was added to a 1 L separate flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, and heated to 80°C. Subsequently, 3,4-epoxytricyclo[5.2.1.0,2,6]decane-9-ylacrylate and 3,4-epoxytricyclo[5.2.1.0,2,6]decane-8-ylacrylate were prepared. A mixed solution in which 321 g of a mixture, 32 g of methacrylic acid, and 20 g of azobisdimethylvaleronitrile were mixed at a molar ratio of 50:50 was dissolved in 350 g of methoxybutyl acetate was prepared. The mixed solution was added dropwise to the flask over 5 hours using a dropping funnel, and then reacted for 3 hours to prepare dispersion resin A4 (solid content (NV) 35.0% by weight). The acid value (dry) of the prepared alkali-soluble resin A4 was 59.8 mgKOH/g, the weight average molecular weight (Mw) was 9,300, the dispersion degree (Mw/Mn) was 1.9, and the epoxy equivalent was 665.

Preparation Examples 5 to 7. Preparation of colored dispersion

A mixture of the alkali-soluble resin, a colorant, a dispersant, and a solvent was prepared. Subsequently, zirconia beads (average particle diameter of 0.1 mm) were mixed with the mixture in a weight ratio of 50:50 and dispersed for 6 hours using a bead mill. After the dispersion was completed, a colored dispersion was prepared by filtering, and the contents thereof are shown in Table 1 below.

(Unit: g) division Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 coloring agent V29 30.0 30.0 30.0 OBP 48.0 48.0 48.0 B60 51.0 51.0 51.0 CB 25.0 25.0 25.0 alkali
Availability
Suzy A1 65.0 - - A2 - 65.0 - A3 - - 65.0 Dispersant 94.0 94.0 94.0 solvent 687 687 687 -V29: CI pigment violet 29
-OBP: Organic Black Pigment
-B60: CI Pigment Blue 60
-CB: carbon black
-A1: Alkali-soluble resin prepared in Preparation Example 1
-A2: Alkali-soluble resin prepared in Preparation Example 2
-A3: Alkali-soluble resin prepared in Preparation Example 3
-Dispersant: DisperBYK-2000 (BYK)
-Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Examples 1 to 3 and Comparative Examples 1 to 9

The colored dispersion was mixed with an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an additive, and a solvent to prepare a colored photosensitive resin composition, and the contents are shown in Table 2 below.

(Unit: g) division Example Comparative example One 2 3 One 2 3 4 5 6 7 8 9 coloring
Dispersion B1 59.34 59.34 59.34 59.34 59.34 59.34 - - - - - - B2 - - - - - - 59.34 59.34 59.34 - - - B3 - - - - - - - - - 59.34 59.34 59.34 Alkali-soluble resin A1 10.50 15.00 6.00 21.00 - - 21.00 - - 21.00 - - A2 - - - - 21.00 - - 21.00 - - 21.00 - A3 - - - - - 21.00 - - 21.00 - - 21.00 A4 10.50 6.00 15.00 - - - - - - - - - Photopolymerization
compound 4.09 4.09 4.09 4.09 4.09 4.09 4.09 4.09 4.09 4.09 4.09 4.09 Photopolymerization initiator 0.51 0.51 0.51 0.51 0.51 0.51 0.51 0.51 0.51 0.51 0.51 0.51 additive 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 solvent 44.81 44.81 44.81 44.81 44.81 44.81 44.81 44.81 44.81 44.81 44.81 44.81 -A1: Alkali-soluble resin prepared in Preparation Example 1
-A2: Alkali-soluble resin prepared in Preparation Example 2
-A3: Alkali-soluble resin prepared in Preparation Example 3
-A4: Alkali-soluble resin prepared in Preparation Example 4
-B1: colored dispersion prepared in Preparation Example 5
-B2: colored dispersion prepared in Preparation Example 6
-B3: colored dispersion prepared in Preparation Example 7
-Photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)
-Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369:
Ciba company)
-Additive: DisperBYK-163 (BYK)
-Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Experimental Example 1. Coating film solvent resistance evaluation

After drying a 5cmX5cm glass substrate (Corning) washed with a neutral detergent and water, each of the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 9 was spin-coated to a final film thickness of 3.0 μm. . Then, it was placed on a heating plate and dried for 1 to 2 minutes at a temperature of 80 to 120°C to remove the solvent. Subsequently, it was exposed at an exposure amount of 25 to 35 mJ/cm 2, and fired at 200 to 250° C. for 10 to 30 minutes to prepare a colored substrate coated with a colored photosensitive resin composition on the entire surface without a pattern.

The substrate was cut into a size of 3cmx3cm and immersed in N-Methyl pyrrolidone (NMP) solvent at 100°C for 60 minutes. Then, after extracting only the NMP solvent, the solvent resistance was evaluated by measuring the absorbance at a visible wavelength using a UV-vis spectrometer (UV-2600, Shimadzu Corporation). The measurement results of absorbance are shown in Table 3 below.

Experimental Example 2. Storage stability evaluation

Storage stability was evaluated by measuring the viscosity change rate (viscosity after 3 months at 5°C/initial viscosity×100) of the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 9.

The evaluation criteria are as follows, and the measurement results are shown in Table 3 below.

<Evaluation criteria>

◎: Less than 105% viscosity change rate

○: Viscosity change rate of 105% or more, less than 110%

△: Viscosity change rate of 110% or more, less than 115%

×: Viscosity change rate of 115% or more

Experimental Example 3. Evaluation of residual film rate

The residual film ratio of the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 9 was measured, and the measurement results are shown in Table 4 below.

After drying a 5cmX5cm glass substrate (Corning) washed with a neutral detergent and water, and then spin coating each of the colored photosensitive resin compositions prepared in Examples 2 to 4 and Comparative Examples 3 to 8 to a final film thickness of 3.0 μm. I did. Then, it was placed on a heating plate and dried for 1 to 2 minutes at a temperature of 80 to 120°C to remove the solvent. Subsequently, exposure was performed at an exposure amount of 25 to 35 mJ/cm 2, and the film thickness (film thickness 1) was measured. Then, each of the substrates was developed in a developer having a concentration of 0.04% KOH, and fired at 200 to 250° C. for 10 to 30 minutes to prepare a colored substrate. The film thickness (film thickness 2) of the produced colored substrate was measured, and the residual film ratio (film thickness 2/film thickness 1*100) was confirmed.

Experimental Example 4. Evaluation of elastic recovery rate

After drying a 5cmX5cm glass substrate (Corning) washed with a neutral detergent and water, and then spin coating each of the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 9 to a final film thickness of 3.0 μm. I did. Then, it was placed on a heating plate and dried for 1 to 2 minutes at a temperature of 80 to 120°C to remove the solvent. Subsequently, a pattern was formed by exposure with an exposure amount of 25 to 35 mJ/cm 2, and an unexposed portion was removed using an alkaline aqueous solution. Then, baking was performed at 200 to 250° C. for 10 to 30 minutes to prepare a colored substrate coated with a colored photosensitive resin composition.

The fabricated substrate is measured with the thickness and height of the pattern in the reference state through a three-dimensional surface shape measuring equipment (SIS-2000, SNU). Then, using a hardness tester (Nano-indenter HM500, Fisher) is pressed to the point where the pattern is deformed 1㎛. The hardness tester uses a flat indenter and presses it at a speed of 2mN/sec. It has a holding time of 5 seconds at the point where 1㎛ is deformed. Thereafter, the thickness and height of the pattern were measured using a three-dimensional surface shape measuring device (SIS-2000, SNU), and the elastic recovery rate was measured by the change in the thickness of the pattern before and after. Comparative Example 1 was used as the standard (STD) to evaluate the relative elastic recovery rate, and the results are shown in Table 3.

division Absorbance
(abs, @520nm) preservation
stability Film remaining rate (%) Elastic recovery rate
(%) Example 1 0.0016 ◎ 90.1 109 Example 2 0.0012 ◎ 90.0 110 Example 3 0.0011 ◎ 90.2 107 Comparative Example 1 0.0015 ○ 90.1 STD Comparative Example 2 0.0056 ○ 89.2 99 Comparative Example 3 0.0042 ○ 89.5 99 Comparative Example 4 0.0103 △ 87.9 93 Comparative Example 5 0.0271 × 87.3 92 Comparative Example 6 0.0198 △ 86.1 88 Comparative Example 7 0.0369 × 86.9 92 Comparative Example 8 0.0185 △ 85.7 93 Comparative Example 9 0.0456 × 84.5 83

The colored photosensitive resin compositions of Examples 1 to 3 of the present application including both alkali-soluble resins A1 and A4 showed excellent results in evaluation of solvent resistance, storage stability, residual film rate, and elastic recovery rate.

On the other hand, the colored photosensitive resin compositions of Comparative Examples 4 to 9 including alkali-soluble resin A2 or A3 showed poor results in evaluation of solvent resistance, storage stability, residual film rate, and elastic recovery rate. In particular, the colored photosensitive resin compositions of Comparative Examples 1 to 3 containing only alkali-soluble resin A1 also measured relatively high absorbance compared to Examples 1 to 3, resulting in insufficient solvent resistance, and the viscosity change rate after 3 months was also slightly lowered. , The elastic recovery rate was also relatively low.

Claims (18)

A colored photosensitive resin composition comprising a colored dispersion containing a colorant, an alkali-soluble resin containing a copolymer represented by the following formula (1), a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The colorant includes an organic black pigment, a blue pigment and a violet pigment,
The alkali-soluble resin is a copolymer represented by the following formula (1) and includes two or more copolymers having different epoxy equivalents,
The organic black pigment comprises lactam black,
A black photosensitive resin composition for forming a cured film by performing a post-baking at a temperature of 80 to 220°C.
[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and in Formula 1, the molar ratio of the monomer a and the monomer b is 1:20 to 20:1.) The black photosensitive resin composition according to claim 1, wherein the alkali-soluble resin comprises a copolymer (a1) having an epoxy equivalent of 500 to 800 and a copolymer (a2) having an epoxy equivalent of 1,000 to 1,300. The black photosensitive resin composition according to claim 1, wherein the blue pigment does not contain a central metal. The method of claim 3, wherein the blue pigment is C.I. Pigment Blue 16, 60, 63, and a black photosensitive resin composition comprising at least one selected from the group consisting of 66. The method of claim 1, wherein the violet pigment is C.I. Pigment violet 19, 23, 29, 31, and a black photosensitive resin composition comprising at least one selected from the group consisting of 37. The black photosensitive resin composition according to claim 1, wherein the black photosensitive resin composition further comprises a black pigment other than the lactam black as an additional colorant. The black photosensitive resin composition according to claim 6, wherein the black pigment comprises at least one selected from the group consisting of titanium black and carbon black. The method according to claim 6, of the colorant organic black pigment, blue pigment, violet pigment And the black pigment is mixed in a weight ratio of 1:0.08 to 2.5:0.2 to 3.3:0.12 to 1.7. The black photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight of 3,000 to 100,000. The method according to claim 1, based on the total weight of the solid content in the black photosensitive resin composition, 13 to 60% by weight of a colorant, 5 to 60% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound, and 0.1 to 20% by weight of a photopolymerization initiator. Including,
A black photosensitive resin composition comprising 60 to 90% by weight of a solvent based on the total weight of the black photosensitive resin composition. The method according to claim 1, wherein the black photosensitive resin composition further comprises at least one additive selected from the group consisting of a filler, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent. The black photosensitive resin composition made into. The method according to claim 1, wherein the colored dispersion further comprises a dispersion resin and a solvent,
The dispersion resin is a black photosensitive resin composition, characterized in that it comprises a copolymer represented by the following formula (1).
[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and in Formula 1, the molar ratio of the monomer a and the monomer b is 1:20 to 20:1.) A pattern layer made of the black photosensitive resin composition of claim 1. The pattern layer according to claim 13, wherein the pattern layer is at least one selected from the group consisting of a column spacer, a black matrix, and a black column spacer. A color filter comprising the pattern layer of claim 13. A display device comprising the color filter of claim 15. delete delete