KR102377188B1 - Colored photosensitive resin composition and color filter and display device using the same - Google Patents

Abstract

The present invention relates to a colorant; A non-reactive alkali-soluble resin containing at least one member selected from the group consisting of repeating units of Formulas 1 to 3; Photopolymerizable compounds; photopolymerization initiator; Antioxidants; and a solvent, wherein the colorant is a green colorant, and the photopolymerizable compound includes two or more types of compounds, including at least one trifunctional or lower photopolymerizable compound represented by Formula 4. In addition, the photopolymerization initiator includes two or more different types selected from the group consisting of oxime ester-based photopolymerization initiators represented by Chemical Formula 6, and a colored photosensitive resin composition, a color filter, and a display device containing the same are provided.

Description

Colored photosensitive resin composition, color filter and display device manufactured using the same {COLORED PHOTOSENSITIVE RESIN COMPOSITION AND COLOR FILTER AND DISPLAY DEVICE USING THE SAME}

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

Color filters are widely used in various display devices such as imaging devices, liquid crystal displays (LCDs), and organic light emitting diodes (OLEDs), and their application range is rapidly expanding.

The color filter used in the above display device consists of a coloring pattern of three colors: Red, Green, and Blue, or a color pattern of Yellow, Magenta, and Cyan. It consists of three color 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 photopolymerization initiator, and a solvent. Colored pattern processing using the colored photosensitive resin composition is typically performed through a lithography process.

Recently, flat panel display devices proposed to replace existing cathode ray tube display devices include liquid crystal display, field emission display, and plasma. There are display panels (Plasma Display Panel) and Organic Light-Emitting Diode Display (OLED Display).

Recently, market demand for high-quality displays with high color reproduction is growing. Accordingly, the content of colorants included in the colored photosensitive resin composition used to manufacture color filters is continuously increasing, and the use of colorants with better coloring power and contrast ratio is being considered.

However, as the content of the colorant increases, problems such as reduced sensitivity, tearing of the pattern lines, and reduced developability occur. In order to solve the above problems, the purpose of the present invention is to provide a colored photosensitive resin composition that has improved adhesion to prevent line tearing when manufacturing a color filter, and has excellent developability.

Korean Patent Publication No. 10-2012-0105575

The present invention was made to solve the problems of the prior art, and provides a colored photosensitive resin composition with improved adhesion to prevent line tearing, excellent reliability in terms of solvent resistance, etc., and excellent developability. The purpose.

Additionally, the object is to provide a color filter and a display device manufactured using the colored photosensitive resin composition.

The present invention relates to a colorant; A non-reactive alkali-soluble resin containing at least one member selected from the group consisting of repeating units of Formulas 1 to 3; Photopolymerizable compounds; photopolymerization initiator; Antioxidants; A photosensitive resin composition comprising a solvent,

The colorant is a green colorant,

The photopolymerizable compound includes two or more types of compounds, and includes at least one trifunctional or lower monomer represented by Formula 4,

The photopolymerization initiator provides a colored photosensitive resin composition, wherein the photopolymerization initiator is two or more different types selected from the group consisting of oxime ester-based photopolymerization initiators represented by Formula 6.

[Formula 1]

[Formula 2]

[Formula 3]

In Formula 3, R is hydrogen or methyl.

[Formula 4]

에서 선택될 수 있으며, In Formula 4, R is each independently

can be selected from,

및

에서 선택되는 1종 일 수 있으며, a는 1~3의 정수이고, b는 0 또는 1~12의 정수일 수 있다. A is a divalent linking group,

and

It may be one type selected from, a is an integer of 1 to 3, and b may be an integer of 0 or 1 to 12.

In Formula 6 above,

n is 0 or 1,

이고, R ₁ is -R ₄ -R ₅ or

ego,

R ₄ is an alkylene group having 1 to 4 carbon atoms, R ₅ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms,

R ₂ is an alkyl group or phenyl group having 1 to 8 carbon atoms,

,

,

,

,

,

,

,

또는

이다. R ₃ is a hydroxy group, a nitro group, or an alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group,

,

,

,

,

,

,

,

or

am.

In the above structure, R ₆ to R ₁₀ are each independently an alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms.

Additionally, the present invention provides a color filter and/or display device manufactured using the above-described colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention includes a non-reactive alkali-soluble resin, two or more different photopolymerizable compounds containing at least one trifunctional or less photopolymerizable compound, and two or more types of oxime ester-based photopolymerization initiators represented by Chemical Formula 6. , by including antioxidants, it has the excellent effect of improving adhesion to prevent line tearing and improving developability to prevent residues from being generated.

Additionally, color filters and display devices manufactured using the colored photosensitive resin composition have excellent driving characteristics.

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

The present invention includes a non-reactive alkali-soluble resin, two or more different photopolymerizable compounds containing at least one trifunctional or less photopolymerizable compound, two or more oxime ester-based photopolymerization initiators represented by Chemical Formula 6, and an antioxidant. By doing so, it provides a colored photosensitive resin composition that has excellent effects in that it improves adhesion to prevent line tearing and improves developability to prevent residues from occurring.

The present invention more specifically relates to a colorant; A non-reactive alkali-soluble resin containing at least one member selected from the group consisting of repeating units of Formulas 1 to 3; Photopolymerizable compounds; photopolymerization initiator; Antioxidants; A photosensitive resin composition containing a solvent,

The colorant is a green colorant, the photopolymerizable compound includes two or more compounds, and includes at least one trifunctional or lower monomer represented by Formula 4, and the photopolymerization initiator is an oxime ester represented by Formula 6. Provided is a colored photosensitive resin composition comprising two or more different types of photopolymerization initiators selected from the group consisting of photopolymerization initiators.

[Formula 1]

[Formula 2]

[Formula 3]

In Formula 3, R is hydrogen or methyl.

[Formula 4]

에서 선택될 수 있으며, In Formula 4, R is each independently

can be selected from,

및

에서 선택되는 1종 일 수 있으며, a는 1~3의 정수이고, b는 0 또는 1~12의 정수일 수 있다. A is a divalent linking group,

and

It may be one type selected from, a is an integer of 1 to 3, and b may be an integer of 0 or 1 to 12.

[Formula 6]

In Formula 6 above,

n is 0 or 1,

이고, R ₁ is -R ₄ -R ₅ or

ego,

R ₄ is an alkylene group having 1 to 4 carbon atoms, R ₅ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms,

R ₂ is an alkyl group or phenyl group having 1 to 8 carbon atoms,

,

,

,

,

,

,

,

또는

일 수 있다. R ₃ is a hydroxy group, a nitro group, or an alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group,

,

,

,

,

,

,

,

or

It can be.

In the above structure, R ₆ to R ₁₀ may each independently be an alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms.

Additionally, the present invention provides a color filter and/or display device manufactured using the above-described colored photosensitive resin composition.

Pigment dispersion composition

coloring agent

The pigment constituting the coloring agent of the present invention is a green coloring agent, and may preferably contain a green pigment. By including the green pigment, it is possible to obtain the effect that pattern tearing does not occur and at the same time, no residue is generated. The pigment constituting the coloring composition of the present invention is characterized by containing a pigment represented by the formula (10), particularly a pigment where M is Zn.

<Formula 10>

In Formula 10, the central metal element M is Zn and Cu, and X1 to X16 are each independently an element selected from the group consisting of H, Cl, and Br.

As a preferred form of the pigment constituting the coloring composition of the present invention, the average number of hydrogen atoms in X is 0 to 2, the average number of Cl elements in X is 0 to 5, and the average number of Br elements in If the representative pigment of Chemical Formula 10 is expressed by color index (C.I.) number, C.I. Green pigments such as Pigment Green 58 can be mentioned.

The pigment contained in the coloring composition of the present invention can be used in combination with not only the zinc halide phthalocyanine pigment, which is the main pigment, but also other green pigments or yellow pigments for color adjustment or complementary color purposes.

As a green pigment that can be used together, if expressed by color index (C.I.) number, for example, C.I. Pigment Green 7, 10, 36, and 37 are used as yellow pigments, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36 :1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147 , 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 199, etc.

A more preferred embodiment is C.I. Pigment Green 58 may be an example of a green pigment, but is not limited thereto.

It is preferable that the particle size of the pigment is sufficiently small for the wavelength of visible light in terms of the absorption coefficient of visible light (adequacy of the spectrum) and transparency. That is, the pigment preferably has an average primary particle size of 10 nm or more and 300 nm or less, especially 10 nm or more and 100 nm or less. Additionally, the primary particle size refers to the diameter of the pigment particle in the smallest unit, and is measured with an electron microscope. The primary particle size of the pigment can be controlled within an appropriate range using a known dispersion device, such as a sand mill, kneader, two-roll, etc.

The content of the colorant in the pigment dispersion composition may be 12 to 16 parts by weight based on the total weight of the pigment dispersion composition.

The colorant is C.I. as a pigment in order to provide a green colored layer with high contrast and brightness. Contains Pigment Green 58. The colorant may be added to the C.I. for color control. Pigment Green 58 can be mixed with other pigments commonly used in the field without departing from the purpose of the present invention. At this time, C.I. Pigment Green 58 and other pigments are preferably mixed at a mass ratio of 40:60 to 80:20, and more preferably, they are mixed at a mass ratio of 60:40 to 70:30. When the mass ratio between C.I. Pigment Green 58 and other pigments is within the above range, high contrast and brightness can be obtained. The above C.I. Pigments other than Pigment Green 58 include C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Green 7, C.I. At least one selected from Pigment Green 36 and the like can be preferably used, and among these, Pigment Yellow 139 and C.I. It is more preferable to use at least one type selected from Pigment Yellow 150 in terms of improving brightness and contrast characteristics.

The content of the colorant is usually in the range of 5 to 60% by mass, preferably 5 to 55% by mass, and more preferably 5 to 30% by mass, based on the total weight of solids in the colored photosensitive resin composition. When the content of the colorant is within the above range, the color density of the pixel is sufficient even when a thin film is formed, and the missingness of the non-pixel portion is not reduced during development, so no residue is generated, which is preferable. In the present invention, the solid content in the colored photosensitive composition for a green colored layer means the total of the components from which the solvent has been removed.

pigment dispersant

As the pigment dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and polyacrylic-based surfactants may be mentioned, and these may be used alone or in combination of two or more types. You can use it. It is preferable to use an acrylic block copolymer as the dispersant, but it is not necessarily limited thereto, and any known dispersant can be used.

It is more preferable that the acrylic block copolymer contains a nitrogen atom. The acrylic block copolymer includes at least one of an X-Y block copolymer and a Y-X-Y block copolymer consisting of an It is desirable to select and use it.

The X block may contain either a quaternary ammonium base or an amino group, or both may be included. The solubility of the quaternary ammonium base in a low polarity solvent is low, and the solubility of the amino group is high. Therefore, when a lot of low polarity solvents are used in the resist, the quaternary ammonium base in the and amino groups.

There is no particular limitation as long as the Y block does not have a quaternary ammonium base or an amino group and is made of a monomer that can be copolymerized with the above monomer. The Y block is a solventophilic site that does not have a nitrogen atom-containing functional group that serves as a pigment adsorbent, and has affinity for the solvent, so it has the function of stabilizing the pigment adsorbed on the dispersant in the solvent.

The amine value of the acrylic block copolymer is 1 to 150 mgKOH/g, preferably 10 to 100 mgKOH/g, and the acid value is 1 to 100 mgKOH/g, preferably 1 to 80 mgKOH/g or less.

The molecular weight of the acrylic block copolymer is 1,000 to 100,000 or less, preferably 3,000 to 30,000 or less, in terms of polystyrene conversion weight average molecular weight (Mw) measured by GPC. If the molecular weight is too small, dispersion stability tends to decrease, and if the molecular weight is too large, developability and resolution tend to decrease.

The acrylic block copolymer may be included in an amount of 2.5 to 3.0 parts by mass based on the total weight of the pigment dispersion composition. When contained within the above range, the dispersibility of the pigment dispersion composition containing the acrylic block copolymer is excellent, improving storage stability, lowering the viscosity, improving the optical properties of the optical element containing the pigment dispersion composition, and improving the optical properties of the pigment dispersion composition containing the acrylic block copolymer at an appropriate level. Sensitivity and patterns can be formed, and voltage maintenance, an electrical characteristic, can be greatly improved.

The acrylate-based dispersant may be 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-2020, DISPER BYK-2025, DISPER BYK-2070 or DISPER BYK. -2150 and the like can be mentioned, and the above acrylate-based dispersants can be used alone or in a mixture of two or more types.

As the dispersant, in addition to the acrylic block copolymer and the acrylate-based dispersant, other resin types of dispersants may be used. Examples of the other resin-type dispersants include known resin-type dispersants, especially polyurethanes, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partial) amine salts of polycarboxylic acids. , ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and their modification products, or free carboxyl groups. oily dispersants such as amides or salts thereof formed by the reaction of polyester with poly(lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, or polyvinyl pyrrolidone; Polyester; modified polyacrylate; Adduct of ethylene oxide/propylene oxide; and phosphate ester.

Commercially available products of the above-mentioned other resin types of dispersants include, for example, BYK Chemistry's product names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK as a cationic resin dispersant. -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184, DISPER BYK-2000; BASF's product 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; Brand names from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's product names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto's product names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Product names of Kyoeisha Chemical Co., Ltd.: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. are mentioned.

The dispersants of the different resin types can be used alone or in combination of two or more, and can be used in combination with the acrylate-based dispersant.

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 Alkylaryl sulfonates, such as sodium dodecylnaphthalenesulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, Examples include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

In addition, the above dispersants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethylene imines, etc. can be used.

dispersion solvent

The dispersion solvent is not particularly limited and various organic solvents used in the field can be used. Specific examples 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 dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol. Diethylene glycol dialkyl ethers such as dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene Alkylene glycol alkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone, Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; ethyl 3-ethoxypropionate, 3-methyl Ester, such as methyl toxypropionate, and cyclic ester, such as γ-butyrolactone, are mentioned. Preferably, esters such as alkylene glycol alkyl ether acetate, ketone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether acetate or propylene glycol mono. Ethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, or methyl 3-methoxypropionate can be used.

The above dispersion solvents can be used individually or in combination of two or more types.

The dispersion solvent may be included in an amount of 75 to 85 parts by weight based on the total weight of the pigment dispersion composition. When the above-mentioned range is satisfied, it is preferable because the storage stability of the pigment dispersion composition can be excellent.

dispersion resin

The dispersion resin acts as a dispersion medium for the pigment and can be added selectively, and it is possible to produce a better pigment dispersion composition by mixing the dispersion resins compared to using the dispersant alone. In the case of a dispersion resin, it can be used without limitation as long as it can function as a dispersion medium. However, considering the developability of the colored photosensitive resin composition prepared from the pigment dispersion composition, it is preferable that it has an acid value in order to have solubility in an alkaline developer.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

In the case of a dispersion resin with an acid value, it can be produced by copolymerizing compound (b1), which has a carboxyl group and an unsaturated bond, and compound (b2), which has an unsaturated bond that can be copolymerized with compound (b1). Specific examples of the compound (b1) having a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Examples include polymer mono(meth)acrylates having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, with acrylic acid and methacrylic acid being preferred. The compounds exemplified by the above compound (b1) can be used individually or in combination of two or more types. Specific examples of compound (b2) having an unsaturated bond capable of copolymerization with compound (b1) are as follows, but are not necessarily limited thereto. Styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl Aromatic vinyl compounds such as benzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinylbenzyl 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 or t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl(meth)acrylate, 2- Alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate or isobornyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate or benzyl (meth)acrylate; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide;

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane or 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. unsaturated oxetane compounds, etc.

The compounds exemplified by the above compound (b2) can be used individually or in combination of two or more types.

The dispersion resin may be included in an amount of 2.5 to 3.0 parts by weight based on the total weight of the pigment dispersion composition. When the above range is satisfied, it is preferable in that an excellently atomized pigment dispersion composition can be obtained.

Alkali soluble resin

The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention may be a non-reactive alkali-soluble resin containing one or more types selected from the repeating units of the following formulas 1 to 3. It is preferable that the alkali-soluble resin of the present invention is a non-reactive alkali-soluble resin containing at least one type selected from the repeating units of the above-described formulas 1 to 3 because it can provide a highly reliable composition with better solvent resistance.

[Formula 1]

[Formula 2]

[Formula 3]

In Formula 3, R is hydrogen or methyl.

In Formula 3, R is hydrogen or methyl.

Alkali-soluble resins containing repeating units of Formulas 1 to 3 include, for example, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxytricyclo[ It can be prepared by copolymerizing one or more monomers selected from 5.2.1.02.6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02.6]decan-9-yl acrylate. The repeating units of Formulas 1 to 3 are preferably contained in an amount of 5 to 40% by weight based on the total weight of the alkali-soluble resin of the present invention. In the present invention, it is also possible to copolymerize by further including other monomers during the copolymerization. At this time, in order to ensure the developability of the resin composition of the present invention, it may be desirable to copolymerize an ethylenically unsaturated monomer having a carboxyl group as the other monomer. Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; etc. can be mentioned. Among these, acrylic acid and methacrylic acid are preferable. When preparing the alkali-soluble resin, polymerization may be performed by adding an unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having the carboxyl group. Specific examples of the copolymerizable unsaturated monomer include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, aromatic vinyl compounds such as m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; 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]decan-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; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. unsaturated oxetane compounds, etc. The above-mentioned monomers can be used individually or in combination of two or more types, but are not necessarily limited to these.

The alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH/g in order to ensure developability of the colored photosensitive resin composition. If the acid value of the alkali-soluble resin is less than 30 mgKOH/g, it is difficult for the colored photosensitive resin composition to secure a sufficient development speed. On the other hand, if it exceeds 150 mgKOH/g, adhesion to the substrate is reduced and short circuiting of the pattern is likely to occur.

The alkali-soluble resin is preferably contained in an amount of 10 to 80% by weight, and more preferably in an amount of 10 to 70% by weight, based on the total weight of solids in the colored photosensitive resin composition. If the content of the alkali-soluble resin is within the range of 10 to 80% by weight based on the above standard, the solubility in the developer is sufficient so that pattern formation is easy, and film reduction in the pixel portion of the exposed area is prevented during development, thereby reducing the thickness of the non-pixel portion. This is desirable because the omission property becomes good.

photopolymerizability compound

The photopolymerizable compound contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and the present invention may include two or more types of photopolymerizable compounds, and have at least one chemical formula. It is characterized by containing a trifunctional monomer represented by 4. Photopolymerizable compounds other than the trifunctional monomer represented by Chemical Formula 4 included in the colored photosensitive resin composition of the present invention are not limited thereto, and may include monofunctional monomers, difunctional monomers, and other multifunctional monomers.

[Formula 4]

에서 선택될 수 있으며, In Formula 4, R is each independently

can be selected from,

및

에서 선택되는 1종 일 수 있으며, a는 1~3의 정수이고, b는 0 또는 1~12의 정수일 수 있다. A is a divalent linking group,

and

It may be one type selected from, a is an integer of 1 to 3, and b may be an integer of 0 or 1 to 12.

The compound represented by Formula 4 is preferably selected from the compounds represented by Formula 4-1 below.

[Formula 4-1]

Specific examples of other monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl. Pyrrolidone, etc. can be mentioned. Specific examples of bifunctional monomers include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, etc. can be mentioned. Among these, polyfunctional monomers having two or more functions are preferably used. The photopolymerizable compound is usually used in a mass fraction of 5 to 50% by mass, preferably 7 to 45% by mass, based on the solid content in the colored photosensitive resin composition. When the photopolymerizable compound is contained within the above-mentioned range, it is preferable because the strength and smoothness of the pixel portion tend to be good.

light curing initiator

The colored photosensitive resin composition of the present invention may contain two or more different types selected from the group consisting of oxime ester-based photopolymerization initiators represented by Chemical Formula 6,

The above initiator combination can be done by mixing two or more different types of oxime ester photopolymerization initiators in a ratio of 1:9 to 9:1, with a more preferred range of 3:7 to 7:3. It can be.

In Formula 6 above,

n is 0 or 1,

이고, R ₁ is -R ₄ -R ₅ or

ego,

R ₄ is an alkylene group having 1 to 4 carbon atoms, R ₅ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms,

R ₂ is an alkyl group or phenyl group having 1 to 8 carbon atoms,

,

,

,

,

,

,

,

또는

이다. R ₃ is a hydroxy group, a nitro group, or an alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group,

,

,

,

,

,

,

,

or

am.

In the above structure, R ₆ to R ₁₀ may each independently be an alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms.

When the composition of the present invention includes the oxime ester-based photopolymerization initiator of the formula (6), it can exhibit better adhesion, and is especially preferable because this effect can be provided even when the colorant of the present invention is used.

Specific examples of the oxime ester-based photopolymerization initiator of Formula 6 include 1,2-Octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) ( 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)), and 1-[4-(phenylthio)phenyl)]-3-cyclohexyl-propane-1,2-dione-2 -(O-acetyloxime) (1-[4-(phenylthio)phenyl)]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime)), etc., and commercially available products include Tron Examples include, but are not limited to, Nyssa's PBG-329, PBG-327, and PBG-305, and Adeka's NCI-831.

More preferred examples include compounds represented by the following formulas 7 and 8, but are not limited thereto.

<Formula 7>

<Formula 8>

The oxime ester-based photopolymerization initiator of Formula 6 is preferably included in an amount of 10 to 100% by weight, and more preferably in an amount of 20 to 100% by weight, based on the total weight of the photopolymerization initiator. When the content of the oxime ester-based photopolymerization initiator is included within the above-mentioned range, the problem of reduced sensitivity caused by the colorant can be improved, and the short circuit phenomenon of the pattern during the development process can be improved. In addition, the composition of the present invention may further include a photopolymerization initiator other than the oxime ester-based photopolymerization initiator of Formula 6, within a range that does not impair the effect of the present invention. Representative examples of the other photopolymerization initiators include acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, and thioxanthone-based compounds, and one or more compounds selected from these may be used. You can. Specific examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2- Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-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, etc. Specific examples of the benzophenone-based compounds include benzophenone, 0-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone. Specific examples of the triazine-based compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-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-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl) and methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine. Specific examples of the biimidazole-based compounds include 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)bi Imidazole, 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 an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group, etc. there is. Among these, 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 are preferred. can be used Specific examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. can be mentioned.

The photopolymerization initiator is preferably contained in an amount of 0.1 to 40% by weight, and more preferably in an amount of 1 to 10% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention. When the content of the photopolymerization initiator is included within the above-mentioned range, the coloring photosensitive resin composition becomes highly sensitive and the exposure time is shortened, thereby improving productivity and maintaining high resolution. Additionally, the strength of the pixel portion and the smoothness on the surface of the pixel portion can be improved.

In addition, the photopolymerization initiator may further include a photopolymerization initiator in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. By containing a photopolymerization initiation auxiliary agent, the colored photosensitive resin composition according to the present invention can further increase sensitivity and improve productivity. As the photopolymerization initiation aid, for example, one or more compounds selected from amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds may be preferably used. As the amine compound, it is preferable to use an aromatic amine compound, specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) ), 4,4'-bis(diethylamino)benzophenone, etc. The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenylthioacetic acid. Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned. The polyfunctional thiol compounds include Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylopropane Tris-3- Trimethylolpropane tris -3-mercaptopropionate), Pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate (Dipentaerythritol hexa-3-mercaptopropionate), etc. When using the photopolymerization initiation aid, the photopolymerization initiation aid is preferably contained in an amount of 0.01 to 20% by weight, and more preferably in an amount of 0.1 to 10% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention. do. When the content is within the range of 0.01 to 20% by weight based on the above-mentioned standards, the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter formed using the composition is improved.

antioxidant

The present invention can achieve the effect of reducing the occurrence of reverse taper by including an antioxidant. Examples of the antioxidants generally include 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-sec-butylphenol, 2,6- Di-sec-butylphenol, 2,4-di-sec-butylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2,4-diisopropylphenol, 2-t-octylphenol, 2 ,6-di-t-octylphenol, 2,4-di-t-octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol, 2,4-dicyclopentylphenol, 2-t-butyl -p-cresol, 2,6-di-t-amylphenol, 2,4-di-t-amylphenol, 6-t-butyl-o-cresol, 2,6-di-t-dodecylphenol , 2,4-di-t-dodecylphenol, 2-sec-butyl-p-cresol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 6-sec- Butyl-o-cresol, 2-t-octyl-p-cresol, 2-t-dodecyl-p-cresol, 2-t-butyl-6-isopropylphenol, 6-t-octyl-o- Cresol, 6-t-dodecyl-o-cresol, 4,4'-butyridenebis(3-methyl-6-t-butylphenol), octadecyl-3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate, 4,4'-butyridenebis(6-tetra-butyl-3-methylphenol), 4,4'-thio-bis(3-methyl-6-t- butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis-[3-(3,5 -di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-ethylphenol, 2, 2'-methylenebis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5- tris(4-hydroxybenzyl)benzene and tetrakis[methylene-3-(3,5'-di-t-butyl-4'-hydroxyphenylpropionate)]methane, etc., and these are one type. Or, two or more types can be used.

More preferably, as the antioxidant (D), an antioxidant represented by the following formula (9) is more preferable in terms of brightness or straightness.

<Formula 9>

The antioxidant is preferably contained in an amount of 0.1 to 2.5% by weight, and more preferably in an amount of 0.25 to 1% by weight, based on the total weight of solids in the composition. When the content of the antioxidant is contained within the above-mentioned range, the occurrence of reverse taper can be reduced and excellent solvent resistance can be achieved.

Solvent (E)

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited as long as the colored photosensitive resin composition of the present invention has an appropriate viscosity and can easily dissolve the remaining components, and various organic solvents used in the field of colored photosensitive resin compositions are used. Solvents can be used.

Specific examples of the solvent 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; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as γ-butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100°C to 200°C are preferred in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy. Examples include esters such as ethyl propionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and cyclohexanone, 3-ethyl ether. Ethyl toxypropionate, methyl 3-methoxypropionate, etc. are mentioned.

The above solvents can be used individually or in combination of two or more.

The content of the solvent in the colored photosensitive resin composition of the present invention may be 50 to 90% by mass, preferably 55 to 80% by mass, based on the total amount of the colored photosensitive resin composition containing it. When the solvent is contained within the above-mentioned range, the applicability tends to improve when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), or inkjet. desirable.

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of colored photosensitive resin compositions can be used. Specific examples 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 dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol Alkylene glycol alkyl ether acetates such as mono ethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone, and acetone. , Ketones such as methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, and 3-methoxy Ester, such as methyl propionate, and cyclic ester, such as γ-butyrolactone, are mentioned. Among the above solvents, organic solvents having a boiling point of 100°C to 200°C are preferred in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy. Examples include esters such as ethyl propionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3- Methyl methoxypropionate, etc. can be mentioned. These solvents (E) can be used individually or in mixture of two or more types.

additive

The ink composition may further include a nonionic, anionic, or cationic dispersant as needed to improve the dispersibility of the pigment.

The dispersant includes polyalkylene glycol and its esters, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylic acid salt, alkyl Amide alkylene oxide adducts, alkylamines, etc. may be added alone or in combination of two or more types. The dispersant may be included in an amount of 10 to 20 parts by weight based on 100 parts by weight of the pigment. In addition, the ink composition may further include, if necessary, a coating improver such as silicone-based or fluorine-based to improve coating properties and anti-foaming properties, or an adhesion improver to improve adhesion to the substrate. The coating improver and adhesion improver may be included in an amount of 0.01 to 1% by weight based on the total amount of the photosensitive resin composition. In addition, in order to prevent stains or spots during application and to prevent the creation of residues due to leveling properties or undeveloped, an epoxy compound; malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agent having a vinyl group or (meth)acryloxy group; leveling agent; Fluorine-based surfactant; Other additives such as radical polymerization initiators may be further included. The amount of these additives used can be easily adjusted depending on the desired physical properties.

Examples of the epoxy compound include phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, cycloaliphatic epoxy resin, ortho-cresol novolak resin. The epoxy compound may be 0.01 to 10% by weight based on the total content of the photosensitive resin composition for the color filter protective film. When the content of the epoxy compound is within the above range, storage properties and process margins are excellent.

Specific examples of the silane-based coupling agent include vinyl trimethoxysilane, vinyl tris (2-methoxyethoxysilane), 3-glycidoxypropyl trimethoxysilane, and 2-(3,4-epoxy cyclohexyl). Examples include ethyl trimethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-mercaptopropyl trimethoxysilane. The silane-based coupling agent may be 0.01 to 2% by weight based on the total content of the photosensitive resin composition for the color filter protective film. When the content of the silane-based coupling agent is within the above range, adhesion, storage stability, and coating properties are excellent.

color filter

In order to achieve another object of the present invention, the present invention provides a color filter comprising a color layer formed by applying the colored photosensitive resin composition according to the present invention on a substrate and exposing and developing it in a predetermined pattern. to provide. The color filter of the present invention includes a substrate and a colored pattern made with the colored photosensitive resin composition of the present invention on the substrate. The substrate is a transparent material, and a material having sufficient strength and support for the stability of the color filter can be used. Preferably, glass with excellent chemical stability and high strength can be used. That is, the present invention provides a color filter including a colored pattern manufactured with the colored photosensitive resin composition of the present invention, and the manufacturing method of the color filter may use a conventional method well known in the art. Additionally, the present invention includes a liquid crystal display device including the color filter. The liquid crystal display device includes a configuration known to those skilled in the art except that it includes the color filter, and can be manufactured by a conventional method. That is, the present invention includes a liquid crystal display device to which the color filter of the present invention can be applied. Hereinafter, the present invention will be described in more detail using examples. However, the following examples are for illustrating the present invention, and the present invention is not limited by the following examples, and may be variously modified and changed within the scope of the present invention. The scope of the present invention will be determined by the technical spirit of the claims described later.

Example and Comparative example

Synthesis example 1: Alkali-soluble resin synthesis

< Synthesis example 1>

120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 5 parts by weight of Azobisisobutyronitrile (AIBN), and 10.0 parts by weight of methacrylic acid in a flask equipped with a stirrer, thermometer reflux cooling pipe, dropping lot, and nitrogen introduction pipe. , a mixture of 3,4-epoxytricyclo[5.2.1.02.6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02.6]decan-9-yl acrylate (content ratio is 90 parts by weight (molar ratio 50:50) were added and replaced with nitrogen. Afterwards, the temperature of the reaction solution was raised to 85°C by stirring, and the reaction was continued for 6 hours. The solid acid value of the alkali-soluble resin synthesized in this way was 110 mgKOH/g, and the weight average molecular weight Mw measured by GPC was 8,100.

< Synthesis example 2>

180 parts by weight of propylene glycol monomethyl ether, 5 parts by weight of Azobisisobutyronitrile (AIBN), 10.0 parts by weight of methacrylic acid, and 3,4-epoxytricyclo[5.2] were added to a flask equipped with a stirrer, thermometer reflux cooling pipe, dropping funnel, and nitrogen introduction pipe. Add 90 parts by weight of a mixture of .1.02.6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02.6]decan-9-yl acrylate (content ratio is 50:50 in molar ratio). and nitrogen substitution. Afterwards, the temperature of the reaction solution was raised to 85°C by stirring, and the reaction was continued for 6 hours. The solid acid value of the alkali-soluble resin synthesized in this way was 80 mgKOH/g, and the weight average molecular weight Mw measured by GPC was 9,100.

< Synthesis example 3>

In a four-necked flask equipped with a dropping funnel, thermometer, cooling tube, and stirrer, 37.5 g of methacrylic acid (manufactured by Kyoeisha), 19.0 g of methyl methacrylate (manufactured by Kyoei), and 2,5-dihydrofuran (manufactured by TCI). 9.1 g of product) and 225.0 g of propylene glycol methyl ether (manufactured by TCI) were added, and the inside of the four-necked flask was replaced with nitrogen. Next, the flask was heated to 70°C, and then 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 9.1 g of 2,5-dihydrofuran, 225.0 g of propylene glycol methyl ether, and 2,2'-azobisisobutyrate were added. 3.2 g of nitrile (manufactured by Wako) mixed solution was slowly added dropwise over 1 hour. After polymerization for 8 hours, the result was left to cool to room temperature, the inside of the four-necked flask was replaced with nitrogen, and then 61.5 g of glycidyl methacrylate (manufactured by Mitsubishi Rayon) and tetra-n-butylammonium bromide (manufactured by TCI) were added to the flask. 3.6 g and 0.15 g of methoquinone (product of Junsei) were added and the reaction was carried out at 80°C for 12 hours to add glycidyl methacrylate (GMA) to the carboxyl group of the copolymer to produce binder resin B-8. got it The weight average molecular weight of binder resin B-8 measured by GPC was 17,000.

Manufacturing example 1: Preparation of colorant dispersion 1

14 parts by weight of CI Pigment Green 58 as a colorant, Acrylic dispersant [Disperbyk (registered trademark) 2000; Manufactured by Big Chemistry] 2.8 parts by weight, 2.9 parts by weight of the resin prepared in Synthesis Example 1, 80 parts by weight of the solvent propylene glycol monomethyl ether acetate, along with 360 parts by weight of zirconia beads with a diameter of 0.2 mm, were added to a 140 ml mayonnaise bottle and mixed with a paint conditioner at 60°C for 10 hours to perform dispersion treatment. Afterwards, the zirconia beads were removed and a dispersion was obtained. The dispersion was filtered through a membrane filter with a pore size of 1.0 μm to obtain colorant dispersion 1.

Example

Below, the present invention will be described in more detail based on examples. However, the embodiments of the present invention disclosed below are merely examples and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and further includes all changes within the scope and meaning equivalent to the record of the claims. Hereinafter, the present invention will be described in more detail by way of examples, but of course, the present invention is not limited by the examples. In addition, in the following examples and comparative examples, “%” and “part” indicating content are based on mass unless otherwise specified.

[Table 1] (Unit: parts by weight)

Alkali-soluble resin (A1): non-reactive resin obtained through the preparation of Synthesis Example 1 above.

Alkali-soluble resin (A2): non-reactive resin obtained through the preparation of Synthesis Example 2 above.

Alkali-soluble resin (A3): reactive resin obtained through preparation of Synthesis Example 3 above.

Photopolymerizable compound (B1): Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerizable compound (B2): A-TMPT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

Photopolymerization initiator (C1): NCI-831 (manufactured by ADEKA)

Photopolymerization initiator (C2): Irgacure®OXE01 (manufactured by BASF)

Photopolymerization initiator (C3): Irgacure® 907 (manufactured by BASF)

Photopolymerization initiator (C4): Irgacure® 369 (manufactured by BASF)

Antioxidant (D1): Sumilizer GP (Sumitomo Chemical Co., Ltd.)

Antioxidant (D2): AO-80 (ADEKA CORPORATION)

Solvent (E): Propylene glycol monomethyl ether acetate (PGMEA)

Additive (F): SH-8400 (Dow Corning)

Colorant dispersion (G): Pigment dispersion composition of Preparation Example 1

Experiment example One.

The physical properties of the colored photosensitive resin compositions prepared in the examples and comparative examples were measured by the following method, and the results are shown in Table 2 below.

(One) Developability ( Residue characteristics )

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were applied to 5 Х 5 cm glass, dried, and bar coated to a thickness of 2.5 ㎛. Afterwards, the solvent was removed by drying in an oven at 100°C for 3 minutes, and then the distance from the photo mask was set to 300㎛, and the color filter was manufactured by exposing the fusion lamp to an integrated light amount of 40mJ at a wavelength of 313nm.

The color filters were immersed in a KOH aqueous solution of pH 14 for 3 minutes and then taken out. Then, they were again immersed in distilled water for 1 minute and taken out. The color filters were observed for the presence and amount of residues that were not washed away in the area to be developed. If there were no residues, it was evaluated as good, and if there were residues, it was evaluated as bad.

(2) Pattern tearing evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were applied to 5 Х 5 cm glass, dried, and then bar coated to a thickness of 2.5 ㎛. Afterwards, the solvent was removed by drying in an oven at 100°C for 3 minutes, and then the distance from the photo mask was set to 300㎛, and the color filter was manufactured by exposing the fusion lamp to an integrated light amount of 40mJ at a wavelength of 313nm.

The color filters were immersed in a KOH aqueous solution at pH 14 for 3 minutes and then taken out. Then, they were again immersed in distilled water for 1 minute and cured in an oven at 150°C for 20 minutes to measure the degree of pattern tearing of the color filters.

The evaluation criteria for pattern tearing were as follows.

<Pattern tear evaluation criteria>

○: No pattern tearing,

△: 1 to 3 pattern tears,

×: 4 or more pattern tears

(3) Solvent resistance evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were applied to 5 Х 5 cm glass, dried, and then bar coated to a thickness of 2.5 ㎛. After drying in an oven at 100°C for 3 minutes to remove the solvent, the gap between the photomask was set to 300㎛, exposure was made to an integrated light amount of 40mJ at a wavelength of 313nm from the fusion lamp, and cured in an oven at 150°C for 20 minutes to prepare a color filter. .

The color filter was immersed in an NMP solution at room temperature for 30 minutes, then washed with ultrapure water and dried on a hot plate heated to 120°C for 2 minutes, and then the chromaticity before and after immersion was measured.

The equation used at this time is calculated by Equation 1 below, which represents the color change in a three-dimensional colorimeter defined by L*, a*, and b*. The smaller the color change value, the more highly reliable a color filter can be manufactured.

[Equation 1]

△Eab* = [(△L*)2+(△a*)2+(△b*)2]1/2

The evaluation criteria for solvent resistance were as follows.

○: 0 < △Eab* < 1.5

△: 1.5 ≤ △Eab* < 2.0

×: 2.0 ≤ △Eab*

[Table 2]

In the case of Examples 1 to 5, which include all the components of the present invention, developability (residue) was good, there was almost no pattern tearing, so it was confirmed that adhesion was improved, and it was confirmed that reliability was improved due to excellent solvent resistance. On the other hand, it was confirmed that Comparative Examples 1 to 6, which do not include all of the components of the present invention, were significantly poor in any one or more of the developability, pattern tearing, and solvent resistance evaluations. In particular, in the case of Comparative Example 6, which did not contain an antioxidant, there was no problem with developability, but it was confirmed that pattern tearing and solvent resistance were significantly reduced.

Claims (6)

coloring agent;
A non-reactive alkali-soluble resin containing at least one member selected from the group consisting of repeating units of Formulas 1 to 3;
Photopolymerizable compounds;
photopolymerization initiator;
Antioxidants; and
A photosensitive resin composition containing a solvent,
The colorant is a green colorant,
The photopolymerizable compound includes two or more types of compounds, and includes at least one trifunctional or lower monomer represented by Formula 4,
The photopolymerization initiator includes two or more different types selected from the group consisting of oxime ester-based photopolymerization initiators represented by Formula 6,
The oxime ester-based photopolymerization initiator represented by Formula 6 is 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), and 1-[4-(phenylthio) ) phenyl)] -3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), a colored photosensitive resin composition comprising two or more species selected from the group consisting of.
[Formula 1]

[Formula 2]

[Formula 3]

(In Formula 3, R is hydrogen or methyl.)
[Formula 4]

(In Formula 4, R is each independently

can be selected from,
A is a divalent linking group,

and

is selected from,
a is an integer from 1 to 3,
b is 0 or an integer from 1 to 12. )
[Formula 6]

(In Formula 6 above,
n is 0 or 1,
R ₁ is -R ₄ -R ₅ or

ego,
R ₄ is an alkylene group having 1 to 4 carbon atoms, R ₅ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms,
R ₂ is an alkyl group or phenyl group having 1 to 8 carbon atoms,
R ₃ is a hydroxy group, a nitro group, or an alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group,

,

,

,

,

,

,

,

or

am.
In the above structure, R ₆ to R ₁₀ are each independently an alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms. ) In claim 1,
A colored photosensitive resin composition wherein the green colorant includes a green pigment. delete In claim 1,
Regarding the total weight of solids in the composition
5 to 60% by weight of colorant,
10 to 80% by weight of an alkali-soluble resin containing at least one member selected from the group consisting of repeating units of Formulas 1 to 3,
5 to 45% by weight of a photopolymerizable compound;
0.1 to 40% by weight of photopolymerization initiator;
Antioxidant 0.1 to 5% by weight; and
A colored photosensitive resin composition comprising 50 to 90% by weight of a solvent based on the total weight of the composition. A color filter manufactured using the colored photosensitive resin composition of any one of claims 1, 2, and 4. A liquid crystal display device including the color filter of claim 5.