TWI675254B - Blue photosensitive resin composition, blue color filter and display device having the same - Google Patents

Abstract

The present invention relates to a blue photosensitive resin composition, a blue filter, and a display device having the blue filter. The blue photosensitive resin composition includes a blue colorant, an alkali-soluble resin, and a photopolymerizable compound. , A photopolymerization initiator and a solvent, wherein the content of the alkali-soluble resin is 20% to 80% by weight based on the total weight of the solids of the blue photosensitive resin composition; based on the total weight of the alkali-soluble resin, the alkali-soluble resin includes 40% to 100% by weight of an alkali-soluble resin having a molecular weight of 15,000 or more; the photopolymerization initiator includes an oxime ester compound; and, based on the total weight of the solvent, the solvent includes a boiling point of more than 0% by weight and not more than 8% by weight A solvent of 180 ° C or higher.

Description

Blue photosensitive resin composition, blue filter, and display device having the same [Cross Reference of Related Applications]

This application claims the rights of Korean patent application KR 10-2014-0028436 filed on March 11, 2014 and Korean patent application KR 10-2015-0026937 filed on February 26, 2015, which are incorporated by reference in their entirety. Into this application.

The present invention relates to a blue photosensitive resin composition, a blue filter, and a display device having the blue filter.

Filters are widely used in imaging devices, liquid crystal display devices (LCD), and the like, and their applications are rapidly expanding. The color filters used in color liquid crystal display devices or imaging devices are manufactured in such a manner that each color repeats a series of procedures to form pixels corresponding to each color. The series of procedures includes: The colored photosensitive resin composition of each of the green, blue, and blue pigments is evenly coated on a substrate patterned by a black matrix; it is dried with heat (hereinafter also referred to as "pre-baking") to form a paint film, Then subject the paint film to photographic exposure (photo-exposure) and development; and optionally further performing heating (hereinafter also referred to as "post-baking"). Similarly, the patterned black matrix usually forms a black photosensitive resin composition.

A composition containing a photopolymerizable compound and a photopolymerization initiator together with a pigment and a binder resin are widely used for coloring a photosensitive resin composition. Recently, the content of the coloring material of the display panel and the thickness of the paint film have continuously increased, reflecting the trend of high quality with high color reproduction and the expansion of the use of imaging devices, liquid crystal display devices, and the like.

However, in particular, as the paint film is thickened, the colored photosensitive resin composition that provides blue pixels often causes pattern defects; and the problem of pattern flatness of the manufactured color filter continuously occurs. When the pattern flatness problem occurs, the color coordinates in one pixel are not equal, and therefore a visibility problem occurs, and it is difficult to manufacture a high-quality display device.

Therefore, research is needed to solve the above problems.

Patent Document 1: Korean Patent Application Publication No. 10-2010-0051395A.

Therefore, in order to solve the above problems, an object of the present invention is to provide a blue photosensitive resin composition that can maintain a constant color coordinate in one pixel by maintaining flatness, and there is no pattern even in a thickened pattern Shortage.

Furthermore, another object of the present invention is to provide a high-quality display device using a blue photosensitive resin composition.

In order to achieve the above object, the present invention provides a blue photosensitive resin composition including: a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the blue photosensitive resin composition is based on The total solid weight of the product, the content of the alkali-soluble resin is 20% to 80% by weight; based on the total weight of the alkali-soluble resin, the alkali-soluble resin includes 40% to 100% by weight of the alkali-soluble resin with a molecular weight of 15,000 or higher ; The photopolymerization initiator includes a compound represented by the following Chemical Formula 1; and, based on the total weight of the solvent, the solvent includes more than 0% by weight and not more than 8% by weight of a solvent having a boiling point of 180 ° C or higher,

Wherein R _{1 is} represented by the following chemical formula 2, R ₂ is a C1 to C8 alkyl group, a phenyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, R ₃ is a diphenyl sulfide group, and [Chemical Formula 2] -R ₄ -R ₅

R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group, a C3 to C8 cycloalkyl group, or a C6 to C8 aromatic hydrocarbon.

Further, the present invention provides a blue filter including a blue photosensitive resin composition.

Further, the present invention provides a display device including a blue filter.

The blue photosensitive resin composition according to the present invention does not cause a shortage of a pattern in a blue pattern having a low content of a colorant, and has an effect of improving the flatness, and therefore can be used for manufacturing a color that can be obtained in one pixel Color filters with constant coordinates.

Therefore, it has the effect of providing a color filter without the problem of sharpness.

Hereinafter, the configuration and operation of the present invention will be described in detail.

The invention relates to a blue photosensitive resin composition, which includes a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the total weight of the blue photosensitive resin composition is based on the total solids of the blue photosensitive resin composition. The content of the alkali-soluble resin is 20% to 80% by weight; wherein, based on the total weight of the alkali-soluble resin, the alkali-soluble resin includes 40% to 100% by weight of the alkali-soluble resin having a molecular weight of 15,000 or more; The photopolymerization initiator includes a compound represented by the following Chemical Formula 1; and wherein the solvent includes more than 0% by weight and not more than 8% by weight of a solvent having a boiling point of 180 ° C. or more, based on the total weight of the solvent,

Wherein R _{1 is} represented by the following chemical formula 2, R ₂ is a C1 to C8 alkyl group, a phenyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, R ₃ is a diphenyl sulfide group, and [Chemical Formula 2] -R ₄ -R ₅

R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group, a C3 to C8 cycloalkyl group, or a C6 to C8 aromatic hydrocarbon.

Generally, a color filter containing a colored photosensitive resin composition is prepared through steps of coating, vacuum drying, soft baking, photographic exposure, development, and hard baking. In order to ensure the flatness of the color filter, it is important to minimize the fluidity of the coating film in the soft baking and hard baking steps. It is especially important to ensure the flatness of the pattern in the soft baking step, because if the flatness of the pattern cannot be ensured in the soft baking step, it displays to the last color filter produced, and thus produces unevenness in one pixel Color coordinates.

In the present invention, based on the total weight of the alkali-soluble resin, an alkali-soluble resin having a molecular weight of 15,000 or more is used in an amount of 40% to 100% by weight, and thereby the fluidity of the paint film can be suppressed in the soft baking step, so that The pattern flatness is obtained, and thus a blue filter that can achieve a constant color coordinate in one pixel can be prepared.

However, based on the total weight of the alkali-soluble resin, if the amount of the alkali-soluble resin having a molecular weight of 15,000 or more is less than 40% by weight, the fluidity of the paint film is improved in the soft baking step, and it is difficult to ensure pattern flatness, and therefore It is difficult to achieve constant color coordinates in one pixel.

Further, in the present invention, a solvent having a boiling point of 180 ° C. or higher based on the total weight of the solvent is used in an amount of more than 0% by weight and not more than 8% by weight. Agent to ensure pattern flatness.

If the amount of the solvent exceeds 8% by weight, increasing the amount of the residual solvent makes it possible to improve the fluidity of the paint film in the soft baking step, and thus it is difficult to maintain the pattern flatness.

Hereinafter, the configuration and operation of the present invention will be described in detail.

Blue colorant (A)

The blue colorant includes at least one pigment, at least one dye, or a combination thereof.

The pigment may include an organic pigment or an inorganic pigment generally used in the art. Furthermore, if necessary, it may be treated with a resin, a surface treatment using a pigment derivative that introduces an acidic group or a basic group, a graft treatment of a pigment surface by a polymer compound, or the like, a sulfuric acid atomization method, or the like. Atomization treatment, cleaning treatment using organic solvents, water, etc. to remove impurities, or ionic impurity removal processing, such as ion exchange methods, to treat pigments.

The organic pigment may include a variety of pigments used in printing inks, inkjet inks, and the like, and specific examples thereof may include: water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline Ketone pigments, isoindoline pigments, pyrene pigments, ringtone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone-based pigments, anthracene pigments, anthracene anthraquinone pigments, indanthrone pigments, flavanes Ketone pigments, dermatanthone pigments, diketopyrrolopyrrole pigments, and the like.

Further, the inorganic pigment may include a metal compound such as a metal oxide or a metal complex, and specific examples thereof include: metal oxidation of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony Gold or compound Metal oxides; carbon black; organic black pigments; titanium black; black pigments made by mixing red, green and blue.

In particular, organic pigments and inorganic pigments may specifically include compounds classified as pigments by a color index (published by the Association of Colorists and Colorists), and more specific examples thereof may include, but are not necessarily limited to, the following color index (CI ): CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60 , 64 and 76, and so on.

One or more selected from the group consisting of C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, and C.I. Pigment Blue 15: 6 may be preferably used.

When a pigment is used as the colorant, a pigment having a uniform particle diameter is preferably used. One example of a method of making the particle diameter uniform may be a method of treating a distribution process by adding a pigment dispersant (a2), and according to this method, a pigment dispersion solution having a uniformly dispersed pigment state may be obtained.

Pigment dispersant (a2)

The pigment dispersant is added to de-aggregate the pigment and maintain the stability of the pigment, and specific examples of the pigment dispersant can be surfactants, such as cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants. Agents, polyester-based surfactants, polyamine-based surfactants, etc., which can be used alone or in a combination of two or more.

Specific examples of the cationic surfactant may be an amine salt or a quaternary ammonium salt, and the like, such as stearylamine hydrochloride, lauryltrimethylammonium chloride, and the like.

A specific example of the anionic surfactant may be a higher alcohol sulfate Salts such as sodium lauryl sulfate and sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; and alkylaryl sulfonates such as dodecylbenzenesulfonic acid Sodium and dodecylnaphthalene sulfonate.

Specific examples of the nonionic surfactant may be polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, Sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

In addition, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethylene can be used. Imine and so on.

Further, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as "acrylate dispersant"), including: butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate Ester (DMAEMA).

As such, the acrylate dispersant preferably includes those acrylate dispersants prepared by existing control methods, and commercially available products of the acrylate dispersant may include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK -2150 and so on. Examples of the acrylic dispersant as listed above may be used alone or in a combination of two or more.

In addition to the acrylate dispersant described above, the pigment dispersant may include other resin-based pigment dispersants. Other resin-based pigment dispersants can include: Known resin-based pigment dispersants, especially oily dispersants, such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamines, (partial) amine salts of polycarboxylic acids, Ammonium salts, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxyl-containing polycarboxylic acid esters and modified products thereof, or via polyesters and polymers having free carboxyl groups Ammonium amines or their salts produced by the reaction between (lower alkyleneimines); water-soluble resins or polymer compounds such as (meth) acrylic-styrene copolymers, (meth) acrylic- (methyl) ) Acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinylpyrrolidone; polyesters; modified polyacrylates; ethylene oxide / propylene oxide adducts; and phosphates, etc. .

Commercial products of other resin-based pigment dispersants may include cationic resin dispersants, such as 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 (all are trade names sold by BYK Chemie); 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 (all trade names sold by BASF); SOLSPERS-24000, SOLSPERS-32550, and NBZ-4204 / 10 (all are trade names sold by Lubirzol); HINOACT T-6000, HINOACT T-7000, and HINOACT T-8000 (all trade names sold by Kawaken Fine Chemicals) ; AJISPUR PB-821, AJISPUR PB-822, and AJISPUR PB-823 (all Ajinomoto commercially available under the trade name); FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 (all trade names sold by Kyoeisha Chemical), and the like.

In addition to the above-mentioned acrylate dispersant, examples of other resin-based pigment dispersants are used alone or in combination of two or more kinds, and can be used together with the acrylate dispersant.

The amount of the pigment dispersant is 5 to 60 parts by weight, and preferably 15 to 50 parts by weight based on 100 parts by weight of the solid content of the pigment. If the amount of the dispersant exceeds 60 parts by weight, the viscosity may increase. In contrast, if the amount of the dispersant is less than 5 parts by weight, it is difficult to make the pigment fine or gelation may occur after the dispersion treatment.

Dye (a3)

Any dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye having solubility in an organic solvent and ensuring the solubility in an alkaline developer and having reliability such as heat resistance, solvent resistance, and the like.

The dye may be selected from acid dyes having acidic groups such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, amidine products of acid dyes and derivatives thereof, and may also be selected from azo-type acid dyes , Xanthene acid dyes, phthalocyanine acid dyes and their derivatives.

The dye preferably includes a compound classified as a dye by a color index (published by the Society of Colorists and Colorists), or a known dye disclosed in Dyeing Note (published by Shikisensha).

Specific examples of the dye may include the following C.I. solvent dyes: CI solvent blue 5, 35, 36, 37, 44, 59, 67, and 70; CI solvent violet 8, 9, 13, 14, 36, 37, 47, and 49; among CI solvent dyes, CI is preferably useful Solvent Blue 35, 36, 44, 45, and 70; and CI Solvent Violet 13.

Moreover, examples of CI acid dyes are as follows: CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, and 340; CI Acid Violet 6B, 7, 9, 17, 19, and 66; etc. Among CI acid dyes, preferably CI Acid Blue 80, 90; and CI Acid Purple 60.

Moreover, examples of CI direct dyes include: CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, and 293; CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79 , 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104.

These dyes may be used alone or in a combination of two or more.

The dye amount of the blue colorant is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, and still more preferably 1 to 50% by weight, based on the total weight of the solid content of the blue colorant. When the amount of the additional dye of the colorant falls within the above range of 0.5 to 80% by weight, the problem of deterioration in reliability due to dissolution of the dye in an organic solvent, which occurs after pattern formation, can be prevented, and high sensitivity can be generated degree.

The amount of the blue colorant is set to 5 to 60% by weight, and preferably 10 to 45% by weight based on the total weight of the solid content of the blue photosensitive resin composition. It is desirable that the amount of the colorant is based on the aforementioned 5 to 60% by weight, because the pixel portion has sufficient color density even when forming a thin film, and the non-pixel portion does not fall off during development, making it difficult to generate a residue. .

As used herein, the total solid content of the blue photosensitive resin composition represents the total amount of components of the blue photosensitive resin composition other than the solvent.

Alkali-soluble resin (B)

The alkali-soluble resin of the present invention is characterized by including an alkali-soluble resin having a molecular weight of 15,000 or more based on the total weight of the alkali-soluble resin. The above amount is desirable because it can suppress the fluidity of the paint film in the soft baking step, one of the manufacturing steps of the color filter, can obtain the pattern flatness, and therefore can be prepared to achieve a constant color coordinate in one pixel Blue filter.

In contrast, if the amount is less than 40% by weight, the fluidity of the paint film is improved in the soft baking step, and it is difficult to ensure the flatness of the pattern, and therefore it is difficult to achieve a constant color coordinate in one pixel.

In addition, in order to ensure the compatibility and storage stability of the blue photosensitive resin composition with the dye, the acid value of the alkali-soluble resin is preferably 30 to 150 mgKOH / g. If the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to ensure a sufficient development rate of the blue photosensitive resin composition. On the contrary, if the acid value of the alkali-soluble resin exceeds 150 mgKOH / g, the adhesion to the substrate may decrease, so that it is easy to cause a shortage of patterns and cause compatibility problems with the dye, and thus in the blue photosensitive resin composition The dye may be precipitated or the storage stability of the blue photosensitive resin composition may be deteriorated, thereby increasing the viscosity, which is not desirable.

Further, in order to achieve solubility in an alkaline developing solution used in the developing process when forming a pattern, an alkali-soluble resin is prepared by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group.

Further, in order to add a hydroxyl group to the alkali-soluble resin, (1) an alkali-soluble resin can be prepared by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group, and (2) An alkali-soluble resin can be prepared by additionally reacting a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group with a compound (b3) having a glycidyl group. (3) Alternatively, the resin can be prepared by reacting a copolymer of a carboxyl ethylenically unsaturated monomer (b1) and a hydroxyl ethylenically unsaturated monomer (b2) with a glycidyl compound (b3) additionally. .

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group include: monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and the like; dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid, and the like ; Their dicarboxylic acid anhydrides; mono (meth) acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxy polycaprolactone mono (meth) acrylate and the like. Preferred useful are acrylic acid and methacrylic acid.

Specific examples of the ethylenically unsaturated monomer (b2) having a hydroxyl group include: hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylpropenamide, and the like.

Specific examples of the monomer (b3) having a glycidyl group include: butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl Methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-tert-butyl benzoate, glycidyl stearate, aromatic Glycidyl ether, glycidyl methacrylate, and the like, and preferably useful are butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate, which can be used in combination of two or more.

In preparing the alkali-soluble resin, a copolymerizable unsaturated monomer (b4) other than the ethylenically unsaturated monomer (b2) having a hydroxyl group and the compound (b3) having a glycidyl group may be additionally added to The carboxyl ethylenically unsaturated monomer (b1) is used for copolymerization.

Examples of the copolymerizable unsaturated monomer (b4) are as follows, but are not limited thereto.

Specific examples of the polymerizable monomer (b4) having a copolymerizable unsaturated bond include: aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and p-vinyl Toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl Ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene, etc .; N-substituted maleimide imine compounds, such as N-cyclohexyl horseradish Imine, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-para Hydroxyphenylmaleimide, N-o-tolylmaleimide, N-m-tolylmaleimide, N-p-tolylmaleimide, N-o-methoxyphenylimine Lymeimine, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, etc .; (meth) acrylic acid alkyl esters such as (meth) acrylate, ( (Meth) ethyl acrylate, ( N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tertiary (meth) acrylate Butyl, etc .; cycloaliphatic (meth) acrylates, such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (meth) Tricyclo [5.2.1.0 2,6] dec-8-yl acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, isobornyl methacrylate, etc .; aryl (meth) acrylate, such as Phenyl (meth) acrylate, benzyl (meth) acrylate, etc .; and unsaturated oxetane compounds, such as 3- (methacrylic acid) Oxetane, 3- (methacrylic oxomethyl) -3-ethyloxetane, 3- (methacrylic oxomethyl) -2-trifluoromethyloxetane Alkane, 3- (methacrylic acid oxomethyl) -2-phenyloxetane, 2- (methacrylic acid oxomethyl) oxetane, 2- (methacrylic acid oxetane) Group) -4-trifluoromethyloxetane and the like.

The exemplified monomers may be used alone or in a combination of two or more.

The amount of the alkali-soluble resin (B) is 20 to 80% by weight, and preferably 20 to 70% by weight based on the total weight of the solid content of the blue photosensitive resin composition. When the amount of the alkali-soluble resin is 20 to 80% by weight based on the above, a pattern is easily formed due to sufficient solubility in a developing solution, and a film of a pixel portion of a photographic exposure portion is prevented from becoming small during development, and therefore non- Missing pixels are improved.

Photopolymerizable compound (C)

In the present invention, the photopolymerizable compound should be a compound that can be polymerized by the action of a photopolymerization initiator (D) described below. In the present invention, a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer may be used, and the difunctional monomer may be preferably used, but is not limited thereto.

Specific examples of the monofunctional monomer include, but are not limited to, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxy Ethyl acrylate, or N-vinylpyrrolidone.

Specific examples of the difunctional monomer include, but are not limited to, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, or 3-methylpentanediol di (meth) acrylate, etc. .

Specific examples of the polyfunctional monomer include, but are not limited to, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate , Propoxylated dipentaerythritol hexa (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, and the like.

The amount of the photopolymerizable compound is set to 5 to 45% by weight, and preferably 7 to 45% by weight based on the total weight of the solid content of the blue photosensitive resin composition. When the amount of the photopolymerizable compound falls within the range of 5 to 45% by weight based on the foregoing, the strength or smoothness of the pixel portion can be improved.

Photopolymerization initiator (D)

The photopolymerization initiator of the present invention is characterized by including an oxime ester compound represented by the following Chemical Formula 1.

Wherein R _{1 is} represented by the following chemical formula 2, R ₂ is a C1 to C8 alkyl group, a phenyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, R ₃ is a diphenyl sulfide group, and [Chemical Formula 2] -R ₄ -R ₅

R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group, a C3 to C8 cycloalkyl group, or a C6 to C8 aromatic hydrocarbon.

The above-mentioned oxime ester compound represented by Chemical Formula 1 preferably includes a member selected from the group consisting of 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (o-benzohydrazine) And 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (o-benzophenoxime) (1,2-octanedione, 1- [4- (phenylthio) phenyl]- , 2- (o-benzoyloxime)).

A photopolymerization initiator containing a compound represented by Chemical Formula 1 prevents sensitivity and light transmittance from being decreased due to a dye, and thus exhibits effective photopolymerization performance in a blue photosensitive resin composition containing a colorant dye.

Further, based on the total weight, the content of the photopolymerization initiator is 10 to 100% by weight, and preferably 20 to 100% by weight. If the amount of Chemical Formula 1 is less than 10% by weight, the decreased sensitivity cannot be overcome due to the dye, and it is easy to cause a shortage of a pattern during development.

In addition to the photopolymerization initiator described above, the photopolymerization initiator may be further added within a range that does not inhibit the effect of the present invention. It is preferably useful at least one selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone-based compound.

Specific examples of acetophenone-based compounds may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethylketal, 2- Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl Thiophenyl) -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one, 2-hydroxy- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4 -Morpholinylphenyl) butane-1-one and the like.

Examples of benzophenone-based compounds include: benzophenone, methyl o-benzophenanthrene benzoate, 4-phenylbenzophenone, 4-benzylmethyl-4'-methyldiphenylsulfide Ether, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

Specific examples of triazine compounds include: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro (Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-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) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) Vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1, 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-di (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy) Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 2,2-bis (2, 6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, imidazole substituted at the 4,4', 5,5 'position of the phenyl group by an alkoxycarbonyl group Turn into 组合 等。 And other. Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2, 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole.

Examples of thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone Wait.

Further, in order to improve the sensitivity of the blue photosensitive resin composition according to the present invention, the photopolymerization initiator may further include a photoinitiator assistant. Due to the photoinitiation aid contained therein, the blue photosensitive resin composition according to the present invention can have further improved sensitivity, thereby improving productivity.

The photoinitiation aid preferably includes, for example, an amine compound or a carboxylic acid compound.

The amine compound may include, for example, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and an aromatic amine compound such as methyl 4-dimethylaminobenzoate, 4-dimethylamino Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, N, N-dimethyl para Toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly referred to as ligustone), 4,4'-bis (diethylamino) benzophenone, and the like. And an aromatic amine compound can be preferably used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethyl Phenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid Naphthylthio Acetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The amount of the photopolymerization initiator may be set to 0.1 to 30% by weight, and preferably 1 to 20% by weight based on the total solid weight of the blue photosensitive resin composition. When the amount of the photopolymerization initiator falls within the above range of 0.1 to 30% by weight, the sensitivity of the photosensitive resin composition may increase, and the exposure time for photography may decrease, thereby improving productivity and maintaining high resolution. Moreover, when the composition is used under the above-mentioned conditions, the strength and surface smoothness of the formed pixel portion can be improved.

In the case where a photoinitiator is additionally used, the photoinitiator can be set to 0.1 to 30% by weight, and preferably 1 to 20% by weight, based on the total solid weight of the blue photosensitive resin composition. When the amount of the photoinitiation aid falls within the above range of 0.1 to 30% by weight, it is preferable because the sensitivity of the blue photosensitive resin composition is further increased, and the color filter formed by using the above composition The productivity of the light sheet can be improved.

Solvent (E)

Based on the total weight of the solvent, the solvent of the present invention is characterized by including a solvent having a boiling point of 180 ° C. or more, more than 0% by weight and not more than 8% by weight.

If the amount of the solvent exceeds 8% by weight, increasing the amount of residual solvent makes the fluidity of the paint film formed in the soft baking step, and thus it is difficult to maintain the pattern flatness.

The solvent having a boiling point of 180 ° C or higher includes a solvent selected from the group consisting of dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol dibutyl ether, and 1,2-propylene glycol di One or more of the group consisting of acetate And preferably includes one or more selected from the group consisting of dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, and 1,2-propylene glycol diacetate.

Further, as long as the other components can be effectively dissolved, any solvent used in the usual blue photosensitive resin composition may be additionally mixed and used. Among these solvents, ethers, aromatic hydrocarbons, ketones, alcohols, esters, and amidines are preferred.

Ethers can include, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Alcohol dipropyl ether, diethylene glycol dibutyl ether, and the like.

Aromatic hydrocarbons may include, for example, benzene, toluene, xylene, and mesitylene.

Ketones may include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.

The alcohol may include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and the like.

Esters may include, for example: ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 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, 2-amino-2-methyl-1,3-propanediol, 2- Amino-2-ethyl-1,3-propanediol, ethyl lactate, propylene glycol, n-propyl ether, ethyl 3-ethoxypropionate, propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, Ethylene glycol monobutyl ether, diethylene glycol methyl ether, 1,2-propylene glycol di Acetate, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, γ-butyrolactone, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate , Diethylene glycol monobutyl ether, 1,3-butanediol 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 monomethyl ether acetate, ethylene carbonate, and propylene carbonate and γ-butyrolactone.

The above-listed solvents may be used alone or in a combination of two or more.

Further, among the exemplified solvents, an organic solvent having a boiling point of 100 to 200 ° C is preferred in terms of applicability and drying ability, and more preferably, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Acid esters, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

Further, most preferably, the solvent of the present invention includes one or more selected from the group consisting of dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, and 1,2-propylene glycol diacetate as a boiling point of Solvents at 180 ° C or higher, and propylene glycol monomethyl ether acetate.

Further, the amount of the solvent may be 60 to 90% by weight, and preferably 70 to 85% by weight, based on the total weight of the blue photosensitive resin composition according to the present invention. When the amount of the solvent falls within the above range of 60 to 90% by weight, when using, for example, a roll coater, a spin coater, a slit-spin coater, a slit coater (also referred to as Mode coater), When coating is performed by a coating machine such as a spray coater, reverse printing, gravure printing, screen printing, pad printing, and inkjet, the application performance can be improved.

Additive (F)

The additives may be selectively added as needed, and may include, for example, one or more selected from other polymer compounds, curing agents, adhesion promoters, UV absorbers, polymerization inhibitors, and the like.

Specific examples of other polymer compounds may include: curable resins such as epoxy resins, maleimide resins, and the like; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and perfluoroalkane Acrylate, polyester, polyurethane, and the like, but are not limited thereto.

The curing agent is used to cure the core and improve mechanical strength, and may include, for example, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

In the curing agent, specific examples of the epoxy compound may include, but are not limited to: bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin , Phenolic epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of epoxy resins, except epoxy resins and brominated derivatives thereof Aliphatic, alicyclic or aromatic epoxy compounds, epoxidized butadiene (co) polymer, epoxidized isoprene (co) polymer, glycidyl (meth) acrylate (co) polymer Products, triglycidyl isocyanurate, etc.

In the curing agent, specific examples of the oxetane compound may include: carbonate dioxetane, xylene dioxetane, adipate bis Oxetane, terephthalate dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

The curing agent may further include an auxiliary curing compound, which together with the curing agent causes the epoxy group of the epoxy compound and the oxetane main chain of the oxetane compound to undergo a ring-opening polymerization reaction.

The auxiliary curing compound may include, for example, a polycarboxylic acid, a polycarboxylic acid anhydride, an acid generator, and the like. The polycarboxylic acid anhydride may include those commercially available as epoxy resin curing agents. Examples of commercially available epoxy resin curing agents include: Adeka hardener EH-700 (available from Adeka), Rikkad HH (available from New Japan Chemicals), MH-700 (available from New Japan Chemicals), and the like.

Examples of the above-listed curing agents and auxiliary curing compounds may be used alone or in combination of two or more.

The adhesion promoter is not particularly limited, and specific examples thereof are: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2-amino (Ethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidyl ether oxypropyltrimethoxysilane, 3-glycidyl ether oxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloro Propylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyl Trimethoxysilane, 3-isocyanatepropyltriethoxysilane and the like.

The adhesion promoters listed above can be used alone or in two or more A combination of these.

The amount of the adhesion promoter may be 0.01 to 10% by weight, and preferably 0.05 to 2% by weight, based on the total solid weight of the blue photosensitive resin composition.

Specific examples of the UV absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.

Specific examples of the aggregation inhibitor include, but are not limited to, sodium polyacrylate and the like.

The method for producing the blue photosensitive resin composition according to the present invention is as follows.

Specifically, the pigment (a1) of the blue colorant (A) is mixed with the solvent (E) and dispersed using a ball mill until the average particle diameter of the pigment is 0.2 μm or less. Similarly, a part or all of the pigment dispersant (a2), the alkali-soluble resin (B), or the dye (a3) and the solvent (E) may be mixed, and these may be dissolved or dispersed as necessary.

The dye (a3), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and optional additives (F), and the solvent (E) are added at a predetermined concentration. Into the mixed dispersion solution to prepare a blue photosensitive resin composition according to the present invention.

In addition, the present invention provides a blue filter prepared from a blue photosensitive resin composition and a display device equipped with the same.

First, by coating a blue photosensitive resin composition on a substrate (usually glass) or a layer made of a solid content of a blue photosensitive resin composition with a predetermined solid content, and thereafter by heating And drying to remove volatile components such as solvents, resulting in a smooth paint film.

The coating method may include, for example, a spin coating method, a flexible coating method, A roll coating method, a slit spin coating method, or a slit coating method.

Volatile components such as solvents are volatilized by heating and drying (pre-baking) after coating or by heating after drying under reduced pressure.

Similarly, the heating temperature is usually 70 to 200 ° C, and preferably 80 to 130 ° C.

After heating and drying, the thickness of the paint film is usually about 1 to 8 μm. The resulting paint film was irradiated with UV light using a mask to form a desired pattern. Also, it is preferable to use a device such as a mask aligner and a stepper so that a parallel beam can be irradiated on the entire photographic exposure portion and also the mask and the substrate can be calibrated correctly. When irradiated with UV, the UV-irradiated area is cured.

For UV, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), and the like can be used. The dose of UV irradiation can be appropriately selected according to needs, but is not limited to the present invention. When the curing is completed, the paint film comes into contact with the developing solution and the unphotographically exposed portions are dissolved, and thereby a spacer having a bullseye pattern shape can be obtained.

The developing method is a liquid addition method, a immersion method, a spray method, and the like, and this is not particularly limited.

Further, the substrate may be inclined at any angle during development. The developing solution is usually an aqueous solution containing a basic compound and a surfactant.

The basic compound is an organic basic compound or an inorganic basic compound, which is not particularly limited. The inorganic basic compound may include, for example: sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, carbonic acid Sodium, potassium carbonate, Sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate and ammonia.

Further, the organic basic compound may include, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethyl, ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, Triethylamine, monoisopropylamine, diisopropylamine and ethanolamine.

Either the inorganic basic compound or the organic basic compound may be used alone or in a combination of two or more. The concentration of the basic compound in the developing solution is set to 0.01 to 10% by weight, and preferably 0.03 to 5% by weight based on the total weight of the developing solution.

For the surfactant in the developing solution, one or more selected from the above-mentioned nonionic surfactants, anionic surfactants, and cationic surfactants can be used. Based on the total weight of the developing solution, the concentration of the surfactant in the developing solution is set to 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1% to 5% by weight.

After development, it is washed with water, and after that, post-baking can be performed at 150 to 230 ° C. for 10 to 60 minutes.

By performing each of the above processes using the blue photosensitive resin composition of the present invention, a specific pattern can be formed on a substrate.

The following examples, which are presented by way of illustration and are not to be construed as limiting the invention, will be described in more detail below. The scope of the present invention is shown in the claims, and furthermore, it includes the meaning equivalent to the description of the claims and all modifications within the scope.

<Preparation of Pigment Dispersion Composition>

[Preparation Example 1]: Preparation of pigment dispersion composition

By using a ball mill, 12.0 parts by weight of CI Pigment Blue 15: 6, 4.0 parts by weight of DISPERBYK-2001 (commercially available from BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent were performed. Mixing / dispersing for 12 hours to prepare a pigment dispersion composition.

<Synthesis of alkali-soluble resin>

Synthesis Example 1: Synthesis of alkali-soluble resin

120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13.0 parts by weight of methacrylic acid, 10 parts by weight of benzyl methacrylate, 57 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecyl mercaptan are put in a mixer equipped with a stirrer, a thermometer, a reflux condenser, a dripping lot and Nitrogen was supplied to the flask of the tube, and the inside of the flask was purged with nitrogen. Thereafter, the obtained mixture was stirred, the temperature of the reaction mixture was raised to 110 ° C, and the reaction was allowed to proceed for 6 hours, thereby synthesizing an alkali-soluble resin. The acid value of the solid of the alkali-soluble resin thus synthesized was 100.2 mgKOH / g, and its weight-average molecular weight as measured by gel permeation chromatography (GPC) was about 15,110.

Synthesis Example 2: Synthesis of alkali-soluble resin

200 parts by weight of propylene glycol monomethyl ether acetate, 45 parts by weight of propylene glycol monomethyl ether, 4 parts by weight of azobisisobutyronitrile (AIBN), 15 parts by weight of acrylic acid, and 70 parts by weight of benzyl methacrylate Esters, 15 parts by weight of styrene and 3 parts by weight of n-dodecyl mercaptan are placed in a flask equipped with a stirrer, thermometer, reflux condenser, drip dispenser and nitrogen supply tube, and purged with nitrogen The interior of the flask. Thereafter, the obtained mixture was stirred, and The temperature of the reaction mixture was raised to 110 ° C, and the reaction was allowed to proceed for 2 hours, whereby an alkali-soluble resin was synthesized. The acid value of the solid of the alkali-soluble resin thus synthesized was 110.4 mgKOH / g, and its weight average molecular weight was about 8900 as measured by GPC.

<Preparation of colored photosensitive resin composition>

Example 1

By adding 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 1.2 parts by weight of TR-PBG-305 (oxime ester compound; purchased from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight as a boiling point 1,2-propanediol diacetate, which is a solvent of 180 ° C or higher, is mixed to prepare a blue photosensitive resin composition.

Example 2

By adding 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 1.2 parts by weight of OXE-01 (oxime ester compound; purchased from BASF) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of a boiling point of 180 1,2-Propanediol diacetate, which is a solvent at or higher, is mixed to prepare a blue photosensitive resin composition.

Example 3

By adding 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 0.6 parts by weight of OXE-01 (oxime ester compound; purchased from BASF) as a photopolymerization initiator and 0.6 parts by weight of TR-PBG-305 (oxime ester compound; purchased from TRONLY), 41 parts by weight Propylene glycol monomethyl ether acetate as a solvent and 5.2 parts by weight of 1,2-propylene glycol diacetate as a solvent having a boiling point of 180 ° C. or higher were mixed to prepare a blue photosensitive resin composition.

Example 4

By adding 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 1.2 parts by weight of TR-PBG-305 (oxime ester compound; purchased from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight as a boiling point Dipropylene glycol monomethyl ether in a solvent of 180 ° C. or higher was mixed to prepare a blue photosensitive resin composition.

Example 5

By adding 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 1.2 parts by weight of TR-PBG-305 (oxime ester compound; purchased from TRONLY) as a photopolymerization initiator, 41 Part by weight of propylene glycol monomethyl ether acetate as a solvent and 5.2 parts by weight of dipropylene glycol methyl ether acetate as a solvent having a boiling point of 180 ° C. or higher were mixed to prepare a blue photosensitive resin composition.

Example 6

By dissolving 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 10.7 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 1.2 parts by weight of TR-PBG-305 (oxime ester compound; purchased from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight as a boiling point 1,2-propanediol diacetate, which is a solvent of 180 ° C or higher, is mixed to prepare a blue photosensitive resin composition.

Comparative Example 1

By adding 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 2, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 1.2 parts by weight of TR-PBG-305 (oxime ester compound; purchased from TRONLY) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight as a boiling point 1,2-propanediol diacetate, which is a solvent of 180 ° C or higher, is mixed to prepare a blue photosensitive resin composition.

Comparative Example 2

By mixing 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, 6.2 KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (oxime ester compound; available from TRONLY) as a photopolymerization initiator, and 38 parts by weight as A propylene glycol monomethyl ether acetate as a solvent and 8.2 parts by weight of 1,2-propylene glycol diacetate as a solvent having a boiling point of 180 ° C. or higher were mixed to prepare a blue photosensitive resin composition.

Comparative Example 3

By adding 27.9 parts by weight of the pigment dispersion composition prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (purchased from NIPPON KAYAKU) ), 1.2 parts by weight of Irgacure 369 (oxime ester compound; purchased from BASF) as a photopolymerization initiator, 41 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 5.2 parts by weight of 180 ° C. as a boiling point Or higher solvent 1,2-propanediol diacetate is mixed to prepare a blue photosensitive resin composition.

Comparative Example 4

By adding 27.9 parts by weight of the pigment dispersion prepared in Preparation Example 1, 18.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, and 6.2 parts by weight of KAYARAD DPHA (commercially available from NIPPON KAYAKU) ), 1.2 parts by weight of TR-PBG-305 (oxime ester compound; available from TRONLY) as a photopolymerization initiator and 46.2 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a blue photosensitive resin combination.

Comparative Example 5

By mixing 27.9 parts by weight of the pigment dispersion prepared in Preparation Example 1, 6.0 parts by weight of the alkali-soluble resin prepared in Synthesis Example 1, 12.5 parts by weight of the alkali-soluble resin prepared in Synthesis Example 2, and 6.2 parts by weight KAYARAD DPHA (available from NIPPON KAYAKU) as a photopolymerizable compound, 1.2 parts by weight of TR-PBG-305 (oxime ester compound; available from TRONLY) as a photopolymerization initiator, and 41.0 parts by weight as a solvent Propylene glycol monomethyl ether acetate and 5.2 parts by weight of 1,2-propylene glycol diacetate as a solvent having a boiling point of 180 ° C. or higher were mixed to prepare a blue photosensitive resin composition.

Test Example 1: Production of Blue Filter and Evaluation of Adhesiveness

Each of the blue photosensitive resin compositions in Examples 1 to 6 and Comparative Examples 1 to 5 was coated on a glass substrate ("EAGLE XG"; available from Corning) with a 2 inch angle using spin coating, and Vacuum drying was performed in a vacuum drying apparatus under reduced pressure until 65 Pa. After that, the glass substrate was placed on a hot plate and held at 100 ° C for 3 minutes, thereby forming a thin film. Subsequently, a test photomask having a line width / space pattern of 1 μm to 100 μm was placed on the film, and UV light was applied at a distance of 300 μm from the test photomask. Similarly, a 1 KW high-pressure mercury lamp containing all rays of g, h, and i was used to irradiate UV light at a dose of 40 mJ / cm ² , and no specific optical filter was used. The UV-irradiated film was immersed in a KOH aqueous solution having a pH of 10.5 as a developing solution for 2 minutes, thereby developing it. The thin-coated glass substrate was washed with distilled water, dried with nitrogen, and heated in an oven at 220 ° C. for 25 minutes, thereby manufacturing a blue filter.

The film thickness of the blue filter manufactured in this manner was 3.4 μm.

Evaluation of the adhesiveness of the blue filter prepared above was as follows. The number of defects in the 20 μm pattern of the blue filter was evaluated by using an optical microscope. The results are listed in Table 1 below.

<Number of defects>

○: No pattern defect

△: 1 ~ 3 pattern defects

X: 4 or more pattern defects

Test Example 2: Production of blue filter and evaluation of pattern flatness

Each of the blue photosensitive resin compositions in Examples 1 to 6 and Comparative Examples 1 to 5 was coated on a glass substrate having a 2 inch angle and patterned with a black matrix of 100 μm line width / space using spin coating, And vacuum drying was performed in a vacuum drying apparatus under reduced pressure until 65 Pa. After that, the glass substrate was placed on a hot plate and held at 100 ° C for 3 minutes, thereby forming a thin film. Subsequently, UV light was applied to the film without using a photomask. Similarly, a 1 KW high-pressure mercury lamp containing all rays of g, h, and i was used to irradiate UV light at a dose of 40 mJ / cm ² , and no specific optical filter was used. The UV-irradiated film was immersed in a KOH aqueous solution having a pH of 10.5 as a developing solution for 2 minutes, thereby developing it. The thin-coated glass substrate was washed with distilled water, dried with nitrogen, and heated in an oven at 220 ° C. for 25 minutes, thereby manufacturing a blue filter.

The film thickness of the blue filter manufactured in this manner was 3.4 μm.

The evaluation of the flatness of the blue filter prepared above was as follows. Prepared on a black matrix using a colorimeter (OSP-200, commercially available from Olympus) Blue filter. The color of the dots at a distance of 50 μm from the black matrix pattern and the color of the dots at a distance of 10 μm from the black matrix pattern were measured, and the color difference (By) between the two points is listed in Table 1 below. The correlation between the color difference (By) and the pattern flatness is as follows.

<Comparison threshold of color difference (By) and pattern flatness>

○: 1/10000 <color difference (By) <9/10000

×: color difference (By) 10/10000

Comparative Example 1 is a blue photosensitive resin composition prepared using an alkali-soluble resin having a molecular weight of less than 15,000, and Comparative Example 2 is a solvent-containing More than 8% by weight of a blue photosensitive resin composition having a boiling point of 180 ° C. or higher, Comparative Example 3 is a blue photosensitive resin composition prepared using a photopolymerization initiator not containing an oxime ester compound. Further, Comparative Example 4 is a blue photosensitive resin composition that does not include a boiling point of 180 ° C. or higher, and Comparative Example 5 includes a molecular weight of 15,000 or higher that contains less than 40% by weight based on the total weight of the alkali-soluble resin. Blue photosensitive resin composition of alkali-soluble resin.

As apparent from Table 1, the blue filter using the blue photosensitive resin composition of Examples 1 to 6 exhibited excellent adhesion, good color difference (By), and excellent pattern flatness. In particular, the pattern flatness is excellent, and thus a constant color coordinate can be obtained in one pixel.

On the other hand, the blue filter prepared using the blue photosensitive resin composition of Comparative Examples 1 to 5 has a high color difference (By) because pattern flatness cannot be obtained even if it has excellent adhesion.

Therefore, the blue photosensitive resin of the present invention has excellent adhesion and does not cause pattern separation even with a low amount of photographic exposure, and has excellent effects of achieving constant color coordinates in one pixel because of excellent pattern flatness. .

Claims (10)

A blue photosensitive resin composition for improving flatness, comprising: a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the blue photosensitive resin composition is based on the blue photosensitive resin composition The total weight of the solid, the content of the alkali-soluble resin is 20% to 80% by weight; wherein, based on the total weight of the alkali-soluble resin, the alkali-soluble resin includes 40% to 100% by weight and the molecular weight is 15000 Or higher alkali-soluble resin; wherein the photopolymerization initiator includes a compound represented by the following Chemical Formula 1; wherein, based on the total weight of the solvent, the solvent includes more than 0% by weight and not more than 8% by weight A solvent having a boiling point of 180 ° C or higher; and the solvent wherein the boiling point is 180 ° C or higher includes a solvent selected from the group consisting of ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol di One or more of the group consisting of butyl ether and 1,2-propylene glycol diacetate; Among them, R _{1 is} represented by the following chemical formula 2, R ₂ is a C1-C8 alkyl group, a phenyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and R ₃ is a diphenyl sulfide group, [ Chemical formula 2] -R ₄ -R ₅ R ₄ is a C1 to C4 alkylene group, and R ₅ is a C3 to C8 alkyl group, a C3 to C8 cycloalkyl group, or a C6 to C8 aromatic hydrocarbon. The blue photosensitive resin composition for improving flatness according to claim 1, wherein the blue colorant includes one or more pigments, one or more dyes, and combinations thereof. The blue photosensitive resin composition for improving flatness according to claim 1, wherein the alkali-soluble resin has an acid value in a range of 30 mgKOH / g to 150 mgKOH / g. The blue photosensitive resin composition for improving flatness according to claim 1, wherein the chemical formula 1 includes a member selected from the group consisting of 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane Composition of -1,2-dione-2- (o-benzophenoxime) and 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (o-benzophenoxime) One or more of the group. The blue photosensitive resin composition for improving flatness according to claim 1, wherein the solvent having a boiling point of 180 ° C or higher includes a solvent selected from the group consisting of dipropylene glycol methyl ether acetate and 1,2-propylene glycol One or more of the group consisting of diacetates. The blue photosensitive resin composition for improving flatness according to claim 1, wherein the solvent comprises: a solvent selected from the group consisting of dipropylene glycol methyl ether acetate and 1,2-propylene glycol diacetate One or more of them are used as a solvent having a boiling point of 180 ° C or higher, and propylene glycol monomethyl ether acetate. The blue photosensitive resin composition for improving flatness according to claim 1, wherein the blue photosensitive resin composition includes: based on the total solid weight of the blue photosensitive resin composition, 0 5 to 60% by weight of the blue colorant, 5 to 45% by weight of the photopolymerizable compound, and 0.1 to 30% by weight of the photopolymerization initiator; and The total weight of the blue photosensitive resin composition is 60% to 99% by weight of the solvent. The blue photosensitive resin composition for improving flatness according to claim 7, wherein the photopolymerization initiator includes from 10% by weight to 100% by weight based on the total weight of the photopolymerization initiator. The compound represented by Chemical Formula 1. A blue filter including the blue photosensitive resin composition according to claim 1. A display device includes the blue filter according to claim 9.