KR20170111133A - Colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a colored photosensitive resin composition, and more specifically, to an alkali-soluble resin; And a silicone-based surfactant, wherein the alkali-soluble resin is composed of a first cadosporous binder resin which is polymerized with a compound represented by the formula (1) and a second cadidate binder resin which is polymerized with a compound represented by the formula (2) And the silicone surfactant is represented by the following formula (3), and a color filter and an image display device manufactured using the colored photosensitive resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, and a color filter and an image display device using the same. BACKGROUND ART < RTI ID = 0.0 >

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

BACKGROUND ART [0002] Color filters are widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and their application range is rapidly expanding. The color filter may be formed of three color patterns of red, green, and blue, or may be formed of three color patterns of yellow, magenta, and cyan, Lt; / RTI >

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition comprising a coloring agent such as pigment or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a lithography process.

On the other hand, in recent years, color filters for various display devices including solid-state image pickup devices such as digital cameras have been required to have excellent developability, adhesion, and high sensitivity for improvement of processability and quality.

Specifically, recently, color filter materials are required to have high sensitivity, high reliability in pattern formation, and high color reproducibility with high transmittance. Accordingly, the pigment concentration of the colored photosensitive resin composition used for manufacturing the color filter is continuously increased, and a colored photosensitive resin composition having the same sensitivity and reliability at a low exposure dose is required in order to improve process productivity and yield. However, when a color filter is manufactured using a colored resin composition having a high contrast ratio or a high definition to improve development speed and sensitivity, unevenness or surface abnormality occurs in vacuum drying, and color filter defects frequently occur . This problem is further increased when the process time is shortened to increase the production amount of the color filter.

Korean Patent Publication No. 2001-0062984 discloses a photopolymerizable photosensitive resin composition which is excellent in coating property and developability and in which the incidence of surface stain is reduced. The photopolymerizable photosensitive resin composition comprises (1) 1-40 parts by weight of a cardo binder resin, 1 to 20 parts by weight of an acrylic photopolymerizable monomer, (3) 0.1 to 10 parts by weight of a photopolymerization initiator, (4) 0 to 10 parts by weight of an epoxy resin, (5) 0.1 to 20 parts by weight of a pigment, , And (7) 0.005 to 4 parts by weight of a fluorine-based surfactant. However, the photopolymerizable photosensitive resin composition is not excellent in developability, adhesion, and sensitivity, There is a problem that development unevenness occurs.

Korean Patent Publication No. 2001-0062984 (July, 2001)

An object of the present invention is to provide a colored photosensitive resin composition which is excellent in developability or adhesiveness and can reduce the occurrence of development unevenness.

The present invention also provides a color filter and an image display device manufactured using the above-mentioned colored photosensitive resin composition.

Specifically, the present invention aims to provide a color filter and an image display device which are excellent in developability, adhesion, or sensitivity using the above-mentioned colored photosensitive resin composition.

To achieve the above object, the colored photosensitive resin composition according to the present invention comprises an alkali-soluble resin; And a silicone-based surfactant, wherein the alkali-soluble resin comprises a first cationic binder resin that is polymerized by including a compound represented by the following formula (1), and a second cationic binder resin that is polymerized by including a compound represented by the following formula , And the silicone surfactant is represented by the following general formula (3).

[Chemical Formula 1]

(2)

(3)

In formula (1)

이고,R1 and R2 are each independently

ego,

X is hydrogen, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group,

R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

In formula (2)

이고,R4 and R5 are each independently

ego,

X is hydrogen, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group,

R6 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

In formula (3)

x, y and n are each independently an integer of 1 to 10,

And Z is an alkylene glycol group having 2 to 4 carbon atoms.

The present invention also provides a color filter made of the above-mentioned colored photosensitive resin composition and an image display device including the same.

The colored photosensitive resin composition of the present invention can provide a colored photosensitive resin composition excellent in developability or adhesion. Further, the colored photosensitive resin composition according to the present invention can lower the occurrence of development unevenness.

Further, the color filter made of the colored photosensitive resin composition of the present invention and the image display device including the color filter have an advantage of being excellent in developability, adhesion, or sensitivity.

1 is a diagram showing the measurement result of development unevenness.

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

When a member is referred to as being " on "another member in the present invention, this includes not only when a member is in contact with another member but also when another member exists between the two members.

Whenever a part is referred to as "including " an element in the present invention, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

≪ Colored photosensitive resin composition &

An aspect of the present invention relates to an inkjet ink comprising an alkali-soluble resin; And a silicone-based surfactant, wherein the alkali-soluble resin comprises a first cationic binder resin that is polymerized by including a compound represented by the following formula (1), and a second cationic binder resin that is polymerized by including a compound represented by the following formula , And the silicone surfactant is represented by the following formula (3): " (3) "

[Chemical Formula 1]

(2)

(3)

In formula (1)

이고,R1 and R2 are each independently

ego,

X is hydrogen, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group,

R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

In formula (2)

이고,R4 and R5 are each independently

ego,

X is hydrogen, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group,

R6 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

In formula (3)

x, y and n are each independently an integer of 1 to 10,

And Z is an alkylene glycol group having 2 to 4 carbon atoms.

Alkali-soluble resin

The alkali-soluble binder resin according to the present invention includes a first cadmium-based binder resin polymerized by including a compound represented by the following formula (1), thereby improving adhesion to a substrate and exhibiting excellent developing adhesion, thereby realizing a fine pattern for high resolution do.

[Chemical Formula 1]

이며, In the formulas, R 1 and R 2 are each independently

Lt;

X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group, R3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably X is a hydroxyl group and R3 is a hydrogen atom or a methyl group.

The compound represented by the formula (1) can be synthesized using the following formula (4).

[Chemical Formula 4]

For example, the compound represented by Chemical Formula 4 is mixed with t-butylammonium bromide, heated and reacted with a solvent, an alkali aqueous solution is added dropwise, and the mixture is precipitated and separated to synthesize an epoxy compound. -Butylammonium bromide, acrylic acid, a phenol-based compound, and a solvent, and reacting them. However, the present invention is not limited thereto.

In addition, the alkali-soluble binder resin according to the present invention includes a second cadmium-based binder resin polymerized by including a compound of the following formula (2), thereby improving the adhesion with the substrate and providing a fine pattern for high resolution .

(2)

이며,Wherein R4 and R5 are each, independently,

Lt;

X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group, R6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably X is a hydroxyl group, and R6 is a hydrogen atom or a methyl group.

The compound represented by the formula (2) can be synthesized using the following formula (5).

 [Chemical Formula 5]

For example, the compound represented by the formula (5) is mixed with t-butylammonium bromide and a solvent, followed by heating and reacting. Then, an aqueous alkaline solution is added dropwise to precipitate and separate an epoxy compound. -Butylammonium bromide, acrylic acid, a phenol-based compound, and a solvent, and reacting them. However, the present invention is not limited thereto.

The position of the hydroxyl group (-OH) in the formulas (4) and (5) is not particularly limited, and may be, for example, 2-, 3- or 4- Lt; RTI ID = 0.0 > 1-up < / RTI >

As a result, depending on the position of the hydroxyl group (-OH) of the formula (4) or (5), the substitution positions of R1 and R2 in the formula (1) or the substitution positions of R4 and R5 in the formula (2) can be determined.

More specific examples of the compound represented by Formula 1 include 9,9-bis (3-cinnamic diester) fluorene, 9,9-bis (3-cinnamic diester) 3-cinnamoyl, 4-hydroxyphenyl) fluorene, 9,9-bis (glycidyl methacrylate ether) fluorene (9,9- 9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester, 9,9-bis (glycidyl methacrylate ether) fluorene, , 6-diglycidyl methacrylate ether spiro (fluorene-9,9-xanthene), 9,9-bis (3- Allyl, 4-hydroxyphenylfluorene, 9,9-bis (4-allyloxyphenyl) fluorene, ) fluorene, and 9,9-bis (3,4-methacrylic diester) fluorene. And may be at least one selected, but is not limited thereto.

More specific examples of the compound represented by the formula (2) include 9,9-bis (3,4-methacrylic diester) xanthene, but the present invention is not limited thereto.

The acid value of the first cadmium-based binder resin or the second cadmium-based binder resin in the alkali-soluble binder resin may be 10 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g. When the acid value is in the range of 10 to 200 mgKOH / g, a sufficient developing rate can be ensured, and a fine pattern for high resolution can be realized.

The alkali-soluble binder resin may have a weight average molecular weight of 1,000 to 30,000, preferably 1,500 to 10,000, When the weight average molecular weight is within the above range, the adhesiveness and developability can be improved.

The content of the alkali-soluble binder resin is not particularly limited, but may be 1 to 40 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the colored photosensitive resin composition. When the content of the binder resin is within the above range, solubility in a developing solution is sufficient and pattern formation is easy.

Silicone surfactant

The colored photosensitive resin composition according to the present invention includes a silicone surfactant. Specifically, the silicone surfactant may include a non-reactive polyether-modified silicone compound represented by the following general formula (3).

(3)

In formula (3)

x, y and n are each independently an integer of 1 to 10,

And Z is an alkylene glycol group having 2 to 4 carbon atoms.

The non-reactive polyether-modified silicone compound represented by Formula 3 performs leveling agent dynamics in the composition of the present invention. Further, since the solvent has an affinity for the solvent, the surface tension can be controlled so that the pattern of the colored photosensitive resin composition can be formed with a uniform film thickness. In addition, it also functions to prevent stains during coating film formation.

If y is 0, the content of the hydrophobic (= lipophilic) group is too small to cause unevenness in the formation of the coating film. If y exceeds 10, the hydrophobicity becomes too strong, Occurs. When Z is an alkylene glycol having less than 2 carbon atoms, it is difficult to expect it to serve as a surfactant. In the case of an alkylene glycol having more than 4 carbon atoms, the hydrophobicity increases and the flatness at the time of film formation deteriorates.

The non-reactive polyether-modified silicone compound represented by Formula 3 may be synthesized directly, or a commercially available form may be used. For example, the non-reactive polyether-modified silicone compound represented by Formula 3 may be SH 8400 of Toray Silicone Co.,

In still another embodiment of the present invention, the silicone surfactant represented by Formula 3 may be contained in an amount of 0.001 to 1.5 parts by weight, preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the solid content of the colored photosensitive resin composition. When the silicone surfactant represented by the above formula (3) is contained in the above range, it is possible to form a pattern or a coating film having a uniform film thickness and it is preferable from the viewpoint of the uniformity of the mixing in the composition.

If the amount of the silicone surfactant represented by Formula 3 is less than the above range, it may be difficult to achieve the desired effect, and if it exceeds the above range, formation of a pattern or coat having a uniform film thickness may be somewhat difficult have.

The colored photosensitive resin composition according to the present invention may further include a surfactant other than the silicone surfactant represented by Formula 3, but is not limited thereto.

Specifically, examples of the surfactant that may further include surfactants such as fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants, or mixtures thereof .

More specifically, examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes and polyethyleneimines Surfactants can be used. The product names include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC ), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol Co., ), EFKA (EFKA Chemical Co.), PB 821 (Ajinomoto Co., Ltd.), and Disperbyk-series (BYK-chemi).

coloring agent

The colorant comprises at least one pigment. Specifically, the pigment may be an organic pigment or an inorganic pigment generally used in the art.

Examples of the organic pigment include various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, indanthrone pigments, Pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon An oxide of a metal such as black or a composite metal oxide.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58;

C.I. Pigment Brown 28;

C.I. Pigment Black 1 and 7, etc .;

The pigments may be used alone or in combination of two or more, but the present invention is not limited thereto.

The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment selected from Pigment Green 58 can be preferably used.

It is preferable to use a pigment dispersion composition in which the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment by adding a pigment dispersant. According to this method, a pigment dispersion composition in which the pigment is uniformly dispersed in a solution can be obtained.

Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used alone or in combination of two or more.

The content of the pigment may be 10 to 75 parts by weight, specifically 15 to 75 parts by weight, based on 100 parts by weight of the total solid content in the pigment dispersion composition. When the content of the pigment satisfies the above range, it is preferable because the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective in increasing the contrast ratio.

The pigment dispersant is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. Specifically, it is preferable to contain an acrylate-based dispersant containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). In this case, it is preferable to apply the acrylate-based dispersing agent prepared by the living control method as disclosed in Korean Patent Publication No. 2004-0014311. DISCLOSURE OF THE INVENTION The acrylate- BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The amount of the dispersant may be 5 to 60 parts by weight, specifically 15 to 50 parts by weight based on 100 parts by weight of the pigment solid used. If the content of the pigment dispersant is within the above range, The pigment is easily atomized, and there is an advantage that problems such as gelation after dispersion can be prevented.

The content of the colorant may be 5 to 60 parts by weight, preferably 10 to 45 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the colorant is contained within the above range, even if a thin film is formed, the color density of the pixel is sufficient, and the occurrence of residue can be prevented because the non-curing portion of the non-cured portion is not deteriorated. When the colorant is contained in an amount of less than 5 parts by weight, the color density of a pixel in the case of forming a thin film is somewhat insufficient, and the color separation performance as a color filter may be somewhat lowered. Can cause problems.

Photopolymerization  compound

The photopolymerizable compound according to the present invention may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer as a component for enhancing the strength of a pattern, and preferably a monomer having two or more functions is preferably used.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate N-vinylpyrrolidone, and the like.

The type of the bifunctional monomer is not particularly limited and examples thereof include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The type of the polyfunctional monomer is not particularly limited and includes, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The photopolymerizable compound may be contained in an amount of 5 to 45 parts by weight, preferably 7 to 45 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. When the photopolymerizable compound is contained within the above range, the strength and smoothness of the pixel portion are improved. If the photopolymerizable compound is less than the above range, the strength may be somewhat lowered, and if it exceeds the above range, the viscosity may increase to some extent, which may be undesirable from a viewpoint of processability.

Light curing Initiator

The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound. Specifically, the photopolymerization initiator is preferably selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound and a thioxanthone compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, But not limited to, at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound 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, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compounds include o-ethoxycarbonyl-? -Oxyimino-1-phenylpropan-1-one and commercially available products such as OXE-01 and OXE-02 from BASF.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

The photopolymerization initiator may be contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight based on the total amount of the alkali-soluble resin and the photopolymerizable compound based on the total solid content of the colored photosensitive resin composition. When the photopolymerization initiator is within the above range, the colored photosensitive resin composition becomes highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Further, there is an advantage that the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion are improved.

The colored photosensitive resin composition according to the present invention may further comprise a photopolymerization initiation auxiliary besides the above-described photoinitiator.

When the colored photosensitive resin composition further contains the photopolymerization initiation auxiliary, there is an advantage that the sensitivity is further increased and the productivity is improved. The photopolymerization initiation auxiliary is not limited, but at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

When the photopolymerization initiator is further used, it is contained in an amount of 0.1 to 40 parts by weight, specifically 1 to 30 parts by weight based on the total amount of the alkali-soluble binder resin and the photopolymerizable compound based on the total solid content of the colored photosensitive resin composition . When the content of the photopolymerization initiator is within the above range, the sensitivity of the colored photosensitive resin composition becomes higher, and the productivity of the color filter formed using the colored photosensitive resin composition can be improved.

solvent

The solvent used in the conventional colored photosensitive resin composition may be used without particular limitation as long as it is effective in dissolving the other components contained in the colored photosensitive resin composition of the present invention. Specifically, at least one selected from the group consisting of ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides can be used.

More specifically, 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 dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dialkyl ethers such as 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 monomethyl ether acetate , Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, Ke , 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- Esters such as methyl methoxypropionate, and cyclic esters such as? -Butyrolactone.

The solvent may be an organic solvent having a boiling point in the range of 100 ° C to 200 ° C in terms of coatability and dryness. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, , Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent may be used alone or in admixture of two or more, and may be contained in an amount of 50 to 90 parts by weight, specifically 55 to 85 parts by weight, based on the total amount of the colored photosensitive resin composition. When the solvent is contained within the above range, the coating property is improved when applied with a coating apparatus such as a roll coater, a skin coater, a slit and spin coater, a slit coater (die coater), or an ink jet.

The colored photosensitive resin composition according to the present invention may further contain additives such as other polymer compounds, dyes, curing agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like as necessary, It is possible to use them in an appropriate amount by those skilled in the art.

The method for producing the above-mentioned colored photosensitive resin composition is not limited thereto, but it can be produced, for example, by the following method.

The pigment in the colorant is mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant and the alkali-soluble resin may be mixed and dissolved or dispersed with the solvent, and the remainder of the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator The coloring photosensitive resin composition according to the present invention can be prepared by further adding an additive and a solvent of a coloring agent to a predetermined concentration.

≪ Color filter and image display device >

Another aspect of the present invention relates to a color filter manufactured using the above-mentioned colored photosensitive resin composition.

Further, another aspect of the present invention relates to an image display apparatus including the color filter described above.

The image display apparatus of the present invention is provided with the above-described color filter, and a specific example thereof is a liquid crystal display, an OLED, a flexible display, and the like, but is not limited thereto.

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art. In the following, "%" and "part" representing the content are by weight unless otherwise specified.

Pigment dispersion preparation

<Pigment dispersion composition M1>

C.I. , 12.0 parts by weight of Pigment Blue 15: 6, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate as a solvent and 40 parts by weight of propylene glycol methyl ether by means of a bead mill Followed by mixing / dispersing to prepare a pigment dispersion M1.

Synthesis of alkali-soluble resin

< Synthetic example  1: Synthesis of compound of formula (1)

A 3,000 ml three-necked round flask was charged with 364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xanthene) (3', 6 " And 0.4159 g of bromide were mixed and 2359 g of epichlorohydrin was added and reacted by heating at 90 DEG C. When 3,6-dihydroxy spiro (fluorene-9,9-chanthylene) was completely consumed by liquid chromatography After cooling to 30 DEG C, 50% NaOH aqueous solution (3 equivalents) was added slowly. When the epichlorohydrin was completely removed by analysis by liquid chromatography, the reaction solution was extracted with dichloromethane, washed three times with water, and the organic layer was dried with magnesium sulfate The dichloromethane was distilled off under reduced pressure and recrystallized using a dichloromethane / methanol mixture ratio of 50:50.

One equivalent of the thus synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid were mixed and 24.89 g of solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound.

< Synthetic example  2: Synthesis of compound of formula (2)

A 3,000 ml three-necked round-bottomed flask was charged with 364.4 g of 4,4 '- (9H-xanthene-9,9-diyl) diphenol (4,4' And 2359 g of epichlorohydrin were charged and reacted by heating at 90 占 폚. (9H-xanthene-9,9-diyl) diphenol) was completely depleted, the reaction mixture was cooled to 30 ° C Cooled and slowly added 50% NaOH aqueous solution (3 eq.). When the epichlorohydrin was completely exhausted, the reaction mixture was extracted with dichloromethane and then washed three times. The organic layer was dried over magnesium sulfate, and the dichloromethane was distilled off under reduced pressure. The dichloromethane-methanol mixture ratio was 50:50 And recrystallized.

One equivalent of the thus synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid were mixed and 24.89 g of solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound.

< Synthetic example  3: Carometer  Synthesis of binder resin (b-1) &gt;

600 g of propylene glycol monomethyl ether acetate was added to and dissolved in 307.0 g of the compound of the formula (1) as Synthesis Example 1, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 110 to 115 And reacted for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum.

< Synthetic example  4 : Carometer  Synthesis of binder resin (b-2) &gt;

600 g of propylene glycol monomethyl ether acetate was added to and dissolved in 307.0 g of the compound of formula (2) as synthesis example 2, 78 g of biphenyltetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 110 to 115 And reacted for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum.

< Comparative Synthetic Example  One : Carometer  Synthesis of binder resin (b-3)

200 g of a THF (tetrahydrofuran) solution as a reaction solvent was charged into a 500 ml four-necked flask and maintained at 50 캜. 89 g of the compound represented by the formula 6 was introduced and 44.5 g of the epichlorohydrin solution represented by the formula 7 was introduced at a rate of 5.25 g per minute using a dropping funnel and reacted for 1 hour and 30 minutes. At this time, n in the formula (7) was 1. 348 g of the bisphenol-based fluorene-type epoxy resin compound obtained by the reaction was charged into a 1000-mL reactor, 140.52 g of an acrylic acid solution was added, and the temperature was raised to 80 ° C to conduct the reaction. Thereafter, 13.5 g of tetraethylammonium bromide was slowly added thereto, and the reaction was allowed to proceed for 60 hours. 150 g of the above reaction product was placed in a reactor, and 180.5 g of anhydride (phthalic anhydride) and 348.8 g of anhydride (anhydrous pyromellitic acid) were added thereto and maintained at 120 ° C. At this time, 0.718 g of Fascat 4101 as a catalyst was slowly added thereto and reacted for 5 hours to prepare a binder resin.

[Chemical Formula 6]

(7)

Example  1 to 2 and Comparative Example  1 to 3

The colored photosensitive resin composition was prepared using the components and the content (unit: parts by weight, based on 100 parts by weight of the colored photosensitive resin composition) shown in Table 1 below.

division coloring agent Alkali-soluble resin Photopolymerizable compound Light curing
Initiator Solvent Silicone surfactant a b-1 b-2 b-3 b-4 c d e-1 e-2 f Example 1 25.0 12.8 - - - 5.2 1.0 21.5 34.3 0.2 Example 2 25.0 - 12.8 - - 5.2 1.0 21.5 34.3 0.2 Comparative Example 1 25.0 - - 12.8 - 5.2 1.0 21.5 34.3 0.2 Comparative Example 2 25.0 - - - 12.8 5.2 1.0 21.5 34.3 0.2 Comparative Example 3 25.0 12.8 - - - 5.2 1.0 21.5 34.5 - a: Pigment dispersion composition M1
b-1: Cathode binder resin of Synthesis Example 3 (cadmium-based binder resin of the present invention)
b-2: Cathode binder resin of Synthesis Example 4 (Cathode binder resin of the present invention)
b-3: The binder resin of Comparative Synthesis Example 1
b-4: Acrylic binder (benzylmethacrylate / N-phenylmaleimide / styrene / methacrylic acid) (molar ratio 55/9/11/25, Mw = 20,000, acid value 100 mgKOH / g)
c: KAYARAD DPHA (manufactured by Nippon Kayaku)
d: OXE-01 (manufactured by BASF)
e-1: Propylene glycol monomethyl ether acetate
e-2: Propylene glycol monomethyl ether
f: Non-reactive polyether-modified silicone compound SH8400 (manufactured by Toray Silicone Co., Ltd.) represented by the formula (3)

Manufacture of color filters

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3. Specifically, each colored photosensitive resin composition was coated on a 2-inch glass substrate ("EAGLE XG" manufactured by Corning) by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 to 50 m was placed on the thin film, and the distance between the test photomask and the test photomask was set to 100 m. Respectively. At this time, the ultraviolet ray was irradiated at a light intensity of 100 mJ / cm ² using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The ultraviolet irradiated thin film was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. Thereafter, the glass plate coated with the thin film was washed with distilled water, blown with nitrogen gas, dried, and heated in a 200 ° C heating oven for 25 minutes to prepare a color filter. The film thickness of the produced color filter was 2.0 탆.

< Experimental Example  1: Measurement of developing speed and adhesion>

(1) Adhesiveness

When the fishy pattern was evaluated through an optical microscope, the degree of the peeling phenomenon on the pattern was evaluated and shown in Table 2 below.

○: No pattern peeling

△: 1 to 3 pattern peeling

×: 4 or more patterns peeled off

(2) Development speed

The time taken for the unexposed portion to completely dissolve in the developing solution during the above process was measured and is shown in Table 2 below.

< Experimental Example  2: Measurement of development unevenness>

Was measured using a color filter manufactured in the same manner as in Experimental Example 1. The substrate of the color filter was checked for the presence of developing stains under a green lamp. In this case, the case where development unevenness is present is indicated by o, and the case where no development unevenness is indicated by x, which is shown in Table 2 below.

Fig. 1 (a) shows a case where there is no development unevenness, and Fig. 2 (b) shows a case where development unevenness occurs.

< Experimental Example  3: Sensitivity evaluation>

Proceeding in the same manner as in Experimental Example 1, the minimum exposure amount at which 90% or more of (film thickness before development / film thickness after development) was 90% or more was expressed as sensitivity, which is shown in Table 2 below.

example Adhesiveness Development speed (sec) Stain Sensitivity (mJ) Example 1 ○ 15 × 20 Example 2 ○ 14 × 20 Comparative Example 1 △ 18 ○ 40 Comparative Example 2 △ 17 ○ 40 Comparative Example 3 ○ 23 ○ 25

As shown in Table 2, the colored photosensitive resin compositions of Examples 1 and 2 according to the present invention had a faster development speed, superior sensitivity and adhesion, and no development unevenness, as compared with Comparative Examples 1 to 3 .

In addition, the color filter manufactured by the colored photosensitive resin composition of the present invention has an advantage of excellent adhesion and no peeling of the pattern during the development process.

Claims (8)

Alkali-soluble resins; And
A silicon-containing surfactant,
Wherein the alkali-soluble resin is at least one selected from the group consisting of a first cadosystem binder resin that is polymerized including a compound represented by the following formula (1) and a second cadoside binder resin that is polymerized to include a compound represented by the following formula / RTI &gt;
Wherein said silicone surfactant is represented by the following general formula (3): &lt; EMI ID =
[Chemical Formula 1]

(2)

(3)

In formula (1)
R1 and R2 are each independently

ego,
X is hydrogen, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group,
R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms,
In formula (2)
R4 and R5 are each independently

ego,
X is hydrogen, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group,
R6 is hydrogen or an alkyl group having 1 to 5 carbon atoms,
In formula (3)
x, y and n are each independently an integer of 1 to 10,
And Z is an alkylene glycol group having 2 to 4 carbon atoms. The method according to claim 1,
Wherein the alkali-soluble resin is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the total of the colored photosensitive resin composition. The method according to claim 1,
And the acid value of the first cadmium-based binder resin or second cadmium-based binder resin is 10 to 200 mgKOH / g. The method according to claim 1,
Wherein the first cadmium-based binder resin or the second cadmium-based binder resin has a weight average molecular weight of 1,000 to 30,000. The method according to claim 1,
Wherein the silicone-based surfactant is contained in an amount of 0.001 to 1.5 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive composition. The method according to claim 1,
A colorant, a photopolymerizable compound, a photopolymerization initiator, and a solvent. A color filter produced by using the colored photosensitive resin composition according to any one of claims 1 to 6. An image display device comprising the color filter of claim 7.

Images