KR20130055946A

KR20130055946A - Composition for color filter and color filter prepared from the same

Info

Publication number: KR20130055946A
Application number: KR1020110121635A
Authority: KR
Inventors: 박슬기; 이광호; 정보람
Original assignee: 동우 화인켐 주식회사
Priority date: 2011-11-21
Filing date: 2011-11-21
Publication date: 2013-05-29

Abstract

The present invention relates to a color filter forming composition and a color filter manufactured therefrom, and more particularly, to a color filter forming composition comprising a colorant, a binder resin, a photocurable monomer, a photoinitiator, and a solvent. By using the oxime ester-based compound represented by the present invention, a color filter forming composition and a color filter prepared therefrom having excellent sensitivity and almost no color change after curing, are also excellent.

Description

Composition for forming color filter and color filter manufactured therefrom {COMPOSITION FOR COLOR FILTER AND COLOR FILTER PREPARED FROM THE SAME}

The present invention relates to a color filter forming composition and a color filter manufactured therefrom, and more particularly, to a color filter forming composition excellent in adhesion to a substrate and applicable to a low power image display device, and a color filter manufactured therefrom. It is about.

A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof is rapidly expanding. In particular, in recent years, the use of LCD has been further expanded, and thus color filters have been recognized as one of the most important parts in reproducing the color tone of LCDs.

Such a color filter is manufactured by the method of forming a desired coloring pattern using the photosensitive resin composition containing a coloring agent. Specifically, it is produced by forming a coating layer of a composition for forming a color filter on a substrate, and repeating a series of processes of forming a pattern on the formed coating layer, exposing and developing, heating and thermosetting.

Therefore, the photosensitive resin composition for color filter formation fundamentally requires pattern formation ability and adhesiveness with a board | substrate. In addition, since the colorant contained in the photosensitive resin composition for color filter formation absorbs light of a specific wavelength, the composition needs to have excellent sensitivity. Furthermore, when a yellowing phenomenon occurs after curing, the resin composition for forming a color filter may affect the color of a colorant originally intended.

In order to solve these problems, various studies on various photoinitiators have been carried out. Among them, oxime compounds absorb ultraviolet rays and have almost no color, have high radical generation efficiency, and have good stability in the composition.

As the oxime compounds, α-oxooxime derivatives have been disclosed in JP-A-61-118423, JP-A-1-068750 and JP-A-3-004226, and US Pat. No. 4,255,513 Discloses an oxime ester compound using p-dialkylaminobenzene. U.S. Patent No. 4,202,697 discloses an acrylamino-substituted oxime ester compound, and U.S. Patent No. 4,590,145 discloses a benzophenone oxime ester compound. U.S. Patent No. 5,776,996 discloses a β-aminooxime compound, and U.S. Patent No. 6,051,367 discloses an oxime ester compound in which an ethylenically unsaturated group is contained in a molecular structure. In addition, International Patent Publication No. 00/052530 discloses oxime ether, oxime ester, oxime sulfonate compounds, and International Patent Publication No. 02/100903 discloses a process for the production of oxycarboxylic acids by coupling with alkyl acyl ketones, diarylketones or ketocoumarines &Lt; / RTI > is disclosed.

Of these oxime compounds, long conjugation compounds that absorb light having a long wavelength may have a slight color, which may affect the color when applied for optics. On the other hand, a compound that absorbs light of short wavelength has a disadvantage of low photoreactivity and low efficiency as a photoinitiator.

Japanese Unexamined Patent Application Publication No. 61-118423 (June 6, 1986) Japanese Laid-Open Patent Publication No. 1-068750 (Mar. 14, 1989) Japanese Unexamined Patent Application Publication No. 3-004226 (1991.01.10) U.S. Patent No. 4,255,513 (Mar. 3, 1981) U.S. Patent No. 4,202,697 (May 15, 1980) U.S. Patent No. 4,590,145 (May 5, 1986) U.S. Patent No. 5,776,996 (July 7, 1998) U.S. Patent No. 6,051,367 (Apr. 18, 2000) International Patent Publication No. 00/052530 (September 20, 2000) International Patent Publication No. 02/100903 (December 19, 2002)

An object of the present invention is to provide a composition for forming a color filter which is excellent in sensitivity, does not have a color upon curing, and does not have a discoloration phenomenon such as yellowing after curing, and a color filter prepared therefrom.

Further, an object of the present invention is to provide a color filter forming composition and a color filter manufactured therefrom, which are not only excellent in pattern forming ability and adhesion to a substrate, but also excellent in brightness, to implement a low power image display device.

1. A composition for forming a color filter comprising an oxime ester photoinitiator represented by Formula 1 below:

(Wherein R ₁ is an alkyl group having 1-10 carbon atoms; and R ₂ and R ₃ are independently a hydrogen atom, a halogen atom or an alkyl group having 1-6 carbon atoms).

2. In the above 1, R ₁ is a hexyl group is a composition for forming a color filter.

3. In the above 1, R ₂ and R ₃ is a hydrogen atom composition for forming a color filter.

4. In the above 1, the photoinitiator is a composition for forming a color filter containing 0.1 to 20% by weight relative to the total weight of the composition.

5. In the above 1, selected from the group consisting of triazine compound, acetophenone compound, biimidazole compound, oxime compound, benzoin compound, benzophenone compound, thioxanthone compound and anthracene compound A composition for forming a color filter further comprising at least one photoinitiator.

6. according to the above 1, a color filter forming composition further comprising a colorant, a binder resin, a photocurable monomer and a solvent.

7. In the above 6, the binder resin is a composition for forming a color filter is a polymer copolymerized mixed monomer including a norbornene-based monomer.

8. In the above 7, the norbornene-based monomer is 2 to 30 mol% relative to the total number of moles of the total monomer constituting the binder resin composition for color filters.

9. Color filter prepared by the composition for forming a color filter any one of the above 1 to 8.

10. Image display device having the color filter of the above 9.

The composition for forming a color filter of the present invention uses a photoinitiator having excellent sensitivity, so that the colorant absorbs light having a specific wavelength, thereby reducing photosensitiveness and hardly changing color after curing, thus affecting the color realization of the color filter. Not crazy In addition, the color filter made of the composition for forming a color filter of the present invention is excellent in brightness and can be very usefully used to implement an image display device at low power.

In addition, the composition for forming a color filter of the present invention is basically excellent in the ability to form a pattern, the adhesion to the substrate and the color filter prepared therefrom is excellent in solvent resistance, heat resistance, light resistance.

The present invention is a composition for forming a color filter comprising a colorant, a binder resin, a photocurable monomer, a photoinitiator, and a solvent. The present invention relates to a color filter forming composition having little change and excellent luminance, and a color filter prepared therefrom.

Hereinafter, the present invention will be described in detail.

The composition for forming a color filter of the present invention is characterized by comprising an oxime ester-based photoinitiator represented by Formula 1 below:

[Formula 1]

R ₁ represents an alkyl group having 1-10 carbon atoms such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, Of these, an alkyl group having preferably from 4 to 8 carbon atoms, most preferably a hexyl group.

R ₂ and R ₃ independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and among these, a hydrogen atom is preferable.

The oxime ester compound represented by the formula (1) may be exemplified by the compounds represented by the following formulas (2) to (6), but is not limited thereto.

The oxime ester compound according to the present invention contains benzophenone, which can enhance the photoreactivity and maximize the light efficiency by the energy transfer of benzophenone when irradiated with light, and at the same time, it does not show color even after light irradiation, The city is particularly advantageous.

These oxime ester compounds can be synthesized by a known synthetic process.

Specific examples of the preparation of the oxime ester compound represented by the formula (1) according to the present invention are described in Korean Patent Application No. 10-2011-107552, which is incorporated herein by reference in its entirety.

The composition for forming a color filter of the present invention may further include a photoinitiator used in the art without departing from the present invention. For example, a triazine compound, an acetophenone compound, a nonimidazole compound, an oxime compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, and an anthracene compound, Can be mixed and used.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] Propan-1-one oligomers and the like.

Examples of the acetophenone-based compounds usable in addition to the above-mentioned acetophenone-based compounds include compounds represented by the following general formula (7).

In Formula 7, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group or carbon number which may be substituted by an alkyl group having 1 to 12 carbon atoms. The naphthyl group which may be substituted by the alkyl group of 1-12 is shown.

Specific examples of the compound represented by Formula 7 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan- (4-morpholinophenyl) propane-1-one, 2-amino-2- 2-methyl-2-methylamino (4-morpholinophenyl) propane-1-one, 1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan- have.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole or a phenyl group at the 4,4', 5,5 ' An imidazole compound substituted by an alkoxy group, and the like. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole are preferably used.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

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.

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

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photoinitiators.

Further, in the present invention, the photoinitiator may be used in combination with a photoinitiator. When a photoinitiator is used together with a photoinitiator, the composition for color filter formation containing these is more sensitive, and since productivity at the time of forming a color filter using this composition is preferable, it is preferable.

As the photoinitiator, an amine compound or a carboxylic acid compound is preferably used.

Specific examples of the amine compound in the photoinitiation aid include aliphatic amine compounds such as triethanolamine, methyl diethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid isoamyl, 4 -Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'-bis Aromatic amine compounds, such as (diethylamino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The content of the photoinitiator is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the composition for forming a color filter, and the content of the photoinitiator is 0.1 to 20% by weight, preferably 1 to 10, based on the total weight of the composition. Weight percent. When the amount of the photoinitiator used is in the above range, the composition for color filter formation is highly sensitive, and thus the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion are favorable. Moreover, when the usage-amount of a photoinitiation adjuvant exists in the said range, since the sensitivity of the composition for color filter formation becomes high and the productivity of the color filter formed using this composition improves, it is preferable.

The composition for forming a color filter of the present invention may include a colorant, a binder resin, a photocurable monomer, a photoinitiator, and a solvent. The photoinitiator may include an oxime ester compound represented by Chemical Formula 1, and other components are sugars. Components usable in the field can be used without limitation.

The colorant may be an organic colorant such as a pigment, a dye, a synthetic or natural pigment, or an inorganic colorant such as a metal oxide, a metal complex salt, or barium sulfate (sieve pigment).

As the colorant, compounds classified as pigments and dyes in the Color Index (The Society of Dyers and Colourists) may be used, and these may be used alone or in combination of two or more thereof.

Specific examples of the pigment include C.I. Pigment Yellow No. 1, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Pigment Red No. 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264, 265; C.I. Pigment Blue No. 15, 15: 3, 15: 4, 15: 6, 60; C.I. Pigment Purple No. 1, 14, 19, 23, 29, 32, 33, 36, 37, 38; C.I. Pigment Green No. 7, 10, 15, 25, 36, 47; C.I. Pigment brown 23, 25, 28; C.I. Pigment Black No. 1, 7, carbon black, etc. are mentioned.

Specific examples of the dyes include C.I. Solvent yellow 2, 14, 16, 33, 34, 44, 56, 82, 93, 94, 98, 116, 135; C.I. Solvent orange No. 1, No. 3, No. 7, No. 63; C.I. Solvent Red 1, 2, 3, 8, 18, 23, 24, 27, 35, 43, 45, 48, 49, 91: 1, 119, 135 No. 140, No. 196, No. 197; C.I. Solvent purple 8, 9, 13, 26, 28, 31, 59; C.I. Solvent blue Nos. 4, 5, 25, 35, 36, 38, 70; C.I. Solvent green 3, 5, 7 and the like.

The colorant may be adjusted in accordance with the required color properties, it may be included in 1 to 50% by weight, preferably 1 to 30% by weight in 100% by weight of the total ink composition.

The binder resin usually has reactivity and alkali solubility by the action of light or heat and acts as a dispersion medium of the colorant. The binder resin contained in the resin composition for color filter formation of the present invention can be used as long as it is a binder resin that acts as the binder resin in the colorant and is soluble in the alkaline developer used in the developing step for producing the color filter.

Preferably, in the present invention, the binder resin is preferably prepared including a norbornene-based monomer. The binder resin prepared by using a norbornene-based monomer is not only excellent in chemical resistance but also has a merit of lowering luminance when the color filter is manufactured in combination with the photoinitiator according to the present invention.

For example, the binder resin of the present invention is a copolymer of (a) a norbornene-based monomer represented by the following formula (8), (b) a monomer copolymerizable with a norbornene-based monomer, and (c) a monomer including an unsaturated bond with a monomer. It may be a copolymer prepared by.

(Wherein n is 0 or 1; R ₁ , R ₂ are independently from each other hydrogen, an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 1 to 12 carbon atoms; R ₃ , R ₄ , R ₅ , R ₆ is an aliphatic or aromatic hydrocarbon containing or without hydrogen, a hydroxy group, a hetero atom having 1 to 30 carbon atoms, depending on the position, and preferably, independently of each other, hydrogen, a carboxy group, a hetero atom having 1 to 30 carbon atoms Alkylene or alkenylene containing or without, wherein two selected from R ₃ , R ₄ , R ₅ , R ₆ may have a linked ring form, R ₃ , R ₄ , R in the form of a chain or ring ₅ , R ₆ independently of one another may include a carbonyl group or may be substituted with an alkyl, hydroxy or phenyl group having 1 to 5 carbon atoms.)

The norbornene-based monomer represented by Formula (a) 8 may be more specifically selected from at least one of compounds having the structural formulas of Formulas 9 to 24 below.

Specific examples of the monomer copolymerizable with the (b) norbornene-based monomer are as follows.

First, styrene, chlorostyrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether and aromatic vinyl monomers such as p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene. It is preferable because it is excellent in developability and processability.

Further, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, N-phenyl maleimide, No-hydroxyphenyl maleimide, Nm-hydroxyphenyl maleimide, Np-hydroxyphenyl maleimide , N-substituted maleimide monomers such as No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide Among these, N-benzyl maleimide is preferable because it is excellent in developability and processability.

In addition, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylic 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) ) Acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylic Latex, methoxytripropyl Glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth ) Acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluoro Rhodecyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acyloloxyethylhydrogen succinate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, (Meth) acrylates, such as propyl (alpha)-hydroxymethyl acrylate and butyl (alpha)-hydroxymethyl acrylate, are mentioned, Among these, benzyl methacrylate is preferable because it is excellent in developability and processability.

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

The monomer having an unsaturated bond with the (c) carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and specific examples thereof include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, at least one other acid may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen at least 1 sort (s) from other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.

According to the present invention, in the copolymers obtained by copolymerizing the above-mentioned (a) to (c) (which is included in the present invention even when a monomer other than a to c is further included and copolymerized), each of (a) to (c) The proportion of the constituents derived from is preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

structural units derived from (a): 2 to 30 mole%,

structural units derived from (b): 2 to 95 mole%,

structural units derived from (c): 2 to 70 mole%

In particular, the ratio of the constituents derived from each of the above (a) to (c) is more preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

structural units derived from (a): 5 to 30 mole%,

structural units derived from (b): 5 to 80 mole%,

structural unit derived from (c): 5 to 65 mol%

As described above, when the ratio of the constituents derived from each of (a) to (c) is within the above range, a good balance of developability, solubility and heat resistance can be obtained, so that a preferable copolymer can be obtained.

According to an embodiment of the present invention, the binder resin is a compound (c) having an unsaturated bond with a norbornene skeleton compound (a), an aromatic vinyl compound or an N-substituted maleimide compound (b), and a carboxyl group represented by Formula 1 Photo / thermosetting property can be provided to binder resin by adding the compound (d) which has an unsaturated bond and an epoxy group in 1 molecule to the copolymer obtained by the copolymerization reaction of the compound containing these.

Specific examples of the compound (d) having an unsaturated bond and an epoxy group in the above one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth). ) Acrylate, methylglycidyl (meth) acrylate, and the like. Of these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more. In the present invention, (meth) acrylate means acrylate and / or (meth) acrylate.

The compound (d) having an unsaturated bond and an epoxy group in the one molecule is preferably reacted at a molar fraction of 5 to 80 mol% with respect to the number of moles of the constituent derived from the compound (d) having a carboxyl group and an unsaturated bond in the copolymer. In particular, 10 to 80 mol% is preferable. When compound (d) which has an unsaturated bond and an epoxy group exists in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and it is excellent in reliability, and it is preferable.

The binder resin according to the present invention can be prepared by adopting a known method known in the art. An embodiment of the preparation is described as follows.

To a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, 0.5 to 20 times the amount of solvent was introduced together on the basis of the mass with respect to the total mass of (a) to (b). I replace my atmosphere with nitrogen in the air. Then, after raising a solvent to 40-140 degreeC, 0-20 times of the solvent and azo on a mass basis with respect to the predetermined amount of (b) and (c), and the total mass of (b)-and (c3). A solution in which a polymerization initiator, such as bisisobutyronitrile or t-butylperoxy 2-ethylhexyl carbonate, is added in an amount of 0.1 to 10 mol% by mole fraction with respect to the total number of moles of (a) to (c) (agitated and dissolved at room temperature or under heating). ) Is added dropwise to the flask from 0.1 dropping lot over 0.1 to 8 hours, and further stirred at 40 to 140 ° C for 1 to 10 hours.

In said process, one part or whole quantity of a polymerization initiator may be put in a flask, and a part or whole quantity of (a)-(c) may be put in a flask. When (d) is polymerized to the copolymer obtained by copolymerizing the said (a)-(c), the remainder of (a)-(c) may be added in the process.

As the solvent used in the above process, a solvent used in a normal radical polymerization reaction may be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether , Toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

As the polymerization initiator to be used in the above step, a commonly used polymerization initiator may be added and is not particularly limited. Specifically, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexyl carbonate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl 2,2'-azobis (2-methylpropionate), etc. And nitrogen compounds. These can be used individually or in combination of 2 or more types.

In addition, in the copolymer obtained by copolymerizing the above-mentioned (a) to (c), in order to control molecular weight and molecular weight distribution in a polymerization process, (alpha) -methylstyrene dimer or a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005-5 mass% in mass fraction with respect to the total mass of (a)-(c). In addition, the above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

In the present invention, the binder resin preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. If the weight average molecular weight of the binder resin is in the range of 3,000 to 100,000, film reduction is unlikely to occur at the time of development, and it is preferable because the missing property of the non-pixel portion at the time of development is good.

The acid value of the binder resin is preferably in the range of 30 to 150 mgKOH / g based on solid content. When the acid value is less than 30 mgKOH / g, the developability against alkaline water is lowered and the residue may remain on the substrate. If the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern increases.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin, it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because it is excellent in developability.

The content of the binder resin is in the range of 1 to 30% by weight, preferably 1 to 20% by weight based on the total weight of the color filter forming composition. When the content of the binder resin is 1 to 15% by weight based on the above criteria, the solubility in the developing solution is sufficient, so that development residues are less likely to occur on the substrate of the non-pixel portion, and it is difficult to reduce the film portion of the pixel portion of the exposed portion during development. It is preferable because the omission of the pixel portion is good.

The photocurable monomer contained in the composition for color filter formation of this invention is a compound which can superpose | polymerize by the action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

The photocurable monomer used in the present invention may be used by mixing two or more photocurable monomers having different functional groups or functional groups in order to improve the developability, sensitivity, adhesion, and surface problems of the color filter forming composition. Does not limit its scope

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, multifunctional monomers having two or more functional groups are preferably used.

The photocurable monomer is used in the range of 1 to 15% by weight, preferably 1 to 10% by weight, based on the total weight of the color filter forming composition. If the photocurable monomer is in the range of 1 to 15% by weight based on the above criteria, the strength and smoothness of the pixel portion will be good, which is preferable.

The solvent contained in the composition for color filter formation of the present invention is not particularly limited and various solvents used in the art may be used without limitation. Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc .; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; Alkylene glycol alkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether; (Alkoxy) alkyl esters such as ethyl acetate, ethyl lactate, methyl cellosolve acetate, ethyl cellosolve acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, can be used individually or in mixture of 2 or more types, respectively.

Among the solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferable in the solvents in terms of applicability and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy. Ester, such as ethyl propionate and the methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. are mentioned. These solvents (E) may be used alone or in combination of two or more.

The content of the solvent in the color filter-forming composition of the present invention is 40 to 90% by weight, preferably 50 to 85% by weight relative to the total weight of the color filter-forming composition. If the solvent content is in the range of 40 to 90% by weight, the applicability becomes good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable because of that.

Optionally, the composition for forming a color filter of the present invention is a filler, another polymer compound, a curing agent, a pigment dispersant. It may further include additives such as adhesion promoters, antioxidants, ultraviolet absorbers, and anti-agglomerates.

Specific examples of the filler include glass, silica, alumina and the like.

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

The curing agent is used for enhancing deep curing and mechanical strength. Examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins and other aromatic epoxy resins and alicyclic compounds. Epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

As said oxetane compound in the said hardening | curing agent, carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, a terephthalate bis oxetane, a cyclohexane dicarboxylic acid bis oxetane, etc. are mentioned, for example. .

The curing agent may be used together with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents can be used. As the epoxy resin curing agent, for example, there may be mentioned epoxy resin curing agents such as trade name (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade name (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.).

The said hardening | curing agent can be used individually or in mixture of 2 or more types.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, Polyethyleneimines and the like, and other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (made by Dainippon Ink & Chemicals Co., Ltd.), Florad (made by Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, manufactured by Asahi Glass Co., Ltd.), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned.

These adhesion promoters may be used alone or in combination of two or more.

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

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

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

The composition for color filter formation of this invention can be manufactured by the following method, for example. The colorant is previously mixed with the solvent and dispersed using a bead mill or the like until the average particle diameter of the colorant is about 0.2 µm or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin may be blended. The remaining color of the binder resin, the photocurable monomer and the photoinitiator, other components used as necessary, and additional solvents as necessary, are further added to the obtained dispersion liquid (sometimes referred to as a mill base) to a desired color. The composition for filter formation can be obtained.

The present invention provides a color filter comprising a color layer formed by forming the color filter forming composition according to the present invention in a predetermined pattern and then exposing and developing the same, and an image display device having the same.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Example 1-5 and Comparative example 1-3

< Synthetic example Synthesis of Binder Resin

Into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen inlet tube, 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether and 11.0 g (0.10 mol) of 2-norbornene were mixed. The atmosphere in the flask was introduced into nitrogen from air, and after heating up to 80 ° C., 70.5 g (0.4 mol) of benzyl methacrylate, 45.0 g (0.5 mol) of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate were included. A solution obtained by adding 3.2 g of t-butylperoxy 2-ethylhexyl carbonate to the mixture was added dropwise to the flask over 2 hours from the dropping lot, followed by further stirring at 100 ° C for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate [0.2 mol (40 mol% relative to the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 of hydroquinone g was put in the flask, the reaction was continued at 110 ° C for 6 hours to obtain a resin having a solid acid value of 100 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 31,000, and molecular weight distribution (Mw / Mn) was 2.3.

At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin were measured by using an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, and the detector RI was used, and the measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), for calibration. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as a standard material.

<Production of Composition for Color Filter Formation>

A composition for color filter formation was prepared using the components and compositions shown in Table 1 below (unit: wt%).

Example Comparative Example One 2 3 4 5 One 2 3 coloring agent Colorant (A1) 2.98 2.98 2.98 2.98 2.98 2.98 2.98 2.98 Colorant (A2) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Binder Resin (B) of Synthesis Example 1 6.52 6.52 6.52 6.52 6.52 6.52 6.52 6.52 Photocurable monomer (C) 6.16 6.16 6.16 6.16 6.16 6.16 6.16 5.83 Photoinitiator
(D) Initiator (D1) 1.46 - - - - - - - Initiator (D2) - 1.46 - - - - - - Initiator (D3) - - 1.46 - - - - - Initiator (D4) - - - 1.46 - - - - Initiator (D5) 1.46 Initiator (D6) - - - - - 1.46 - 1.79 Initiator (D7) - - - - - - 1.46 - Initiator (D-1) 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 Solvent (E) 80.46 80.46 80.46 80.46 80.46 80.46 80.46 80.46 Additive (F) Additive (F1) 1.49 1.49 1.49 1.49 1.49 1.49 1.49 1.49 Additive (F2) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Colorant (A1): Blue Pigment Dispersion (CI Pigment Green 58)
Colorant (A2): Yellow Pigment Dispersion (CI Pigment Yellow 150)
Photocurable monomer (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Photoinitiator (D1): Oxime ester compound represented by the formula (2)
Photoinitiator (D2): Oxime ester compound represented by the formula (3)
Photoinitiator (D3): Oxime ester compound represented by the formula (4)
Photoinitiator (D4): Oxime ester compound represented by the formula (5)
Photoinitiator (D5): Oxime ester compound represented by the formula (6)
Photoinitiator (D6): 1,2-octanedione-1- [4- (phenylthio) phenyl] -2-O-benzoyloxime (Ciba)
Photoinitiator (D7): 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1-O-acetyloxime (Ciba)
Photoinitiator (D-1): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.)
Solvent (E): Propylene Glycol Monomethyl Ether Acetate
Additive (F1): Pigment Dispersant (Acrylic)
Additive (F2): 3-methacryloxypropyltrimethoxysilane

Test Example

< Test Specimen Production>

A glass substrate of 2 square inches (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On the glass substrate, the above-mentioned composition for color filter formation (Table 1) is exposed to an exposure amount (365 nm) of 100 mJ / cm 2 and spin-coated so that the film thickness after post-firing when the developing step is omitted is 3.2 占 퐉, Subsequently, it was pre-dried at 100 degreeC for 3 minutes in the clean oven. After cooling, the substrate and the quartz glass photomask coated with the composition for forming a color filter (a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space from 1 μm to 50 μm (L / S) The pattern was spaced at 100 μm, and was irradiated with an exposure dose (365 nm) of 100 mJ / cm 2 under an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd. Thereafter, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 230 ° C. for 60 minutes after washing with water. No surface roughness was found in the obtained pixel portion. In addition, the development residue did not generate | occur | produce on a non-pixel part on a board | substrate.

One. Tearing

In forming the pattern with the composition of the Examples and Comparative Examples, the minimum required exposure amount necessary to prevent line tearing in the L / S after the development process was measured, and the results are shown in Table 2 below after evaluating according to the following criteria. Described.

○: 20 mJ or less

X: 20 mJ or more

2. Transmittance

After forming a pattern with the compositions of Examples and Comparative Examples, the transmittance was measured. The transmittance (Y) of the pattern cured with the composition of Example 1 on the same (x, y) color coordinate was 100% and evaluated according to the following criteria, and the results are shown in Table 2 below.

○: transmittance decrease is less than 5%

X: transmittance fall is 5% or more

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Tearing ○ ○ ○ ○ ○ X ○ ○ Permeability
(Same x, y to Y) ○ ○ ○ ○ ○ ○ X X

As shown in Table 2, in Examples 1 to 5 using the photoinitiator according to the present invention, it can be confirmed that there is no decrease in line tearing and transmittance of the pattern even at low exposure doses compared to Comparative Examples 1 to 3 which do not include the same. .

Claims

A composition for forming a color filter comprising an oxime ester photoinitiator represented by Formula 1 below:
[Formula 1]

The composition for forming a color filter of claim 1, wherein R ₁ is a hexyl group.

The composition for forming a color filter of claim 1, wherein R ₂ and R ₃ are hydrogen atoms.

The composition of claim 1, wherein the photoinitiator is included in an amount of 0.1 to 20 wt% based on the total weight of the composition.

The method according to claim 1, at least one selected from the group consisting of triazine compound, acetophenone compound, biimidazole compound, oxime compound, benzoin compound, benzophenone compound, thioxanthone compound and anthracene compound The composition for forming a color filter further comprising the above photoinitiator.

The composition for forming a color filter according to claim 1, further comprising a colorant, a binder resin, a photocurable monomer, and a solvent.

The composition for forming a color filter of claim 6, wherein the binder resin is a polymer in which a mixed monomer including a norbornene-based monomer is copolymerized.

The composition for forming a color filter of claim 7, wherein the norbornene-based monomer is 2 to 30 mol% with respect to the total moles of all monomers constituting the binder resin.

The color filter manufactured with the composition for color filter formation of any one of Claims 1-8.

An image display device provided with the color filter of claim 9.