KR20150028464A - Polyfunctional photocurable monomers having the carboxyl and acrylamide compounds, and photocurable resin composition comprising the same - Google Patents

Abstract

The present invention relates to a photo-curable resin composition comprising a photo-curable compound, a photoinitiator and a solvent, wherein the photo-curable compound comprises at least one carboxyl group, at least one acrylamide group and at least two acrylamide groups, Wherein the photocurable resin composition comprises a compound containing at least one photocurable vinyl group.

Description

[0001] The present invention relates to a photo-curable resin composition containing a carboxyl group and an acrylamide group, a photo-curable resin composition containing the photo-curable resin composition,

The present invention relates to a compound containing a carboxyl group and an acrylamide group, and a photocurable resin composition containing the same.

A color filter used in a liquid crystal display device is formed by forming fine pixels such as red, green, and blue on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like. In recent years, a pigment dispersion method having high productivity and excellent in fine workability, that is, a method using a photosensitive resin composition in which pigments are dispersed is widely used for the production of a color filter for a liquid crystal display device. In this method, a photosensitive resin composition in which a pigment is dispersed is coated on a transparent substrate such as glass to form a coating film, and the coating film is exposed to radiation through a photomask, and then the non-visible portion is removed by development And then the pattern is formed. Hereinafter, the photosensitive resin composition in which the pigment used for producing the color filter is dispersed is referred to as a photosensitive resin composition for a color filter.

The photosensitive resin composition for a color filter usually contains a pigment, a polymer resin for a binder, a photopolymerizable monomer, a photoinitiator, and a solvent, and a surfactant, an adhesion promoter, a residue reducing compound and the like are added thereto. In recent years, color filters have become increasingly colored in color and reproduced in high color, so that the pigment concentration in a composition for a color filter is increasing. However, as the concentration of the pigment in the composition for a color filter becomes higher, a metal oxide film such as glass, a chromium black matrix or ITO (indium tin oxide), or a metal oxide film such as a silicon nitride film There is a problem in that the amount is increased.

Accordingly, as a method for producing a composition so as not to leave a developing residue in order to reduce development residue, a technique for improving development characteristics by using a multifunctional photocurable monomer as a photocurable compound has been developed.

Specific examples of the multifunctional photocurable monomer include a multifunctional monomer including a carboxyl group, a multifunctional monomer including a phosphoric acid / sulfuric acid group, a multifunctional monomer including a urea / urethane, a multifunctional monomer including a hydroxyl group, Polyfunctional monomers including polyfunctional monomers and PEG / PPG, and the like.

However, when the multifunctional photo-curable monomer is used, the hydrolysis of the ester occurs unevenly on the surface of the cured part during development as shown in the following reaction formula, and the surface roughness is increased. As a result, the scattering of light increases on the surface, the haze increases, and the contrast decreases. Therefore, there is a need to study a multifunctional photocurable monomer for improving the above problems.

Korean Patent Publication No. 10-2006-0007600 Korean Patent Publication No. 10-2007-0056962

An object of the present invention is to produce a photo-curable resin composition having improved development and development resistance by using a compound containing at least one carboxyl group, at least one acrylamide group and at least two photocurable vinyl groups as a photo-curable compound .

In order to achieve the above object,

The present invention provides a compound represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

The present invention also provides a process for preparing a compound of Formula 1, which comprises reacting diethanolamine with maleic anhydride.

The present invention also provides a process for preparing the compound of Formula 2, wherein N, N'-bis (2-hydroxyethyl) ethylenediamine and maleic anhydride are reacted.

The present invention also provides a photo-curable resin composition comprising a photo-curable compound, a photoinitiator and a solvent, wherein the photo-curable compound is a compound having at least one carboxyl group, at least one acrylamide group and at least two photo- Wherein the photo-curable resin composition comprises a compound represented by the general formula (3).

(3)

Wherein R ₁ is an aliphatic hydrocarbon having 1 to 20 carbon atoms, which may or may not contain a carboxyl group, an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without a carboxyl group, an aliphatic hydrocarbon having 1 to 20 carbon atoms, Or an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without O or N,

R < _{2 >} is hydrogen or a methyl group,

Each of R ₃ to R ₆ is independently hydrogen or a carboxyl group,

Wherein R < ₇ > is a direct bond or NH,

Wherein R < ₈ > is O or NH,

M is an integer of 0 to 5,

Wherein n is an integer of 1 to 6,

When R ₁ does not contain a carboxyl group, at least one selected from the group consisting of R ₃ to R ₆ is a carboxyl group.

The photocurable resin composition of the present invention comprising at least one carboxyl group, at least one acrylamide group and at least two photocurable vinyl groups as a photocurable compound improves developability of an uncured portion and development resistance of a cured portion, And optical characteristics.

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

The present invention relates to a compound represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

The compounds of formulas (1) and (2) are characterized by containing a carboxyl group, an acrylamide group and a photocurable vinyl group.

In addition, the present invention provides a process for preparing the compounds represented by Chemical Formulas 1 and 2 above.

The compound of Formula 1 may be prepared by mixing diethanolamine and maleic anhydride in a molar ratio of 1: 2 to 1: 4, preferably 1: 3. The compound of Formula 2 may be obtained by mixing N, N'-bis (2-hydroxyethyl) ethylenediamine and maleic anhydride in a molar ratio of 1: 2 to 1: 6, preferably 1 : 4. Since the amine group in the molecule serves as an intramolecular catalyst, the catalyst is not necessary and can be obtained by heating under the condition of a solvent or a solvent-free condition.

The solvent which can be used in the production method using the solvent of the compounds of the formulas (1) and (2) is a carboxylic acid solvent containing an aprotic solvent or a hydroxyl group not containing a hydroxyl group. If it does not contain a hydroxyl group, it does not react with an acid anhydride, and even if it contains a hydroxyl group, the presence of a carboxylic acid group does not cause decomposition of an acid anhydride by a nucleophilic substitution reaction. Further, in order to omit the step of removing the solvent, it is more preferable to use the same solvent as that used for the color resist, and as the solvent, propylene glycol monomethyl acetate which is a solvent which does not contain a hydroxyl group is preferable.

The present invention also provides a photo-curable resin composition comprising a photo-curable compound, a photoinitiator and a solvent, wherein the photo-curable compound is a compound having at least one carboxyl group, at least one acrylamide group and at least two photo- And a compound represented by the general formula (3).

(3)

Wherein R ₁ is an aliphatic hydrocarbon having 1 to 20 carbon atoms, which may or may not contain a carboxyl group, an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without a carboxyl group, an aliphatic hydrocarbon having 1 to 20 carbon atoms, Or an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without O or N,

R < _{2 >} is hydrogen or a methyl group,

Each of R ₃ to R ₆ is independently hydrogen or a carboxyl group,

Wherein R < ₇ > is a direct bond or NH,

Wherein R < ₈ > is O or NH,

M is an integer of 0 to 5,

Wherein n is an integer of 1 to 6,

When R ₁ does not contain a carboxyl group, at least one selected from the group consisting of R ₃ to R ₆ is a carboxyl group.

When the photo-curable compound contained in the compound of Formula 3 is used in the photo-curing resin composition, a photo-curable resin composition having excellent developability and development resistance can be obtained.

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

(A) Photocurable  compound

The photocurable compound of the present invention is characterized by including a compound represented by the following general formula (3). The compound of formula (3) should have at least one carboxyl group, at least one acrylamide group and at least two photocurable vinyl groups in the molecule.

(3)

Wherein R ₁ is an aliphatic hydrocarbon having 1 to 20 carbon atoms, which may or may not contain a carboxyl group, an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without a carboxyl group, an aliphatic hydrocarbon having 1 to 20 carbon atoms, Or an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without O or N,

R < _{2 >} is hydrogen or a methyl group,

Each of R ₃ to R ₆ is independently hydrogen or a carboxyl group,

Wherein R < ₇ > is a direct bond or NH,

Wherein R < ₈ > is O or NH,

M is an integer of 0 to 5,

Wherein n is an integer of 1 to 6,

When R ₁ does not contain a carboxyl group, at least one selected from the group consisting of R ₃ to R ₆ is a carboxyl group.

Also, R ₁ is preferably one kind of compound selected from the group consisting of the following formulas (4) to (6).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The compound of formula (3) is characterized in that it is at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2) and the following formulas (7)

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

The photocurable compound is contained in an amount of 3 to 35% by weight based on the total weight of the photocurable resin composition of the present invention. When the photo-curing compound is included in the above range, it is possible to satisfy not only development and development resistance but also other optical and mechanical properties.

(B) Light Initiator

The photoinitiator (B) can be used without any particular limitation as long as it can polymerize the photo-curable compound (A).

In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, or price, the photoinitiator is preferably an acetophenone compound, a benzophenone compound, a triazine compound, a non- It is preferable to use 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 -On or 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 or 2,4,6-trimethylbenzophenone.

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 or 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) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Is used.

Specific examples of the oxime compounds include o-ethoxycarbonyl- [alpha] -oxyimino-1-phenylpropan-1-one, and commercially available products are OXE-01 and OXE-02 from BASF.

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

In addition, other photoinitiators and the like may be further used in combination within the range not impairing the effect of the present invention. For example, a benzoin compound or an anthracene compound may be used, and these may be used alone or in combination of two or more.

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

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

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid A methyl or a titanocene compound can be used in combination as a photoinitiator.

In order to improve the sensitivity of the photocurable resin composition of the present invention, the photoinitiator may further include a photopolymerization initiator (B-1). The photocurable resin composition according to the present invention contains a photopolymerization initiator auxiliary (B-1), so that the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation auxiliary, for example, 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 ) Or 4,4'-bis (diethylamino) benzophenone.

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 or naphthoxyacetic acid.

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 hexaquis (3-mercaptopropionate), or tetraethylene glycol bis (3-mercaptopropionate). .

The photoinitiator may be contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the total weight of the photocurable resin composition of the present invention. When the amount of the photoinitiator is within the above range, the photosetting resin composition is highly sensitized and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator is further used, it is preferable to use the same amount of the photopolymerization initiator as the photopolymerization initiator. When the photopolymerization initiator is used in the above amount, the sensitivity of the photocurable resin composition is further improved, The productivity of the filter can be improved.

(C) Solvent

The solvent used in the conventional photo-curable resin composition may be selected from solvents, aromatic hydrocarbons, ketones, alcohols, esters, and the like, as long as they are effective in dissolving other components contained in the photo- And amides are preferred.

Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as? -Butyrolactone.

Of these solvents, organic solvents having a boiling point of 100 ° C to 200 ° C are more preferably used in terms of coatability and dryness. Examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butylacetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

The solvents exemplified above may be used alone or in combination of two or more. The solvent may be contained in an amount of 60 to 95% by weight, preferably 70 to 85% by weight based on the total weight of the photocurable resin composition of the present invention. When the amount of the solvent is in the range of 60 to 95% by weight, the coating property becomes good when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) Effect.

The photo-curing resin composition may further contain a colorant, an alkali-soluble resin and a surfactant, if necessary.

(D) Colorant

The colorant may be added as needed, and is characterized by containing one or more pigments or one or more dyes.

( d1 ) Pigment

The pigment may be an organic pigment or an inorganic pigment generally used in the art.

The organic pigments or inorganic pigments may be 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 An anthanthrone pigment, an indanthrone pigment, an anthraquinone pigment, an anthraquinone pigment, an anthanthrone pigment, an anthanthrone pigment, an indanthrone pigment, an anthanthrone pigment, Pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides.

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.

These pigments (a1) may be used alone or in combination of two or more.

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.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (d2) by containing the pigment dispersant (d2), and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

( d2 ) Pigment Dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants and polyamine surfactants. , Which may be used alone or in combination of two or more.

It is also preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

As the pigment dispersant (a2), 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 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 content of the pigment dispersant (d2) is 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (d1). When the content of the pigment dispersant (d2) is more than 60 parts by weight, the viscosity may be high. When the content of the pigment dispersant (d2) is less than 5 parts by weight, it may be difficult to atomize the pigment or gelation after dispersion.

dyes( d3 )

The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and derivatives thereof. Preferably, the dye is a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70;

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent Orange Orange dye such as 2, 7, 11, 15, 26, 56

C.I. And green dyes such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 79, 93, 151; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferable, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent orange 45, 62 is more preferable.

Also, C.I. As an acid dye

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214,

Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169,

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like;

Violet color dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66

Green dyes such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

C.I. Acid Yellow 42 having excellent solubility in an organic solvent in C.I. acid dye; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

As a C.I. direct dye,

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , Yellow dyes such as 136, 138, and 141;

Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

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

Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Green dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77,

As C.I. modantoic dyes,

Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84;

Violet colored dyes such as C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Green dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

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

(E) an alkali-soluble resin

The alkali-soluble resin may be optionally added as needed. The alkali-soluble resin is copolymerized with an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development process when a pattern is formed do.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Anhydrides of dicarboxylic acids; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

A hydroxyl group may be imparted to the alkali-soluble resin in order to secure further developability. As a method for imparting the hydroxyl group, a method of copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, a method of adding a compound having a glycidyl group to a copolymer of an ethylenically unsaturated monomer having a carboxyl group And a method of reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group with a compound having a glycidyl group, and the like.

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer having hydroxyl group Can be used in combination.

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butylate, glycidyl methyl ether, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, And glycidyl methacrylate. Of these, butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are exemplified. The glycidyl group-containing compounds may be used in combination of two or more. .

The unsaturated monomers copolymerizable in the preparation of the alkali-soluble resin are exemplified below, but are not limited thereto.

Specific examples of the polymerizable monomer having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;

3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

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

In order to ensure compatibility of the alkali-soluble resin with the dye and storage stability of the photo-curable resin composition, the acid value is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the developing rate of the photo-curable resin composition is slow. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, Problems arise, the dye in the photocurable resin composition precipitates or the storage stability is lowered, and the viscosity tends to rise.

(F) Surfactant

The surfactant may be optionally added as needed, and may be used for further improving the film formation of the photocurable resin composition. The surfactant may be a silicone, a fluorine, an ester, a cation, an anion, a nonionic, And specific examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes , Polyethylene imines and the like.

Examples of the silicone surfactant include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF -4460, and TSF-4452.

Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

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

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

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

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.

≪ Synthesis of Compounds of Formulas (1) and (2)

Synthetic example  1. Synthesis of Compound (1)

Diethanolamine (52.5 g, 0.5 mol) was added to a 1 L reactor equipped with a cooling device to regulate the temperature of the nitrogen gas and reflux. Glacial acetic acid (500 mL) was added as a solvent and dissolved by stirring. A solution prepared by dissolving maleic acid anhydride (150 g, 1.51 mol) in 200 mL of glacial acetic acid at room temperature was added dropwise to the diethanolamine solution using a dropping funnel for 1 hour, stirred at room temperature for 5 hours, The solvent and the unreacted material were removed to obtain 200 g of a compound represented by the following formula (1). The reaction formula was as follows.

[Reaction Scheme 1]

NMR measurement revealed that the compound had the structure of the compound of formula (1).

¹ H-NMR (DMSO-d ₆ , 400 MHz):? 12.8 (3H), 6.70 (1H), 6.38 (4H), 6.00 (1H), 4.23 (4H), 3.59 (4H).

Synthetic example  2. Synthesis of Compound (2)

Except that N, N'-bis (2-hydroxyethyl) ethylenediamine (74.1 g, 0.5 mol) was used instead of diethanolamine and maleic anhydride (150 g, 1.51 mol) To obtain 270 g of a compound represented by the following formula (2). The reaction formula is shown below.

[Reaction Scheme 2]

NMR measurement revealed that the compound had the structure of the compound of formula (2).

¹ H-NMR (DMSO-d ₆ , 400 MHz):? 12.8 (4H), 6.70 (2H), 6.38 (4H), 6.00 (2H), 4.23 (4H), 3.24 (4H), 3.22

< Photocurable  Preparation of resin composition &gt;

Example  One.

10 g of the compound of Formula 1 prepared in Synthesis Example 1 and 0.1 g of I-184 as a photoinitiator were dissolved in 100 g of propylene glycol monomethyl acetate to prepare a photo-curable resin composition of Example 1 as a photo-curing compound.

Example  2.

10 g of the compound of Formula 2 prepared in Synthesis Example 2 and 0.1 g of I-184 as a photoinitiator were dissolved in 100 g of propylene glycol monomethyl acetate to prepare a photo-curable resin composition of Example 2 as a photo-curing compound.

Example  3.

5 g of the compound of the formula 1 prepared in Synthesis Example 1, 5 g of the compound of the formula 2 prepared in the above Synthesis Example 2 and 0.1 g of I-184 as the photoinitiator were dissolved in 100 g of propylene glycol monomethyl acetate as photo-curable compounds, 3 was prepared.

Example  4.

5 g of the compound of the formula 1 prepared in Synthesis Example 1, 5 g of the compound of the following formula 14 and 0.1 g of I-184 as a photoinitiator were dissolved in 100 g of propylene glycol monomethyl acetate as a photocurable compound to prepare a photocurable resin composition .

[Chemical Formula 14]

Comparative Example  1-4.

Each of the photo-curing resin compositions of Comparative Examples 1 to 4 was prepared by dissolving the compound of Formula 14, 10 g of the compound of Formula 15 to 17, and 0.1 g of I-184 as a photoinitiator in 100 g of propylene glycol monomethyl acetate as photo- .

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

Experimental Example  One. Photocurable  The resin composition Developability  evaluation

Each of the photo-curing resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4 was applied to a soda glass of 10 x 10 cm, dried, and then bar-coated to a thickness of 5 μm. And dried in an oven at 100 ° C for 1 minute to remove the solvent to prepare a color filter before exposure to evaluate developability.

The color filter before exposure was immersed in a KOH aqueous solution having a pH of 14 for 1 minute, then taken out of the apparatus, immersed in distilled water for 1 minute and then taken out and dried in an oven at 100 DEG C for 1 minute to check the surface state of the color filter before exposure.

The criteria for developing property are as follows.

No residual surface resin is observed at all:

Residual surface resin visible, but slightly visible:

The remaining surface resin was visually observed: x

Experimental Example  2. Photocurable  The resin composition Developmental resistance  evaluation

Each of the photo-curing resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4 was applied to a soda glass of 10 x 10 cm, dried, and then bar-coated to a thickness of 5 μm. After drying for 1 minute in a 100 ° C oven to remove the solvent, the color filter was prepared by exposing the Fusion Lamp to a total light intensity of 2000 mJ at a wavelength of 313 nm.

The color filter was immersed in a KOH aqueous solution having a pH of 14 for 10 minutes and then taken out. The color filter was then immersed in distilled water for 1 minute and taken out, followed by drying in an oven at 100 DEG C for 1 minute.

Haze characteristics determination criteria are as follows.

Haze is not visible on the surface at all: ○

Haze is visible on the surface, but is slightly visible: Δ

Haze visually observed on the surface: x

The results of Experimental Example 1 and Experimental Example 2 are shown in Table 2 below.

Developability Developmental resistance Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Comparative Example 1 △ × Comparative Example 2 ○ × Comparative Example 3 × × Comparative Example 4 △ ×

From the above results, the photocurable resin compositions of Examples 1 to 4 of the present invention containing the compound of Formula 3 as a photocurable compound showed no developability and no haze in the developability of the uncured portion and the development resistance of the cured portion Therefore, it can be said that it has excellent characteristics. On the other hand, the photocurable resin compositions of Comparative Examples 1 to 4 are excellent in developability, but haze is observed on the surface of all of the photocurable resin compositions, which is not suitable for the present invention. Therefore, the photo-curable resin composition of the present invention is a photo-curable resin composition which is excellent in developability and development resistance, has an effect of improving contrast, and can simultaneously improve processability and optical characteristics.

Claims (7)

A compound of the formula (1) or (2)
[Chemical Formula 1]

(2)

The method of claim 1, wherein the diethanolamine is reacted with maleic anhydride. A process for preparing a compound of formula (2) according to claim 1, wherein N, N'-bis (2-hydroxyethyl) ethylenediamine and maleic anhydride are reacted. A photocurable resin composition comprising a photocurable compound, a photoinitiator and a solvent, wherein the photocurable compound is a compound represented by the following formula (3), which comprises at least one carboxyl group, at least one acrylamide group and at least two photocurable vinyl groups, Wherein the photo-curable resin composition is a photocurable resin composition.
(3)

Wherein R ₁ is an aliphatic hydrocarbon having 1 to 20 carbon atoms, which may or may not contain a carboxyl group, an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without a carboxyl group, an aliphatic hydrocarbon having 1 to 20 carbon atoms, Or an aromatic hydrocarbon having 4 to 10 carbon atoms, with or without O or N,
R &lt; _{2 &gt;} is hydrogen or a methyl group,
Each of R ₃ to R ₆ is independently hydrogen or a carboxyl group,
Wherein R &lt; ₇ &gt; is a direct bond or NH,
Wherein R &lt; ₈ &gt; is O or NH,
M is an integer of 0 to 5,
Wherein n is an integer of 1 to 6,
When R ₁ does not contain a carboxyl group, at least one selected from the group consisting of R ₃ to R ₆ is a carboxyl group. The photo-curing resin composition according to claim 4, wherein R ₁ is one kind of compound selected from the group consisting of the following formulas (4) to (6).
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

5. The photocurable resin composition according to claim 4, which comprises 3 to 35% by weight of a photocurable compound, 0.01 to 10% by weight of a photoinitiator and 60 to 95% by weight of a solvent based on the total weight of the photocurable resin composition. [5] The photocurable resin composition according to claim 4, wherein the compound of Formula 3 is at least one compound selected from the group consisting of compounds represented by Chemical Formulas 1 and 2 and compounds represented by Chemical Formulas 7 to 13 below.
[Chemical Formula 1]

(2)

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]