KR101225955B1 - Ink jet resin composition - Google Patents

Abstract

The present invention relates to a resin composition for inkjet, wherein the composition is (A) iii) 20 to 80% by weight of dioxolane compound, ii) 5 to 40% by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof, And iii) an acrylic copolymer obtained by copolymerizing 5 to 50% by weight of an epoxy group-containing unsaturated compound; (B) photopolymerizable monomer; (C) photoinitiator; (D) a black pigment; And (E) a solvent.

The resin composition according to the present invention has excellent performances such as adhesion, flatness, optical density, and the like, and is suitable for use for forming an inkjet partition by improving adhesion with an organic insulating film.

Inkjet, light shield, bulkhead

Description

Resin composition for inkjet {INK JET RESIN COMPOSITION}

The present invention relates to an inkjet resin composition, and more particularly, to an inkjet resin composition which is excellent in adhesiveness, flatness, optical density, and the like, and has significantly improved physical properties such as adhesion to organic insulating films and coating properties. will be.

A display device such as a liquid crystal display has a structure in which a liquid crystal layer is interposed between two substrates on which paired electrodes are formed to face each other. In addition, a color filter having pixels consisting of colors such as red (R), green (G), and blue (B) is formed inside one substrate. In this color filter, in order to prevent the mixing of different colors in each pixel or to hide the pattern of the electrode, the color filter is usually arranged in a matrix so as to partition pixels of R, G, and B colors. A light shielding film is formed. In general, color filters are formed by lithography. 1 is a diagram illustrating a process of manufacturing a color filter. As shown in FIG. 1, a black photosensitive composition is coated on the substrate 10 and then softbaked to form a light shielding film 12 (S11). Subsequently, the light shielding film 12 is patterned after exposure to a predetermined mask pattern (S12). Subsequently, by repeating application, exposure, and development for each of the photosensitive compositions of each of the red (R), green (G), and blue (B) colors, a pattern of each color is formed at a predetermined position to form a color filter ( 14) (S14). The patterned light shielding film serves as a partition wall when the color filter is formed by an inkjet method. Ink is drawn into the partition wall by an ink jet method to form a color filter 14. Then, the organic insulating layer 16 is formed on the color filter 14 (S15).

And when forming a color filter by an inkjet method, the partition for inkjet type color filter formation formed from the black photosensitive composition is used. Since this partition is black, it also serves as a light shielding film. The partition wall is formed to have an opening (part enclosed by the partition wall) for collecting ink. On the other hand, when the inkjet method is applied to the lower plate, that is, the upper portion of the TFT (Thin Film Transistor), the organic insulating layer 16 is raised on the color filter 14 due to the dielectric constant and flatness of the black photosensitive material used in the light shielding film 12. A problem arises in the applicability and adhesion of the black photosensitive material. In addition, since the organic insulating film 16 is raised on the pixels of the red (R), green (G), and blue (B) colors for forming the color filter, the color visibility and the reduction of the luminance portion are expected.

One embodiment of the present invention is to provide an inkjet resin composition having excellent adhesion to an organic insulating film and excellent adhesion to a lower film, flatness, and optical density.

Another embodiment of the present invention is to provide a liquid crystal display device comprising a light shielding film manufactured using the resin composition.

Another embodiment of the present invention is to provide a method for producing a color filter using the resin composition.

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, and other technical problems will be clearly understood by those skilled in the art from the following description.

According to one embodiment of the present invention, an acrylic copolymer obtained by copolymerizing (A) iii) a dioxolane-based compound, ii) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, and iii) an epoxy group-containing unsaturated compound; (B) photopolymerizable monomer; (C) photoinitiator; (D) a black pigment; And (E) provides a resin composition for ink jet comprising a solvent.

According to another embodiment of the present invention, a liquid crystal display device including a light shielding film manufactured using the resin composition for inkjet is provided.

According to another embodiment of the present invention, a method of manufacturing a color filter using the resin composition is provided.

Other specific details of embodiments of the present invention are included in the following detailed description.

The resin composition for inkjets according to the present invention is excellent in adhesion to the organic insulating film, and excellent in heat resistance, flatness, and optical density. In addition, the manufacturing method of the color filter using the said inkjet resin composition can prevent a white color visibility and a fall of brightness by not apply | coating an organic insulating film on an inkjet ink composition.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

An inkjet resin composition according to an embodiment of the present invention is obtained by copolymerizing (A) iii) a dioxolane-based compound, ii) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, and iii) an epoxy group-containing unsaturated compound. Acrylic copolymers; (B) photopolymerizable monomer; (C) photoinitiator; (D) a black pigment; And (E) a solvent.

In this specification, unless specified otherwise, "substituted" means that at least one hydrogen of the compound is substituted with a substituent selected from the group consisting of halogen, alkyl group, aryl group, alkoxy group, amino group, and alkenyl group.

In the present specification, unless otherwise specified, an "alkyl group" means an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, an "aryl group" means an aryl group having 6 to 30 carbon atoms. Preferably an aryl group having 6 to 18 carbon atoms, and an alicyclic group means a cycloalkyl group, a cycloalkenyl group, or a cycloalkynyl group having 3 to 20 carbon atoms.

Hereinafter, each component included in the black resin composition for inkjet according to one embodiment of the present invention will be described in detail.

(A) an acrylic copolymer

The said acryl-type copolymer is a copolymer specifically, containing a (A) 'dioxolane type compound, ii) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, and (iv) an epoxy-group-containing unsaturated compound as a monomer.

Iii) dioxolane compounds

The dioxolane-based compound improves the adhesion to the interlayer organic insulating film, the etch resistance and the heat resistance of the resin composition, and preferably has a structure represented by the following formula (1).

[Formula 1]

(In the formula 1,

R ₁ and R ₂ are the same or independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alicyclic group, or are connected to each other and fused to a fused ring Form the

R ₃ is a hydrogen atom or a substituted or unsubstituted alkyl group, wherein the alkyl group is preferably a methyl group,

R and R 'are the same or independently of each other a hydrogen atom and a substituted or unsubstituted alkyl group,

n is an integer from 1 to 5.)

The fused ring means a fused ring of the same or different aryl groups, a fused ring of the same or different alicyclic groups, or a fused ring of an aryl group and an alicyclic group.

Specific examples of the dioxolane-based compound include 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate, 2-isobutyl-2-methyl-1,3-dioxolan-4yl-methyl Acrylate, 1,4-dioxane spiro- [4,5] -dec-2yl-methylacrylate, 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl methacrylate, 2 Isobutyl-2-methyl-1,3-dioxolan-4yl-methyl methacrylate, 1,4-dioxaspiro- [4,5] -dec-2yl-methacrylate, 2,2- Dimethyl-1,3-dioxolane-4yl-methacrylate and mixtures thereof can be used. 　

The dioxolane-based compound may be used alone or in mixture of two or more thereof, preferably contained in an amount of 10 to 80% by weight, and more preferably in an amount of 20 to 80% by weight, based on the total amount of monomers used in preparing the acrylic copolymer. It is more preferable that it is included in 30 to 60% by weight. If it is less than 10% by weight may cause a problem that the heat resistance of the acrylic copolymer is lowered, if it exceeds 80% by weight may cause a problem that the storage stability of the acrylic copolymer is lowered is not preferable.

Ii) unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof

As said unsaturated carboxylic acid and unsaturated carboxylic anhydride, Unsaturated monocarboxylic acids, such as acrylic acid and methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And those selected from the group consisting of these anhydrides, and these may be used alone or in combination of two or more thereof. Among these, it is more preferable to use those selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof having better copolymerization reactivity and solubility in aqueous alkali solution.

The unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof is preferably included in an amount of 5 to 40% by weight, and more preferably in an amount of 10 to 30% by weight, based on the total amount of monomers used in preparing the acrylic copolymer. Do. If it is less than 5% by weight, there is a problem of hardening action, which is not preferable. If it exceeds 40% by weight, there is a problem that the chemical resistance of the acrylic copolymer to the developer is inferior.

Viii) epoxy group-containing unsaturated compounds

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid β- Acrylic glycidyls such as -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethyl glycidyl and methacrylic acid-beta -ethyl glycidyl; Acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxy Acrylic acid epoxy alkyls such as heptyl; vinyl benzyl glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, or p-vinyl benzyl glycidyl ether, and the like can be used. Can be used. Among these, methacrylic acid glycidyl, methacrylic acid-(beta) -methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, It is preferable to use one selected from the group consisting of p-vinylbenzyl glycidyl ether and mixtures thereof because it can improve the copolymerization reactivity and the heat resistance of the resulting pattern.

The epoxy group-containing unsaturated compound is preferably contained in 5 to 50% by weight, more preferably in 10 to 40% by weight relative to the total amount of the monomer used in the production of the acrylic copolymer. If it is less than 5% by weight, there is a problem that the heat resistance of the resulting pattern is lowered, which is not preferable. If it exceeds 50% by weight, there is a problem that the storage stability of the acrylic copolymer is lowered, which is not preferable.

The acrylic copolymer may be prepared by radically polymerizing the unsaturated monomers of (i) to (i) in the presence of a solvent and a polymerization initiator, and removing unreacted monomers by a process such as precipitation, filtration, and vacuum drying.

At this time, the solvent used in the preparation of the copolymer is methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methylethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol ethyl ether propionate, propylene glycol Lofil ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl lactate , Butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propyl propionate, 3-hydroxy butyl propionate, 2-hydroxy 3-methyl butyrate, methyl methoxy acetate, methoxy Ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, prop Butyoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropionic acid Butyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionate Butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-Ethoxy Propionate, 3-Ethoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propyl Propionate, 3-Butoxy Propionate, 3 Ethers such as ethyl butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate, or a combination thereof;

In addition, a radical polymerization initiator may be used as the polymerization initiator. The radical polymerization initiator is 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy 2,4-dimethyl Valeronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2'-azobisisobutylate, and the like can be used.

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion of the said (A) acrylic copolymer is 3,000-30,000, and it is more preferable that it is 5,000-20,000. If the weight average molecular weight is less than 3,000, the residual film ratio, flatness and the like tends to be lowered, or heat resistance or adhesive strength tends to be lowered.

In addition, the acrylic copolymer may be included in 0.1 to 30% by weight, preferably 0.5 to 20% by weight relative to the total amount of the photosensitive resin composition. Within the above range, the etching resistance and adhesion can be improved, which is preferable.

(B) photopolymerizable monomer

The photopolymerizable monomer functions to maintain the heat resistance and pattern stability of the black resin composition, and preferably a polyhydric acrylic monomer may be used.

Examples of the polyhydric acrylic monomers include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having a number of ethylene oxide groups of 2 to 14, trimethylolpropanedi (meth) acrylate, and trimethylolpropane tri (meth). Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene glycol di (meth) acrylate having 2 to 14 propylene oxide groups, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate. 　 Compounds obtained by esterifying a polyhydric alcohol selected from the group consisting of dipentaerythritol tri (meth) acrylate with acrylic acid or methacrylic acid; Compounds obtained by adding (meth) acrylic acid to glycidyl group-containing compounds such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Ester compounds or polyisocyanates with compounds having a hydroxyl group and an acryl group such as phthalic acid diester of β-hydroxyethyl (meth) acrylate, toluene diisocyanate adduct of β-hydroxyethyl (meth) acrylate, and polyhydric carboxylic acid; Adducts of; One or two or more selected from alkyl esters of acrylic acid or methacrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate can be used in combination. have. The polyvalent acrylic monomer is preferably included in 0.1 to 30% by weight based on the total amount of the photosensitive resin composition. If the content is less than 0.1% by weight, the formability of the pattern may be inferior. If the content is more than 30% by weight, the crosslinking degree of the film may be increased, resulting in deterioration of physical properties and thermal stability of the film.

(C) photopolymerization initiator

The photoinitiator used in the present invention is a photoinitiator generally used in the photosensitive resin composition, for example, triazine compound, acetophenone compound, benzophenone compound, thioxanthone compound, benzoin compound, oxime system Compounds and the like can be used.

Examples of the triazine compound used as the photopolymerization initiator include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl)- s-triazine, 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, nybis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1- Il) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-1-yl) -4,6-bis (trichloromethyl) -s-triazine, '2, 4-trichloromethyl (piperonyl) -6-triazine, 2,4-trichloro methyl (4'-methoxystyryl) -6-triazine, and the like, but the present invention is not limited thereto. no.

Examples of the acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyl trichloroacetophenone, and pt-butyl Dichloroacetophenone, '4-chloroacetophenone,' 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc., but the present invention is not limited thereto.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'- Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, # 4,4'-dichlorobenzophenone, # 3,3'-dimethyl-2-methoxybenzophenone, and the like. It is not limited to this.

Examples of the thioxanthone-based compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diisopropylthione. Orcanthone, and the like, but the present invention is not limited thereto.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like, but the present invention is not limited thereto.

Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone; and the like, but the present invention is not limited thereto.

The photopolymerization initiator is 0.1 to 15% by weight based on the total amount of the photosensitive resin composition 　 It is preferably included, and more preferably contained in 0.5 to 10% by weight. If it is less than 0.1% by weight, the use effect of the photopolymerization initiator is inadequate and may be undesirable. If it is more than 15% by weight, the optical density may be reduced.

(D) Black pigment

As said black pigment, all can be used if it is a pigment with light-shielding property.

Specifically, metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, composite oxides, metal sulfides, metal lead sulfate or metals Inorganic pigments, such as a carbonate, etc. are mentioned. It is more preferable to use carbon black which has high light-shielding property among these black pigments.

The carbon black may be a known carbon black such as channel black, furnace black, thermal black, lamp black, or the like.

It is also possible to use carbon black coated with resin. Since the resin-coated carbon black has lower conductivity than carbon black not coated with resin, when used as a light shielding film of a liquid crystal display element such as a liquid crystal display, leakage of current is low and reliability is high. It is preferable because a liquid crystal display can be formed.

It is preferable that the said black pigment is contained by 0.1 to 20 weight% with respect to the said total amount of photosensitive resin composition. If the amount is less than 0.1% by weight, optical density may be reduced to cause light leakage in the panel. When it exceeds 20% by weight, scratch resistance may be reduced by lowering the curing property of the film.

In addition, the pigment can be used by dispersing with a dispersant. In this case, as the dispersant used, it is preferable to use a polymer dispersant of polyethyleneimine, urethane resin, or acrylic resin. As a typical example, the brand name BYK-161, 162, 163, 164, 166, 170, 182, the product made by Vik Chemi Japan Co., Ltd., the brand name Sopars S3000, S9000, S17000, S20000, S27000, S24000, S26000, S28000 Etc. can be mentioned.

(E) Solvent

As the solvent, propylene glycol monomethyl ether acetate, methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ethyl acetate, propylene glycol ethyl ether acetate, Propylene Glycol Propyl Ether Acetate, Propylene Glycol Butyl Ether Acetate, Propylene Glycol Methyl Ethyl Propionate, Propylene Glycol Ethyl Propionate, Propylene Glycol Propyl Ether Propione , Propylene glycol butyl ether propylene propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy Ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy ethyl 2-methylpropionate, hydroxymethyl acetate, hydroxyethyl acetate, hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl propyl, butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propyl propionate, 3-hydroxy butyl propionate, 2-hydroxy 3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy Oxy propyl acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl methoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, Methyl oxyacetate, butoxy acetate, butyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-e Methyl oxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-butoxy Butyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Propyl, butyl 3-ethoxypropionate, 3-propoxypropionate methyl, 3-propoxypropionate propyl, 3-propoxypropionic acid propyl, 3-propoxypropionate butyl, 3-butoxypropionate methyl, Esters such as ethyl 3-butoxypropionate, propyl 3-butoxypropionic acid, and butyl 3-butoxypropionate; and the like can be used.

Preferably, those selected from the group consisting of glycol ethers, ethylene alkyl ether acetates, diethylene glycols, and combinations thereof are advantageous in terms of solubility, reactivity with each component, and easy formation of a coating film. have.

The solvent may be included in the remainder in the photosensitive resin composition for color filters, preferably 20 to 90% by weight based on the total amount of the photosensitive resin composition. When the solvent content is in the above range, the coating property of the photosensitive resin composition is excellent, and even in a film having a thickness of 1 µm or more, flatness is preferable.

(F) Other additives

The black resin composition may further include an adhesive, a surfactant, or an epoxy resin, if necessary, in addition to the components (A) to (D).

The adhesive may be added to improve the adhesion with the substrate. The adhesive may be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer. Representative examples of the adhesive include silane coupling agents having reactive substituents such as carboxyl groups, methacryl groups, isocyanate groups, epoxy groups, and the like, and specifically, γ-methacryloxypropyltrimethoxysilane and vinyltriacetoxysilane. , Vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-3,4-epoxy cyclohexyl ethyltrimethoxysilane and the like.

The surfactant may be added to improve the coatability or developability of the black resin composition. As the surfactant, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, trade name F171, F172, F173 manufactured by Japan Nippon Inks Co., Ltd., trade name FC430, FC431 manufactured by Sumitomo Triem Co., or trade name KP341 manufactured by Shinwol Chemical Co., Ltd. may be used. have. The surfactant is preferably used in 0.0001 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer. When added in the above range, the coatability and developability of the black resin composition can be improved, which is preferable.

The epoxy resin may be added to improve the heat resistance and sensitivity of the pattern obtained from the black resin composition. Examples of the epoxy resins include bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and heterocyclic epoxy resins. Etc. can be mentioned. The epoxy resin is preferably used in 0.1 to 35 parts by weight based on 100 parts by weight of the acrylic copolymer. When it exceeds 35 parts by weight, there is a problem in that the compatibility with the acrylic copolymer is poor and sufficient coating performance cannot be obtained, which is not preferable .

In addition, according to another embodiment of the present invention, there is provided a liquid crystal display device including a light shielding film made of the inkjet resin composition.

Further, according to another embodiment of the present invention, after applying the resin composition to the surface of the substrate, prebaking (prebake) to form a light shielding film (S21), after applying the composition for forming an organic insulating film on the light shielding film Drying to form an organic insulating film (S22), placing a mask on which the predetermined pattern is formed on the organic insulating film and exposing (S23) to develop and patterning the organic insulating film (S24), using the organic insulating film as a mask And etching the light shielding film to pattern the light shielding film, and forming a color filter between the light shielding film patterns (S25).

The manufacturing method of the color filter is a method of forming a light shielding film by an inkjet method of forming a color filter on a lower TFT TFT, wherein the light shielding film is formed using an inkjet resin composition according to the present invention and an organic insulating film is placed thereon. .

2 is a process chart showing a manufacturing method of a color filter according to the present invention. Hereinafter, a method of manufacturing the color filter of the present invention will be described in detail with reference to FIG. 2.

Referring to FIG. 2, first, a resin composition is applied to a substrate 20 'surface, and prebaked to form a light shielding film 22 (S21). As a method of apply | coating the said resin composition, a spray method, a roll coating method, a rotary coating method, etc. are mentioned, It is not limited to this. The prebaking is preferably carried out at 70 to 110 ° C, preferably 1 to 10 minutes, at which time the solvent contained in the black resin composition is removed.

Subsequently, the organic insulating film forming composition is coated on the light shielding film 22 and dried to form an organic insulating film 24 (S22). Subsequently, the organic insulating film 24 is exposed to a predetermined mask pattern (S23), and then developed to pattern the organic insulating film 24 of the predetermined pattern (S24).

As the light source during the exposure, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. may be used, but is not limited thereto.

It is preferable to use aqueous alkali solution as a developing solution used for the said developing process, Specifically, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate; primary amines such as n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethyl ethanol amine, methyl diethanol amine and triethanol amine; Or aqueous solutions of quaternary ammonium salts such as tetramethyl ammonium hydroxide and tetraethylammonium hydroxide can be used. In addition, the developer may be used by dissolving the alkaline compound at a concentration of 0.1 to 10% by weight, and may be used by adding an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol and ethanol.

In addition, after the development, washing with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dry to form a pattern, and after irradiating the formed pattern with light such as ultraviolet rays, the pattern is heated to 150 to 250 ℃ The pattern can be obtained by heat treatment at a temperature of 30 to 90 minutes.

Subsequently, the light blocking film 22 is dry etched using the patterned organic insulating film 24 as a mask to pattern the light blocking film 22, and ink is applied to the exposed openings to form a color filter (S25). .

In addition, the ink of R, G, and B may be discharged to the openings in an inkjet manner to be collected into the partition walls, and then the collected ink may be cured with heat or light, and then a color filter may be formed.

The resin composition of the present invention is excellent in optical density, heat resistance, scratch resistance, and the like, and adhesion with an organic insulating film is improved to form a color filter on an TFT by an inkjet method. In addition, according to the manufacturing method of the color filter using the same, it is possible to form a thin pattern, it is possible to increase the color visibility and brightness by not forming another organic insulating film on the inkjet ink.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Preparation Example 1 Preparation of Acrylic Copolymer A

In a flask equipped with a cooling tube and a stirrer, 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, and 45 parts by weight of a compound of formula 1a , 15 parts by weight of methacrylic acid, and 20 parts by weight of glycidyl methacrylate were added thereto, and stirring was started slowly under a nitrogen atmosphere. The reaction solution was raised to 60 ° C. to prepare a polymer solution including an acrylic copolymer while maintaining this temperature for 5 hours.

In order to remove the unreacted monomer in the polymer solution including the acrylic copolymer, 100 parts by weight of the polymer solution is precipitated in 1,000 parts by weight of an ether solvent, and a filtering process using a mesh is performed. The poor solvent in which the unreacted substance was dissolved was removed. Thereafter, the mixture was vacuum dried at 30 ° C. or lower to completely remove the solvent containing the unreacted monomer remaining after the filtering process, thereby preparing an acrylic copolymer having a weight average molecular weight of 8,000. At this time, a weight average molecular weight is polystyrene conversion average molecular weight measured using GPC (gel permeation chromatography).

[Formula 1a]

Preparation Example 2 Preparation of Acrylic Copolymer B

An acryl-based copolymer was prepared in the same manner as in Preparation Example 1, except that the compound of Formula 1a was changed to the compound of Formula 1b.

[Chemical Formula 1b]

Preparation Example 3 Preparation of Acrylic Copolymer C

An acryl-based copolymer was prepared in the same manner as in Preparation Example 1, except that the compound of Formula 1a was changed to the compound of Formula 1c.

[Chemical Formula 1c]

Examples 1-12

Each component was mixed according to the following Table 1, and the resin compositions of Examples 1 to 12 were prepared using propyleneglycol monomethyl ether acetate as a solvent so that the concentration of the solid content was 25% by weight.

Comparative Examples 1 to 2: Preparation of Inkjet Resin Compositions

Each component was mixed according to the following Table 1, and the resin compositions of Comparative Examples 1 to 3 were prepared using propyleneglycol monomethyl ether acetate as a solvent so that the concentration of the solid content was 25% by weight.

At this time, as the resin D, cardo-based resin (molecular weight (Mw) = 5,000) represented by the following formula (2) was used.

[Formula 2]

(In Formula 2, R ₄ is a methacryl group, Z is a derivative of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, k means a degree of polymerization and is a value determined by molecular weight. It is .

[Table 1] (g)

(A) acrylic
Copolymer (B) photopolymerizable monomer (C) photopolymerization initiator (D) Black pigment A B C D Dipentaerythritol
Hexaacrylate
(Doagosei Corporation) Igacure 369
(Shiba Corporation) CGI-242
(Shiba Corporation) Color Black FW2
(Daegusa) Example 1 10 - - - 3 One - 4 Example 2 - 10 - - 3 One - 4 Example 3 - - 10 - 3 One - 4 Example 4 10 - - - 3 - One 3 Example 5 - 10 - - 3 - One 3 Example 6 - - 10 - 3 - One 3 Example 7 10 - - - 3 - One 2 Example 8 - 10 - - 3 - One 2 Example 9 - - 10 - 3 - One 2 Example 10 10 - - - 3 - One 1.5 Example 11 - 10 - - 3 - One 1.5 Example 12 - - 10 - 3 - One 1.5 Comparative Example 1 - - - 10 3 One - 1.5 Comparative Example 2 - - - 10 3 - One 1.5

Each of the resin compositions of Examples 1 to 12 was applied onto a glass substrate using a spin coater, and prebaked at 90 ° C. for 2 minutes to form respective resin composition layers. Each of the resin composition layers was post-baked in an oven at 230 ° C. for 30 minutes to form a black matrix pattern having a thickness of 1.0 μm.

Using the resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 3, the physical properties were evaluated by the following method, and the results of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 2 below. Indicated.

1) Flatness: The presence or absence of irregularities in the obtained film height was measured.

(Circle): The height difference ((DELTA) H) of a pattern on the same board | substrate is ± 0.2 or less

Δ: The height difference ΔH of the pattern on the same substrate is ± 0.2 to ± 0.3

X: The height difference (ΔH) of the pattern on the same substrate is ± 0.3 or more

2) Adhesiveness: The organic insulating film composition was apply | coated on the obtained resin composition layer using a spin coater, and it dried at 90 degreeC for 2 minutes, and formed the resin composition layer. Subsequently, a photomask was placed on the coating film, exposed using a high pressure mercury lamp having a wavelength of 365 nm, developed with 0.4 wt% tetramethyl ammonium hydroxide aqueous solution for 130 seconds at 25 ° C., and then washed with ultrapure water for 90 seconds. Then, the resultant was blown with compressed air and dried, and abnormalities of the 10 μm pattern were observed.

○: no pattern loss

△: partly missing pattern

X: When coating is not possible or pattern formation is impossible

3) Optical density (OD): The optical density of the coating film was measured using the 310TR optical density meter (Exlite) of the obtained coating film. At this time, the thickness of the coating film was 1.0 micrometer.

4) Heat resistance: The thickness after prebake and the postbake of the coating film were measured and based on the difference value.

[Table 2]

division Flatness Adhesiveness Optical Density (OD) Heat resistance (㎛) Example 1 ○ ○ 5.9 -0.02 Example 2 ○ ○ 5.8 -0.01 Example 3 ○ ○ 5.9 -0.02 Example 4 ○ ○ 5.7 0 Example 5 ○ ○ 5.6 0.01 Example 6 ○ ○ 5.5 0.01 Example 7 ○ ○ 5.3 -0.1 Example 8 ○ ○ 5.4 -0.1 Example 9 ○ ○ 5.3 -0.15 Example 10 ○ ○ 5.1 -0.05 Example 11 ○ ○ 5.1 -0.06 Example 12 ○ ○ 5.0 -0.05 Comparative Example 1 △ X 4.9 -0.12 Comparative Example 2 △ X 4.6 -0.15

Referring to Table 2, in the case of Examples 1 to 12 compared with Comparative Examples 1 to 2, the flatness and the adhesion was excellent excellent. In addition, the optical density and the heat resistance were also superior or equivalent to those of the comparative example.

Hereinafter, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. It is possible.

1 is a process chart showing a manufacturing method of a conventional color filter.

2 is a process chart showing a manufacturing method of a color filter according to the present invention.

Claims (8)

(A) 20 to 80% by weight of dioxolane-based compound, ii) 5 to 40% by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof, and iii) 5 to 50% by weight of epoxy group-containing unsaturated compound. Acrylic copolymer obtained by making it; (B) photopolymerizable monomer; (C) photoinitiator; (D) a black pigment; And (E) The resin composition for inkjets containing a solvent. delete The method of claim 1, (A) 0.1 to 30% by weight of acrylic copolymer (B) 0.1 to 30 wt% of the photopolymerizable monomer (C) 0.1-15 wt% of a photopolymerization initiator (D) 0.1% to 20% by weight of black pigment; And (F) solvent residue Resin composition for an inkjet comprising a. The method of claim 1, (Iii) The dioxolane-based compound has a structure of the following formula (1). [Formula 1]

(In the formula 1, R ₁ and R ₂ are the same or independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alicyclic group, or are connected to each other to form a fused ring and , R ₃ is a hydrogen atom or a substituted or unsubstituted alkyl group, R and R 'are the same or independently of each other a hydrogen atom or a substituted or unsubstituted alkyl group, n is an integer from 1 to 5.) The method of claim 1, The unsaturated carboxylic acid and unsaturated carboxylic anhydride are inkjet resins selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides thereof, and combinations thereof. Composition. The method of claim 1, The epoxy group-containing unsaturated compound may be glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid β- Methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3 , 4-Epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl A resin composition for inkjet, which is selected from the group consisting of benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and combinations thereof. A liquid crystal display device comprising a light shielding film made of the resin composition according to any one of claims 1 and 3 to 6. Applying a resin composition according to any one of claims 1 and 3 to 6 to the surface of the substrate and prebaking to form a light shielding film; Forming an organic insulating film by coating the composition for forming an organic insulating film on the light-shielding film and then drying it; Patterning the organic insulating film by depositing and then exposing the mask having a predetermined pattern on the organic insulating film; And Etching the light shielding film using the organic insulating film as a mask to pattern the light shielding film, and forming a color filter between the light shielding film patterns Method of manufacturing a color filter comprising a.

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