JP5502038B2 - Thermosetting protective film resin composition - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention is a thermosetting protective film capable of providing a protective film that can serve as a white portion that has excellent flatness and can guide white light without an additional coating process. The present invention relates to a resin composition.

  In a color liquid crystal display (LCD), a color filter is formed by patterning a black matrix on a substrate such as glass, plastic, or silicon wafer. Thereafter, a pixel coloring layer of red, green, and blue is formed, and an overcoat film is formed on the pixel coloring layer.

  The color liquid crystal display element can emit various hues by adjusting the amount of light illuminating the pixels of the three primary colors of RGB (Red, Green, Blue). However, in a situation where white derivation is required, all of the above RGB pixels must be turned on or a separate white portion must be applied, and research on this is desired.

  In recent years, with the increase in size of display elements such as color liquid crystal display elements (LCD), the size of the substrate used has also increased. As a result, the color filter layer needs to be flattened. In order to increase the area of the LCD, development of a protective film material for flattening the color filter layer is required.

  The present invention provides a thermosetting protection that can provide an overcoat film that is excellent in flatness and can turn on all the RGB pixels, or enables a white color to be derived with a color filter even without a separate white portion coating process. The object is to provide a membrane resin composition.

  In addition, the objective of this invention is providing the protective film of the color filter formed from the said thermosetting protective film resin composition.

  In addition, the objective of this invention is providing the liquid crystal display element containing the said color filter.

  The thermosetting protective film resin composition of the present invention contains 1 to 28% by weight of binder resin, 68 to 95% by weight of multifunctional monomer, and 4 to 31% by weight of other additives based on the total solid content.

  The solid content concentration of the thermosetting protective film resin composition is 10 to 30% by weight, and the viscosity at room temperature is 2 to 4 cps, so that the fluidity of the composition can be improved. As appropriate.

  The binder resin is a copolymer of an epoxy group-containing unsaturated compound and an ethylenically unsaturated compound, and the epoxy group-containing unsaturated compound and the ethylenically unsaturated compound are mixed in a weight ratio of 25:75 to 60:40. The obtained mixture is obtained by copolymerization, and its weight average molecular weight (Mw) is within 5,000 to 10,000.

  As the epoxy group-containing unsaturated compound, known compounds can be used without limitation, but non-limiting examples include epoxy alkyl (meth) acrylate, allyl glycidyl ether, allyl glycidyl ester, aryl glycidyl ether, aryl glycidyl ester, glycidyl. 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, glycidyl (meth) acrylate, glycidyl α-ethyl (Meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxy Pentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate, - an epoxy heptyl α- ethyl acrylate and mixtures thereof.

  As the ethylenically unsaturated compound, known compounds can be used without limitation, but non-limiting examples include benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, ethyl (Meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclofentanyl (meth) acrylate, caprolactone-modified (meth) acrylate, styrene, 4-methoxystyrene, 4-methylstyrene, 1, Examples include 3-butadiene, isoprene, and mixtures thereof.

  The ethylenically unsaturated compound further includes at least one functional group selected from the group consisting of a hydroxy group, a silyl group, a functional group in which an acid group is formed by hydrolysis, a carboxyl group, and a carboxylic anhydride group. Can do.

  As the ethylenically unsaturated compound further containing one or more kinds of functional groups, known compounds can be used without limitation. Specifically, examples of the ethylenically unsaturated compound containing a hydroxy group include 2-hydroxyethyl ( Examples of ethylenically unsaturated compounds containing silyl groups include vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane or vinyltris (β-methoxyethoxy) silane, methylvinyldimethoxy. Silane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, γ- (Meth) acryloxypropylmethyldimethoxysilane, γ -(Meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyldimethylethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, etc. Examples of the ethylenically unsaturated compound containing a functional group in which an acid group is formed by hydrolysis include tetrahydro-2H-pyran-2-yl (meth) acrylate, t-butyl (meth) acryloxysilane, and the like. Examples of ethylenically unsaturated compounds containing a carboxyl group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, isoprenesulfonic acid, Examples include styrene sulfonic acid, norbornene-2-carboxylic acid, and carboxylic anhydride Examples of ethylenically unsaturated compounds containing groups include (meth) acrylic anhydride, crotonic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, citraconic anhydride, mesaconic anhydride , Isoprenesulfonic acid anhydride, styrenesulfonic acid anhydride, norbornene-2-carboxylic acid anhydride, and the like.

  As the polyfunctional monomer, known ones can be used without limitation, but as non-limiting examples, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, Propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate having 2 to 14 propylene groups, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Dipentaerythri Compounds obtained by esterifying polyhydric alcohols such as tall penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate with α, β-unsaturated carboxylic acids and pentaerythritol obtained by esterifying the above compounds with succinic acid Examples include tri (meth) acrylate-succinic acid ester, dipentaerythritol tetra (meth) acrylate-disuccinic acid ester, dipentaerythritol penta (meth) acrylate-succinic acid ester, and mixtures thereof.

  One or more of the polyfunctional monomers can be used, and in particular, the use of two or more is more desirable because the transparency of the protective film formed from the thermosetting protective film resin composition is improved.

  The thermosetting protective film resin composition according to the present invention can be added with other additives as necessary, and the other additives include a curing agent, an adhesion assistant, a surfactant, an initiator, a storage stabilizer, It may be one or more selected from the group consisting of a striation inhibitor, a curing accelerator, a thermal polymerization inhibitor, and a plasticizer.

  Examples of the curing agent include phthalic anhydride, tetra-hydrophthalic anhydride, hexa-hydrophthalic anhydride, methyltetra-hydrophthalic anhydride, methylendomethylenetetra-hydrophthalic anhydride, hexachloroendomethylenetetra-hydrophthalic acid. Anhydride, dodecyl succinic anhydride, trimellitic anhydride and mixtures thereof can be used, but are not limited thereto.

  As the adhesion assistant, it is appropriate to use an alkoxy group-containing silane-modified epoxy resin obtained by reacting an epoxy compound having a biphenyl group or an epoxy compound having a silyl group and an alkoxysilane.

  The epoxy compound having a silyl group can be used without limitation as long as it is a known one. As a non-limiting example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycol Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, and the like are limited thereto. Not.

  The alkoxysilane can be used without limitation as long as it is a known one. Non-limiting examples include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercapto Examples include, but are not limited to, propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and partial condensates thereof.

  As the surfactant, a fluorine-based surfactant or a silicon-based surfactant can be used.

  The thermosetting protective film resin composition is benzene, toluene, ethylbenzene, xylene, methanol, ethanol, isopropyl alcohol, tetraglycol, methoxypropanol, ethoxypropanol, butoxypropanol, benzyl alcohol, monomethylamine, monoethylamine, monoethanolamine. 1-amino-2-propanol, 2-methylaminoethanol, dimethylethanolamino, methylpyrrolidone, diethanolamine, diethylaminoethanol, triethanolamine, tetrahydrofuran, 1,4-dioxane, butyl cellosolve, 2-methoxyethyl ether, 1-methoxy -2-propanol, methoxybenzene, dibutyl ether, diphenyl ether, ethylene glycol ethyl methyl ether, ethylene Glycol diethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, Methyl ethyl ketone, methyl butyl ketone, cyclohexanone, 2-heptanone, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol butyl acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, butyrolactone, ethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propyl acetate, butyl acetate, 3-methoxybutyl Acetate, ethyl propionate, methyl 3-methoxypropionate, ethyl pyruvate, methyl-2-hydroxyisobutyrate, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monoacetate, ethylene glycol di Solvents such as acetate and mixtures thereof can be used, but are not limited thereto.

  The present invention provides a protective film for a color filter formed from the thermosetting protective film resin composition, wherein the step of the protective film of the color filter is within 0 to 5,000 mm.

  In addition, this invention provides the liquid crystal display element containing the said color filter protective film.

  The overcoat film formed from the thermosetting protective film resin composition according to the present invention is excellent in flatness and can be used in manufacturing a large-area LCD.

  In addition, the overcoat film formed from the thermosetting protective film resin composition according to the present invention performs a role of an existing overcoat film and can also guide white light (white portion). According to the present invention, it is not necessary to turn on all the RGB pixels or go through a separate white portion coating process in order to derive white color with the color filter.

  Therefore, when the thermosetting protective film resin composition according to the present invention is used, there is an effect of reducing time and cost in LCD production.

It is a graph which shows schematically the profile of the overcoat film formed with the thermosetting protective film resin composition of Examples 1-3 and the overcoat film formed with the thermosetting protective film resin composition of Comparative Example 1. . The profile according to which the thickness of the overcoat (over coat, OC) formed with the thermosetting protective film resin composition of Examples 1 to 3 becomes as thick as 2.0 μm, 2.5 μm, and 3.0 μm is roughly shown. FIG. It is the photograph which compared the transparency after apply | coating the thermosetting protective film resin composition of Examples 2-3 on a glass substrate, and forming a protective film.

  The present invention provides a thermosetting protective film that is excellent in flatness and can provide an overcoat film that enables all RGB pixels to light up or allows a white color to be derived with a color filter without a separate white portion coating step. The present invention relates to a resin composition.

  The thermosetting protective film resin composition according to the present invention comprises a binder resin and a polyfunctional monomer.

  The binder resin is suitably in the range of 1 to 28% by weight, particularly in the range of 1 to 16% by weight, based on 100% by weight of the total solid content in the composition. 3 to 14% by weight is more desirable. Within this range, the storage stability and fluidity of the thermosetting protective film resin composition are excellent.

  The polyfunctional monomer is suitably in the range of 68 to 95% by weight, particularly preferably in the range of 80 to 95% by weight, and more preferably in the range of 80 to 91% by weight. .

  When the polyfunctional monomer is less than 68% by weight, the optimized fluidity of the composition cannot be secured, and when it exceeds 95% by weight, the adhesion to the glass substrate, the coating property, the permeability and the binder Not only does this cause a problem in the mixed solubility with the resin, but fumes may be generated during the baking process in the color filter process, which is undesirable from the viewpoint of purification.

  Since the thermosetting protective film resin composition according to the present invention improves the fluidity, it improves the flatness of the protective film formed from now on and performs the role of the white part. The solid content of the curable protective film resin composition is 10 to 30% by weight, and its viscosity is adjusted to 2 to 4 cps at room temperature, and preferably 2 to 2.5 cps.

  The weight average molecular weight (Mw) of the binder resin for optimizing the fluidity of the thermosetting protective film resin composition is within 5,000 to 10,000, preferably 6,000 to 8,000, Most preferably, it is 6,500-7,500.

  The binder resin is a copolymer of an epoxy group-containing unsaturated compound and an ethylenically unsaturated compound, and the copolymer comprises an epoxy group-containing unsaturated compound and an ethylenically unsaturated compound in a weight ratio of 25: 75-60. : Copolymerized by mixing within the range of 40.

  The epoxy group-containing unsaturated compound can be used without limitation as long as it is a known compound, and as non-limiting examples, epoxy alkyl (meth) acrylate, allyl glycidyl ether, allyl glycidyl ester, aryl glycidyl ether, aryl glycidyl ester, Glycidyl 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, glycidyl (meth) acrylate, glycidyl α- Ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5- Epoxypentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate, And 7-epoxy-heptyl α- ethyl acrylate and mixtures thereof.

The ethylenically unsaturated compound can be used without limitation as long as it is a known compound, and as non-limiting examples, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, Aliphatic or aromatic (meth) acrylates such as ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclofentanyl (meth) acrylate;
Caprolactone-modified (meth) acrylates such as TONE M-100, TONE M-101, TONE M-201 (above, manufactured by DOW Chemical), FM-1, FM-2, FM-3 (above, made by Daicel UCB) ;
Styrene monomers such as styrene, 4-methoxystyrene, 4-methylstyrene;
Examples thereof include conjugated diene compounds such as 1,3-butadiene and isoprene, and mixtures thereof.

  In the present invention, together with the ethylenically unsaturated compound mentioned above, or alone, a functional group such as a hydroxy group, a silyl group, a functional group in which an acid group is formed by hydrolysis, a carboxyl group, and a carboxylic acid anhydride group. Further, an ethylenically unsaturated compound is used.

  The functional group in which an acid group is formed by the hydrolysis is a specific temperature range, preferably a temperature range of 150 to 250 ° C. where post-bake of the thermosetting protective film resin composition of the present invention is performed. It can be decomposed to generate an acid that can react with the epoxy group of the epoxy group-containing unsaturated compound.

  Any ethylenically unsaturated compound further containing the above functional group can be used as long as it is a known one.

Specifically, examples of the ethylenically unsaturated compound containing a hydroxy group include 2-hydroxyethyl (meth) acrylate,
Examples of ethylenically unsaturated compounds containing silyl groups include vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane or vinyltris (β-methoxyethoxy) silane, methylvinyldimethoxysilane, β- (meth) acrylic. Oxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyl Methyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyldimethylethoxysilane, 3- (meth) acryloxypropyltri Methoxysilane Which (meth) include acryloxy silane,
Examples of ethylenically unsaturated compounds containing functional groups that form acid groups upon hydrolysis include tetrahydro-2H-pyran-2-yl (meth) acrylate, t-butyl (meth) acrylate, and the like.
Examples of ethylenically unsaturated compounds containing carboxyl groups include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, isoprene sulfonic acid, styrene sulfonic acid, norbornene-2- Carboxylic acid, etc.
Examples of ethylenically unsaturated compounds containing carboxylic anhydride groups include (meth) acrylic anhydride, crotonic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, citraconic anhydride, Examples thereof include mesaconic acid anhydride, isoprenesulfonic acid anhydride, styrenesulfonic acid anhydride, norbornene-2-carboxylic acid anhydride, and the like.

  The polyfunctional monomer contained in the thermosetting protective film resin composition of the present invention can be used without limitation as long as it is a known one, and as a non-limiting example, ethylene glycol di (meth) acrylate, the number of ethylene groups Is a polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate having 2 to 14 propylene groups, 1,3-butanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol Compounds obtained by esterifying polyhydric alcohols such as tra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate with α, β-unsaturated carboxylic acid and the above compounds are succinic acid Pentaerythritol tri (meth) acrylate-succinic acid ester, dipentaerythritol tetra (meth) acrylate-disuccinic acid ester, dipentaerythritol penta (meth) acrylate-succinic acid ester obtained by esterification with Can be mentioned.

  The thermosetting protective film resin composition of the present invention contains one or more of the above-mentioned multifunctional monomers, and as shown in FIG. Is desirable.

  More specifically, the left side (Example 3) of FIG. 3 is a photograph of a protective film formed from a thermosetting protective film resin composition containing one kind of polyfunctional monomer, and the right side (Example 2) is a photograph. It is the photograph of the protective film formed from the thermosetting protective film resin composition containing two types of polyfunctional monomers, and the right side protective film using two types of polyfunctional monomers is further transparent also visually. I can confirm that.

  Other additives that are added as necessary to the thermosetting protective film resin composition according to the present invention are known for other purposes such as film forming performance, adhesion to a substrate, and chemical stability. Can be used without limitation, and non-limiting examples include curing agents, adhesion aids, surfactants, initiators, storage stabilizers, striation inhibitors, curing accelerators, thermal polymerization inhibitors and plastics. Other additives such as an agent can be used in the range of 4 to 31% by weight, preferably 4 to 19% by weight, more preferably 6 to 17% by weight, based on 100% by weight of the total solid content in the composition. Can be used within.

  When the other additive is used at less than 4% by weight, there is a problem that the thermosetting of the thermosetting protective film resin composition is not smoothly performed. When the other additive is used at more than 19% by weight, The content of the binder resin and the polyfunctional monomer is relatively small, which is not desirable from the viewpoint of film strength, storage stability of the protective film, and flattening of the white portion.

  The curing agent can be used without limitation as long as it is a known one. Non-limiting examples include phthalic anhydride, tetra-hydrophthalic anhydride, hexa-hydrophthalic anhydride, methyltetra-hydrophthalic anhydride, Examples include methyl endomethylenetetra-hydrophthalic anhydride, hexachloroendomethylenetetra-hydrophthalic anhydride, dodecyl succinic anhydride, trimellitic anhydride, and the like. In particular, it is desirable to use trimellitic anhydride having high reactivity with the binder resin and excellent in mixed solubility.

  As the adhesion assistant, it is appropriate to use an alkoxy group-containing silane-modified epoxy resin obtained by reacting an epoxy compound having a biphenyl group or an epoxy compound having a silyl group and an alkoxysilane.

  The epoxy compound having a biphenyl group can be used without limitation as long as it is a known one. Specifically, YX-4000H (manufactured by Yuka Shell Epoxy Co., Ltd.), NC-3000, NC-3000-L, NC-3000 Epoxy compounds commercially available under trade names such as -H, CER-3000, CER-3000-L, CER-3000-H (Nippon Chemical Co., Ltd.) can be used. It is not done.

  The epoxy compound having a silyl group can be used without limitation as long as it is a known one. As a non-limiting example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycol Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, and the like are limited thereto. Not.

  The alkoxysilane can be used without limitation as long as it is a known one. Non-limiting examples include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercapto Examples include, but are not limited to, propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and partial condensates thereof.

The surfactants are BM-1000 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC- 170C, Florard FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 (above, Asahi Glass SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, manufactured by Toray Silicon Co., Ltd.), F-488 (Arakawa) Fluorine-based surfactant or silicon-based surfactant marketed under the trade name of
The initiator is an azo compound as a thermal polymerization initiator, and is manufactured by Wako Pure Chemical Industries. Ltd .. Azonitrile type V-60, V-65, V-59, V-70, V-40 and azo ester type V-601, azoamide type VA-086, VA-085, VA-080, Vam-110, Vam-111, VF-096, azoamidine-based V-50, VA-044, VA-046B, Aam-027, VA-066, VA-057, VA-061, macroazo initiator VPS-0501, VPS- 1001, VPE-0201, VPE-0401, VPE-0601, VPTG-0301, and the like can be used, but are not limited thereto.

  The solvent contained in the thermosetting resin composition according to the present invention includes aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; methanol, ethanol, isopropyl, taking into account the solubility and coatability of the binder resin. Alcohols such as alcohol, tetraglycol, methoxypropanol, ethoxypropanol, butoxypropanol, benzyl alcohol; monomethylamine, monoethylamine, monoethanolamine, 1-amino-2-propanol, 2-methylaminoethanol, dimethylethanolamino, methyl Amines such as pyrrolidone, diethanolamine, diethylaminoethanol, triethanolamine; tetrahydrofuran, 1,4-dioxane, butyl cellosolve, 2-methoxyethyl ether, 1-methoxy-2-propyl Lopanol, methoxybenzene, dibutyl ether, diphenyl ether, ethylene glycol ethyl methyl ether, ethylene glycol diethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, dipropylene Ethers such as glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether; alkyl ketones such as methyl ethyl ketone, methyl butyl ketone, cyclohexanone, 2-heptanone; methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol butyl ether Acetate, diethylene Ethylene glycol alkyl ether acetates such as recall ethyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether Propylene glycol alkyl ether acetates such as acetate; butyrolactone, ethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl propionate, methyl 3-methoxypropio Nate, ethyl pyruvate, methyl-2-hydroxy Examples thereof include esters such as cyisobutyrate, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monoacetate, ethylene glycol diacetate; or a mixture thereof.

  The protective film of a color filter can be provided using the thermosetting protective film resin composition according to the present invention.

  As a method for forming a protective film from the thermosetting protective film resin composition, a conventional method known in the art can be used.

  A method for forming the thermosetting protective film will be described with reference to an example.

  After the thermosetting protective film resin composition is applied onto the substrate by an appropriate method, pre-baking is performed to remove the solvent to form a coating film, and then post-baking is performed by performing post-baking. A curable protective film is formed.

  The application method is not particularly limited, and a spray method, a roll coating method, a spin coating method, a slit nozzle coating method, and the like can be used, and a spin coating method is generally used. In some cases, the residual solvent can be partially removed under reduced pressure after coating and before pre-baking.

  Pre-baking and post-baking conditions vary depending on the composition of the composition and the intended use. For example, prebaking can be carried out usually at 60 to 130 ° C. for 0.5 to 5 minutes. Moreover, post-baking can be normally performed in the temperature range of 150-250 degreeC over 10 minutes-2 hours. In addition, each pre-bake and post-bake can be performed in one step or a combination of more than one.

  The protective layer formed through the above-described process is formed on the upper surfaces of the red, green, and blue pixel coloring layers and the blank pixel portion.

  The protective film formed on the upper surface of the empty pixel portion receives white light from a backlight to form a white portion that embodies white light, and is formed on the upper surface of the red, green, and blue pixel coloring layers. The applied protective film serves as an overcoat film.

  At this time, the level difference of the protective film is within 0 to 5,000 mm and excellent in flatness. According to a preferred embodiment of the present invention, the level difference is less than 3,000 mm. It is not necessary to go through a step of applying a photoresist, and the white portion can be used only in the step of applying an overcoat on the substrate on which the pixel coloring layer and the empty pixel portion are formed. An excellent overcoat film can be formed.

  That is, the present invention improves the fluidity by optimizing the molecular weight of the binder resin contained in the thermosetting protective film resin composition and the content of each component including the binder resin. Thus, it is possible to provide a protective film for a color filter that can perform up to the above role.

  In addition, this invention provides the liquid crystal display element provided with the color filter containing the said protective film. The liquid crystal display device includes a black matrix and a color filter, and can be manufactured by an ordinary method known in the art.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Synthesis example 1
37.5 parts by weight of glycidyl methacrylate, 37.5 parts by weight of styrene, 7.5 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 17.5 parts of 3-methacryloxypropyltrimethoxysilane with respect to 100 parts by weight of all monomers. Part by weight was added to 400 parts by weight of propylene glycol methyl ether acetate (PGMEA) as a solvent, and mixed for 30 minutes using a mechanical stirrer under a nitrogen atmosphere.

  When the temperature of the reactor was raised to 70 ° C. under a nitrogen atmosphere and the temperature of the mixture reached 70 ° C., 9 parts by weight of 2,2′-azobisisobutyronitrile (AIBN) as a thermal polymerization initiator was added. The mixture was stirred for a time to obtain a binder resin having a weight average molecular weight (Mw) of 7000.

Example 1
6 parts by weight of binder resin obtained in Synthesis Example 1 (based on 100 parts by weight of solid content of composition), 75 parts by weight of dipentaerythritol hexaacrylate (DPHA), dipentaerythritol penta (meth) acrylate-succinic acid ester (TO -1382) 10 parts by weight, 0.05 part by weight of a fluorosurfactant (F-488), 0.95 part by weight of trimellitic anhydride as a curing agent, and a biphenyl type epoxy adhesion aid (CER-3000-L) ) 8 parts by weight was added to a 60:40 mixed solvent of propylene glycol methyl ether acetate and diethylene glycol diethyl ether and stirred.

  The mixture having a total solid content of 20% that had undergone the above process was filtered through a filter having a diameter of 0.2 μm to obtain a thermosetting protective film resin composition.

  Using a pigment dispersion type color resist (R, G, B) on a glass substrate, three color filters of red, green, and blue were formed in stripes with a line width of 100 μm. After applying the prepared thermosetting protective film resin composition on the substrate on which the RGB color filter is made, it is pre-baked on a hot plate at 90 ° C. for 2 minutes, and then cleaned at 220 ° C. An overcoat film having a thickness of 2.0 μm was manufactured by post-baking in an oven for about 30 minutes.

Example 2
Except for using 21 parts by weight of the binder resin obtained in Synthesis Example 1, 60 parts by weight of dipentaerythritol hexaacrylate, and 10 parts by weight of dipentaerythritol penta (meth) acrylate-succinate (TO-1382). In the same process as in Example 1, a thermosetting protective film resin composition and an overcoat film on the top of the color filter were produced.

Example 3
In the same process as in Example 2 above, except that dipentaerythritol penta (meth) acrylate-succinate (TO-1382) was not used and 70 parts by weight of dipentaerythritol hexaacrylate was used alone. A curable protective film resin composition and an overcoat film on the color filter were produced.

Comparative Example 1
A thermosetting protective film resin composition and a color filter in the same process as in Example 1 except that 71 parts by weight of the binder resin obtained in Synthesis Example 1 and 20 parts by weight of dipentaerythritol hexaacrylate are used. An overcoat film was manufactured on top of the substrate.

Experimental Example The profiles of Examples 1 to 3 and Comparative Example 1 were measured with an alpha stepper, and the flatness (DOP, Degree of Planarization) was calculated. The results are shown in FIGS. .

  The flatness was measured as follows.

  Measure the profile of red, green, and empty pixel, and set the largest value in the step at the center of the sub-pixel to D1, and then coat and cure the overcoat. Measurement was performed, and the flattening degree was obtained by using the following formula 1, with D2 being the largest value in the step at the center of the subpixel.

D1 in Examples 1 to 3 and Comparative Example 1 is the same as 22650cm.

  FIG. 1 schematically shows profiles of an overcoat film formed from the thermosetting protective film resin compositions of Examples 1 to 3 and an overcoat film formed from the thermosetting protective film resin composition of Comparative Example 1. It is shown.

  In the overcoat films of Examples 1 to 3, the heights of the overcoat film applied on the color filter layer (red, green) and the overcoat film applied on the empty pixel portion are approximately equal. While the degree of flatness is excellent, the overcoat film of Comparative Example 1 is formed along the bend of the color filter layer, so that the degree of flatness is inferior. It was confirmed that the thermosetting protective film resin composition of Comparative Example 1 could not form an overcoat film that could perform the role of the white part.

  Such a result can be confirmed by the data in Table 1.

  From Table 1 above, in the case of Examples 1 to 3, the step of the overcoat film is 2,600 to 4,300 mm and the DOP value is 81% or more, whereas in the case of Comparative Example 1, the overcoat film It is possible to numerically confirm that the level difference is 14,700 mm and the DOP value is only about 35.1%, and there is a very large difference in the flatness of the overcoat film of the example and the comparative example. did it.

  Thus, the difference in the flatness of the overcoat films of the examples and comparative examples is that the content of each component included in the thermosetting protective film resin composition according to the present invention is optimized, and the thermosetting This is because the fluidity of the protective film resin composition is greatly improved.

  FIG. 2 shows that the thickness of the overcoat (OC) formed from the thermosetting protective film resin compositions of Examples 1 to 3 increased to 2.0 μm, 2.5 μm, and 3.0 μm. The profile is schematically shown.

  As a result, it was confirmed that the degree of planarization was excellent even when the thickness of the overcoat was only 2.0 μm.

  FIG. 3 compares the transparency of the thermosetting protective film resin compositions of Examples 2 to 3 after coating on a glass substrate to form a protective film.

  Example 2 was prepared by mixing dipentaerythritol hexa (meth) acrylate (DPHA) and dipentaerythritol penta (meth) acrylate-succinate (TO-1382) as a polyfunctional monomer in a ratio of 60:10. In the case of Example 3, a thermosetting protective film resin composition was produced using DPHA alone as a polyfunctional monomer in an amount of 70 parts by weight.

  When the protective film is formed with the thermosetting protective film resin composition produced by using a polyfunctional monomer alone as in Example 3 above, the haze phenomenon of the protective film is visually observed. I was able to confirm.

  However, when the protective film is formed with a thermosetting protective film resin composition produced by mixing two or more polyfunctional monomers as in Example 2, the phenomenon that the protective film becomes transparent is confirmed. We were able to.

Therefore, the polyfunctional monomer of the thermosetting protective film resin composition according to the present invention is used by mixing two or more kinds of the overcoat film according to the present invention when used alone. Therefore, it has been confirmed that it is more desirable in fulfilling the role as the white part.
[Item 1]
For all solids
A thermosetting protective film resin composition comprising 1 to 28% by weight of a binder resin, 68 to 95% by weight of a polyfunctional monomer, and 4 to 31% by weight of other additives.
[Item 2]
The thermosetting protective film resin composition according to Item 1, wherein the solid content is 10 to 30% by weight.
[Item 3]
3. The thermosetting protective film resin composition according to item 1 or 2, wherein the thermosetting protective film resin composition has a viscosity of 2 to 4 cps at room temperature.
[Item 4]
4. The thermosetting protective film resin composition according to any one of items 1 to 3, wherein the binder resin is a copolymer of an epoxy group-containing unsaturated compound and an ethylenically unsaturated compound.
[Item 5]
Item 5. The thermosetting according to Item 4, wherein the binder resin is a copolymer of a mixture containing an epoxy group-containing unsaturated compound and an ethylenically unsaturated compound in a weight ratio of 25:75 to 60:40. Protective film resin composition.
[Item 6]
6. The thermosetting protective film resin composition according to any one of items 1 to 5, wherein the binder resin has a weight average molecular weight (Mw) of 5,000 to 10,000.
[Item 7]
The epoxy group-containing unsaturated compound includes epoxy alkyl (meth) acrylate, allyl glycidyl ether, allyl glycidyl ester, aryl glycidyl ether, aryl glycidyl ester, glycidyl 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture) ), 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate The thermosetting protective film resin composition according to item 4, which is an epoxy group-containing unsaturated compound selected from the group consisting of 6,7-epoxyheptyl α-ethyl acrylate, or a mixture thereof. .
[Item 8]
The ethylenically unsaturated compound includes benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl ( It must be at least one selected from the group consisting of (meth) acrylate, dicyclofentanyl (meth) acrylate, caprolactone-modified (meth) acrylate, styrene, 4-methoxystyrene, 4-methylstyrene, 1,3-butadiene and isoprene. Item 6. The thermosetting protective film resin composition according to Item 4 or 5, wherein
[Item 9]
The ethylenically unsaturated compound further includes at least one functional group selected from the group consisting of a hydroxy group, a silyl group, a functional group in which an acid group is formed by hydrolysis, a carboxyl group, and a carboxylic anhydride group. Item 6. The thermosetting protective film resin composition according to Item 4 or 5, wherein
[Item 10]
The ethylenically unsaturated compound is
2-hydroxyethyl (meth) acrylate as an ethylenically unsaturated compound containing a hydroxy group,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, methylvinyldimethoxysilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, 3- (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meta ) Containing one silyl group selected from the group consisting of acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyldimethylethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane. Ren unsaturated compound,
An ethylenically unsaturated compound containing a functional group in which an acid group is formed by one kind of hydrolysis selected from tetrahydro-2H-pyran-2-yl (meth) acrylate and t-butyl (meth) acrylate;
One kind of carboxyl group selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, isoprenesulfonic acid, styrenesulfonic acid and norbornene-2-carboxylic acid An ethylenically unsaturated compound, and
(Meth) acrylic anhydride, crotonic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, citraconic anhydride, mesaconic anhydride, isoprenesulfonic anhydride, styrenesulfonic anhydride and An ethylenically unsaturated compound containing one carboxylic anhydride group selected from the group consisting of norbornene-2-carboxylic anhydride,
10. The thermosetting protective film resin composition according to item 9, which is at least one selected from the group consisting of:
[Item 11]
The polyfunctional monomer includes ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, propylene glycol di (meth) acrylate, and 2 to 14 propylene groups. Propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (me ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate-succinate, dipentaerythritol tetra (meth) acrylate-disuccinate and dipentaerythritol penta (meth) acrylate-succinate 11. The thermosetting protective film resin composition according to any one of items 1 to 10, wherein the thermosetting protective film resin composition is one or more selected from the group consisting of:
[Item 12]
The other additives are selected from the group consisting of a curing agent, an adhesion assistant, a surfactant, an initiator, a storage stabilizer, a striation inhibitor, a curing accelerator, a thermal polymerization inhibitor, and a plasticizer. The thermosetting protective film resin composition according to any one of items 1 to 11, wherein the composition is one or more.
[Item 13]
The curing agents are phthalic anhydride, tetra-hydrophthalic anhydride, hexa-hydrophthalic anhydride, methyl tetra-hydrophthalic anhydride, methyl endomethylene tetra-hydrophthalic anhydride, hexachloroendomethylene tetra-hydrophthalic anhydride. Item 13. The thermosetting protective film resin composition according to Item 12, which is at least one selected from the group consisting of a product, dodecyl succinic anhydride, and trimellitic anhydride.
[Item 14]
14. The heat according to item 12 or 13, wherein the adhesion aid is an alkoxy group-containing silane-modified epoxy resin obtained by reacting an epoxy compound having a biphenyl group or an epoxy compound having a silyl group and an alkoxysilane. Curable protective film resin composition.
[Item 15]
The epoxy compound having a silyl group includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Item 15. The thermosetting protective film resin composition according to Item 14, which is at least one selected from the group consisting of 3,4-epoxycyclohexylethyltrimethoxysilane and 3,4-epoxycyclohexylethyltriethoxysilane. .
[Item 16]
The above alkoxysilane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyl Trimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and partial condensates thereof 16. The thermosetting protective film resin composition according to item 14 or 15, which is one or more selected from the group consisting of:
[Item 17]
17. The thermosetting protective film resin composition according to any one of items 12 to 16, wherein the surfactant is a fluorine-based surfactant or a silicon-based surfactant.
[Item 18]
18. The thermosetting protective film resin composition according to any one of items 1 to 17, wherein the polyfunctional monomer is used as a mixture of two or more.
[Item 19]
The thermosetting protective film resin composition is benzene, toluene, ethylbenzene, xylene, methanol, ethanol, isopropyl alcohol, tetraglycol, methoxypropanol, ethoxypropanol, butoxypropanol, benzyl alcohol, monomethylamine, monoethylamine, monoethanolamine. 1-amino-2-propanol, 2-methylaminoethanol, dimethylethanolamino, methylpyrrolidone, diethanolamine, diethylaminoethanol, triethanolamine, tetrahydrofuran, 1,4-dioxane, butyl cellosolve, 2-methoxyethyl ether, 1-methoxy 2-propanol, methoxybenzene, dibutyl ether, diphenyl ether, ethylene glycol ethyl methyl ether , Ethylene glycol diethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, methyl ethyl ketone, methyl butyl ketone, cyclohexanone 2-heptanone, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, propylene Glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, butyrolactone, ethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propyl acetate, butyl acetate, 3-methoxy Butyl acetate, ethyl propionate, methyl 3-methoxypropionate, ethyl pyruvate, methyl-2-hydroxyisobutyrate, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monoacetate, ethylene glycol One or more solvents selected from the group consisting of diacetate and a mixture thereof are used. 19. The thermosetting protective film resin composition according to any one of items 1 to 18.
[Item 20]
Item 20. A protective film for a color filter formed from the thermosetting protective film resin composition according to any one of items 1 to 19.
[Item 21]
Item 21. The color filter protective film according to Item 20, wherein the step of the color filter protective film is 0 to 5,000 mm or less.
[Item 22]
Item 22. A liquid crystal display device comprising the color filter protective film according to Item 20 or 21.

Claims (19)

For all solids
Binder resin 1 to 28% by weight, polyfunctional monomer 68-95 wt%, and other additives 4-31% by weight only free,
The binder resin is a copolymer of a mixture containing an epoxy group-containing unsaturated compound and an ethylenically unsaturated compound in a weight ratio of 25:75 to 60:40,
The ethylenically unsaturated compound includes a styrene monomer, an ethylenically unsaturated compound containing a silyl group, and an ethylenically unsaturated compound containing a functional group in which an acid group is formed by hydrolysis,
The polyfunctional monomer includes ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, propylene glycol di (meth) acrylate, and 2 to 14 propylene groups. Propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (me ) Acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate-succinate, dipentaerythritol tetra (meth) acrylate-disuccinate, and dipentaerythritol penta (meth) acrylate-succinate One or more selected from the group consisting of:
The other additives are selected from the group consisting of a curing agent, an adhesion assistant, a surfactant, an initiator, a storage stabilizer, a striation inhibitor, a curing accelerator, a thermal polymerization inhibitor, and a plasticizer. One or more
Thermosetting protective film resin composition.   The thermosetting protective film resin composition according to claim 1, wherein the solid content has a concentration of 10 to 30% by weight.   The thermosetting protective film resin composition according to claim 1 or 2, wherein the thermosetting protective film resin composition has a viscosity of 2 to 4 cps at room temperature. The thermosetting protective film resin composition according to any one of claims 1 to 3 , wherein the binder resin has a weight average molecular weight (Mw) of 5,000 to 10,000. The epoxy group-containing unsaturated compound includes epoxy alkyl (meth) acrylate, allyl glycidyl ether, allyl glycidyl ester, aryl glycidyl ether, aryl glycidyl ester, glycidyl 5-norbornene-2-methyl-2-carboxylate (endo, exo mixture) ), 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl alpha-n-butyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxy butyl (meth) acrylate, 4,5-epoxy pentyl (meth) acrylate, 5,6-epoxyheptyl (meth) acrylate And 6,7-epoxy-heptyl α- ethyl one epoxy group-containing unsaturated compound selected from the group consisting of acrylate, or according to claims 1, characterized in that a mixture thereof in any one of the 4 Thermosetting protective film resin composition. The styrene-based monomer, scan styrene, 4-methoxystyrene, and 4-methylstyrene down or heat as claimed in any one of claims 1 to 5, characterized in that Ranaru is from 1 or more selected group Curable protective film resin composition. Ethylenically unsaturated compounds comprising the above silyl group, vinyl-trimethoxysilane, vinyl triethoxysilane, vinyl tris (beta-methoxyethoxy) silane, methyl vinyl dimethoxy silane, beta-(meth) acryloxy ethyl trimethoxysilane, beta -(Meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- ( Meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyldimethylethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane At least one element selected from Ranaru group,
Ethylenically unsaturated compounds comprising a functional group which the acid group is formed by the hydrolysis, tetrahydro -2H- pyran-2-yl (meth) acrylate and t- butyl (meth) acrylate bets or found one selected It is the above, The thermosetting protective film resin composition of any one of Claim 1 to 6 characterized by the above-mentioned. The curing agents are phthalic anhydride, tetra-hydrophthalic anhydride, hexa-hydrophthalic anhydride, methyl tetra-hydrophthalic anhydride, methyl endomethylene tetra-hydrophthalic anhydride, hexachloroendomethylene tetra-hydrophthalic anhydride. The thermosetting protective film resin composition according to any one of claims 1 to 7, wherein the thermosetting protective film resin composition is one or more selected from the group consisting of a product, dodecyl succinic anhydride, and trimellitic anhydride. object. 9. The adhesion aid is an alkoxy group-containing silane-modified epoxy resin obtained by reacting an epoxy compound having a biphenyl group or an epoxy compound having a silyl group and an alkoxysilane . 2. The thermosetting protective film resin composition according to item 1. The epoxy compound having a silyl group includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3,4-epoxy cyclohexylethyl trimethoxysilane, and 3,4-epoxycyclohexyl ethyl thermosetting protective layer resin according to claim 9, characterized in that from one or more selected group consisting of triethoxysilane Composition. The above alkoxysilane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyl Trimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane , and partial condensation thereof The thermosetting protective film resin composition according to claim 9 or 10 , wherein the thermosetting protective film resin composition is one or more selected from the group consisting of products. The thermosetting protective film resin composition according to any one of claims 1 to 11 , wherein the surfactant is a fluorine-based surfactant or a silicon-based surfactant. The thermosetting protective film resin composition according to any one of claims 1 to 12 , wherein the polyfunctional monomer is used by mixing two or more kinds. The thermosetting protective film resin composition according to any one of claims 1 to 13, further comprising a solvent for mixing the binder resin, the polyfunctional monomer, and the other additives. The solvent is at least one selected from the group consisting of aromatic hydrocarbons, alcohols, amines, ethers, alkyl ketones, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, and esters. The thermosetting protective film resin composition according to claim 14. The solvent is
Benzene, toluene, ethylbenzene, and xylene belonging to the above aromatic hydrocarbons ,
Methanol, ethanol, isopropyl alcohol, tetraglycol, methoxypropanol, ethoxypropanol, butoxypropanol, and benzyl alcohol belonging to the above alcohols ,
Monomethylamine, monoethylamine, monoethanolamine, 1-amino-2-propanol, 2-methylaminoethanol, dimethylethanolamino, methylpyrrolidone, diethanolamine, diethylaminoethanol, and triethanolamine belonging to the above amines ,
Tetrahydrofuran belonging to the ethers, 1,4-dioxane, butyl cellosolve, 2-methoxyethyl ether, 1-methoxy-2-propanol, methoxy benzene, dibutyl ether, diphenyl ether, ethylene glycol ethyl methyl error over Te le, ethylene glycol diethyl et over Te Le, diethylene glycol ethyl ether, diethylene glycol dimethyl error over Te Le, diethylene glycol ethyl methyl error over Te Le, diethylene glycol diethyl error over Te Le, diethylene glycol butyl error over Te Le, dipropylene glycol methyl error over Te Le, dipropylene glycol ethyl ether, and dipropylene glycol butyl error over Te le,
Methyl ethyl ketone, methyl butyl ketone, cyclohexanone, and 2-heptanone belonging to the above alkyl ketones ,
The methyl cellosolve acetate belonging to ethylene glycol alkyl ether acetates, ethyl cellosolve acetate, ethylene glycol butyl error over Te le acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl error over Te le acetate and diethylene glycol butyl error over Te le acetate,
The propylene glycol Propylene glycol methyl error over Te le acetate belonging to alkyl ether acetates, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and dipropylene glycol methyl error over Te le acetate,
Butyrolactone, ethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propyl acetate, butyl acetate, 3-methoxybutyl acetate, ethyl propionate, methyl 3-methoxypropionate, ethyl pyruvate belonging to the above esters , methyl 2-hydroxyisobutyrate, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monoacetate and ethylene glycol diacetate, and one or more members selected from the group consisting of a mixture thereof, thermosetting protective layer resin composition according to claim 15, wherein the solvent der Rukoto. The protective film of the color filter formed from the thermosetting protective film resin composition of any one of Claim 1 to 16 . The color filter protective film according to claim 17 , wherein the step of the color filter protective film is within a range of 0 to 5,000 mm. The liquid crystal display device comprising a color filter protective film according to claim 17 or 18.