KR20140020497A - A thermosetting resin composition, color filter having protective film and liquid crystal display device using thereof - Google Patents

Abstract

The present invention is a thermosetting resin composition comprising an acrylic resin (A) containing fluorine, a thermosetting compound (B), and a solvent (C), and relates to a thermosetting resin composition in which the acrylic resin (A) is a copolymer comprising repeating units of a chemical formula 1 and the thermosetting compound (B) is a bisphenol novolac type of an epoxy resin.

Description

Thermosetting resin composition, color filter and liquid crystal display device having a protective film manufactured using the same {A THERMOSETTING RESIN COMPOSITION, COLOR FILTER HAVING PROTECTIVE FILM AND LIQUID CRYSTAL DISPLAY DEVICE USING THEREOF}

The present invention relates to a color filter and a liquid crystal display device having a thermosetting resin composition, a protective film manufactured using the same.

In general, a color liquid crystal display device protects a colored layer, that is, a pixel part, in a chemical treatment such as an acid or an alkali, which is performed in a color filter post-process, and a high-temperature sputtering process, and colorizes to flatten a step generated by each pixel of the colored layer. A protective film is provided on the surface of the layer. Accordingly, the color filter protective film is required to have physical properties such as transparency, heat resistance, chemical resistance and flatness, and particularly excellent heat resistance is required. This is because, when the transparent electrode such as indium tin oxide (ITO) is produced on the protective film by the sputtering method, the protective film needs to be heated to a temperature of 250 ° C or higher when firing the liquid crystal alignment layer on the ITO or higher. to be.

As a mononuclear thermosetting resin composition for forming a conventional protective film, JP-A-2005-008847 discloses a mononuclear thermosetting resin composition containing an acrylic resin and a thermosetting compound. However, the composition has problems in heat resistance and storage stability at high temperatures.

Japanese Patent Laid-Open No. 2005-008847

In order to solve the above problems, an object of the present invention is to provide a thermosetting resin composition excellent in transparency, heat resistance, alkali resistance, flatness and long-term storage stability.

In addition, another object of the present invention to provide a color filter having a protective film produced using the thermosetting resin composition.

Another object of the present invention is to provide a liquid crystal display device comprising the color filter.

The present invention is a thermosetting resin composition containing an acrylic resin (A), a thermosetting compound (B) and a solvent (C),

The acrylic resin (A) is a copolymer containing a repeating unit of the formula (1),

The thermosetting compound (B) is a bisphenol novolak-type epoxy resin provides a thermosetting resin composition, characterized in that.

≪ Formula 1 >

In <Formula 1>, R1 is each independently hydrogen or a methyl group, R2 is <Formula 2>,

<Formula 2>

In <Formula 2>, R1 is each independently hydrogen or a methyl group, R3 is the following <Formula 3>,

<Formula 3>

R4 represents a C1-C6 alkyl group substituted with 2-12 fluorine atoms, and R5 is a carboxyl group.

In addition, the present invention provides a color filter having a protective film prepared by forming a coating film of the thermosetting resin composition and then heat treatment.

In addition, the present invention provides a liquid crystal display device including the color filter.

The thermosetting resin composition of the present invention is a mononuclear type, and exhibits excellent properties of heat resistance, transparency, alkali resistance, flatness, and long-term storage stability, and thus can be usefully used in the production of a protective film for color filters. Therefore, the thermosetting resin composition may be usefully applied to color filters and liquid crystal displays.

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

The present invention is a thermosetting resin composition containing an acrylic resin (A), a thermosetting compound (B) and a solvent (C),

The acrylic resin (A) is a copolymer containing a repeating unit of the formula (1),

The thermosetting compound (B) is a bisphenol novolak-type epoxy resin provides a thermosetting resin composition, characterized in that.

&Lt; Formula 1 >

In <Formula 1>, R1 is each independently hydrogen or a methyl group, R2 is <Formula 2>,

<Formula 2>

In <Formula 2>, R1 is each independently hydrogen or a methyl group, R3 is the following <Formula 3>,

<Formula 3>

R4 represents a C1-C6 alkyl group substituted with 2-12 fluorine atoms, and R5 is a carboxyl group.

Each component is explained in full detail.

(A) acrylic resin

The acrylic resin (A) is a copolymer containing a repeating unit of the formula (1),

&Lt; Formula 1 >

In <Formula 1>, R1 is each independently hydrogen or a methyl group, R2 is <Formula 2>,

<Formula 2>

In <Formula 2>, R1 is each independently hydrogen or a methyl group, R3 is the following <Formula 3>,

<Formula 3>

R4 represents a C1-C6 alkyl group substituted with 2-12 fluorine atoms, and R5 is a carboxyl group.

The acrylic resin having the structure of <Formula 1> may be synthesized by the following method, but is not limited thereto.

After glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylic acid, an acid anhydride substituted with a fluorine atom can be further reacted to synthesize. Moreover, synthesis | combination is possible even if (meth) acrylic acid reacts with the copolymer of glycidyl group (meth) acrylate, and the acid anhydride substituted by fluorine atom is further reacted.

The acid anhydrides substituted with the fluorine atoms include tetrafluorosuccinic anhydride, hexafluoroglutaric anhydride, and the like.

The acrylic resin (A) is a copolymer further comprising at least one selected from vinyltoluene, N-phenylmaleimide, phenylthioethyl acrylate, cyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. It is more preferable.

In addition, the said acrylic resin (A) can be synthesize | combined using the polymerization monomer which has an unsaturated bond which can be copolymerized further.

Specific examples of the polymerization monomer having an unsaturated bond capable of copolymerization include styrene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-vinylbenzylmethyl ether. aromatic vinyl compounds such as m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No N-substituted maleimide compounds such as -methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) Alicyclic (meth) acrylates such as acrylate and isobornyl (meth) acrylate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

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

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds. The polymerization monomers having an unsaturated bond capable of copolymerization can be used alone or in combination of two or more thereof.

The structural unit represented by Formula 1 included in the acrylic resin (A) is preferably contained in a mole fraction of 5 to 80 mol%, more preferably 20 to 60 mol% based on the total moles of the acrylic resin. Can be .

The content of the acrylic resin (A) is preferably 1 to 40% by weight, more preferably 10 to 30% by weight based on the total weight of the thermosetting resin composition. When the content of the acrylic resin (A) is 1 to 40% by weight based on the above standards, a good balance of alkali resistance and heat resistance can be obtained .

(B) a thermosetting compound

The thermosetting compound (B) includes an epoxy resin satisfying the following conditions (B1), (B2) and (B3).

(B1) an epoxy equivalent of 2000 g / eq or less,

(B2) a bisphenol A novolak type epoxy resin in an amount of 50% by weight or more based on the total amount of the thermosetting compound (B)

(B3) a curing aid selected from a carboxylic acid, a carboxylic acid anhydride and a polyvalent carboxylic acid anhydride.

The average molecular weight of the thermosetting compound is preferably 20,000 or less, more preferably 1,000 to 20,000. When the average molecular weight of the thermosetting compound (B) satisfies the above-mentioned conditions, transparency, flatness and heat resistance are excellent.

The thermosetting compound (B) is preferably composed of a bisphenol A novolak type epoxy resin in an amount of 50% by weight or more based on the total amount of the thermosetting compound. When the content of the bisphenol A novolak type epoxy resin is less than 50% by weight, the storage stability of the thermosetting resin composition is lowered.

The bisphenol A novolac-type epoxy resin is preferably represented by the following formula (4). In this case, the thermosetting resin composition is excellent in transparency and heat resistance.

&Lt; Formula 4 >

In Formula 4, n is 0 or a positive integer.

The thermosetting compound (B) preferably does not contain a curing aid selected from a carboxylic acid, a carboxylic acid anhydride and a polycarboxylic acid anhydride. If the curing aid is included, there is a problem that the storage stability of the thermosetting resin composition deteriorates.

As a bisphenol A novolak-type epoxy resin which satisfy | fills the above conditions, as a specific example, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- ([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- Mixture with [1- [4- (2,3-epoxypropoxyphenyl) -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, 2- [4- (2,3-epoxypropoxy ) Phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane and the like. Commercially available products include JER 157S65, 157S70 (trade name; JER Corporation). These may be used alone or in combination of two or more.

The thermosetting compound according to the present invention may further include an epoxy resin other than the bisphenol A novolak type epoxy resin. Preferred examples of the epoxy resin which can be used together with the bisphenol A novolak-type epoxy resin, further include, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydrokinone Type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene epoxy resin, phenol noblock type epoxy resin, allocresol noblock type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenol Ethane type epoxy resin, dicyclomethane dienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy Resin, glyoxal epoxy resin, alicyclic polyfunctional epoxy resin, heterocyclic epoxy Resin and the like can be used. These epoxy resins may be used alone or in combination of two or more in addition to the bisphenol A novolak type epoxy resin.

As the above-mentioned epoxy resin, commercially available products such as the following can be used. More specifically, bisphenol F-type epoxy resins such as YDF-175S (manufactured by Toyo Chemical Co., Ltd.), bisphenol A-type epoxy resins such as YDB-715 (manufactured by Toyo Chemical Co., Ltd.), etc. Biphenyl type epoxy resin such as EPICLON EXA4032 (manufactured by Dainippon Inkyaka Chemical Co., Ltd.) as a naphthalene type epoxy resin, such as YDC-1312 (manufactured by Tosho Chemical Co., Ltd.) as a hydrokinone type epoxy resin, and the like. As a bisphenol A novolak type epoxy resin, such as epicoat YX4000H (made by JER Corporation) as resin, EPPN-201 (Nippon Kayaku (Nippon Kayaku) as a phenol novolak type epoxy resin, such as JER 157S65 or 157S70 (made by JER Corporation) Product), JER152 154 (JER Co., Ltd.) such as cresol novolac type epoxy resin, EOCN-102S, 103S, 104S or 1020 (manufactured by Nippon Kayaku Co., Ltd.), trishydroxyphenylmethane epoxy resin As epicoat 1032H60 (product of JER Co., Ltd.), trifunctional type As a epoxy resin, VG3101M80 (manufactured by Mitsui Chemical Co., Ltd.), Epicoat 10315 (manufactured by JER Co., Ltd.) as a tetraphenolethane type epoxy resin, ST-3000 (manufactured by Tokyo Chemical Co., Ltd.), etc. As a glycidyl ester type epoxy resin, Epicoat 190P (manufactured by JER Co., Ltd.), and a glycidylamine type epoxy resin, such as YH-434 (manufactured by Toyo Chemical Co., Ltd.), as a glyoxal type epoxy resin, YDG-414 (東 都) As an alicyclic polyfunctional epoxy resin, EHPE3150 or Eporide GT-401 (made by Daicel Kagaku Co., Ltd.) etc. are mentioned, The said epoxy resin can be used individually or in combination of 2 or more types, respectively. .

The content of the thermosetting compound (B) is preferably 0.1 to 30% by weight, more preferably 0.1 to 10% by weight based on the total weight of the thermosetting resin composition. Since the transparency and flatness become favorable if a thermosetting compound (B) is the range of 0.1-30 weight% on the said reference | standard, it is preferable.

(C) Solvent

The solvent is not particularly limited as long as it is effective in dispersing or dissolving the other components included in the thermosetting resin composition, and various organic solvents used in the field of the thermosetting resin composition can be used.

Examples of the solvent (C) include an organic solvent having a boiling point of 100 ° C. to 200 ° C. in view of applicability and drying properties. Specific examples of the solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Ethylene glycol monoalkyl ethers such as monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, is mentioned. More preferably, alkylene glycol alkyl ether acetates, ketones, esters, such as 3-ethoxy propionate ethyl and 3-methoxy propionate methyl, are mentioned, Most preferably, propylene glycol monomethyl ether acetate and propylene glycol Monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The above-mentioned solvents (C) may be used alone or in combination of two or more.

It is preferable that the said solvent (C) is contained in 60 to 89.9 weight% with respect to the total weight of the said thermosetting resin composition, More preferably, it is 70 to 85 weight%. When the content of the solvent (C) is in the range of 60 to 89.9% by weight on the basis of the above criteria, when the solvent (C) is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater Is preferable.

(D) additive

The thermosetting resin composition of the present invention may contain components other than the above-mentioned components as other additives, if necessary, within the range not impairing the object of the present invention. Such other additives include coupling agents, surfactants, and antioxidants.

The coupling agent is used for improving the adhesion with the substrate and may be contained in an amount of 10% by weight or less based on the total weight of the solid content in the thermosetting resin composition.

In the present invention, the total solid weight in the thermosetting resin composition means the total content of the remaining components excluding the solvent from the thermosetting resin composition.

As the coupling agent, a silane-based, aluminum-based or titanate-based compound may be used. Specific examples of the coupling agent include silane coupling agents such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane, acetoalkoxy aluminum di Aluminum titanate such as isopropyl acetate and titanate such as tetraisopropyl bis (dioctylphosphate) titanate. Among them, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving the adhesion.

The surfactant is used for improving the wettability, leveling property, or coatability of the base substrate, and may be included in an amount of 0.01 to 5% by weight based on the total weight of the solid content in the thermosetting resin composition. Examples of the silicone surfactant include silicone surfactants such as TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 manufactured by Jitoshiba Silicone Co., KP321, KP323, KP324, KP326, KP340, and KP341 manufactured by Shin-Etsu Silicone Co., Ltd. under trade names; And BYK-Chemie, trade names BYK-333, 358N and UV3500,390,306,340.

Examples of the fluorine-based surfactant include Florinate FC430 and Florinate FC431 manufactured by Sumitomo Forest Co., Ltd.; Manufactured by Dainippon Ink and Chemicals, Inc. under the trade names Megapak F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Megapack R30, Megapack R08, Megapack R09, Park F475, Mega Park F489, Mega Park F544, Mega Park F443, and the like.

The said antioxidant is used in order to improve transparency and to prevent yellowing when a cured film encounters high temperature, It can add and use within 0.1 to 3 weight% with respect to the total weight of solid content in the said thermosetting resin composition.

As the antioxidant, a hindered system, a hindered phenol system, or the like can be used. Specific examples thereof include IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 and IRGANOX 1520L manufactured by Chiba Specialty Chemicals Co., Ltd.

The color filter according to the present invention includes a protective film formed by forming a coating film of the thermosetting resin composition according to the present invention described above on a substrate, followed by heat treatment.

As the coating film forming method, a coating film can be formed by a conventionally known method such as spin coating, roll coating, dipping, and slit coating.

The thickness of the coating film is preferably 0.15 to 8.0 mu m, more preferably 0.20 to 4.5 mu m. Here, the thickness of the coating film is the thickness after removal of the solvent.

The coating film is heated (prebaked) by a hot plate, an oven or the like. Heating conditions are usually 1 to 15 minutes in an oven or hot plate at 70 to 120 ° C., and then 20 to 90 minutes in an oven or hot plate at 180 to 250 ° C., preferably 200 to 250 ° C., in order to cure the coating film. By heat-processing, the hardened coating film, ie, the protective film for color filters, can be obtained. The present invention provides a color filter having the protective film for the color filter manufactured above.

The present invention provides a liquid crystal display device including the color filter. The liquid crystal display of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover contains all changes within the meaning and range equivalent to the scope of the claims. In the following, "%" and "part" representing the content are by weight unless otherwise specified.

Synthetic example  1-4. Synthesis of Acrylic Resin (A)

&Lt; Synthesis Example 1 &

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 3.2 parts of methacrylic acid, 64.0 parts of vinyltoluene, in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 10 parts of clofentanyl methacrylate, 10 parts of phenylthioethyl acrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, after reducing the temperature of the reaction solution to room temperature and replacing the flask atmosphere with nitrogen from air, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol and 5.0 part of glycidyl methacrylate were added thereto, followed by reaction at 100 ° C. for 6 hours. It was. Thereafter, the reaction solution was cooled to room temperature, 7.8 parts of hexafluoroglutaric anhydride was added thereto, and reacted at 80 ° C. for 12 hours to obtain an acrylic resin (a-1).

The solid acid value of the acrylic resin thus synthesized was 20.0 mgKOH / g, and the weight average molecular weight Mw of polystyrene conversion measured by GPC was about 24,774.

Synthesis Example 2

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 3.2 parts of methacrylic acid, 64.0 parts of vinyltoluene, in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 10 parts of -phenyl maleimide, 10 parts of cyclohexyl methacrylates, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, after reducing the temperature of the reaction solution to room temperature and replacing the flask atmosphere with nitrogen from air, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol and 5.0 part of glycidyl methacrylate were added thereto, followed by reaction at 100 ° C. for 6 hours. It was. Thereafter, the reaction solution was cooled to room temperature, 7.8 parts of hexafluoroglutaric anhydride was added thereto, and reacted at 80 ° C. for 12 hours to obtain an acrylic resin (a-2).

The solid acid value of the acrylic resin thus synthesized was 20.0 mgKOH / g, and the weight average molecular weight Mw of polystyrene conversion measured by GPC was about 21,850.

&Lt; Synthesis Example 3 &

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 3.2 parts of methacrylic acid, 68.3 parts of vinyltoluene, in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 10 parts of clofentanyl methacrylate, 10 parts of phenylthioethyl acrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and the flask atmosphere was replaced with nitrogen from air, followed by 0.2 parts of triethylamine, 0.1 parts of 4-methoxy phenol, and 5.0 parts of glycidyl methacrylate, followed by reaction at 100 ° C. for 6 hours. It was. Thereafter, the reaction solution was cooled to room temperature, 3.5 parts of succinic anhydride was added thereto, and reacted at 80 ° C. for 12 hours to obtain an acrylic resin (a-3).

The solid acid value of the acrylic resin thus synthesized was 20.7 mgKOH / g, and the weight average molecular weight Mw of the polystyrene conversion measured by GPC was about 22,830.

Synthesis Example 4

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 3.2 parts of methacrylic acid, 64.0 parts of vinyltoluene, benzyl in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 10 parts of methacrylate, 10 parts of methyl methacrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 80 ° C. and reacted for 8 hours. Subsequently, after reducing the temperature of the reaction solution to room temperature and replacing the flask atmosphere with nitrogen from air, 0.2 part of triethylamine, 0.1 part of 4-methoxy phenol and 5.0 part of glycidyl methacrylate were added thereto, followed by reaction at 100 ° C. for 6 hours. It was. Thereafter, the reaction solution was cooled down to room temperature, 7.8 parts of hexafluoroglutaric anhydride was added thereto, and the mixture was reacted at 80 ° C. for 12 hours to obtain an acrylic resin (a-4).

The solid acid value of the acrylic resin thus synthesized was 20.8 mgKOH / g, and the weight average molecular weight Mw of the polystyrene conversion measured by GPC was about 19,950.

Example  1 to 3 and Comparative Example  1 to 4. Preparation and Evaluation of Thermosetting Resin Compositions

&Lt; Example 1 >

11.50 weight% (solid content) of the acrylic resin (a-1) obtained by the said synthesis example 1, and 3.50 weight of bisphenol A novolak-type epoxy resin (JER157S70; JER Corporation make, epoxy equivalent: 210 g / eq) as a thermosetting compound (B) %, Γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shinnetsu Chemical Co., Ltd.) as coupling agent (D-1) and Megapak F475, Dinihon Ink as surfactant (D-2) Chemical Industry Co., Ltd.) 0.02% by weight was added, and 74.88% by weight of propylene glycol monomethyl ether acetate (C1) and 10.0% by weight of methyl 3-methoxypropionate (C2) were added as a solvent (C). Filtration with a pore filter produced a curable resin composition.

&Lt; Examples 2 to 3 and Comparative Examples 1 to 4 >

The thermosetting resin composition was prepared in the same manner as in Example 1, except that each component and its content were carried out as shown in Table 1 below.

(Unit: wt%)
Example Comparative Example One 2 3 One 2 3 4 Acrylic resin
(A) Synthesis Example 1 11.5 0 0 0 11.5 0 0 Synthesis Example 2 0 11.5 0 0 0 11.5 0 Synthesis Example 3 0 0 0 11.5 0 0 0 Synthesis Example 4 0 0 11.5 0 0 0 11.5 The thermosetting compound (B) B1 3.5 3.5 3.5 3.5 0 0 0 B2 0 0 0 0 3.5 3.5 3.5 Solvent (C) C1 74.88 74.88 74.88 74.88 74.88 74.88 74.88 C2 10 10 10 10 10 10 10 Additive (D) D1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 D2 0.02 0.02 0.02 0.02 0.02 0.02 0.02

Acrylic resin (A): (a-1 to a-4, see Synthesis Example)

Thermosetting compound (B1): bisphenol A novolak type epoxy resin (JER157S70 epoxy equivalent: 210 g / eq, manufactured by JER Co., Ltd.)

Thermosetting compound (B2): polyfunctional alicyclic epoxy resin (EHPE3150 epoxy equivalent: 740 g / eq, manufactured by Daicel Chemical Co., Ltd.)

Solvent (C1): propylene glycol monomethyl ether acetate

Solvent (C2): methyl 3-methoxypropionate

Additive (D1): 3-glycidoxyoxytrimethoxysilane (KBM-403, manufactured by Shinnetsu Chemical Co., Ltd.)

Additive (D2): Megapak F-544 (manufactured by Dainippon Ink and Chemicals, Inc.)

<Experimental Example>

Experimental Example  One. Flatness  evaluation

A glass substrate of 2 square inches (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. A color resist (trade name: YR-800 Red, YG-800 Green, YB-800 blue, manufactured by Dongwoo Fine-Chem Co., Ltd.) was exposed on this glass substrate at an exposure amount of 365 nm (100 mJ / , And then preliminarily dried in a clean oven at 100 DEG C for 3 minutes. After cooling, the gap between the substrate coated with this colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) Was made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C for a predetermined time, developed, and then washed with water and dried at 230 ° C for 60 minutes.

The unevenness of the surface of the substrate on which the color filter was formed was measured by a surface roughness meter (Dektak 6M, manufactured by Beko Corporation) and found to be 1.0 탆. The measurement length was 2,000 占 퐉, the measurement range was 2,000 占 퐉, and the number of measurement points was n = 5. That is, the measurement direction is set to two directions, that is, the short axis direction of the stripe line in the red, green, and blue directions and the long axis direction of the stripe line of the same color of red / red, green / green, and blue / blue, (The total number of n is 10).

After applying the thermosetting resin composition thereon using a spin coater, a pre-fired at 80 ° C. for 5 minutes on a hot plate to form a coating film, followed by heat treatment at 230 ° C. for 60 minutes in an oven to form a protective film having a thickness of 1.5 μm. It was.

The unevenness of the surface of the protective film was measured with a surface roughness meter (Dektak 6M, manufactured by Beko Corporation) of the contact type film thickness measuring apparatus with respect to the substrate formed as described above. However, the measurement length was 2,000 占 퐉 and the measurement range was 2,000 占 퐉. The number of measurement points was n = 5. That is, the measurement direction was set to be in the direction of the major axis of the stripe line of the same color in the red, green, and blue directions, and in the direction of the short axis of the stripe line and in red, red, green, The total number of n is 10). For each measurement, ten average values of the height difference (nm) of the highest part and the lowest part are obtained. When this value is 300 nm or less, the flatness is good.

For the substrate formed as described above, when the maximum value of the step between red, green, and blue pixels was less than 0.2 µm, the case where ○ and 0.2 µm or more was regarded as x.

Experimental Example  2. Transparency Assessment

With respect to the substrate having the protective film formed as described above, the transmittance with respect to the wavelength from 380 nm to 700 nm is shown in Table 2 using a colorimeter (Olympus) with reference to the same glass substrate coated with the coating film.

At this time, a case where the transmittance is 95% or more is referred to as ○, a case where the case where the transmittance is less than 95% and 90% or more is Δ and less than 90%.

Experimental Example  3. Heat resistance evaluation

The substrate having the protective film formed as described above was heated in an oven at 250 DEG C for one hour, and the film thickness before and after heating was measured. The film thickness change rate computed according to following <Equation 1> is calculated | required. At this time, a case where the film thickness change rate is 95% or more is referred to as ○, less than 95% and 90% or more, Δ and less than 95%.

&Lt; Formula 1 >

(Film thickness after heating) / (film thickness before heating)] * 100 (%)

Experimental Example  4. Alkali resistance  evaluation

The substrate having the protective film formed as described above was immersed in a 5% aqueous solution of sodium hydroxide heated to 40 캜 for 30 minutes, and then washed with ultrapure water and dried on a hot plate heated to 120 캜 for 2 minutes to form a film The thickness was measured. At this time, the case where the film thickness change rate is 95% or more is referred to as ○, and the case where the film thickness change rate is less than 95% and 90% or more is Δ and less than 95%.

Experimental Example  5. Evaluation of storage stability

The viscosity of the thermosetting resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was measured after 1 hour at room temperature on the day of manufacture using a Rotational Viscometer viscometer (VM-150III, manufactured by Toki Sangyo Co., Ltd.). Thereafter, while leaving the composition at 25 ° C., the number of days required to thicken 5% based on the viscosity immediately after preparation was confirmed, and when the number of days was 30 days or more, △, less than 30 days and 20 days or more △ Is less than 20 days.

Flatness, transparency, heat resistance, alkali resistance and storage stability were measured through Experimental Examples 1 to 5 described above using the thermosetting resin compositions prepared in Examples and Comparative Examples, and the results are shown in Table 2 below.

Example Comparative Example One 2 3 One 2 3 4 Flatness ○ ○ ○ X ○ ○ ○ Transparency ○ ○ ○ ○ ○ ○ Δ Heat resistance ○ ○ Δ ○ X X X Alkali resistance ○ ○ Δ ○ Δ Δ Δ Storage stability ○ ○ Δ ○ Δ Δ Δ

As shown in Table 2, the thermosetting resin composition for the color filter protective film of the embodiment including the acrylic resin and the thermosetting compound according to the present invention exhibits excellent storage stability as compared to the comparative example, as well as flatness, alkali resistance, transparency, heat resistance, and the like. It was found that the physical properties were excellent.

Claims (7)

As a thermosetting resin composition containing an acrylic resin (A), a thermosetting compound (B), and a solvent (C),
The acrylic resin (A) is a copolymer containing a repeating unit of the formula (1),
The thermosetting compound (B) is a bisphenol novolak-type epoxy resin, the thermosetting resin composition, characterized in that.
<Formula 1>

In <Formula 1>, R1 is each independently hydrogen or a methyl group, R2 is <Formula 2>,

(2)

In <Formula 2>, R1 is each independently hydrogen or a methyl group, R3 is the following <Formula 3>,

<Formula 3>

R4 represents a C1-C6 alkyl group substituted with 2-12 fluorine atoms, and R5 is a carboxyl group. The method of claim 1, wherein the acrylic resin (A) is 1 selected from the group consisting of vinyltoluene, N-phenylmaleimide, phenylthioethyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate. It is a copolymer which contains a species or more, The thermosetting resin composition characterized by the above-mentioned. The method of claim 1, wherein the acrylic resin is a copolymer of (meth) acrylic acid and glycidyl (meth) acrylate or a copolymer of glycidyl group (meth) acrylate and (meth) acrylic acid after reacting the substituted with a fluorine atom A thermosetting resin composition characterized in that the acid anhydride is further reacted to prepare the compound. The thermosetting resin composition according to claim 3, wherein the acid anhydride substituted with a fluorine atom is at least one selected from tetrafluorosuccinic anhydride and hexafluoroglutaric anhydride. The method according to claim 1, with respect to the total weight of the thermosetting resin composition,
Acrylic resin (A) is 1 to 40% by weight;
Thermosetting compound (B) is 0.1 to 30% by weight and
It is contained by 60-89.9 weight% of solvents (C), The thermosetting resin composition characterized by the above-mentioned. The protective film manufactured by heat-processing after forming the coating film of the thermosetting resin composition of any one of Claims 1-5, The color filter characterized by the above-mentioned. The liquid crystal display device containing the color filter of Claim 6.