KR20110068418A - Curable resin composition for protective film of color filter, color filter and liquid crystal display device using thereof - Google Patents

Abstract

PURPOSE: A thermosetting resin composition is provided to ensure excellent heat resistance, transparency, alkali resistance, flatness, long-term storage stability. CONSTITUTION: A thermosetting resin composition comprises an acrylic resin(A), a thermoplastic compound(B), and a solvent(C). The acrylic resin(A) is an unsaturated group-containing resin obtained by reacting a compound of chemical formula 1 with a copolymer obtained by copolymerizing aromatic vinyl compounds and compounds having an unsaturated group and an epoxy group in one molecule.

Description

Thermosetting resin composition, color filter and liquid crystal display device having a protective film manufactured using the same

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 that 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 requires physical properties such as transparency, heat resistance, chemical resistance, and flatness, and particularly, excellent heat resistance. This means that when a transparent electrode such as indium tin oxide (ITO) is produced on the protective film by a sputtering method, the protective film needs to be heated to a temperature of 250 ° C or higher when firing the liquid crystal alignment film on the ITO or higher. Because

Background Art A thermosetting resin composition containing a polymer having a glycidyl group in an acrylic resin backbone is known as a material for forming a protective film (JP-A-5-78453). However, since the composition does not meet the physical properties required in the protective film, a protective resin composition (Japanese Patent Laid-Open Publication No. Hei 4-170421) containing a thermosetting epoxy resin and a polyhydric anhydride as essential components has recently been used. have. However, the protective film resin composition has a problem of poor storage stability and yellowing.

The present invention is to solve the problems of the prior art as described above, the object is to provide a thermosetting resin composition excellent in heat resistance, transparency, alkali resistance, flatness, long-term storage stability.

It is 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.

In order to achieve the above object, the present invention comprises an acrylic resin (A), a thermosetting compound (B) and a solvent (C), the acrylic resin (A) is a compound containing the following (A1) and (A2) It provides a thermosetting resin composition characterized by being an unsaturated group-containing resin obtained by further reacting (A3) with a copolymer obtained by copolymerization:

(A1): aromatic vinyl compound,

(A2): compound which has an unsaturated bond and an epoxy group in 1 molecule,

(A3): The compound represented by following formula (1).

<Formula 1>

(In Formula 1, R1 and R2 are each independently substituted with a halogen element or a C1 to C6 alkyl group including a ketone group, an ester group, a thiol group, or an unsubstituted C1 to C6 alkyl group, A is a halogen group, methoxy An aliphatic polycyclic group, an allyl group, a halogen group, a methoxy group, an ethoxy group or an unsubstituted aromatic polycyclic group substituted or unsubstituted with a period or an ethoxy group, n and m are 0 or 1 .)

Compound (A3) represented by the formula (1) preferably comprises at least one selected from the group consisting of compounds represented by the following formula (2) to (6).

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

As for the said acrylic resin (A), the ratio of the component derived from each of said (A1) and (A2) is with respect to the total number of moles of the component of the said copolymer,

Structural unit derived from (A1): 20 to 60 mol%,

Structural unit derived from (A2): in the range of 20-60 mol%,

It is preferable to make said (A3) react with 20-120 mol% with respect to the epoxy equivalent of said (A2).

The thermosetting compound (B) is preferably an epoxy resin that satisfies the conditions of the following (B1), (B2) and (B3):

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

(B2) 50 mass% or more is comprised by bisphenol A noblock type epoxy resin by mass fraction with respect to the thermosetting compound (B) whole quantity,

(B3) It does not contain a curing aid selected from carboxylic acids, carboxylic acid anhydrides and polyhydric carboxylic anhydrides.

The thermosetting compound (B) is at least one selected from the group consisting of a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a glycidyl ether type epoxy resin, an aliphatic polyglycidyl ether, and an alicyclic aliphatic epoxy resin. It may further include.

In order to achieve the other object of the present invention, the present invention provides a color filter comprising a protective film prepared by applying the thermosetting resin composition according to the present invention on a substrate to form a coating film and then heat treatment.

In order to achieve another object of the present invention, the present invention provides a liquid crystal display device comprising a color filter according to the present invention described above.

The thermosetting resin composition according to the present invention exhibits excellent properties of heat resistance, transparency, alkali resistance, flatness, and long-term storage stability as a one-component type, and 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 thermosetting resin composition which concerns on this invention consists of acrylic resin (A), a thermosetting compound (B), and a solvent (C). Each component is explained in more detail as follows.

Acrylic resin (A)

The acrylic resin (A) includes an unsaturated group-containing resin obtained by further reacting (A3) with a copolymer obtained by copolymerizing compounds including the following (A1) and (A2).

(A1): aromatic vinyl compound,

(A2): compound which has an unsaturated bond and an epoxy group in 1 molecule,

(A3): The compound represented by following formula (1).

<Formula 1>

(In Formula 1, R1 and R2 are each independently substituted with a halogen element or a C1 to C6 alkyl group including a ketone group, an ester group, a thiol group, or an unsubstituted C1 to C6 alkyl group, A is a halogen group, methoxy An aliphatic polycyclic group, an allyl group, a halogen group, a methoxy group, an ethoxy group or an unsubstituted aromatic polycyclic group substituted or unsubstituted with a period or an ethoxy group, n and m are 0 or 1 .)

The acrylic resin (A) may be polymerized together by adding other monomers in addition to the compounds of (A1) to (A3). That is, acrylic resin (A) which concerns on this invention is contained in this invention also when the monomer other than said (A1)-(A3) is contained and polymerized further.

Specific examples of the aromatic vinyl compound (A1) include vinyltoluene, styrene, a-methylstyrene, a-chlorostyrene, vinylpyrrolidone, divinylbenzene, and the like, each of these alone or in combination of two or more thereof. Can be used. Preferably, in consideration of ease of manufacture, reliability, and the like, the aromatic vinyl compound (A1) may preferably use vinyltoluene. Particularly, when the aromatic vinyl compound (A1) includes vinyltoluene, the colored photosensitive resin composition including the acrylic resin (A) produced was found to have excellent effects such as reduction of outgas generation as a result of performance test.

Compound (A2) which has an unsaturated bond and an epoxy group in the said 1 molecule specifically, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, 3, 4- epoxycyclohexyl methyl (meth) Acrylate, methylglycidyl (meth) acrylate, and the like. These can be used individually or in combination of 2 types or more, respectively. In particular, in the above-exemplified (A2), glycidyl (meth) acrylate is excellent in the ease and reliability of production and can be used more preferably.

In the present invention, (meth) acrylate means acrylate and / or methacrylate.

The compound (A3) represented by Formula 1, which is further reacted to the copolymer obtained by copolymerizing the compounds including the above (A1) and (A2), is not particularly limited, but is preferably a compound represented by the following Formulas 2 to 6 It is preferable to include at least one selected from the group consisting of.

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

According to the present invention, in the process of further reacting (A3) with the copolymer of (A1) and (A2), unsaturated carboxylic acid may be reacted together as necessary.

Specific examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen from 1 type or more of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid. The said unsaturated carboxylic acid can be used individually or in combination of 2 types or more, respectively.

Also included in the present invention when the acrylic resin (A) according to the present invention further copolymerizes monomers other than the copolymers (A1) and (A2) obtained by copolymerizing the above-mentioned (A1) and (A2). do.

As monomers other than said (A1)-(A2), specifically methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, aminoethyl (meth) acrylate, benzyl methacrylate, and cyclopentyl (Meth) acrylate, clohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, methyl (meth) acrylate, cyclopentenyl ( Meta) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, Pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl (meth) acrylate, oligoethylene glycol monoalkyl (meth) acrylate, benzyl Can the Mid-Ray, etc.

However, the acrylic resin (A) according to the present invention does not include a carboxylic acid compound having an unsaturated bond generally used in the art as a monomer.

Specific examples of the carboxylic acid compound having an unsaturated bond in the molecule include unsaturated polycarboxylic acids having unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid and the like, and unsaturated polyhydric carboxylic acid having one or more carboxyl groups. Can be.

As said unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example.

As said unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.

When the acrylic resin (A) according to the present invention does not contain a carboxylic acid compound having an unsaturated bond as exemplified above as a monomer, it is easy to prepare a copolymer, and a one-component thermosetting resin composition having better storage safety is obtained. You can get it.

 In the case of the unsaturated group-containing resin obtained by further reacting (A3), the copolymer obtained by copolymerizing the above-mentioned (A1) and (A2) has the ratio of the structural unit derived from each of the said (A1) and (A2) said It is preferable to exist in the following ranges by mole fraction with respect to the total mole number of the structural unit which comprises a copolymer.

The ratio of the structural unit derived from each of said (A1) and (A2) is 20-60 mol% of the structural unit derived from said (A1) with respect to the total mole number of the said copolymer structural unit, and derived from said (A2) It is 20-60 mol% of structural units.

It is preferable to make said (A3) react at 20-120 mol% with respect to the epoxy equivalent of (A2).

When the ratio of the constituents is in the above range, the balance of chemical resistance and heat resistance is good, so that a preferable acrylic resin (A) can be obtained.

An example of the manufacturing method in the case where the said acrylic resin (A) is unsaturated group containing resin obtained by making (A3) further react with the copolymer obtained by copolymerizing (A1) and (A2) is as follows.

To a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen introduction tube, 0.5 to 20 times the amount of solvent was introduced on a mass basis with respect to the total amount of (A1) and (A2), and the atmosphere in the flask was changed from air to nitrogen. Replace. Then, after heating up a solvent at 40-140 degreeC, 0-20 times the amount of a solvent and a polymerization initiator with respect to the predetermined amount of (A1) and (A2) and the total amount of (A1) and (A2) is mentioned above. To the total moles of (A1) and (A2) was added 0.1-10 mol% of the solution (stirred and dissolved under room temperature or heating) dropwise into the flask above 0.1 to 8 hours from the dropping lot, and at 40 to 140 ° C. The mixture is stirred for further 1 to 10 hours to obtain a copolymer.

In the above process, a part or whole quantity of the polymerization initiator may be added, and when using a part, it may be used when making (A3) further react with the said copolymer. In addition, in order to control molecular weight and molecular weight distribution in the said process, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% by mass with respect to the total amount of said (A1) and (A2). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

In addition, the solvent used in the said process can use the solvent used at the time of a normal radical polymerization reaction, Specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents can be used individually or in combination of 2 or more types, respectively.

Moreover, as a polymerization initiator used for said process, the polymerization initiator normally used can be added, It does not restrict | limit in particular. Specifically, the polymerization initiator is diisopropylbenzenehydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butylperoxy isopropyl carbonate, t- amylperoxy-2-ethylhexanoate organic peroxides such as t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl2,2'-azobis (2-methylpropionate), etc. And nitrogen compounds. These can be used individually or in combination of 2 types or more, respectively.

By doing it above, the copolymer of said (A1) and (A2) can be obtained.

Subsequently, (A3) is added to the copolymer obtained by the above, and it reacts by heating to about 50-150 degreeC preferably 80-130 degreeC.

Thereby, acrylic resin (A) which is a polymer containing the unsaturated group obtained by making said (A3) react with the copolymer obtained by copolymerizing the said (A1) and (A2) further can be obtained.

Polystyrene reduced weight average molecular weight (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) of the acrylic resin (A) realizes flatness and storage stability. It does not specifically limit as long as it can. Preferably, the weight average molecular weight of the acrylic resin (A) is appropriately in the range of about 2,000 to 100,000, and more preferably in the range of 3,000 to 100,000. When the weight average molecular weight of the acrylic resin (A) is 2,000 or less, there is a problem that the film forming and reliability of the composition are insufficient, and when the molecular weight is 100,000 or more, flatness and storage safety are deteriorated.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said acrylic resin (A), it is more preferable that it is 1.8-4.0. If the molecular weight distribution is 1.5 to 6.0, it is preferable because the storage stability is excellently maintained.

The acrylic resin (A) is contained in a mass fraction of 5 to 85% by mass, preferably 10 to 70% by mass, based on the solid content in the thermosetting resin composition. When content of the said acrylic resin (A) is 5-85 mass% on the said reference | standard, it will be excellent in the storage stability of a thermosetting resin composition, and will become excellent in transparency, heat resistance, and alkali resistance.

Thermosetting Compound (B)

The said thermosetting compound (B) contains the epoxy resin which satisfy | fills the conditions of following (B1), (B2), and (B3).

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

(B2) 50 mass% or more is comprised by bisphenol A noblock type epoxy resin by mass fraction with respect to the thermosetting compound (B) whole quantity,

(B3) It does not contain a curing aid selected from carboxylic acids, carboxylic acid anhydrides and polyhydric carboxylic anhydrides.

It is preferable that the average molecular weight of the said thermosetting compound is 20000 or less, and it is especially preferable that it is 1000-20000. When the average molecular weight of the thermosetting compound (B) satisfies the above conditions, transparency, flatness and heat resistance are excellent.

It is preferable that the said thermosetting compound (B) is 50 mass% or more by mass fraction with respect to whole quantity, and is comprised from bisphenol A noblock type epoxy resin. When content of bisphenol A novolak-type epoxy resin is less than 50 mass% on the said reference | standard, the storage stability of a thermosetting resin composition will fall.

The bisphenol A novolac-type epoxy resin is preferably represented by the following formula (7). In this case, the thermosetting resin composition becomes excellent in transparency and heat resistance.

<Formula 7>

In Formula 7, n is 0 or a positive integer.

Moreover, it is preferable that the said thermosetting compound (B) does not contain the hardening adjuvant chosen from carboxylic acid, carboxylic anhydride, and polyhydric carboxylic anhydride. If the curing aid is included, there is a problem of poor storage stability of the thermosetting resin composition.

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 can be used individually or in combination of 2 types or more, respectively.

As the thermosetting compound according to the present invention, an epoxy resin other than the bisphenol A novolac type epoxy resin may be used together. Preferred examples of the epoxy resin that can be used together with the bisphenol A novolak-type epoxy resin, 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, bisphenol A noblock type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin , Tetraphenol ethane epoxy resin, dicyclomethane diene phenol epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol A nucleated polyol epoxy resin, polypropylene glycol epoxy resin, glycidyl ester epoxy resin, glycidyl Amine type epoxy resin, glyoxal type epoxy resin, alicyclic polyfunctional epoxy resin, It can be used to summon the epoxy resin and the like. These epoxy resins can be used individually or in combination of 2 types or more, respectively.

As said epoxy resin, the following commercial items 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), etc. 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.) as a hydrogenated bisphenol A type epoxy resin, 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. .

Content of the said thermosetting compound (B) is used in the mass fraction with respect to solid content in a thermosetting resin composition in 1-60 mass%, Preferably it is used in the range of 5-50 mass%. Since a transparency and flatness become favorable if a thermosetting compound (B) is the range of 1-60 mass% on the said reference | standard, it is preferable.

Solvent (C)

The said solvent is not specifically limited, Various organic solvents used in the field of a thermosetting resin composition can be used.

Specific examples of the solvent (C) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

The said solvent (C) can mention the organic solvent whose boiling point is 100-200 degreeC from an applicability | paintability and dryness, More preferably, alkylene glycol alkyl ether acetates, ketones, 3-ethoxy propionate, and 3 Ester, such as methyl methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3-methoxy propionic acid Methyl etc. are mentioned.

The said solvent (C) can be used individually or in mixture of 2 or more types, respectively.

Content of the said solvent (C) is 60-90 mass% normally with a mass fraction with respect to the thermosetting resin composition whole quantity containing it, Preferably it is 70-85 mass%. If content of the said solvent (C) is the range of 60-90 mass% on the said reference | standard, it coats with coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (it may be called a die coater), and inkjet. Since coating property becomes favorable at the time of carrying out, it is preferable.

Additive (D)

The thermosetting resin composition of this invention may contain other components other than the above as an additive (D) as needed in the range which does not impair the objective of this invention. As such an additive (D), a coupling agent, surfactant, antioxidant, a polyfunctional monomer, etc. are mentioned specifically ,.

The said coupling agent can be used in order to improve adhesiveness with a board | substrate, and can contain it in 10 mass% or less by mass fraction with respect to solid content in a thermosetting resin composition.

As the coupling agent, silane-based, aluminum-based, and titanate-based compounds can be used, and specifically, 3-glycidoxyoxydimethyldimethylethoxysilane, 3-glycidoxyoxymethylmethylethoxysilane, and 3-glyside Silane systems, such as oxypropyl trimethoxysilane, aluminum systems, such as acetoalkoxy aluminum diisopropylate, and titanate systems, such as tetraisopropyl bis (dioctyl phosphate) titanate, can be used. Among these, 3-glycidoxy propyl trimethoxysilane is preferable because the effect of improving adhesiveness is large.

The surfactant may be used to improve the wettability, leveling property, or coating property of the substrate, and may be included in a mass fraction of 0.01 to 1 mass% based on the solid content in the thermosetting resin composition.

As the surfactant, a silicone-based or fluorine-based surfactant may be used.

Examples of the silicone-based surfactants include trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 manufactured by GI TOSHIBA SILICONE; Trade names KP321, KP322, KP323, KP324, KP326, KP340, and KP341 manufactured by Shin-Etsu Silicone Co., Ltd .; And BYK-333, 358N and UV3500,390,306,340 manufactured by BYK-Chemie.

Examples of the fluorine-based surfactants include the trade name Florinate FC430 and Florinate FC431 manufactured by Sumitomos Rem Corporation; Mega pack F142D, mega pack F171, mega pack F172, mega pack F173, mega pack F177, mega pack F183, mega pack R30, mega pack R08, mega pack R09, mega pack BL20, mega Park 475, Megapak 489, Megapak 544 and Megapak F443; Etc. can be mentioned.

The said antioxidant is used in order to improve transparency and to prevent yellowing when a cured film encounters high temperature, and it can use it, adding 0.1-3 weight part with respect to solid content in the said thermosetting resin composition.

As said antioxidant, a hindered type, a hindered phenol type, etc. can be used, Specifically, the brand name IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX1520L, etc. which are manufactured by Chibarem Co., Ltd. Can be mentioned.

The said polyfunctional monomer can be used for adjustment of the crosslinking degree of the coating property of a coating film, etc., and can contain 0.1-30 mass% in mass fraction with respect to solid content in a thermosetting resin composition.

Specific examples of the polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tipentaerythritol penta (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate etc. are mentioned.

The thermosetting resin composition of this invention can be obtained by adding an acrylic resin (A), a thermosetting compound (B), a solvent (C), and an additive further as needed, and mixing and dissolving these uniformly.

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

The coating film formation method can form a coating film by a conventionally well-known method, such as a spin coating method, the roll coating method, the dipping method, and the slit coating method.

The thickness of the coating film is preferably 0.15 to 8.0 µm, more preferably 0.20 to 4.5 µm. In addition, the thickness of a coating film is the thickness after solvent removal here.

The coating film is heated (prebaked) by a hot plate or 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 liquid crystal display according to the present invention includes 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 liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention.

Hereinafter, although this invention is demonstrated in detail based on an Example, the following Examples are an illustration to the last and the scope of the present invention is not limited to these embodiment. 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 addition, "%" and "part" which show content below are mass references | standards unless there is particular notice.

Synthesis Example 1 Acrylic Resin (a-1)

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. A solution containing 3.6 g of azobisisobutyronitrile was added dropwise to the mixture containing a rate of 85.2 g (0.6 mole), 23.6 g (0.2 mole) of vinyltoluene, and 136 g of propylene glycol monomethyl ether acetate. It was dripped at and continued stirring at 80 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 29.6 g [0.6 mol (33.33 mol% of the epoxy group of glycidyl methacrylate used in this reaction)] of the compound of formula 4, 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was added to the flask, and the reaction was continued at 110 ° C for 4 hours to obtain an acrylic resin (a-1). The weight average molecular weight of polystyrene conversion measured by GPC was 17,000, and molecular weight distribution (Mw / Mn) was 2.3.

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

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

<Synthesis Examples 2 to 7>

Each component and its content were carried out in the same manner as in Synthesis Example 1 except for changing as shown in Table 1 below.

Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 (A1) vinyl
Toluene 23.6g
(0.2 mole) vinyl
Toluene 23.6g
(0.2 mole) vinyl
Pyrrolidone22.2g
(0.2 mole) vinyl
Toluene 23.6g
(0.2 mole) vinyl
Toluene 23.6g
(0.2 mole) vinyl
Toluene 47.2g
(0.4 moles) vinyl
Toluene 47.2g
(0.4 moles) (A2) 85.2 g (0.6 mol) glycidyl methacrylate 56.8 g (0.4 mol) glycidyl methacrylate 85.2 g (0.6 mol) glycidyl methacrylate 56.8 g (0.4 mol) glycidyl methacrylate 56.8 g (0.4 mol) glycidyl methacrylate 85.2 g (0.6 mol) glycidyl methacrylate 56.8 g (0.4 mol) glycidyl methacrylate (A3) 29.6 g (0.2 mol) of a compound of Formula 4 70.4 g (0.4 mole) of the compound of formula 2 29.6 g (0.2 mol) of a compound of Formula 4 29.6 g (0.2 mol) of a compound of Formula 4 29.6 g (0.2 mol) of a compound of Formula 4 88.8 g (0.6 mol) compound of formula (4) Other monomers Benzylmaleimide 74.8 g (0.2 mol) Benzyl methacrylate 35.2g (0.2 mol) Benzyl methacrylate 70.4 g (0.4 mol) Benzyl methacrylate 35.2g (0.2 mol) Weight average molecular weight (MW) 18,000 19,000 18,500 18,000 19,000 19,000 18,000 19,000 Molecular Weight Distribution (Mw / Mn) 2.3 2.3 2.3 2.4 2.4 2.5 2.4 2.3

<Examples 1 to 4 and Comparative Examples 1 to 3>

As shown in Table 2 below, the acrylic resin (A), the thermosetting compound (B), the additive (D) and the solvent (C) obtained in the above synthesis example were mixed, and then filtered through a Millipore filter having a pore diameter of 0.5 µm, followed by thermosetting resin. The composition was prepared.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Acrylic resin (A) (a-1) 11.50 (a-2) 11.50 (a-3) 11.50 (a-4) 11.50 (a-5) 11.50 (a-6) 11.50 (a-7) 11.50 (a-8) 11.50 Thermosetting Compound (B) (B1) 3.50 2.50 3.50 3.50 3.50 3.50 3.50 3.50 (B2) 1.00 Solvent (C) (C1) 74.88 74.88 74.88 74.88 74.88 74.88 74.88 74.88 (C2) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Additive (D) (D1) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 (D2) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02

Each component described in Table 2 is as follows.

Acrylic Resin (A): ((a-1) to (a-8): See Synthesis Example)

Thermosetting compound (B1): bisphenol A noblock type epoxy resin (JER157S70, manufactured by JER, Epoxy equivalent: 210 g / eq)

Thermosetting compound (B2): alicyclic polyfunctional epoxy resin (EHPE3150, Daisel Kagaku Co., Ltd., epoxy equivalent: 180 g / eq)

Solvent (C1): propylene glycol monomethyl ether acetate

Solvent (C2) 3-methoxypropionate methyl

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

Additive (D2): Surfactant (Megapak 475, manufactured by Dainippon Ink and Chemicals, Inc.)

Experimental Example

The thermosetting resin compositions prepared in Examples and Comparative Examples were evaluated for flatness, transparency, heat resistance, alkali resistance and storage stability as follows, and the results are shown in Tables 5 and 6 below.

1. 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. On this glass substrate, a color resist (trade names YR-800 Red, YG-800 Green, YB-800 blue, manufactured by Dongwoo Finechem Co., Ltd.) is exposed at an exposure amount (365 nm) of 100 mJ / cm 2 to omit the developing step. When it did, it spin-coated so that the film thickness after baking may be set to 2.0 micrometers, and then preliminarily dried at 100 degreeC in the clean oven for 3 minutes. After cooling, the gap between the substrate coated with the 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 at 26 ° C. for a predetermined time in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide, and then dried at 230 ° C. for 60 minutes after washing with water.

After applying the thermosetting resin compositions of Examples and Comparative Examples to the substrate on which the color filter is formed using a spin coater, and then pre-fired at 80 ℃ for 5 minutes on a hot plate to form a coating film, heated at 230 ℃ in an oven for 60 minutes The treatment was carried out to form a protective film having a thickness of 1.5 mu m.

About the board | substrate formed as mentioned above, the unevenness | corrugation of the protective film surface was measured with the contact type film thickness measuring apparatus surface roughness meter (Dektak 6M, Beko make). However, it measured by measuring length 2,000 micrometer and measuring range 2,000 micrometer number n = 5. That is, the measurement direction is set as two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and n = 5 for each direction. It was measured (total number n was 10). With respect to 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 referred to as x.

2. Transparency Assessment

For the substrate having the protective film formed as in the flatness evaluation, the transmittance for the wavelength from 380 nm to 700 nm was measured using a colorimeter (Olympus).

(Circle) and the case where the transmittance | permeability is less than 95% were made into x.

3. Heat resistance evaluation

The substrate having the protective film formed as in the flatness evaluation was heated at 250 ° C. in an oven for 1 hour to measure the film thickness before and after heating. After calculating the film thickness change rate as follows, (circle) and the case where the film thickness change rate were less than 95% were made into (circle).

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

4. Alkali resistance evaluation

The substrate having the protective film formed as in the flatness evaluation was immersed in a 5% aqueous sodium hydroxide solution heated to 40 ° C. for 30 minutes, then washed with ultrapure water and dried for 2 minutes on a hot plate heated to 120 ° C., The film thickness before and after alkali immersion was measured. After calculating the film thickness change rate as follows, (circle) and the case where the film thickness change rate were less than 95% were made into (circle).

5. Evaluation of conservation stability

The viscosity of the thermosetting resin composition was measured after standing for 1 hour at room temperature on the day of manufacture using a Rotational Viscometer viscometer (VM-150III, manufactured by Toki Sangyo Co., Ltd.). Then, while leaving the said composition at 40 degreeC, the number of days required to thicken 5% based on the viscosity immediately after manufacture was confirmed, and when this day was 15 days or more, (circle) and the case below 15 days were made into x.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Flatness ○ ○ ○ ○ ○ × ○ ○ Transparency ○ ○ ○ ○ ○ ○ ○ × Heat resistance ○ ○ ○ ○ ○ × × × Alkali resistance ○ ○ ○ ○ ○ × × × Preservation stability ○ ○ ○ ○ ○ ○ ○ ○

As shown in Table 3, in the case of using the thermosetting resin composition containing the acrylic resin according to the present invention, not only excellent long-term storage stability but also excellent flatness, transparency, heat resistance, and alkali resistance can be confirmed.

Claims (7)

It comprises an acrylic resin (A), a thermosetting compound (B) and a solvent (C), wherein the acrylic resin (A) is a copolymer obtained by copolymerizing compounds containing the following (A1) and (A2) (A3) It is an unsaturated group containing resin obtained by making it react further, The thermosetting resin composition characterized by the above-mentioned: (A1): aromatic vinyl compound, (A2): compound which has an unsaturated bond and an epoxy group in 1 molecule, (A3): The compound represented by following formula (1). <Formula 1>

(In Formula 1, R1 and R2 are each independently substituted with a halogen element or a C1 to C6 alkyl group including a ketone group, an ester group, a thiol group, or an unsubstituted C1 to C6 alkyl group, A is a halogen group, methoxy An aliphatic polycyclic group, an allyl group, a halogen group, a methoxy group, an ethoxy group or an unsubstituted aromatic polycyclic group substituted or unsubstituted with a period or an ethoxy group, n and m are 0 or 1 .) The thermosetting resin composition according to claim 1, wherein the compound (A3) represented by Formula 1 includes at least one selected from the group consisting of compounds represented by Formulas 2 to 6. <Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

The said acrylic resin (A) is a ratio of the structural component guide | induced from each of said (A1) and (A2) with respect to the total number of moles of the structural component of the said copolymer, Structural unit derived from (A1): 20 to 60 mol%, Structural unit derived from (A2): in the range of 20-60 mol%, Said (A3) is made to react 20-120 mol% with respect to the epoxy equivalent of said (A2), The thermosetting resin composition characterized by the above-mentioned. The thermosetting resin composition according to claim 1, wherein the thermosetting compound (B) is an epoxy resin that satisfies the following conditions (B1), (B2), and (B3): (B1) epoxy equivalent is 2000 g / eq or less, (B2) 50 mass% or more is comprised by bisphenol A noblock type epoxy resin by mass fraction with respect to the thermosetting compound (B) whole quantity, (B3) It does not contain a curing aid selected from carboxylic acids, carboxylic acid anhydrides and polyhydric carboxylic anhydrides. The said thermosetting compound (B) is a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, glycidyl ether-type epoxy resin, an aliphatic polyglycidyl ether, and an alicyclic aliphatic epoxy resin. Thermosetting resin composition comprising at least one selected. A color filter comprising a protective film produced by applying the thermosetting resin composition of any one of claims 1 to 5 on a substrate to form a coating film, and then performing heat treatment. A liquid crystal display device comprising the color filter of claim 6.