KR20120100721A - Thermosetting resin composition and cured film from the same - Google Patents

Abstract

PURPOSE: A thermosetting resin composition is provided to a cured membrane having excellent durability solvent resistance acid resistance alkali resistance water resistance adhesion, transparence, spreadability, and especially having excellent photo resistance and flatness. CONSTITUTION: A thermosetting resin composition comprises poly(ester amic acid), epoxy resin, and epoxy hardener. The poly(ester amic acid)], is obtained by a reaction of tetracarboxylic dianhydride, diamine, and polyhydroxy as essential ingredient, specifically reating X moles of the tetracarboxylic dianhydride, Y moles of the diamine, and Z moles of the polyhydroxy, while satisfying formula 1: 0.2<=Z/Y<=8.0 and formula 2: 0.2<=(Y+Z)/X<=1.5. The epoxy resin is obtained by a reaction of the glycidyl(meth)acrylate and bifunctional (meth)acrylate as essential ingredients, and has a weight average molecular weight is 1,000-50,000.

Description

Thermosetting resin composition and cured film {THERMOSETTING RESIN COMPOSITION AND CURED FILM FROM THE SAME}

The present invention relates to a thermosetting resin composition and a cured film obtained by heating and curing the same.

In the manufacturing process of elements, such as a liquid crystal display element, various chemical treatments, such as an organic solvent, an acid, an alkaline solution, are performed, or when forming a wiring electrode film by sputtering, the surface may be heated locally at high temperature. Therefore, a surface protective film may be set in order to prevent deterioration, damage, and deterioration of the surface of various elements. These protective films are required for various properties that can withstand the various treatments in the manufacturing process as described above. Specifically, the chemical resistance such as heat resistance, solvent resistance, acid resistance and alkali resistance, adhesion to substrate substrates such as water resistance, glass, transparency, damage resistance, coating property, flatness, light resistance, and the like are required. In addition, while high performance such as high viewing angle, high-speed response, and high definition of the liquid crystal display device is in progress, when used as a color filter protective film, a material having improved flattening characteristics is desired. Regarding the light resistance, an ultraviolet (UV) ozone treatment has been performed so far for the surface cleaning of the protective film. In recent years, however, in the color filter protective film for the transverse electric field mode, in order to improve the applicability of the photo spacer, a higher energy UV ozone treatment is required, and a photopolymerization step such as PSA mode and an optical alignment step of the alignment film are required. Ultraviolet-ray exposure processes, such as these, are increasing, and light resistance becomes a very important characteristic.

As a protective film material which has these outstanding characteristics, a silicone containing polyamic-acid composition (refer patent document 1), and a polyester amic acid composition (refer patent document 2, patent document 3). The silicone-containing polyamic acid composition is a material which is very excellent in terms of flatness, but has a disadvantage of insufficient heat resistance and poor alkali resistance. The polyester amide acid composition of Patent Document 2 had a drawback that the flatness and heat resistance were insufficient. Although the polyester amide acid composition of patent document 3 is a material excellent in flatness, heat resistance, and chemical-resistance, it has a fault that it is inadequate in light resistance and falls in transparency in a UV ozone process or an ultraviolet exposure process. Therefore, neither material satisfactorily satisfies light resistance, flatness, heat resistance, chemical resistance, and other properties.

Japanese Patent Laid-Open No. 9-291150 Japanese Patent Publication No. 2005-105264 Japanese Patent Publication No. 2008-156546

Under the above-described circumstances, for example, a resin composition having excellent adhesion to substrates such as chemical resistance, water resistance, glass, etc., such as heat resistance, solvent resistance, acid resistance, alkali resistance, transparency, damage resistance, and applicability, is required. Furthermore, especially the cured film excellent in flatness and light resistance, and the resin composition which comprises such a cured film are calculated | required.

MEANS TO SOLVE THE PROBLEM The present inventors examined in order to solve the above-mentioned problem, and, as a result, the polyesteramic acid, glycidyl (meth) acrylate, and bifunctional which are obtained by reaction of the compound containing a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound. The present invention finds that the above object can be achieved by a resin composition containing an epoxy resin and an epoxy curing agent obtained by reacting (meth) acrylate as an essential raw material component and a cured film obtained by curing the resin composition. Came to complete.

This invention has the following structures.

(1) A resin composition comprising a polyester amide acid, an epoxy resin, and an epoxy curing agent, wherein the polyester amide acid is obtained by reacting tetracarboxylic dianhydride, diamine, and a polyhydroxy compound as essential raw materials, and X It is a polyester amic acid obtained by making molar tetracarboxylic dianhydride, Y mole diamine, and Z mole polyhydric compound react at the ratio which makes the relationship of following formula 1 and formula 2,

[Formula 1]

0.2≤Z / Y≤8.0

[Formula 2]

0.2≤ (Y + Z) /X≤1.5

The epoxy resin is an epoxy resin having a weight average molecular weight of about 1,000 to 50,000 obtained by reacting glycidyl (meth) acrylate and difunctional (meth) acrylate as an essential raw material component, to 100 parts by weight of polyesteramic acid. It is 20-400 weight part with respect to an epoxy resin, and an epoxy hardening | curing agent is 0-60 weight part with respect to 100 weight part of epoxy resins, The thermosetting resin composition characterized by the above-mentioned.

(2) The thermosetting resin composition according to the above (1), wherein the polyester amide acid is a reaction product obtained by reacting a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a monohydric alcohol as an essential raw material component.

(3) The above (2) wherein the monohydric alcohol is at least one selected from isopropyl alcohol, aryl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane. Thermosetting resin composition as described in ()).

(4) The thermosetting resin composition according to any one of the above (1) to (3), wherein the polyester amide acid is a polyester amide acid obtained by further adding a styrene-maleic anhydride copolymer as a raw material component.

(5) The thermosetting resin composition according to any one of the above (1) to (4), wherein the polyester amide acid has a structural unit represented by the following general formula (3) and (4).

(3)

[Formula 4]

Wherein R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyhydroxy compound residue.

(6) The thermosetting resin composition according to any one of (1) to (5), wherein the weight average molecular weight of the polyester amide acid is 1,000 to 200,000.

(7) tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2, As described in any one of said (1)-(6) which is at least 1 sort (s) chosen from 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydroprimetate). Thermosetting resin composition.

(8) any one of said (1)-(7) whose diamine is 1 or more types chosen from 3,3'- diaminodiphenyl sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. Thermosetting resin composition.

(9) The polyhydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol The thermosetting resin composition in any one of said (1)-(8) which is 1 or more types.

(10) The bifunctional (meth) acrylate is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di ( The thermosetting resin composition in any one of said (1)-(9) which is 1 or more types chosen from a meta) acrylate, a neopentyl glycol di (meth) acrylate, and a tricyclodecane dimethanol di (meth) acrylate.

(11) The thermosetting resin composition according to any one of the above (1) to (10), wherein the epoxy curing agent is at least one selected from trimellitic acid anhydride and hexahydrotrimeric acid anhydride.

(12) tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, the diamine is 3,3'-diaminodiphenyl sulfone, and the polyhydroxy compound is 1,4-butanediol, wherein the epoxy resin is a copolymer having glycidyl methacrylate and 1,4-butanediol dimethacrylate or 1,3-butanediol dimethacrylate having a weight average molecular weight of 1,000 to 50,000 The thermosetting resin composition as described in said (1) whose said epoxy hardening | curing agent is trimellitic anhydride and contains methyl 3-methoxypropionate as a solvent.

(13) tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, the diamine is 3,3'-diaminodiphenylsulfone, and the polyhydroxy compound is It is 1, 4- butanediol, the said monohydric alcohol is benzyl alcohol, and the said epoxy resin is the weight of glycidyl methacrylate and 1, 4- butanediol dimethacrylate or 1, 3- butanediol dimethacrylate. The thermosetting resin composition as described in said (2) whose copolymer is an average molecular weight of 1,000-50,000, and the said epoxy hardening | curing agent is a trimellitic anhydride and contains methyl 3-methoxypropionate as a solvent.

(14) Cured film obtained from the thermosetting resin composition in any one of said (1)-(13).

(15) A color filter which uses the cured film as described in said (14) as a protective film.

(16) A liquid crystal display element using the color filter according to the above (15).

(17) The solid-state image sensor using the color filter of the said (15).

(18) A liquid crystal display element using the cured film as described in said (14) as a transparent insulating film formed between thin film transistor (TFT) and a transparent electrode.

(19) A liquid crystal display element using the cured film as described in said (14) as a transparent insulating film formed between a transparent electrode and an oriented film.

(20) An organic light emitting diode (LED) light-emitting body using the cured film according to the above (14) as a protective film.

The thermosetting resin composition which concerns on preferable embodiment of this invention is a material which is especially excellent in flatness and light resistance, and when used as a color filter protective film of a color liquid crystal display element, it can improve display quality and reliability. Moreover, the cured film obtained by heating the thermosetting resin composition which concerns on preferable embodiment of this invention has a balance also in transparency, chemical-resistance, adhesiveness, and sputter resistance, and is highly practical. It is especially useful as a protective film of the color filter manufactured by the dyeing method, the pigment dispersion method, the electrodeposition method, and the printing method. It can also be used as a protective film and a transparent insulating film of various optical materials.

1. Thermosetting resin composition

The thermosetting resin composition according to the present invention is a polyester functional acid, glycidyl (meth) acrylate and bifunctional (meth) obtained by reacting tetracarboxylic dianhydride, diamine, and a polyhydroxy compound as essential raw materials. ) A resin composition comprising an epoxy resin obtained by reacting an acrylate as an essential raw material component and an epoxy curing agent, wherein the epoxy resin is 20 to 400 parts by weight based on 100 parts by weight of the polyester amide acid, and 100 parts by weight of the epoxy resin. Epoxy curing agent is 0 to 60 parts by weight relative to the thermosetting resin composition.

1-1. Polyesteramic acid

The said polyester amide acid is obtained by making tetracarboxylic dianhydride, diamine, and a polyhydroxy compound react as an essential raw material component. More specifically, X mole tetracarboxylic dianhydride, Y mole diamine and Z mole polyhydric hydroxy compound are obtained by reacting at a rate at which the relationship of the following formulas 1 and 2 is established: Lose.

[Formula 1]

0.2≤Z / Y≤8.0

[Formula 2]

0.2≤ (Y + Z) /X≤1.5

At least a solvent is required for the synthesis of the polyester amide acid, and the solvent may be left as it is and may be a liquid or gel thermosetting resin composition in consideration of handling properties and the like. It is good also as a composition of shape. In the synthesis of the polyester amide acid, as a raw material, one or more raw materials selected from monohydric alcohol and styrene-maleic anhydride copolymer may be included as necessary, and among them, monohydric alcohol is preferable. . In addition, in the synthesis | combination of polyester amide acid, you may contain other raw materials other than the above as needed as a raw material in the range which does not impair the objective of this invention. As an example of such another raw material, a silicon-containing monoamine is mentioned.

1-1-1. Tetracarboxylic dianhydride

The following are mentioned as a specific example of the tetracarboxylic dianhydride used for this invention. Aromatic tetracarboxylic dianhydrides such as 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3 , 3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylsulfontetracarboxylic acid Dianhydrides, 2,3,3 ', 4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2,2 ', 3,3' -Diphenylethertetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylethertetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane Anhydrides, and ethylene glycol bis (anhydroprimetate) (trade name; TMEG-100, Shin-Nihon Rika Co., Ltd. (New Japan Chemical co., Ltd.)): Alicyclic tetracarboxylic dianhydride For example, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic acid Main dianhydride and cyclohexanetetracarboxylic dianhydride and the like: aliphatic tetracarboxylic dianhydrides such as ethane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride.

Among these, 3,3 ', 4,4'- diphenyl sulfontetracarboxylic dianhydride and 3,3', 4,4'- diphenyl ether tetracarboxylic dianhydride which produce resin with favorable transparency, 2, 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydroprimetate) (trade name; TMEG-100, Shin-Nihon Rika Co., Ltd.) 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride are particularly preferable.

1-1-2. Diamine

As a specific example of the diamine used by this invention, 4,4'- diamino diphenyl sulfone, 3,3'- diamino diphenyl sulfone, 3,4'- diamino diphenyl sulfone, bis [4- (4- Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, and 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane.

Among these, 3,3'- diamino diphenyl sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone which produce resin with good transparency are preferable, and 3,3'- diamino diphenyl sulfone is preferable. Particularly preferred.

1-1-3. Polyhydroxy Compound

Specific examples of the polyhydroxy compound used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene. Glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol , 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1 , 7-heptane diol, 1,2,7-heptane triol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2 -Nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dode Candiol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, Dipentaerythritol, bisphenol A (trade name), bisphenol S (brand name), bisphenol F (brand name), diethanolamine and triethanolamine.

Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol having good solubility in a solvent are preferable. , 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred.

1-1-4. Monohydric alcohol

Specific examples of the monohydric alcohol used in the present invention include methanol, ethanol, 1-propanol, isopropyl alcohol, aryl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, di Propylene Glycol Monoethyl Ether, Dipropylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monoethyl Ether, Phenol, Borneol, Maltol, Linarol, Telpi Neol, dimethylbenzylcarbinol, 3-ethyl-3-hydroxymethyl oxetane, etc. are mentioned.

Among these, isopropyl alcohol, aryl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are preferable. Considering the compatibility when the polyester amide acid which can be used, an epoxy resin, and an epoxy hardening agent is mixed, and the applicability | paintability on the color filter of the thermosetting resin composition which is a final product, benzyl alcohol is used for monohydric alcohol. This is more preferable.

The monohydric alcohol preferably contains 2 to 300 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound. More preferably, it is 5-200 weight part.

1-1-5. Styrene-maleic anhydride copolymer

The polyester amide acid used in the present invention may also be subjected to a synthetic reaction by adding a compound having three or more acid anhydride groups. A styrene-maleic anhydride copolymer is mentioned as a specific example of the compound which has three or more acid anhydride groups. Regarding the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5 to 4, preferably 1 to 3, specifically, about 1, about 2 or about 3 Preferred, about 1 or about 2 is more preferred, and about 1 is particularly preferred.

As a specific example of a styrene maleic anhydride copolymer, commercial items, such as SMA3000P, SMA2000P, and SMA1000P of KAWAHARA PETROCHEMICAL CO., LTD., Are mentioned. Among these, SMA1000P which has favorable heat resistance and alkali resistance is especially preferable.

The styrene-maleic anhydride copolymer preferably contains 0 to 500 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyhydroxy compound. More preferably, it is 10-300 weight part.

1-1-6. Silicone-containing Monoamine

In the synthesis of the polyester amide acid, other raw materials other than the above may be included as necessary as long as they do not impair the object of the present invention. Examples of such other raw materials include silicon-containing monoamines. have.

Specific examples of the silicone-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4 -Aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethicone And oxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane.

Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane which have good acid resistance of a coating film are preferable, and 3-aminopropyltriethoxysilane is especially preferable from a viewpoint of acid resistance and compatibility.

It is preferable that a silicone containing monoamine contains 0-300 weight part with respect to 100 weight part of total amounts of tetracarboxylic dianhydride, diamine, and a polyhydroxy compound. More preferably, it is 5-200 weight part.

1-1-7. Solvents for Synthesis of Polyester Amic Acid

As a specific example of the solvent used for the synthesis reaction to obtain polyester amic acid, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether Acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetoamide. have.

Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.

These solvents can be used alone or as two or more types of mixed solvents. Moreover, if it is a ratio of 30 weight% or less, other solvents other than the said solvent can be mixed and used.

1-1-8. Synthesis method of polyester amide acid

In the synthesis method of the polyester amic acid used in the present invention, X mol of tetracarboxylic dianhydride, Y mol of diamine, and Z mol of a polyhydroxy compound are reacted in the solvent. At this time, it is preferable to set X, Y, and Z by the ratio which makes the relationship of following formula 1 and formula 2 hold | maintain between them. If it is this range, the solubility of a polyesteramic acid in the solvent is high, and the coating property of a composition improves, and the cured film excellent in flatness can be obtained as a result.

[Formula 1]

0.2≤Z / Y≤8.0

[Formula 2]

0.2≤ (Y + Z) /X≤1.5

The relationship of Formula 1 is preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.3 ≦ Z / Y ≦ 7.0. Moreover, the relationship of said Formula 2 becomes like this. Preferably it is 0.5 <= (Y + Z) / X <= 0.9, More preferably, it is 0.7 <= (Y + Z) / X <= 0.8.

When the polyester amic acid used by this invention has an acid anhydride group at the terminal of a molecule | numerator, the above-mentioned monohydric alcohol can be added and made to react as needed. The polyester amic acid obtained by adding and reacting monohydric alcohol improves compatibility with an epoxy resin and an epoxy hardening agent, and improves the coating property of the thermosetting resin composition of this invention containing these.

Moreover, when making the silicon-containing monoamine mentioned above react with the polyester amide acid which has an acid anhydride group in a molecule terminal, the acid resistance of the obtained coating film improves. Furthermore, monohydric alcohols and silicone containing monoamines may be reacted with polyesteramic acid at the same time.

When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of tetracarboxylic dianhydride, diamine and a polyhydroxy compound, the reaction proceeds smoothly and is preferable. It is preferable to make reaction react at 40 degreeC-200 degreeC for 0.2 to 20 hours. In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyhydroxy compound is completed, the reaction solution is cooled to 40 ° C. or lower, and then the silicon-containing monoamine is added. It is good to make it react for 0.1 to 6 hours at -40 degreeC. In addition, monohydric alcohol may be added at any point in the reaction.

The order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, tetracarboxylic dianhydride, diamine, and polyhydroxy compound are simultaneously added to the reaction solvent, or diamine and polyhydroxy compound are dissolved in the reaction solvent, followed by addition of tetracarboxylic dianhydride, or tetracarboxylic dianhydride. After the reaction of the polyhydric compound with the pre-reaction, the diamine is added to the reaction product or the tetracarboxylic dianhydride and the diamine, and then the polyhydroxy compound is added to the reaction product. Can be.

The polyester amide acid synthesized as described above comprises a structural unit consisting of the above formulas (3) and (4), and its ends are acid anhydride groups, amino groups or derived from tetracarboxylic dianhydride, diamine or polyhydroxy compound as raw materials. It is preferable that additives other than these compounds are a hydroxyl group, and comprise the terminal. In Chemical Formulas 3 and 4, R ¹ is a tetracarboxylic dianhydride residue, and preferably an organic group having 2 to 30 carbon atoms. R ² is a diamine moiety, preferably an organic group having 2 to 30 carbon atoms. R ³ is a polyhydroxy compound residue, preferably an organic group having 2 to 20 carbon atoms.

It is preferable that it is 1,000-200,000, and, as for the weight average molecular weight of obtained polyester amide acid, about 3,000-50,000 are more preferable. If it is these ranges, flatness and heat resistance will become favorable.

The weight average molecular weight in this specification is a polystyrene conversion value calculated | required by GPC method (column temperature: 35 degreeC, flow rate: 1 ml / min). The polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 of VARIAN) for the standard polystyrene, PLgel MIXED-D (VARIAN) for the column, and THF as a mobile phase can be measured. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

1-2. Epoxy resin

The epoxy resin used for this invention is obtained by making glycidyl (meth) acrylate and bifunctional (meth) acrylate react as an essential raw material component. An epoxy resin will not be specifically limited if compatibility with the other component which forms the thermosetting resin composition of this invention is good. In addition, the bifunctional (meth) acrylate which glycidyl (meth) acrylate reacts may be one type, or may be two or more types.

Using an epoxy resin obtained by reacting glycidyl (meth) acrylate with another radically polymerizable monomer increases the transparency of the cured film obtained from the thermosetting resin composition, and in the ultraviolet (UV) ozone treatment step or the ultraviolet exposure step. Since the fall of transparency of is suppressed, it is preferable. It is preferable to contain 50-99 weight% of glycidyl (meth) acrylate among the all monomers which comprise an epoxy resin from a viewpoint of flatness, heat resistance, chemical-resistance, etc.

When monofunctional (meth) acrylate is used as another radically polymerizable monomer, heat resistance and chemical resistance of the cured film obtained from a thermosetting resin composition are insufficient, and when trifunctional or higher polyfunctional (meth) acrylate is used, flatness is insufficient. Since the compatibility with polyester amic acid will worsen, bifunctional (meth) acrylate is preferable.

Preferable examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,3-butanediol di (meth). ) Acrylate, neopentyl glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate are mentioned. These are preferable because the compatibility with the polyester amic acid of the epoxy resin obtained by making it react with glycidyl (meth) acrylate becomes favorable. It is preferable from a viewpoint of flatness, heat resistance, chemical resistance, etc. that bifunctional (meth) acrylate contains about 1-30 weight% among all the monomers which comprise an epoxy resin.

The said epoxy resin may contain radically polymerizable monomers other than glycidyl (meth) acrylate and bifunctional (meth) acrylate as a raw material component. It is preferable to contain about 0-20 weight% of such other radically polymerizable monomer from a viewpoint of expressing the characteristic by the said other radically polymerizable monomer, without impairing the effect of this invention.

It is preferable that it is 1,000-50,000, and, as for the weight average molecular weight of the epoxy resin obtained by making glycidyl (meth) acrylate and bifunctional (meth) acrylate react as an essential raw material component, 3,000-20,000 are more preferable. If the molecular weight is in these ranges, sufficient flatness, heat resistance, and chemical resistance are obtained.

1-2-1. Solvents Used in Synthesis Reaction of Epoxy Resin

At least a solvent is required for the synthesis of the epoxy resin.

As a specific example of the solvent used for the polymerization reaction to obtain an epoxy resin, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetoamide.

Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.

These solvents can be used alone or as two or more types of mixed solvents. Moreover, if it is a ratio of 30 weight% or less, you may mix and use other solvent other than the said solvent.

1-2-2. Synthesis method of epoxy resin

Although the synthesis | combining method of the epoxy resin used for this invention is not specifically limited, The radical polymerization in the solution using a solvent is preferable. When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of glycidyl (meth) acrylate, bifunctional (meth) acrylate, and other radically polymerizable monomers, the reaction proceeds smoothly. . The polymerization temperature is not particularly limited as long as the radical is sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 ° C to 150 ° C. Although polymerization time is not specifically limited, either, Usually, it is the range of 1 to 24 hours. In addition, the polymerization can be carried out under any pressure of pressurization, reduced pressure or atmospheric pressure.

A well-known polymerization initiator can be used for the synthesis | combination of an epoxy resin. Examples of the polymerization initiator include compounds which generate radicals by heat, azo initiators such as azobis isobutyronitrile, and peroxide initiators such as benzoyl peroxide. In the said radical polymerization reaction, in order to adjust the molecular weight of the produced copolymer, you may add a suitable amount of chain transfer agents, such as thioglycolic acid.

The epoxy resin used in the present invention may be an epoxy resin solution in which the solvent used for synthesis is left as it is, and handling properties are taken into consideration. Alternatively, the epoxy resin may be a solid epoxy resin in consideration of transportability and the like.

1-3. Epoxy curing agent

In order to improve flatness and chemical resistance, you may add an epoxy hardening | curing agent to the thermosetting resin composition which concerns on this invention. As an epoxy hardening | curing agent, although an acid anhydride type hardening | curing agent, an amine type hardening | curing agent, a phenol type hardening | curing agent, a catalyst type hardening | curing agent, etc. are mentioned, an acid anhydride type hardening | curing agent is preferable at the point of coloring and heat resistance.

The following are mentioned as a specific example of an acid anhydride type hardening | curing agent. Aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimeric anhydride: aromatic polycarboxylic acid anhydrides such as phthalic anhydride, trimellit Acid anhydride: styrene-maleic anhydride copolymer. Among these, trimellitic anhydride and hexahydro trimellitic anhydride are particularly preferable in terms of balance of heat resistance and solubility in solvents.

1-4. Polyester amic acid, epoxy resin, epoxy curing agent ratio

In the thermosetting resin composition according to the present invention, the proportion of the epoxy resin is 20 to 400 parts by weight based on 100 parts by weight of the polyester amide acid. If the ratio of an epoxy resin is this range, the balance of flatness, heat resistance, chemical resistance, and adhesiveness will be favorable. The epoxy resin is more preferably in the range of 50 to 300 parts by weight.

When adding an epoxy curing agent for the purpose of improving flatness and chemical resistance, the ratio of an epoxy resin and an epoxy curing agent is 0-60 weight part of epoxy curing agents with respect to 100 weight part of epoxy resins. About the addition amount of an epoxy hardening | curing agent, It is preferable to add in detail so that a carbonic anhydride group or a carboxyl group in an epoxy hardening | curing agent may be 0.1-1.5 times equivalent with respect to an epoxy group. At this time, the carbonic anhydride group is calculated as two. When the carboxylic acid anhydride group or the carboxyl group is added so as to be 0.15 to 0.8 times the equivalent, the chemical resistance is further improved, which is more preferable.

1-5. Other component materials of thermosetting resin composition

As a solvent used for the resin composition of this invention, the solvent used by the polymerization reaction at the time of synthesize | combining polyester amide acid and an epoxy resin can be used as it is. Although solid content concentration of the said thermosetting resin composition is selected by the film thickness of a coating film, it is common to include in 5 to 50 weight part in 100 weight part of the said resin compositions. In addition, the quantity of a solvent can be suitably determined based on problems, such as handling of a resin composition. In some cases, for example, a resin composition obtained by removing a solvent from the resin composition and bringing it into a solid state may be used.

The thermosetting resin composition of this invention may contain another component of that excepting the above as needed in the range which does not impair the objective of this invention. As such another component, a coupling agent, surfactant, antioxidant, a hardening accelerator, a thermosensitive acid generator, etc. are mentioned. In addition, when polyester amide acid does not contain a styrene maleic anhydride copolymer as a raw material, you may add a styrene maleic anhydride copolymer as another component.

A coupling agent is used in order to improve adhesiveness with a board | substrate, and is used by adding 10 weight part or less with respect to 100 weight part of solid content (the remaining component which removed the solvent from this resin composition) of the said thermosetting resin composition.

As the coupling agent, silane-based, aluminum-based and titanate-based compounds can be used.

Specifically, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3 -Glycidoxypropyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, Silanes such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxy propyltriethoxysilane, aluminum such as acetoalkoxy aluminum diisopropylate, and tetraisopropylbis (dioctylphosphate) titanate Titanate system, such as these, is mentioned. Among these, 3-glycidoxy propyl trimethoxysilane is preferable because the effect of improving adhesiveness is large.

Surfactant is used in order to improve the flowability, leveling property, or applicability | paintability to a base substrate, and 0.01-1 weight part is added and used with respect to 100 weight part of said thermosetting resin compositions.

As such a surfactant, Polypro No.45, Polypro KL-245, Polypro No.75, Polypro No.90, Polypro No.95 (all of these are trade names, Kyoeisha Chemical Co., Ltd.) (KYOEISHA CHEMICAL CO., LTD)), Disperbyk 161, Disperbike 162, Disper Bike 163, Disper Bike 164, Disper Bike 166, Disper Bike 170, Disper Bike 180, Disperbike 181, Disperbike 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-344, BYK-346, BYK-UV3500, BYK-UV3570 BYK Japan KK (BYK Japan KK)), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (both trade names, Shin-Etsu Chemical Co., Ltd. ( (Shin-Etsu Chemicla Co., Ltd), Saffron SC-101, Saffron KH-40 (all trade names, AGC SEIMI CHEMICAL CO., LTD.), Futa Gentle 222F, futagent 251, FTX-218 (all the brand names, Neos Ltd.), EFTOP 'EF-351, EFTOP' EF-3 52, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of the above trade names, Mitsubishi Materials Corporation), Megapack F-410, Megapack F-430, Megapack F- 444, Mega Pack F-472SF, Mega Pack F-475, Mega Pack F-477, Mega Pack F-552, Mega Pack F-553, Mega Pack F-554, Mega Pack F-555, Mega Pack F-556, Mega Pack F-558, Mega Pack R-94, Mega Pack RS-75, Mega Pack RS-72-K, (above all trade names, DIC Corporation), TEGO Rad 2200N, TEGO Rad 2250N (all of the above brand names, Evo Niko Degussa Japan Co., Ltd. can be mentioned.

The surfactant used in the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

Antioxidant is used in order to improve transparency and to prevent yellowing when a cured film is exposed to high temperature, and it is 0.1 thru | or with respect to 100 weight part of solid content (the remainder component except a solvent in this resin composition) of the said thermosetting resin composition. It is used by adding 5 parts by weight.

As antioxidant, a hindered amine type, a hindered phenol type, etc. are used. Specifically, IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (brand name; BASF Japan Co., Ltd.), etc. are mentioned.

A hardening accelerator is used in order to accelerate reaction of an epoxy resin and an epoxy hardening | curing agent, and to improve the heat resistance and chemical-resistance of a cured film, and to 100 weight part of solid content (the remaining component except the solvent in the resin composition) of the said thermosetting resin composition. 0.01 to 5 parts by weight relative to the used.

As the curing accelerator, any one can be used as long as it has a function of promoting the reaction between the epoxy resin and the epoxy curing agent. Examples thereof include imidazole-based curing accelerators, phosphine-based curing accelerators, ammonium-based curing accelerators, Lewis acid-based curing accelerators, and the like. Can be.

The thermosensitive acid generator is used to impart sufficient hardness and chemical resistance to the cured film even when the thermosetting resin composition of the present invention is used under conditions of low temperature curing of less than 200 ° C, and the solid content of the thermosetting resin composition It is used by adding 0.001 to 3 parts by weight based on 100 parts by weight (the rest of the components except the solvent in the resin composition).

Examples of the thermosensitive acid generator include sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like.

2. Cured film obtained from a thermosetting resin composition

The thermosetting resin composition according to the present invention is mixed with a polyester amide acid and an epoxy resin, and depending on the desired properties, additionally selected and added a solvent, epoxy curing agent, coupling agent, surfactant and other additives as needed. It can obtain by mixing and dissolving these uniformly.

The thermosetting resin composition prepared as described above (after being dissolved in a solvent in the case of a solid state without a solvent) is applied to the substrate surface, and the solvent is removed by, for example, heating to form a coating film. Can be. Application | coating of the thermosetting resin composition to a board | substrate surface can form a coating film by conventionally well-known methods, such as a spin coat method, a roll coat method, a dipping method, and a slit coat method. Subsequently, the coating film is heated (prebaked) by a hot plate or an oven or the like. Although heating conditions change with kinds and compounding ratio of each component, they are 5 to 15 minutes in the oven at 70-150 degreeC normally, and 1 to 5 minutes in a hotplate. Then, in order to harden a coating film, a cured film can be obtained by heat-processing at 180-250 degreeC, Preferably it is 200-250 degreeC, if it is an oven for 30 to 90 minutes, and for a hotplate for 5 to 30 minutes.

In the cured film obtained according to the above, at the time of heating, 1) the polyamic acid portion of the polyesteramic acid is dehydrated to form an imide bond, and 2) the carbonic acid of the polyesteramic acid reacts with the epoxy resin, Molecular weight and 3) Since the epoxy resin is hardened and high molecular weight, it is very tough and excellent in transparency, heat resistance, chemical resistance, flatness, adhesiveness, light resistance, and sputter resistance. Therefore, the cured film which concerns on this invention is effective when used as a protective film for color filters, and can manufacture a liquid crystal display element or a solid-state image sensor using this color filter. Moreover, the cured film which concerns on this invention is effective when used as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode, or between a transparent electrode and an orientation film in addition to the protective film for color filters. Moreover, the cured film which concerns on this invention is effective also when used as a protective film of organic light emitting diode (LED) light-emitting body.

Example

Next, the present invention will be described in detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by these Examples.

First, a polyester amide acid solution consisting of a reaction product of tetracarboxylic dianhydride, diamine, and polyhydroxy compound was synthesized as shown below (Synthesis Examples 1, 2, Table 1).

Synthesis Example 1 Synthesis of Polyester Amic Acid Solution (A1)

446.96 g of 3-methoxypropionate (hereinafter abbreviated as "MMP") 446.96 g of 1,4-butanediol, dehydrated and purified in a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet, and a nitrogen gas inlet. , 25.54 g of benzyl alcohol, 183.20 g of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter, abbreviated as "ODPA") were added thereto, and the mixture was stirred at 130 ° C for 3 hours under a dry nitrogen stream. It was. Thereafter, the reaction solution was cooled to 25 ° C, 29.33g of 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as "DDS") and MMP183.04g were charged, followed by stirring at 20 to 30 ° C for 2 hours. Thereafter, the mixture was stirred at 115 ° C. for 1 hour and cooled to 30 ° C. or less to obtain a 30 wt% solution (A1) of pale yellow transparent polyesteramic acid.

The rotational viscosity of this solution was 28.5 mPa · s. In addition, the weight average molecular weight measured by GPC was 4,200 (polystyrene conversion).

Here, the rotational viscosity in this specification is the viscosity measured at 25 degreeC using the E-type viscosity meter (brand name; VISCONIC END, TOKYO KEIKI INC.).

Synthesis Example 2 Synthesis of Polyester Amic Acid Solution (A2)

Dehydrated and refined propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") in a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet and a nitrogen gas inlet (hereinafter referred to as "PGMEA") 504.00 g, ODPA 47.68 g, SMA1000P ( Styrene-maleic anhydride copolymer, Kawagawa Chemical Co., Ltd. 144.97 g, benzyl alcohol 55.40 g, 1,4-butanediol 9.23 g, dehydrated and purified diethylene glycol methyl ethyl ether (hereinafter abbreviated as "EDM") ) 96.32 g were added and stirred at 130 ° C. under a dry nitrogen stream for 3 hours. Thereafter, the reaction solution was cooled to 25 ° C, 12.72 g of DDS and 29.68 g of EDM were added thereto, and stirred at 20 to 30 ° C for 2 hours, followed by stirring at 115 ° C for 1 hour and cooling to 30 ° C or less. A 30 wt% solution (A2) of ester amide acid was obtained.

The rotational viscosity of this solution was 36.2 mPa * s and the weight average molecular weight measured by GPC was 21,000 (polystyrene conversion).

A1
(g) A2
(g) ingredient material Tetracarboxylic acid
Dianhydride ODPA 183.2 47.68 Diamine DDS 29.33 12.72 Polyhydroxy Compound 1,4-butanediol 31.93 9.23 Monohydric alcohol Benzyl alcohol 25.54 55.40 Styrene-maleic anhydride
Copolymer SMA1000P 0 144.97 solvent

MMP 630.0 0 PGMEA 0 504.00 EDM 0 126.00

MMP: 3-Methoxypropionate

ODPA: 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride

DDS: 3,3'-diaminodiphenylsulfone

PGMEA: propylene glycol monomethyl ether acetate

SMA1000P: Styrene-maleic anhydride copolymer (Kawahara Yuka Co., Ltd.)

EDM: diethylene glycol methyl ethyl ether

Next, an epoxy resin solution composed of a reaction product of glycidyl (meth) acrylate and bifunctional (meth) acrylate was synthesized as shown below (Synthesis Example 3, 4, 5, 6, 7, Table 2). ).

Synthesis Example 3: Synthesis of Epoxy Resin Solution (B1)

In a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet, and a nitrogen gas inlet, 300.00 g of dehydrated and purified MMP, glycidyl methacrylate (hereinafter abbreviated as "GMA") 180.00 g, 1, 20.00 g of 4-butanediol dimethacrylate and 20.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) were added as a polymerization initiator, and polymerization was performed by heating at a polymerization temperature of 90 ° C for 2 hours. It was. The reaction solution was cooled to 30 ° C. or lower to obtain a 40 wt% solution (B1) of epoxy resin. The weight average molecular weight measured by GPC of this solution was 12,000 (polystyrene conversion).

Synthesis Example 4 Synthesis of Epoxy Resin Solution (B2)

In a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet, and a nitrogen gas inlet, MMP 300.00 g dehydrated and purified, GMA 180.00 g, 1,3-butanediol dimethacrylate 20.00 g, as a polymerization initiator, 20.00 g of 2'-isobis (2,4-dimethylvaleronitrile) was added thereto, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40 wt% solution (B2) of epoxy resin. The weight average molecular weight measured by GPC of this solution was 12,000 (polystyrene conversion).

Synthesis Example 5 Synthesis of Epoxy Resin Solution (B3)

In a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet and a nitrogen gas inlet, MMP 300.00 g, GMA 180.00 g, neopentylglycol dimethacrylate 20.00 g dehydrated and purified, 2,2 as a polymerization initiator 20.00 g of '-azobis (2,4-dimethylvaleronitrile) was added thereto, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40 wt% solution (B3) of epoxy resin. The weight average molecular weight measured by GPC of this solution was 11,000 (polystyrene conversion).

Synthesis Example 6 Synthesis of Epoxy Resin Solution (B4)

In a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet, and a nitrogen gas inlet, MMP 300.00 g dehydrated and purified, GMA 160.00 g, 1,4-butanediol dimethacrylate, 40.00 g, as a polymerization initiator, 30.00 g of 2'-azobis (2,4-dimethylvaleronitrile) was added thereto, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40 wt% solution (B4) of epoxy resin. The weight average molecular weight measured by GPC of this solution was 18,000 (polystyrene conversion).

Synthesis Example 7 Synthesis of Epoxy Resin Solution (B5)

In a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet, and a nitrogen gas inlet, MMP 300.00 g, GMA 180.00 g, diethylene glycol dimethacrylate 20.00 g, dehydrated and purified, as a polymerization initiator, 2,2 20.00 g of '-azobis (2,4-dimethylvaleronitrile) was added thereto, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40 wt% solution (B5) of epoxy resin. The weight average molecular weight measured by GPC of this solution was 11,000 (polystyrene conversion).

B1
(g) B2
(g) B3
(g) B4
(g) B5
(g) GMA 180 180 180 160 180 1,4-butanedioldimethacrylate 20 0 0 40 0 1,3-butanediol dimethacrylate 0 20 0 0 0 Neopentyl Glycol Dimethacrylate 0 0 20 0 0 Diethylene Glycol Dimethacrylate 20 MMP 300 300 300 300 300 2,2'-azobis (2,4-di
Methylvaleronitrile) 20 20 20 30 20 Weight average molecular weight 12,000 12,000 11,000 18,000 11,000

GMA: glycidyl methacrylate

MMP: 3-Methoxypropionate

Next, an epoxy resin solution composed of a reaction product of glycidyl (meth) acrylate and monofunctional (meth) acrylate was synthesized as shown below (Comparative Synthesis Example 1, Table 3).

Comparative Synthesis Example 1 Synthesis of Epoxy Resin Solution (C1)

In a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet and a nitrogen gas inlet, MMP 300.00 g, GMA 180.00 g, methyl methacrylate 20.00 g, dehydrated and purified, 2,2'-azo as a polymerization initiator 8.00 g of bis (2,4-dimethylvaleronitrile) was added thereto, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40 wt% solution (C1) of epoxy resin. The weight average molecular weight measured by GPC of this solution was 15,000 (polystyrene conversion).

Next, an epoxy resin solution composed of a reaction product of glycidyl (meth) acrylate and bifunctional (meth) acrylate having a weight average molecular weight of 20,000 or more was synthesized as shown below (Comparative Synthesis Example 2, Table 3). ).

Comparative Synthesis Example 2 Synthesis of Epoxy Resin Solution (C2)

In a 1000 ml four-necked flask equipped with a thermometer, each half, a raw material inlet, and a nitrogen gas inlet, MMP 300.00 g dehydrated and purified, GMA 180.00 g, 1,4-butanediol dimethacrylate 20.00 g, as a polymerization initiator, 13.00 g of 2'-azobis (2,4-dimethylvaleronitrile) was added thereto, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C. for 2 hours. The reaction solution was cooled to 30 ° C. or lower to obtain a 40 wt% solution (C1) of epoxy resin. The weight average molecular weight measured by GPC of this solution was 58,000 (polystyrene conversion).

C1
(g) C2
(g) GMA 180 180 Methyl methacrylate 20 0 1,4-butanedioldimethacrylate 0 20 MMP 300 300 2,2'-azobis (2,4-dimethylvaleronitrile) 8 13 Weight average molecular weight 15,000 58,000

GMA: glycidyl methacrylate

MMP: 3-Methoxypropionate

Subsequently, the polyester amide acids (A1, A2) obtained in Synthesis Examples 1 and 2, the epoxy resins (B1, B2, B3, B4, B5) obtained in Synthesis Examples 3, 4, 5, 6 and 7, and Comparative Synthesis Examples Using the epoxy resins (C1, C2) obtained in 1 and 2, and commercially available polyfunctional and weight average molecular weights of less than 3,000, a thermosetting resin composition was prepared as shown below and cured from the thermosetting resin composition. A film was obtained and these cured films were evaluated (Examples 1 to 6, Comparative Examples 1, 2, 3, Tables 4 to 6, and 7).

Example 1

A 500 ml separable flask with a stirring blade was nitrogen-substituted, and 100 g of the polyester amide acid solution (A1) obtained in Synthesis Example 1, 150 g of the epoxy resin solution (B1) obtained in Synthesis Example 3, and trimellitic acid were added to the flask. 6 g of anhydrides, 4.8 g of 3-glycidoxypropyltrimethoxysilane, 0.50 g of Irganox® 1010 (trade name; BASF Japan Co., Ltd.) and 160.8 g of dehydrated and purified MMP were added thereto, and the mixture was stirred at room temperature for 5 hours to give uniformity. To be dissolved. Subsequently, 0.42 g of BYK-344 (trade name, Vikchem Japan Co., Ltd.) was added thereto, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore diameter of 0.2 µm to prepare a coating solution.

Next, the coating solution was spin-coated on the glass substrate and the color filter substrate at 800 rpm for 10 seconds, and then prebaked at 80 ° C. for 3 minutes on a hot plate to form a coating film. Then, the coating film was hardened by heating at 230 degreeC for 30 minutes in oven, and the cured film with a film thickness of 1.5 micrometers was obtained.

About the cured film obtained in this way, the characteristic was evaluated about transparency, light resistance, flatness, heat resistance, and chemical-resistance. Table 7 shows the results of these evaluations.

How to evaluate transparency

The obtained glass substrate with a cured film WHEREIN: The ultraviolet-ray near-infrared spectrophotometer (brand name: V-670, Nippon Bunko Co., Ltd. (JASCO Co.)) has an optical wavelength of 400 nm only for a cured film. The transmittance was measured. (Circle) and the case of less than 97% of the case where the transmittance | permeability is 97% or more are described by x.

Evaluation method of light resistance

The glass substrate with a cured film after evaluating transparency in the transparency evaluation method was subjected to an ultraviolet (UV) ozone cleaning device (trade name; PL2003N-12, light source; low pressure mercury lamp, Sen Special Light Source Co., Ltd.) (SEN LIGHTS Co., Ltd. Ultraviolet visible near-infrared spectrophotometer (trade name; V-670, Nippon Bunko Co., Ltd.) after ultraviolet (UV) ozone treatment at 3J / cm ² (254 nm equivalent) The transmittance | permeability in the wavelength of 400 nm of the light only of a cured film was measured. (Circle) and the case with less than 96% of the case where the transmittance | permeability is 96% or more are shown by x.

Evaluation method of flatness

The level | step difference of the cured film surface of the obtained color filter substrate with a cured film was measured using the level | step difference, surface roughness, a micro shape measuring apparatus (brand name; P-15, KLA TENCOR Co., Ltd.). (Circle) and the case where it is 0.2 micrometer or more in the case where the maximum value (henceforth "maximum step" hereafter) of the level | step difference between R, G, and B pixels containing a black matrix are less than 0.2 micrometer are shown by x. The color filter substrate used is a pigment dispersed color filter (hereinafter abbreviated as "CF") using a resin black matrix having a maximum step of about 1.1 µm.

Evaluation method of heat resistance

After reheating the obtained glass substrate with a cured film at 250 degreeC for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was computed by the following formula. (Circle) and the case where the residual film rate after heating are less than 95% are represented by x when the residual film rate after heating is 95% or more.

Residual film ratio = (film thickness after heating / film thickness before heating) × 100

Evaluation method of chemical resistance

The obtained glass substrate with a cured film was immersed in a 5 wt% sodium hydroxide solution at 60 ° C. for 10 minutes (hereinafter abbreviated as “NaOH treatment”), 36% hydrochloric acid / 60% acetic acid / water = 40/20/40 Immersion treatment at 50 ° C. for 3 minutes (hereinafter abbreviated as “acid treatment”) in the mixed solution (weight ratio) formed, and immersion treatment at 50 ° C. for 30 minutes in N-methyl-2-pyrrolidone (hereinafter referred to as “NMP treatment”). Abbreviated), and reheated at 230 ° C. for 1 hour. The residual film rate after reheating and the transmittance | permeability after reheating were measured. The case where the residual film rate after reheating was 95% or more and the transmittance | permeability in 400 nm after reheating was 95% or more was made into (circle). The case where the residual film rate after reheating is less than 95% or the transmittance | permeability after reheating is less than 95% is represented by x.

Residual film rate after reheating = (film thickness after reheating / film thickness before reheating) × 100

Example 2

500 ml of separable flasks with stirring blades were nitrogen-substituted, and 100 g of the polyester amic acid solution (A2) obtained in Synthesis Example 2, 150 g of the epoxy resin solution (B1) obtained in Synthesis Example 3, and trimellitic acid were added to the flask. 6 g of anhydrides, 4.8 g of 3-glycidoxypropyltrimethoxysilane, 0.50 g of Irganox® 1010 (trade name; BASF Japan Co., Ltd.) and 160.8 g of dehydrated and purified MMP were added thereto, and the mixture was stirred at room temperature for 5 hours to give uniformity. To be dissolved. Next, 0.42 g of BYK-344 (trade name; BIC Chemie Japan Co., Ltd.) was added thereto, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore diameter of 0.2 µm to prepare a coating solution.

As in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

Example 3

The coating liquid was prepared by the method similar to Example 1 except having changed the epoxy resin solution (B1) into the epoxy resin solution (B2).

In the same manner as in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

Example 4

The coating liquid was prepared by the method similar to Example 1 except having changed the epoxy resin solution (B1) into the epoxy resin solution (B3).

In the same manner as in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

Example 5

The coating liquid was prepared by the method similar to Example 1 except having changed the epoxy resin solution (B1) into the epoxy resin solution (B4).

In the same manner as in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

Example 6

The coating liquid was prepared by the method similar to Example 1 except having changed the epoxy resin solution (B1) into the epoxy resin solution (B5).

In the same manner as in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

Comparative Example 1

The coating liquid was prepared by the method similar to Example 1 except having changed the epoxy resin solution (B1) into the epoxy resin solution (C1).

In the same manner as in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

Comparative Example 2

The coating liquid was prepared by the method similar to Example 1 except having changed the epoxy resin solution (B1) into the epoxy resin solution (C2).

In the same manner as in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

Comparative Example 3

500 ml of separable flasks with agitating vanes were nitrogen-substituted, and 100 g of the polyester amide acid solution (A1) obtained in Synthesis Example 1, polyfunctional, and weight-average molecular weight of less than 3,000 epoxy resin TECHMORE® VG3101L (in the flask) Printech Co., Ltd.60g, trimellitic anhydride 6g, 3-glycidoxypropyltrimethoxysilane 4.8g, Irganox 1010 (trade name; BASF Japan Co., Ltd.) 0.50g, dehydrated MMP 250.8g Was added, and the mixture was stirred at room temperature for 5 hours to uniformly dissolve. Next, 0.42 g of BYK-344 (trade name: BIC Chemie Japan Co., Ltd.) was added thereto, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore diameter of 0.2 µm to prepare a coating solution.

In the same manner as in Example 1, characteristics were evaluated for transparency, light resistance, flatness, heat resistance, and chemical resistance. Table 7 shows the results of these evaluations.

ingredient material Example 1
(g) Example 2
(g) Example 3
(g) Polyesteramic acid
A1 100 100 A2 100 Epoxy resin
B1 150 150 B2 150 Epoxy hardener Trimellitic anhydride 6 6 6 Coupling agent 3-GPMS 4.8 4.8 4.8 Antioxidant IRGANOX1010 0.50 0.50 0.50 solvent MMP 160.8 160.8 160.8 Surfactants BYK-344 0.42 0.42 0.42

ingredient material Example 4
(g) Example 5
(g) Example 6
(g) Polyesteramic acid A1 100 100 100 Epoxy resin

B3 150 B4 150 B5 150 Epoxy hardener Trimellitic anhydride 6 6 6 Coupling agent 3-GPMS 4.8 4.8 4.8 Antioxidant IRGANOX1010 0.50 0.50 0.50 solvent MMP 160.8 160.8 160.8 Surfactants BYK-344 0.42 0.42 0.42

ingredient material Comparative Example 1
(g) Comparative Example 2
(g) Comparative Example 3
(g) Polyesteramic acid A1 100 100 100 Epoxy resin

C1 150 C2 150 TECHMORE VG3101L 60 Epoxy hardener Trimellitic anhydride 6 6 6 Coupling agent 3-GPMS 4.8 4.8 4.8 Antioxidant IRGANOX1010 0.50 0.50 0.50 solvent MMP 160.8 160.8 160.8 Surfactants BYK-344 0.42 0.42 0.42

TECHMORE VG3101L: PRINTECH

3-GPMS: 3-glycidoxypropyltrimethoxysilane

Irganox 1010: BASF Japan

MMP: 3-Methoxypropionate

BYK-344: BIC Chemie Japan

Evaluation items
Example Comparative Example
One 2 3 4 5 6 One 2 3 Transparency ○ ○ ○ ○ ○ ○ ○ ○ ○ Light resistance ○ ○ ○ ○ ○ ○ ○ ○ × Flatness ○ ○ ○ ○ ○ ○ ○ × ○ Heat resistance ○ ○ ○ ○ ○ ○ × ○ ○ Chemical resistance ○ ○ ○ ○ ○ ○ × ○ ○

As is clear from the results shown in Table 7, it can be seen that the cured films according to Examples 1 to 6 are excellent in light resistance and flatness, and have a balance in all points of transparency, heat resistance and chemical resistance. On the other hand, the cured film using the epoxy resin obtained by making glycidyl methacrylate and monofunctional methacrylate which concerns on the comparative example 1 have excellent light resistance and flatness, but is poor in heat resistance and chemical-resistance. The cured film using the epoxy resin (Epoxy resin obtained by making glycidyl methacrylate and bifunctional methacrylate react) which has a molecular weight of 50,000 or more according to the comparative example 2 is inferior to flatness. In addition, the cured film which used the polyfunctional and the weight average molecular weight less than 3,000 epoxy resin which concerns on the comparative example 3 was inferior to light resistance. As mentioned above, all the characteristics could be satisfied only when the epoxy resin (weight average molecular weight; 1,000-50,000) obtained by making glycidyl methacrylate and bifunctional methacrylate react.

Since the cured film obtained by the thermosetting resin composition of this invention is excellent also in the characteristics as an optical material, such as transparency, light resistance, and sputter resistance, various optical materials, such as a color filter, an organic light emitting diode (LED) light emitting element, and a light receiving element. And the like, and a transparent insulating film formed between the thin film transistor (TFT) and the transparent electrode, and between the transparent electrode and the alignment film.

Claims (20)

A resin composition comprising a polyester amide acid, an epoxy resin, and an epoxy curing agent, wherein the polyester amide acid is obtained by reacting tetracarboxylic dianhydride, diamine, and a polyhydroxy compound as essential raw materials, and an X mole tetra It is a polyester amic acid obtained by making carbonic acid dianhydride, Y mol diamine, and Z mol polyhydroxy compound react at the ratio which the relationship of following formula 1 and formula 2 holds,
[Formula 1]
0.2≤Z / Y≤8.0
[Formula 2]
0.2≤ (Y + Z) /X≤1.5
The epoxy resin is an epoxy resin having a weight average molecular weight of 1,000 to 50,000 obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as an essential raw material component, and 100 parts by weight of the polyester amide acid. The epoxy resin is 20 to 400 parts by weight, and the epoxy curing agent is 0 to 60 parts by weight based on 100 parts by weight of the epoxy resin. The method of claim 1,
Thermosetting resin composition characterized by the above-mentioned polyester amic acid being a reaction product obtained by making tetracarboxylic dianhydride, diamine, a polyhydroxy compound, and monohydric alcohol react as an essential raw material component. The method of claim 2,
Thermosetting, characterized in that the monohydric alcohol is at least one selected from isopropyl alcohol, aryl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyl oxetane Resin composition. The method according to any one of claims 1 to 3,
The thermosetting resin composition, wherein the polyester amide acid is a polyester amide acid obtained by adding a styrene-maleic anhydride copolymer as a raw material component and reacting. The method according to any one of claims 1 to 4,
Thermosetting resin composition, characterized in that the polyester amide acid has a structural unit represented by the following formula (3) and (4).
(3)

[Chemical Formula 4]

Wherein R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyhydroxy compound residue. 6. The method according to any one of claims 1 to 5,
Thermosetting resin composition, characterized in that the weight average molecular weight of the polyester amide acid is 1,000 to 200,000. 7. The method according to any one of claims 1 to 6,
The tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2,2- [Bis (3,4-dicarboxyphenyl)] A thermosetting resin composition characterized by being at least 1 sort (s) chosen from hexafluoro propane dianhydride and ethylene glycol bis (anhydroprimetate). The method according to any one of claims 1 to 7,
And said diamine is at least one selected from 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. The method according to any one of claims 1 to 8,
The polyhydroxy compound is one selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol It is more than the thermosetting resin composition characterized by the above-mentioned. 10. The method according to any one of claims 1 to 9,
The said bifunctional (meth) acrylate is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, and 1, 3- butanediol di (meth) A thermosetting resin composition, characterized in that at least one selected from acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate. 11. The method according to any one of claims 1 to 10,
Thermosetting resin composition, characterized in that the epoxy curing agent is at least one selected from trimellitic anhydride and hexahydrotrimeric anhydride. The method of claim 1,
The tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, the diamine is 3,3'-diaminodiphenyl sulfone, and the polyhydroxy compound is 1, 4-butanediol, wherein the epoxy resin is a copolymer having glycidyl methacrylate and 1,4-butanediol dimethacrylate or 1,3-butanediol dimethacrylate having a weight average molecular weight of 1,000 to 50,000. The epoxy hardening | curing agent is trimellitic anhydride and contains 3-methoxy propionate as a solvent, The thermosetting resin composition characterized by the above-mentioned. The method of claim 2,
The tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, the diamine is 3,3'-diaminodiphenyl sulfone, and the polyhydroxy compound is 1, 4-butanediol, the monohydric alcohol is benzyl alcohol, the epoxy resin is glycidyl methacrylate and 1,4-butanediol dimethacrylate or 1,3-butanediol dimethacrylate A copolymer of 1,000 to 50,000, wherein the epoxy curing agent is trimellitic anhydride and contains methyl 3-methoxypropionate as a solvent. The cured film obtained from the thermosetting resin composition of any one of Claims 1-13. The color filter which uses the cured film of Claim 14 as a protective film. The liquid crystal display element using the color filter of Claim 15. The solid-state image sensor using the color filter of Claim 15. The liquid crystal display element which uses the cured film of Claim 14 as a transparent insulating film formed between thin film transistor (TFT) and a transparent electrode. A liquid crystal display element using the cured film of Claim 14 as a transparent insulating film formed between a transparent electrode and an oriented film. An organic light emitting diode (LED) light-emitting body using the cured film according to claim 14 as a protective film.