TWI500699B - Thermal curing resin, cured film, color filter, liquid crystal display device, solid photographic device and led luminous body - Google Patents

Description

Thermosetting resin composition, cured film, color filter, liquid crystal display element, solid-state imaging element, and LED illuminator

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

In the manufacturing steps of an element such as a liquid crystal display element, various chemical treatments such as an organic solvent, an acid, and an alkali solution are carried out, or when a wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Therefore, there is a case where the surface protective film is provided for the purpose of preventing surface deterioration, damage, and deterioration of various elements. The protective films are required to withstand various characteristics of the various processes in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, coating property, and flatness are required. Light resistance and the like. Further, in the development of high performance such as high viewing angle, high-speed response, and high definition of a liquid crystal display element, when it is used as a color filter protective film, a material having improved planarization characteristics is desired. Regarding the light resistance, it has heretofore been important to perform ultraviolet ozone treatment for the surface cleaning of the protective film. However, in recent years, in the color filter protective film for a transverse electric field mode, in order to improve the coating property of the photosensitive spacer, a higher energy ultraviolet ozone treatment is required, and the polymer is stable. The ultraviolet light exposure step such as the photopolymerization step of the alignment or PSA) mode or the photoalignment step of the alignment film is increased, and the light resistance becomes a very important characteristic.

As a protective film material having such excellent properties, there are a polyaminic acid composition containing ruthenium (see Patent Document 1) and a polyester phthalic acid composition (see Patent Documents 2 and 3). The polyamine composition containing ruthenium is a material which is excellent in flatness, but has a disadvantage that heat resistance is not sufficient and alkali resistance is poor. The polyester phthalic acid composition of Patent Document 2 has disadvantages in that flatness and heat resistance are insufficient. The polyester phthalic acid composition of Patent Document 3 is a material excellent in flatness, heat resistance, and chemical resistance, but has insufficient light resistance and is disadvantageous in transparency in ultraviolet ozone treatment or ultraviolet exposure step. . Therefore, any material does not sufficiently satisfy light resistance, flatness, heat resistance, chemical resistance, and other characteristics as a protective film material.

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-291150

Patent Document 2: Japanese Patent Laid-Open Publication No. 2005-105264

Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-156546

Under the above circumstances, it is required to have chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, and coating property. The resin composition. Further, in particular, a cured film which is excellent in flatness and light resistance and a resin composition which imparts the cured film are required.

The inventors of the present invention conducted various studies in order to solve the above problems, and as a result, found that by including a polyester phthalic acid (the polyester phthalic acid is composed of a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound) a polyester phthalic acid obtained by reacting a compound, an epoxy resin obtained by reacting glycidyl (meth)acrylate with a bifunctional (meth) acrylate as an essential raw material component The epoxy resin), the resin composition of the epoxy curing agent, and the cured film obtained by curing the resin composition can achieve the above object, and the present invention has been completed.

The present invention has the following constitution.

[1] A thermosetting resin composition which is a resin composition comprising a polyester phthalic acid, an epoxy resin, and an epoxy hardener, characterized in that the polyester phthalic acid is a tetracarboxylic acid The dianhydride, the diamine, and the polyvalent hydroxy compound are obtained by reacting the essential raw material components, and the X-molar tetracarboxylic dianhydride, the Y-mole diamine, and the Z-mole polyhydroxy compound are represented by the following formula: (1) a polyester phthalic acid obtained by reacting a ratio of the relationship of the formula (2),

0.2≦Z/Y≦8.0 ......(1)

0.2≦(Y+Z)/X≦1.5 ......(2)

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 with a bifunctional (meth) acrylate as an essential raw material component, relative to the polyester. The epoxy resin is 20 parts by weight to 400 parts by weight based on 100 parts by weight of the lysine, and the epoxy curing agent is 0 parts by weight to 60 parts by weight based on 100 parts by weight of the epoxy resin.

[2] The thermosetting resin composition according to [1], wherein the polyester proline is made of a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a monohydric alcohol. A reaction product obtained by reacting a component.

[3] The thermosetting resin composition according to [2], wherein the monohydric alcohol is selected from the group consisting of isopropanol, propenol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3- One or more kinds of ethyl-3-hydroxymethyl propylene oxide.

[4] The thermosetting resin composition according to any one of [1], wherein the polyester proline is further reacted by adding a styrene-maleic anhydride copolymer as a raw material component. And the polyester proline obtained.

[5] The thermosetting resin composition according to any one of [1] to [4] wherein the polyester phthalic acid has the following formula (3) and formula (4) Structural unit;

Here, R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue.

[6] The thermosetting resin composition according to any one of [1] to [5] wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000.

[7] The thermosetting resin composition according to any one of [1], wherein the tetracarboxylic dianhydride is selected from 3,3',4,4'-diphenyl groups. Terpene tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene One or more types of alcohol bis (dehydrated trimellitate).

[8] The thermosetting resin composition according to any one of [1], wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4] One or more kinds of -(3-aminophenoxy)phenyl]anthracene.

[9] The thermosetting resin composition according to any one of [1], wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, and 1,4-butanediol. One or more of 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol.

[10] The thermosetting resin composition according to any one of [1], wherein the bifunctional (meth) acrylate is selected from ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(a) One or more of acrylate and tricyclodecane dimethanol di(meth)acrylate.

[1] The thermosetting resin composition according to any one of [1] to [10] wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride and hexahydrotrimellitic anhydride.

[12] The thermosetting resin composition according to [1], wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, the diamine Is 3,3'-diaminodiphenylanthracene, the polyvalent hydroxy compound is 1,4-butanediol, and the epoxy resin is glycidyl methacrylate and 1,4-butanediol a acrylate or 1,3-butanediol dimethacrylate having a weight average molecular weight of 1,000 to 50,000, the epoxy hardener being trimellitic anhydride, and further containing methyl 3-methoxypropionate as a solvent .

[13] The thermosetting resin composition according to [2], wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, the diamine Is 3,3'-diaminodiphenylanthracene, the polyhydric hydroxy compound is 1,4-butanediol, the monohydric alcohol is benzyl alcohol, and the epoxy resin is glycidyl methacrylate and a copolymer of 1,4-butanediol dimethacrylate or 1,3-butanediol dimethacrylate having a weight average molecular weight of 1,000 to 50,000, said epoxy hardener being trimellitic anhydride, further containing 3- Methyl methoxypropionate is used as a solvent.

[14] A cured film obtained by the thermosetting resin composition according to any one of [1] to [13].

[15] A color filter using the cured film as described in [14] as a protective film.

[16] A liquid crystal display element using the color filter as described in [15].

[17] A solid-state imaging element using the color filter according to [15].

[18] A liquid crystal display element using the cured film as described in [14] above as a transparent insulating film formed between a TFT and a transparent electrode.

[19] A liquid crystal display element using the cured film according to [14] above as a transparent insulating film formed between the transparent electrode and the alignment film.

[20] An LED light-emitting body using the cured film according to [14] above as a protective film.

[Effects of the Invention]

The thermosetting resin composition of the preferred embodiment of the present invention is a material which is particularly excellent in flatness and light resistance, and can be used in a case where it is used as a color filter protective film for a color liquid crystal display element. And reliability is improved. Further, the cured film obtained by heating the thermosetting resin composition of the preferred embodiment of the present invention is balanced in transparency, chemical resistance, adhesion, and splash resistance, and is practical. Very very high. In particular, it can be used as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, an electroplating method, and a printing method. Moreover, it can also be used as a protective film of various optical materials and a transparent insulating film.

Thermosetting resin composition

The thermosetting resin composition of the present invention is a resin composition comprising a polyester phthalic acid, an epoxy resin, and an epoxy hardener, which is obtained by using a tetracarboxylic dianhydride or a diamine. And a polyester phthalic acid obtained by reacting a polyvalent hydroxy compound as a necessary raw material component, which is necessary by using glycidyl (meth) acrylate and a bifunctional (meth) acrylate. An epoxy resin obtained by reacting a raw material component, wherein the thermosetting resin composition is characterized in that the epoxy resin is 20 parts by weight to 400 parts by weight relative to 100 parts by weight of the polyester phthalic acid, relative to the ring The epoxy hardener is 0 to 60 parts by weight based on 100 parts by weight of the oxygen resin.

1-1. Polyester proline

The polyester phthalic acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. More specifically, the reaction is carried out at a ratio in which the relationship between the following formula (1) and formula (2) is satisfied by the X-molar tetracarboxylic dianhydride, the Y-mole diamine, and the Z-mole polyvalent hydroxy compound. And get.

0.2≦Z/Y≦8.0 ......(1)

0.2≦(Y+Z)/X≦1.5 ......(2)

In the synthesis of the polyester lysine, it is necessary to use at least a solvent, and the solvent can be left as a thermosetting resin composition in the form of a liquid or a gel in consideration of workability, etc., and the solvent can be removed. A composition having a solid shape in consideration of handling properties and the like is produced. Further, in the synthesis of the polyester phthalic acid, one or more kinds of raw materials selected from the group consisting of a monohydric alcohol and a styrene-maleic anhydride copolymer may be contained as a raw material, and among them, a monohydric alcohol is preferable. Further, in the synthesis of the polyester proline, a raw material other than the above may be contained as a raw material as needed within the range not impairing the object of the present invention. As an example of such another raw material, a monoamine containing a hydrazine is mentioned.

1-1-1. Tetracarboxylic dianhydride

Specific examples of the tetracarboxylic dianhydride used in the present invention include the following: aromatic tetracarboxylic dianhydride, for example, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylfluorene Formic acid dianhydride, 2,2',3,3'-diphenylstilbene tetracarboxylic dianhydride, 2,3,3',4'-diphenylstilbene tetracarboxylic dianhydride, 3,3',4,4 '-Diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2 ,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, and ethylene glycol bis(dehydrated trimellitate) (trade name: TMEG-100, New Japan Physical and Chemical Co., Ltd.) Cycloaliphatic tetracarboxylic dianhydride, such as cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and cyclohexane tetracarboxylic dianhydride; aliphatic four A carboxylic acid dianhydride such as ethane tetracarboxylic dianhydride and butane tetracarboxylic dianhydride.

Preferred among these compounds are 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride and 3,3',4,4'-diphenyl ether tetra which can impart a resin having good transparency. Formic acid dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(hydrogen trimellitate) (trade name TMEG-100, new Japanese physicochemical) Co., Ltd.), particularly preferred are 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride.

1-1-2. Diamine

Specific examples of the diamine used in the present invention include 4,4'-diaminodiphenyl fluorene, 3,3'-diaminodiphenyl fluorene, and 3,4'-diaminodiphenyl. Bismuth, bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]indole, bis[3-(4-aminophenoxy) Phenyl]anthracene, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]anthracene, [4-(3-aminophenoxy) Phenyl][3-(4-aminophenoxy)phenyl]anthracene, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

Preferred among these compounds are 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene which impart a good transparency. It is 3,3'-diaminodiphenylanthracene.

1-1-3. Polyols

Specific examples of the polyvalent hydroxy 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, and dipropylene glycol. , tripropylene glycol, 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-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol , 3,6-octanediol, 1,2,8-octanetriol, 1,2-decanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-anthracene Glycol, 1,10-decanediol, 1,2,10-triol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylolpropane Pentaerythritol, dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine, and triethanolamine.

Preferred among these compounds are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- which have good solubility in a solvent. Heptanediol and 1,8-octanediol are particularly preferred are 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

1-1-4. 1 alcohol

Specific examples of the monohydric alcohol used in the present invention include methanol, ethanol, 1-propanol, isopropanol, propenol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and propylene glycol monomethyl ether. Dipropylene 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, linalool , rosinol, dimethylbenzyl methanol, 3-ethyl-3-hydroxymethyl propylene oxide.

Preferred among these compounds are isopropyl alcohol, propylene alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl propylene oxide. Consider the compatibility in the case where the polyester phthalic acid obtained by using these compounds is mixed with an epoxy resin and an epoxy hardener, or the thermosetting resin composition as a final product on a color filter. More preferably, the coating property is benzyl alcohol using a monohydric alcohol.

The monohydric alcohol is preferably contained in an amount of from 2 parts by weight to 300 parts by weight per 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 parts by weight to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer

Further, the polyester phthalic acid used in the present invention may be subjected to a synthesis reaction by adding a compound having three or more acid anhydride groups. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. With respect to the ratio of the components constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene/maleic anhydride is from 0.5 to 4, preferably from 1 to 3, and more preferably about 1, about 2 or about 3, still more preferably about 1 or about 2, and particularly preferably about 1.

Specific examples of the styrene-maleic anhydride copolymer include commercially available products such as SMA3000P, SMA2000P, and SMA1000P of Chuan crude oil processing company. Among these, the SMA1000P is excellent in heat resistance and alkali resistance.

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

1-1-6. Monoamine containing hydrazine

In the synthesis of the polyester valine acid, other raw materials other than the above may be contained as a raw material as needed within the range not impairing the object of the present invention. Examples of such other raw materials include monoamines containing ruthenium.

Specific examples of the monoamine containing ruthenium used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethylmethyl Oxydecane, 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutylmethyldiethoxylate Base decane, p-aminophenyl trimethoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl methyl dimethoxy decane, p-aminophenyl methyl diethoxy decane, M-aminophenyltrimethoxydecane, and m-aminophenylmethyldiethoxydecane.

Preferred among these compounds are 3-aminopropyltriethoxydecane having good acid resistance of the coating film, and p-aminophenyltrimethoxydecane, which is particularly preferable from the viewpoints of acid resistance and compatibility. It is 3-aminopropyltriethoxydecane.

The monoamine containing ruthenium preferably contains 0 parts by weight to 300 parts by weight based on 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 parts by weight to 200 parts by weight.

1-1-7. Solvent used in the synthesis of polyester proline

Specific examples of the solvent used in the synthesis reaction for obtaining polyester proline include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethylene glycol. Alcohol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexane Ketone, N-methyl-2-pyrrolidone, and N,N-dimethylacetamide.

Preferred among these solvents are propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether.

These solvents may be used singly or in combination of two or more kinds. Further, when the ratio is 30% by weight or less, other solvents than the above solvents may be used in combination.

1-1-8. Synthesis method of polyester proline

The method for synthesizing the polyester phthalic acid used in the present invention can be carried out by reacting a tetracarboxylic dianhydride X-mole, a diamine Y-mole, and a polyvalent hydroxy compound Z-mol in the above solvent. In this case, it is preferable that X, Y, and Z are ratios at which the relationship between the following formulas (1) and (2) is established. When it is this range, since the solubility of a polyester valine acid in a solvent is high, the coating property of a composition improves, and it is set as the hardening film which is excellent in planarity.

0.2≦Z/Y≦8.0 ......(1)

0.2≦(Y+Z)/X≦1.5 ......(2)

The relationship of the formula (1) is preferably 0.7 ≦ Z / Y ≦ 7.0, more preferably 1.3 ≦ Z / Y ≦ 7.0. Further, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) / X ≦ 0.9, more preferably 0.7 ≦ (Y + Z) / X ≦ 0.8.

When the polyester glutamic acid used in the present invention has an acid anhydride group at the molecular terminal, the above-mentioned monohydric alcohol may be added as needed to carry out the reaction. The polyester phthalic acid obtained by the reaction of adding a monohydric alcohol can improve the compatibility with the epoxy resin and the epoxy hardener, and can improve the coating of the thermosetting resin composition of the present invention containing the compounds. Cloth.

Further, in the case where the above monoamine containing ruthenium is reacted with a polyester phthalic acid having an acid anhydride group at the molecular terminal, the acid resistance of the obtained coating film is improved. Alternatively, the monohydric alcohol may be reacted with the polyester proline at the same time as the monoamine containing hydrazine.

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 the tetracarboxylic dianhydride, the diamine and the polyvalent hydroxy compound, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours. When the reaction of the monoamine containing ruthenium is carried out, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the monoamine containing ruthenium is added at 10 ° C. The reaction may be carried out at -40 ° C for 0.1 to 6 hours. Moreover, the monohydric alcohol can be added at any point in the reaction.

The order of addition of the reaction raw material to the reaction system is not particularly limited. That is, tetracarboxylic dianhydride, a diamine, and a polyhydric hydroxy compound may be simultaneously added to the reaction solvent; after dissolving the diamine and the polyhydric hydroxy compound in the reaction solvent, tetracarboxylic dianhydride is added; After the dianhydride and the polyvalent hydroxy compound are reacted in advance, a diamine is added to the reaction product, or a tetracarboxylic dianhydride and a diamine are previously reacted, and then a method such as a polyvalent hydroxy compound is added to the reaction product.

Preferably, the polyester phthalic acid thus synthesized comprises a structural unit composed of the general formula (3) and the general formula (4), and the terminal is derived from a tetracarboxylic dianhydride or a diamine as a raw material. Or an acid anhydride group, an amine group or a hydroxyl group of a polyvalent hydroxy compound, or an additive other than the compounds, constitutes the terminal. In the general formula (3) and the general formula (4), R ¹ is a tetracarboxylic dianhydride residue, and preferably an organic group having 2 to 30 carbon atoms. R ² is a diamine residue, preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue of a polyvalent hydroxy compound, preferably an organic group having 2 to 20 carbon atoms.

The weight average molecular weight of the obtained polyester glutamic acid is preferably from 1,000 to 200,000, more preferably from 3,000 to 50,000. If it is in these ranges, flatness and heat resistance will become favorable.

The weight average molecular weight in the present specification is a value obtained by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 ml/min). Standard polystyrene uses polystyrene with a molecular weight of 645 to 132,900 (for example, VARIAN polystyrene calibration kit PL2010-0102), column for PLgel MIXED-D (VARIAN), and mobile phase for tetrahydrofuran (THF). The measurement was carried out. In addition, the weight average molecular weight of the commercial item in this specification is a catalogue value.

1-2. Epoxy resin

The epoxy resin used in the present invention can be obtained by reacting a glycidyl (meth)acrylate with a bifunctional (meth) acrylate as a raw material component. The epoxy resin is not particularly limited as long as it has good compatibility with the other components forming the thermosetting resin composition of the present invention. Further, the bifunctional (meth) acrylate which is reacted with glycidyl (meth)acrylate may be one type or two or more types.

When an epoxy resin obtained by reacting glycidyl (meth)acrylate with another radical polymerizable monomer is used, the transparency of the cured film obtained from the thermosetting resin composition becomes high, and it can be suppressed to ultraviolet ozone. The transparency in the treatment step or the ultraviolet exposure step is lowered, and therefore it is preferred. From the viewpoints of flatness, heat resistance, and chemical resistance, it is preferred that glycidyl (meth)acrylate contains 50 wt% to 99 wt% of all monomers constituting the epoxy resin.

When a monofunctional (meth) acrylate is used as the other radical polymerizable monomer, the heat-resistant film and the chemical resistance of the cured film obtained from the thermosetting resin composition are insufficient, and a trifunctional or higher polyfunctional group is used. When (meth) acrylate is insufficient in flatness and the compatibility with polyester phthalic acid is deteriorated, a bifunctional (meth) acrylate is preferable.

Preferable examples of the bifunctional (meth) acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and 1,4-butanediol di(methyl). Acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate. These compounds are preferred because they have good compatibility with the polyester phthalic acid of the epoxy resin obtained by the reaction with glycidyl (meth)acrylate. From the viewpoint of flatness, heat resistance, and chemical resistance, it is preferred that the bifunctional (meth) acrylate contains 1 wt% to 30 wt% of all the monomers constituting the epoxy resin.

The epoxy resin may further contain, as a raw material component, a glycidyl (meth)acrylate and a radical polymerizable monomer other than a bifunctional (meth) acrylate. From the viewpoint of exhibiting the characteristics of the other radical polymerizable monomer without impairing the effects of the present invention, it is preferred that the other radical polymerizable monomer contains 0 wt% to 20 wt%.

The weight average molecular weight of the epoxy resin obtained by reacting glycidyl (meth)acrylate with a bifunctional (meth) acrylate as an essential raw material component is preferably 1,000 to 50,000, more preferably 3,000. ~20,000. When the molecular weight is within these ranges, sufficient flatness, heat resistance, and chemical resistance are obtained.

1-2-1. Solvent used in the synthesis of epoxy resin

It is necessary to use at least a solvent in the synthesis of the epoxy resin.

Specific examples of the solvent used in the polymerization reaction for obtaining an epoxy resin include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethylene glycol single. Ethyl 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-dimethylacetamide.

Preferred among these solvents are propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether.

These solvents may be used singly or in combination of two or more kinds. Further, when the ratio is 30% by weight or less, a solvent other than the above solvent may be used in combination.

1-2-2. Synthesis method of epoxy resin

The method for synthesizing the epoxy resin used in the present invention is not particularly limited, and is preferably a radical polymerization in a solution using a solvent. 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 the glycidyl (meth)acrylate, the bifunctional (meth) acrylate, and the other radical polymerizable monomer, the reaction proceeds smoothly. Therefore, it is preferred. The polymerization temperature is not particularly limited as long as the radical is sufficiently generated by the polymerization initiator to be used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is also not particularly limited, but is usually in the range of from 1 hour to 24 hours. Moreover, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

A known polymerization initiator can be used in the synthesis of the epoxy resin. Examples of the polymerization initiator include a compound which generates a radical due to heat, an azo initiator such as azobisisobutyronitrile, and a peroxide initiator such as benzophenone peroxide. In the radical polymerization reaction, a chain transfer agent such as thioglycolic acid may be appropriately added in order to adjust the molecular weight of the copolymer to be produced.

The epoxy resin used in the present invention can be used to form an epoxy resin solution in consideration of operability and the like, and the solvent can be removed to obtain a solid shape in consideration of handling properties and the like. Epoxy resin.

1-3. Epoxy hardener

In the thermosetting resin composition of the present invention, an epoxy curing agent may be added in order to improve flatness and chemical resistance. The epoxy resin is an acid anhydride-based curing agent, an amine-based curing agent, a phenol-based curing agent, and a catalyst-type curing agent. From the viewpoint of coloring and heat resistance, an acid anhydride-based curing agent is preferred.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and six. Hydrogen trimellitic anhydride; aromatic polycarboxylic acid anhydrides such as phthalic anhydride, trimellitic anhydride; styrene-maleic anhydride copolymers. Particularly preferred among these compounds are trimellitic anhydride and hexahydrotrimellitic anhydride in terms of the balance between heat resistance and solubility in a solvent.

1-4. Proportion of polyester proline, epoxy resin and epoxy hardener

In the thermosetting resin composition of the present invention, the ratio of the epoxy resin to 100 parts by weight of the polyester phthalic acid is 20 parts by weight to 400 parts by weight. When the ratio of the epoxy resin is in this range, the balance between flatness, heat resistance, chemical resistance, and adhesion is good. More preferably, the epoxy resin is in the range of 50 parts by weight to 300 parts by weight.

In the case where an epoxy curing agent is added for the purpose of improving flatness and chemical resistance, the ratio of the epoxy resin to the epoxy curing agent is an epoxy curing agent relative to 100 parts by weight of the epoxy resin. It is 0 parts by weight to 60 parts by weight. More specifically, the amount of the epoxy curing agent to be added is preferably 0.1 to 1.5 equivalents per equivalent of the carboxylic anhydride group or the carboxyl group in the epoxy curing agent with respect to the epoxy group. At this time, the carboxylic anhydride group was calculated at a divalent value. When the carboxylic anhydride group or the carboxyl group is added in an amount of from 0.15 equivalents to 0.8 equivalents, the chemical resistance is further improved, which is more preferable.

1-5. Other constituent materials of the thermosetting resin composition

The solvent used in the resin composition of the present invention can be used as it is in the polymerization reaction for synthesizing polyester phthalic acid and epoxy resin. The solid content concentration of the thermosetting resin composition can be selected according to the film thickness of the coating film, and is usually in the range of 5 parts by weight to 50 parts by weight based on 100 parts by weight of the resin composition. Further, the amount of the solvent can be appropriately determined in association with problems such as the operation of the resin composition. In some cases, for example, a resin composition in which a solvent is removed from the resin composition to form a solid state may be used.

The thermosetting resin composition of the present invention may contain other components than those described above as needed within the range not impairing the object of the present invention. Examples of such other components include a coupling agent, a surfactant, an antioxidant, a curing accelerator, and a heat-sensitive acid generator. Further, when the polyester phthalic acid does not contain a styrene-maleic anhydride copolymer as a raw material, a styrene-maleic anhydride copolymer may be added as another component.

The coupling agent is used to increase the adhesion to the substrate, and is added in an amount of 10 parts by weight or less based on 100 parts by weight of the solid matter of the thermosetting resin composition (remaining component from which the solvent is removed from the resin composition). use.

As the coupling agent, a compound of a decane type, an aluminum type, and a titanate type can be used.

Specific examples thereof include vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and 3-condensed water. Glycidoxypropyl dimethyl ethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, 3-glycidoxy propyl triethoxy decane, 3-glycidoxy propyl Trimethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, and 3-methylpropene a decane system such as methoxypropyltriethoxy decane, an aluminum system such as acetamino alkoxydiisopropyl aluminum or a titanate such as tetraisopropylbis(dioctylphosphite) titanate system. Among these coupling agents, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving the adhesion.

The surfactant is used to increase the wettability, the homogenization property, or the coating property of the base substrate, and is added in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the thermosetting resin composition. .

Examples of such a surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all of which are trade names, Kyoeisha Chemical Co., Ltd.), and Disperbyk 161. , Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-344, BYK -346, BYK-UV3500, BYK-UV3570 (all of which are trade names, BYK-CHEMIE JAPAN KK), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (above For the trade name, Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all of which are trade names, AGC Qingmei Chemical Co., Ltd.), Ftergent 222F, Ftergent 251, FTX-218 (all of which are commodities) Name, Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of which are trade names, Mitsubishi Materials Co., Ltd.), Megafac F- 410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Meg Afac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac R-94, Megafac RS-75, Megafac RS-72-K (all above Trade name, DIC Co., Ltd.), TEGO Rad 2200N, TEGO Rad 2250N (all of which are trade names, Evonik Degussa Japan Co., Ltd.).

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

The antioxidant is used to improve the transparency and prevent yellowing of the cured film when exposed to a high temperature, and 100 parts by weight of the solid matter of the thermosetting resin composition (after removing the solvent from the resin composition) The residual component) is used by adding 0.1 part by weight to 5 parts by weight.

As the antioxidant, a hindered amine system, a hindered phenol system or the like can be used. Specific examples include IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (trade name; BASF Japan Co., Ltd.) and the like.

The curing accelerator is used to promote the reaction between the epoxy resin and the epoxy curing agent, and to improve the heat resistance and chemical resistance of the cured film, and 100 parts by weight of the solid matter of the thermosetting resin composition (from the resin) The residual component after removing the solvent in the composition is added in an amount of 0.01 part by weight to 5 parts by weight.

Any curing agent which has a function of promoting the reaction between the epoxy resin and the epoxy curing agent can be used as the curing accelerator, and examples thereof include an imidazole curing accelerator, a phosphine curing accelerator, and an ammonium hardening accelerator. A reagent, a Lewis acid hardening accelerator, and the like are exemplified.

In the case where the thermosetting resin composition of the present invention is used under low-temperature curing conditions of less than 200 ° C, the heat-sensitive acid generator can impart sufficient hardness and chemical resistance to the cured film, and the above-mentioned thermosetting property. 100 parts by weight of the solid content of the resin composition (residual component obtained by removing the solvent from the resin composition) is used by adding 0.001 part by weight to 3 parts by weight.

Examples of the heat-sensitive acid generator include an onium salt, a benzothiazoline salt, an ammonium salt, a phosphonium salt and the like.

2. A cured film obtained from a thermosetting resin composition

The thermosetting resin composition of the present invention can be further selected by adding a solvent, an epoxy hardener, a coupling agent, a surfactant, and the like according to a target characteristic by mixing a polyester phthalic acid and an epoxy resin. An additive is obtained by uniformly mixing and dissolving the compounds.

The thermosetting resin composition prepared as described above (after being dissolved in a solvent in a solid state without a solvent) is applied onto the surface of the substrate, and the solvent is removed by, for example, heating. A coating film is formed. The coating of the thermosetting resin composition on the surface of the substrate can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dip plating method, or a slit coating method. Next, the coating film is heated (prebaked) by a hot plate or an oven or the like. The heating conditions vary depending on the type of each component and the blending ratio, and are usually from 70 ° C to 150 ° C for 5 minutes to 15 minutes in the case of an oven, and from 1 minute to 5 minutes in the case of a hot plate. Thereafter, in order to cure the coating film, at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, if it is an oven, heat treatment is performed for 30 minutes to 90 minutes, and if it is a hot plate, it is performed for 5 minutes. Heat treatment for ～30 minutes, whereby a cured film can be obtained.

When the cured film thus obtained is heated, 1) the polyamic acid of the polyester phthalic acid is partially dehydrated and cyclized to form a quinone bond, and 2) the carboxylic acid of the polyester phthalic acid is reacted with the epoxy resin and is high. Since the molecular weight is increased, and 3) the epoxy resin is cured and polymerized, it is very strong, and is excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention can be effectively used as a protective film for a color filter, and a color filter can be used to manufacture a liquid crystal display element or a solid-state imaging element. Further, the cured film of the present invention can be effectively used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to a protective film for a color filter. Further, the cured film of the present invention is also effectively used as a protective film for an LED illuminator.

[Example]

Next, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the examples.

First, a polyester proline solution containing a reaction product of tetracarboxylic dianhydride, diamine, and a polyvalent hydroxy compound was synthesized as follows (Synthesis Example 1, Synthesis Example 2, Table 1).

[Synthesis Example 1] Synthesis of polyester proline solution (A1)

The dehydrated purified methyl 3-methoxypropionate (hereinafter referred to as "MMP") was charged into a four-necked flask of 1000 ml having a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, and 446.96 g, 1,4- 31.93 g of butanediol, 25.54 g of benzyl alcohol, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as "ODPA") 183.20 g, stirred under a dry nitrogen stream at 130 ° C 3 hour. Thereafter, the reaction liquid was cooled to 25 ° C, and 29.3 g of 3,3'-diaminodiphenyl hydrazine (hereinafter abbreviated as "DDS") and 183.04 g of MMP were charged, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours. The mixture was stirred at 115 ° C for 1 hour and cooled to 30 ° C or lower, whereby a 30 wt% solution (A1) of pale yellow transparent polyester phthalic acid was obtained.

The solution has a rotational viscosity of 28.5 mPa ‧ s. Further, the weight average molecular weight measured by GPC was 4,200 (in terms of polystyrene).

Here, the rotational viscosity in the present specification is a viscosity measured at 25 ° C using an E-type viscometer (trade name: VISCONIC END, Tokyo Keiki Co., Ltd.).

[Synthesis Example 2] Synthesis of polyester proline solution (A2)

Dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") 504.00 g, ODPA 47.68 g, was placed in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. SMA1000P (trade name; styrene-maleic anhydride copolymer, Sichuan Crude Oil Co., Ltd.) 144.97 g, benzyl alcohol 55.40 g, 1,4-butanediol 9.23 g, dehydrated purified diethylene glycol methyl ethyl Ether (hereinafter abbreviated as "EDM") 96.32 g was stirred at 130 ° C for 3 hours under a stream of dry nitrogen. Thereafter, the reaction liquid was cooled to 25 ° C, and 12.72 g of DDS and 29.68 g of EDM were charged, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 115 ° C for 1 hour, and cooled to 30 ° C or lower. A 30 wt% solution of yellow transparent polyester proline (A2).

The rotary viscosity of this solution was 36.2 mPa·s, and the weight average molecular weight measured by GPC was 21,000 (in terms of polystyrene).

MMP: methyl 3-methoxypropionate

ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

DDS: 3,3'-diaminodiphenylanthracene

PGMEA: propylene glycol monomethyl ether acetate

SMA1000P: styrene-maleic anhydride copolymer (Chuan crude oil company)

EDM: diethylene glycol methyl ethyl ether

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

[Synthesis Example 3] Synthesis of epoxy resin solution (B1)

The dehydrated MMP 300.00 g, glycidyl methacrylate (hereinafter referred to as "GMA") 180.00 g, 1, 4 was placed in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 20.00 g of butanediol dimethacrylate, 20.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and carried out at a polymerization temperature of 90 ° C for 2 hours The polymerization is carried out by heating. A 40 wt% solution (B1) of the epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight of this solution measured by GPC was 12,000 (in terms of polystyrene).

[Synthesis Example 4] Synthesis of epoxy resin solution (B2)

A 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen inlet was charged with dehydrated and purified MMP 300.00 g, GMA 180.00 g, and 1,3-butylene glycol dimethacrylate 20.00 g. 20.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. A 40 wt% solution (B2) of the epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight of this solution measured by GPC was 12,000 (in terms of polystyrene).

[Synthesis Example 5] Synthesis of epoxy resin solution (B3)

A 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen inlet was charged with dehydrated purified MMP 300.00 g, GMA 180.00 g, and neopentyl glycol dimethacrylate 20.00 g as a polymerization initiation. 20.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. A 40 wt% solution (B3) of the epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight of this solution measured by GPC was 11,000 (in terms of polystyrene).

[Synthesis Example 6] Synthesis of epoxy resin solution (B4)

Dehydrated and purified MMP 300.00 g, GMA 160.00 g, and 1,4-butanediol dimethacrylate 40.00 g were placed in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 30.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. A 40 wt% solution (B4) of an epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight of this solution as measured by GPC was 18,000 (in terms of polystyrene).

[Synthesis Example 7] Synthesis of epoxy resin solution (B5)

A 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen inlet was charged with dehydrated purified MMP 300.00 g, GMA 180.00 g, and diethylene glycol dimethacrylate 20.00 g as a polymerization initiation. 20.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. A 40 wt% solution (B5) of an epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight of this solution measured by GPC was 11,000 (in terms of polystyrene).

GMA: glycidyl methacrylate

MMP: methyl 3-methoxypropionate

Next, an epoxy resin solution containing a reaction product of glycidyl (meth)acrylate and a monofunctional (meth) acrylate was synthesized by the following method (Comparative Synthesis Example 1, Table 3).

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

A 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen inlet was charged with dehydrated and purified MMP 300.00 g, GMA 180.00 g, methyl methacrylate 20.00 g, and 2 as a polymerization initiator. 2'-Azobis(2,4-dimethylvaleronitrile) 8.00 g, and polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours. A 40 wt% solution (C1) of the epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight of this solution measured by GPC was 15,000 (in terms of polystyrene).

Next, an epoxy resin solution containing a reaction product of glycidyl (meth)acrylate and a bifunctional (meth) acrylate (weight average molecular weight: 20,000 or more) was synthesized by the following method (Comparative Synthesis Example) 2, Table 3).

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

Dehydrated and purified MMP 300.00 g, GMA 180.00 g, and 1,4-butanediol dimethacrylate 20.00 g were placed in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. Polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) 13.00 g was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. A 40 wt% solution (C1) of the epoxy resin was obtained by cooling the reaction liquid to below 30 °C. The weight average molecular weight of the solution as measured by GPC was 58,000 (in terms of polystyrene).

GMA: glycidyl methacrylate

MMP: methyl 3-methoxypropionate

Next, the epoxy resins obtained in the synthetic liminic acid (A1, A2) obtained in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, Synthesis Example 4, Synthesis Example 5, Synthesis Example 6, and Synthesis Example 7 were used ( B1, B2, B3, B4, B5), Comparative Synthesis Example 1, epoxy resin (C1, C2) obtained in Comparative Synthesis Example 2, and commercially available polyfunctional epoxy resin having a weight average molecular weight of less than 3,000, The thermosetting resin composition was prepared as follows, and a cured film was obtained from the thermosetting resin composition, and the cured film was evaluated (Examples 1 to 6, Comparative Example 1, Comparative Example 2, and Comparative Example 3, Table 4 to Table 6 and Table 7).

[Example 1]

A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 100 g of the polyester glutamic acid solution (A1) obtained in Synthesis Example 1 and the epoxy resin obtained in Synthesis Example 3 were placed in the flask. 150 g of solution (B1), 6 g of trimellitic anhydride, 4.8 g of 3-glycidoxypropyltrimethoxydecane, 0.50 g of IRGANOX 1010 (trade name; BASF Japan Co., Ltd.), and 160.8 g of dehydrated purified MMP Stir for 5 hours at a temperature to dissolve it evenly. Next, 0.42 g of BYK-344 (trade name, BYK-CHEMIE JAPAN K.K.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered by a membrane filter having a pore size of 0.2 μm to prepare a coating liquid.

Next, the coating liquid was spin-coated on a glass substrate and a color filter substrate at 800 rpm for 10 seconds, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a coating film. Thereafter, the coating film was cured by heating in an oven at 230 ° C for 30 minutes to obtain a cured film having a film thickness of 1.5 μm.

The cured film obtained in this manner was evaluated for its properties in terms of transparency, light resistance, flatness, heat resistance, and chemical resistance. The evaluation results of these are shown in Table 7.

[Evaluation method of transparency]

In the obtained glass substrate with a cured film, the ultraviolet light-visible near-infrared spectrophotometer (trade name: V-670, Japan Spectrophotometry Co., Ltd.) was used to measure only the cured film at a wavelength of 400 nm. Transmittance. The case where the transmittance was 97% or more was taken as ○, and the case where the transmittance was less than 97% was taken as ×.

[Evaluation method of light resistance]

By the ultraviolet ozone cleaning device (trade name: PL2003N-12, the light source is a low-pressure mercury lamp, SEN LIGHTS Co., Ltd.), the cured film is evaluated for the transparency in the evaluation method of [transparency]. After the glass substrate was subjected to ultraviolet ozone treatment at 3 J/cm ² (254 nm conversion), only the cured film was measured by ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, Japan Optical Co., Ltd.). The wavelength is the transmittance at 400 nm. The case where the transmittance is 96% or more is ○, and the case where the transmittance is less than 96% is ×.

[Evaluation method of flatness]

The step of the surface of the cured film of the obtained color filter substrate with a cured film was measured using a step, a surface roughness, and a fine shape measuring device (trade name: P-15, KLA TENCOR Co., Ltd.). The case where the maximum value of the step difference between the R, G, and B pixels of the black matrix (hereinafter referred to as the maximum step) is less than 0.2 μm is taken as ○, and the case where 0.2 μm or more is used is ×. Further, the color filter substrate used was a pigment dispersion color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step difference of about 1.1 μm.

[Evaluation method of heat resistance]

The obtained glass substrate with a cured film was reheated at 250 ° C for 1 hour, and then the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was calculated by the following calculation formula. The case where the residual film ratio after heating was 95% or more was taken as ○, and the case where the residual film ratio after heating was less than 95% was taken as ×.

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

[Method for evaluating chemical resistance]

The obtained glass substrate with the cured film was immersed in a 5 wt% aqueous sodium hydroxide solution at 60 ° C for 10 minutes (hereinafter referred to as NaOH treatment), and contained 36% hydrochloric acid / 60% nitric acid / water = In a 40/20/40 mixture (weight ratio), immersion treatment (hereinafter abbreviated as acid treatment) at 50 ° C for 3 minutes, and 30 minutes at 50 ° C in N-methyl-2-pyrrolidone The immersion treatment (hereinafter referred to as NMP treatment) was carried out, and then reheating was performed at 230 ° C for 1 hour. The residual film ratio after reheating and the transmittance after reheating were measured. The residual film ratio after reheating was 95% or more, and the transmittance at 400 nm after reheating was 95% or more as ○. The case where the residual film ratio after reheating is less than 95% or the transmittance after reheating is less than 95% is taken as ×.

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

[Example 2]

A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 100 g of the polyester phthalic acid solution (A2) obtained in Synthesis Example 2 and the epoxy resin obtained in Synthesis Example 3 were placed in the flask. 150 g of solution (B1), 6 g of trimellitic anhydride, 4.8 g of 3-glycidoxypropyltrimethoxydecane, 0.50 g of IRGANOX 1010 (trade name; BASF Japan Co., Ltd.), and 160.8 g of dehydrated purified MMP Stir for 5 hours at a temperature to dissolve it evenly. Next, 0.42 g of BYK-344 (trade name, BYK-CHEMIE JAPAN K.K.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered by a membrane filter having a pore size of 0.2 μm to prepare a coating liquid.

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

[Example 3]

The coating liquid was prepared in the same manner as in Example 1 except that the epoxy resin solution (B1) was changed to the epoxy resin solution (B2).

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

[Example 4]

The coating liquid was prepared in the same manner as in Example 1 except that the epoxy resin solution (B1) was changed to the epoxy resin solution (B3).

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

[Example 5]

The coating liquid was prepared in the same manner as in Example 1 except that the epoxy resin solution (B1) was changed to the epoxy resin solution (B4).

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

[Example 6]

The coating liquid was prepared in the same manner as in Example 1 except that the epoxy resin solution (B1) was changed to the epoxy resin solution (B5).

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

[Comparative Example 1]

The coating liquid was prepared in the same manner as in Example 1 except that the epoxy resin solution (B1) was changed to the epoxy resin solution (C1).

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

[Comparative Example 2]

The coating liquid was prepared in the same manner as in Example 1 except that the epoxy resin solution (B1) was changed to the epoxy resin solution (C2).

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

[Comparative Example 3]

A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 100 g of the polyester phthalic acid solution (A1) obtained in Synthesis Example 1 was charged in the flask, and the polyfunctional weight average molecular weight was less than 3,000. Epoxy resin TECHMORE VG3101L (trade name; PRINTEC, INC.) 60 g, trimellitic anhydride 6 g, 3-glycidoxypropyl trimethoxy decane 4.8 g, IRGANOX 1010 (trade name; BASF Japan Co., Ltd.) 0.50 g 250.8 g of dehydrated and purified MMP was stirred at room temperature for 5 hours to be uniformly dissolved. Next, 0.42 g of BYK-344 (trade name, BYK-CHEMIE JAPAN K.K.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered by a membrane filter having a pore size of 0.2 μm to prepare a coating liquid.

The properties of transparency, light resistance, flatness, heat resistance, and chemical resistance were evaluated in the same manner as in Example 1. The evaluation results of these are shown in Table 7.

TECHMORE VG3101L: PRINTEC, INC.

3-GPMS: 3-glycidoxypropyltrimethoxydecane

IRGANOX1010: BASF Japan Corporation

MMP: methyl 3-methoxypropionate

BYK-344: BYK-CHEMIE JAPAN K.K.

According to the results shown in Table 7, the cured films of Examples 1 to 6 were excellent in light resistance and flatness, and further balanced in all aspects of transparency, heat resistance, and chemical resistance. On the other hand, in the comparative example 1, the cured film of the epoxy resin obtained by reacting glycidyl methacrylate with a monofunctional methacrylate has excellent light resistance and flatness, but heat resistance and chemical resistance. Poor sex. The cured film of Comparative Example 2 using an epoxy resin having a molecular weight of 50,000 or more (an epoxy resin obtained by reacting glycidyl methacrylate with a bifunctional methacrylate) was inferior in flatness. Further, the cured film of the epoxy resin of Comparative Example 3 using a polyfunctional epoxy resin having a weight average molecular weight of less than 3,000 was inferior in light resistance. As described above, all the characteristics are satisfied only in the case where an epoxy resin obtained by reacting glycidyl methacrylate with a bifunctional methacrylate (weight average molecular weight: 1,000 to 50,000) is used.

[Industrial availability]

The cured film obtained by the thermosetting resin composition of the present invention is excellent in transparency, light resistance, sputtering resistance, and the like as an optical material. From this point of view, it can be used as a color filter or an LED. A protective film of various optical materials such as a light-emitting element and a light-receiving element, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (20)

A thermosetting resin composition which is a resin composition comprising a polyester phthalic acid, an epoxy resin, and an epoxy hardener, characterized in that the polyester phthalic acid is obtained by using tetracarboxylic dianhydride, The diamine and the polyvalent hydroxy compound are obtained by reacting the essential raw material components, and by using X-molar tetracarboxylic dianhydride, Y-mole diamine, and Z-mole polyhydroxy compound, the following formula (1) And polyester phthalic acid obtained by reacting with the ratio of the relationship of the formula (2), 0.2 ≦Z/Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) / X ≦ 1.5 ...... (2) 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 with a bifunctional (meth) acrylate as an essential raw material component, relative to the polyester. The epoxy resin is 20 parts by weight to 400 parts by weight based on 100 parts by weight of the lysine, and the epoxy curing agent is 0 parts by weight to 60 parts by weight based on 100 parts by weight of the epoxy resin. The thermosetting resin composition according to claim 1, wherein the polyester proline is made of a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a monohydric alcohol. A reaction product obtained by reacting a component. The thermosetting resin composition according to claim 2, wherein the monohydric alcohol is selected from the group consisting of isopropanol, propenol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3- One or more kinds of ethyl-3-hydroxymethyl propylene oxide. The thermosetting resin composition according to any one of claims 1 to 3, wherein the polyester proline is further reacted by adding a styrene-maleic anhydride copolymer as a raw material component. And the polyester proline obtained. The thermosetting resin composition according to any one of claims 1 to 3, wherein the polyester proline has the following formula (3) and formula (4) Structural unit; Here, R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue. The thermosetting resin composition according to any one of claims 1 to 3, wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000. The thermosetting resin composition according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride is selected from 3,3',4,4'-diphenyl groups. Terpene tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene One or more types of alcohol bis (dehydrated trimellitate). The thermosetting resin composition according to any one of claims 1 to 3, wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenyl hydrazine and bis[4] One or more kinds of -(3-aminophenoxy)phenyl]anthracene. The thermosetting resin composition according to any one of claims 1 to 3, wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, and 1,4-butanediol, One or more of 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. The thermosetting resin composition according to any one of claims 1 to 3, wherein the bifunctional (meth) acrylate is selected from ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(a) One or more of acrylate and tricyclodecane dimethanol di(meth)acrylate. The thermosetting resin composition according to any one of the first aspect, wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride and hexahydrotrimellitic anhydride. The thermosetting resin composition according to claim 1, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, the diamine Is 3,3'-diaminodiphenylanthracene, the polyvalent hydroxy compound is 1,4-butanediol, and the epoxy resin is glycidyl methacrylate and 1,4-butanediol a acrylate or 1,3-butanediol dimethacrylate having a weight average molecular weight of 1,000 to 50,000, the epoxy hardener being trimellitic anhydride, and further containing methyl 3-methoxypropionate as a solvent . The thermosetting resin composition according to claim 2, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, the diamine Is 3,3'-diaminodiphenylanthracene, the polyhydric hydroxy compound is 1,4-butanediol, the monohydric alcohol is benzyl alcohol, and the epoxy resin is glycidyl methacrylate and a copolymer of 1,4-butanediol dimethacrylate or 1,3-butanediol dimethacrylate having a weight average molecular weight of 1,000 to 50,000, said epoxy hardener being trimellitic anhydride, further containing 3- Methyl methoxypropionate is used as a solvent. A cured film obtained by the thermosetting resin composition according to any one of claims 1 to 13. A color filter using a cured film as described in claim 14 of the patent application as a protective film. A liquid crystal display element using the color filter as described in claim 15 of the patent application. A solid-state photographic element using the color filter of claim 15 of the patent application. A liquid crystal display element using the cured film as described in claim 14 of the invention as a transparent insulating film formed between a TFT and a transparent electrode. A liquid crystal display element using the cured film as described in claim 14 as a transparent insulating film formed between a transparent electrode and an alignment film. An LED illuminator using a cured film as described in claim 14 of the patent application as a protective film.