TWI401278B - Thermosetting polymer composition - Google Patents

Description

Thermosetting polymer composition

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

In the manufacturing steps of components such as liquid crystal display elements, various chemical treatments such as an organic solvent, an acid, and an alkali solution are present. Further, when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Therefore, a protective film may be provided on the surface of an element such as a liquid crystal display element to prevent deterioration, damage, and deterioration. These protective films are required to have various properties that are resistant to the drug treatment or the local heat treatment in the manufacturing steps as described above. Specifically, it is required to have chemical resistance such as solvent resistance, acid resistance, and alkali resistance, water resistance, heat resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, coating property, flatness, and Light resistance, etc., which are not deteriorated after a long time. In particular, in the case where a color filter protective film is used in recent years, foreign matter characteristics are taken into consideration. Here, the term "foreign matter property" refers to a phenomenon in which foreign matter is easily changed. This phenomenon is caused by the following phenomenon: when the polymer composition is applied and dried on a substrate having foreign matter, the film thickness around the foreign matter is uneven, and as a result, the reflected light around the foreign matter is disordered. Because it looks like a larger shape than the actual foreign matter. The so-called excellent foreign matter characteristics mean that such a phenomenon is difficult to occur and the foreign matter is not obvious. The foreign matter characteristics have a large influence on the yield of the color filter.

As a protective film material having such excellent properties, a polyamine composition containing ruthenium is present (see Patent Document 1). This composition is an excellent composition having excellent solvent resistance, acid resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, coatability, and flatness, but it has poor alkali resistance and poor foreign matter characteristics. The shortcomings. Further, in recent years, it has been confirmed that the decomposition gas generated from the protective film in the heating step in the production of the liquid crystal panel lowers the display quality of the liquid crystal panel, and the protective film is required to have better heat resistance. From this point of view, the heat resistance of the ruthenium-containing lysine composition is not sufficient.

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

An object of the present invention is to provide a solution to the disadvantages of the above-mentioned composition, that is, to satisfy solvent resistance, acid resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, coating properties, flatness, and the like, and A cured film having excellent resistance to alkali or foreign matter, and further having excellent heat resistance, and a polymer composition obtained as the cured film.

The inventors of the present invention conducted various studies to solve the above problems, and as a result, it has been found that a polyester compound obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound as a first component, N-substituted horse, is cured by heat curing. The above object can be attained by the above-described object, which is a cured film obtained by using a ruthenium imine copolymer as a second component and a solvent as a polymer component of the third component, thereby completing the present invention. Here, the N-substituted maleimide copolymer of the second component is a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide and a copolymer of a monomer having an oxetane group.

The present invention has the following constitution.

A thermosetting polymer composition comprising a polyester compound, an N-substituted maleimide copolymer, and a solvent. Here, the polyester compound is a compound having a structural unit represented by the following formula (2) obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound; the N-substituted maleimide copolymer is N a copolymer of a substituted maleimide and a monomer having an oxirane group or a copolymer of an N-substituted maleimide and a monomer having an oxetane group.

R ¹ is a tetracarboxylic dianhydride residue, and R ³ is a residue of a polyvalent hydroxy compound.

2. The thermosetting polymer composition according to 1, wherein the polyester compound is a polyester-polyproline copolymer obtained by reacting using tetracarboxylic phthalic anhydride, a polyvalent hydroxy compound and a diamine. . Here, the polyester compound is a compound having a structural unit represented by the following formulas (1) and (2).

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

3. The thermosetting polymer composition according to 2, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(p-benzoate) One or more compounds; the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol And one or more compounds of 1,8-octanediol; the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium, bis[4-(3-aminophenoxy)phenyl One or more compounds of the formula.

4. The thermosetting polymer composition according to any one of 1 to 3, wherein a copolymer of N-substituted maleimide and a monomer having an oxocyclo group or N-substituted Malay The copolymer of quinone and a monomer having an oxetane group is a two-component copolymer selected from N-phenylmaleimide/glycidyl methacrylate, N-phenyl Malaya A two-component copolymer of amine/methyl methacrylate methyl glycidyl ester, a three-component copolymer of N-phenyl maleimide/glycidyl methacrylate/benzyl methacrylate, N-phenyl Malay a three-component copolymer of phthalimide/glycidyl methacrylate/n-butyl methacrylate, N-phenylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate One or more compounds of the component copolymer and the three-component copolymer of N-phenylmaleimide/glycidyl methacrylate/styrene.

5. The thermosetting polymer composition according to any one of 1 to 3, wherein a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted Malay The copolymer of a quinone imine and a monomer having an oxetane group is a two-component copolymer selected from N-cyclohexylmaleimide/glycidyl methacrylate, N-cyclohexylmalaya A two-component copolymer of amine/methyl methacrylate methyl glycidyl ester, a three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-cyclohexylmalay三Asian stock / glycidyl methacrylate / n-butyl methacrylate copolymer, N-cyclohexylmaleimide / 2-hydroxyethyl methacrylate / glycidyl methacrylate One or more compounds of the component copolymer and the three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/styrene.

6. The thermosetting polymer composition according to any one of 1 to 5, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; a polyvalent hydroxy compound Is 1,4-butanediol; the diamine is 3,3'-diaminodiphenylanthracene; a copolymer of N-substituted maleimide and a monomer having an oxirane group or N- a copolymer of substituted maleimide and a monomer having an oxetane group is a three-component copolymer of N-phenylmaleimide/n-butyl methacrylate/glycidyl methacrylate or a three-component copolymer of N-cyclohexylmaleimide/n-butyl methacrylate/glycidyl methacrylate; the solvent is methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, A solvent of one of diethylene glycol methyl ethyl ether.

7. The thermosetting polymer composition according to 1 or 2, wherein the polyester compound is a polyester-polymer obtained by reacting using a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine and a monohydric alcohol. Proline copolymer.

8. The thermosetting polymer composition according to 7, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(trimellitic acid) ester One or more compounds; a polyhydric hydroxy compound ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1, One or more compounds of 8-octanediol; the diamine is selected from the group consisting of 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene One or more compounds; the monohydric alcohol is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyl oxetane .

9. The thermosetting polymer composition according to 7 or 8, wherein a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted Malayan The copolymer of an amine and a monomer having an oxetane group is a two-component copolymer selected from N-phenylmaleimide/glycidyl methacrylate, N-phenylmaleimide/ Two-component copolymer of methyl glycidyl methacrylate, three-component copolymer of N-phenylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-phenyl Malaya Three-component copolymer of amine/glycidyl methacrylate/n-butyl methacrylate, N-phenylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of the three-component copolymer of N-phenyl maleate subunit/glycidyl methacrylate/styrene.

10. The thermosetting polymer composition according to 7 or 8, wherein a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide The copolymer with the oxetane-containing monomer is a two-component copolymer selected from N-cyclohexylmaleimide/glycidyl methacrylate, N-cyclohexylmaleimide/A Two-component copolymer of methyl glycidyl acrylate, three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-cyclohexylmaleimide Three-component copolymer of glycidyl methacrylate/n-butyl methacrylate, N-cyclohexylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of N-cyclohexylmaleimide/glycidyl methacrylate/styrene three-component copolymer.

The thermosetting polymer composition according to any one of 1 to 5, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; a polyvalent hydroxy compound Is 1,4-butanediol; diamine is 3,3'-diaminodiphenylphosphonium; monohydric alcohol is benzyl alcohol; N-substituted maleimide and monomer having oxirane Copolymer or copolymer of N-substituted maleimide and oxetane-containing monomer is N-phenylmaleimide/n-butyl methacrylate/glycidyl methacrylate a three-component copolymer or a three-component copolymer of N-cyclohexylmaleimide/n-butyl methacrylate/glycidyl methacrylate; the solvent is methyl 3-methoxypropionate, propylene glycol alone a solvent of one of methyl ether acetate and diethylene glycol methyl ether.

The thermosetting polymer composition according to any one of 1 to 11, wherein the polyester compound is produced by using a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a divalent, a monohydric alcohol, and a monoamine containing ruthenium. A polyester-polyglycolic acid copolymer obtained by the reaction.

The thermosetting polymer composition according to any one of 1 to 12, wherein the polyester-polyglycolic acid copolymer is a polyester obtained by further reacting a styrene-maleic anhydride copolymer. - Polyproline copolymer.

14. The thermosetting polymer composition according to any one of 1 to 13, further comprising an epoxy hardener.

The thermosetting polymer composition according to any one of the preceding claims, wherein the epoxy hardener is trimellitic anhydride.

The thermosetting polymer composition according to any one of 1 to 15, wherein the polyester compound has a weight average molecular weight of 1,000 to 200,000.

The thermosetting polymer composition according to any one of 1 to 16, wherein a copolymer of N-substituted maleimide and a monomer having an oxocyclo group or N-substituted Malay The copolymer of the quinoneimine and the monomer having an oxetane group has a weight average molecular weight of 3,000 to 1,000,000.

A cured film obtained by heating the thermosetting polymer composition according to any one of 1 to 17.

A color filter using a cured film as described in 18 as a protective film.

20. A liquid crystal display element using a color filter as described in 19.

A solid-state image pickup element using a color filter as described in 19.

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

A liquid crystal display element using a cured film as described in 18 as a transparent insulating film formed between a transparent electrode and an alignment film.

An LED illuminator using a cured film as described in 18 as a protective film.

The thermosetting polymer composition of the present invention has excellent foreign matter characteristics, and when used as a color filter protective film, the yield is improved. Further, the cured film obtained by heating the thermosetting polymer composition of the present invention has heat resistance, alkali resistance, acid resistance, solvent resistance, water resistance, adhesion to an underlying substrate such as glass, and transparency. The coating property and flatness are balanced and the utility is high. In particular, it can be used as a color filter protective film produced by a dyeing method, a pigment dispersion method, an electroplating method, and a printing method. Further, a protective film and a transparent insulating film which are various optical materials can be used.

[First component: polyester compound]

The polyester compound used in the present invention is a compound obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound. Specific examples of the polyester compound are polyester, polyester-polyglycolic acid copolymer. A preferred polyester compound is a polyester-polyglycolic acid copolymer. The polyester-polyglycolic acid copolymer is obtained by reacting a tetracarboxylic dianhydride, a polyvalent hydroxy compound, and a diamine.

The polyester compound used in the present invention has a structural unit represented by the formula (1) or / and (2). In the case of a polyester compound obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound, the structural unit of the formula (2) is contained. In the case of a polyester compound obtained by reacting a tetracarboxylic dianhydride, a polyvalent hydroxy compound, and a diamine, the structural unit of the formula (1) and (2) is contained.

Specific examples of the tetracarboxylic dianhydride used in the present invention include 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2,2',3,3'-diphenyl. Ketone tetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2, 2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium 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-[ Aromatic four such as bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(trimellitic acid ester) (trade name: TMEG-100, manufactured by Nippon Chemical and Chemical Co., Ltd.) An alicyclic tetracarboxylic acid such as a carboxylic acid dianhydride, a cyclobutane tetracarboxylic dianhydride, a methylcyclobutane tetracarboxylic dianhydride, a cyclopentane tetracarboxylic dianhydride, and a cyclohexane tetracarboxylic dianhydride An aliphatic tetracarboxylic dianhydride such as an anhydride, ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4, 4', which can be made into a resin having good transparency, is preferred. -diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(p-benzoate) (trade name: TMEG- 100, manufactured by New Japan Physical and Chemical (stock company), especially good 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylfluorene Carboxylic dianhydride.

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 molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, and the like. Tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5- Pentandiol, 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-decanediol, 1,10-nonanediol, 1,2,10-nonanetriol, 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, SEO-2 (trade name, manufactured by Rihua Chemical Co., Ltd.), SKY CHDM, RIKABINOL ( ) HB (the above is the trade name, manufactured by New Japan Physical and Chemical Co., Ltd.).

Preferred among these polyvalent hydroxy compounds are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8. -octanediol, SEO-2, SKY CHDM and RIKABINOL ( HB, because 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are excellent in solubility in a solvent, and therefore are particularly preferable.

Specific examples of the diamine used in the present invention include 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, and 3,4'-diaminodiyl. Phenylhydrazine, bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]indole, bis[3-(4-aminobenzene) Oxy)phenyl]indole, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]indole, [4-(3-aminophenoxy) Phenyl][3-(4-aminophenoxy)phenyl]anthracene and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and the like. Preferred among these diamines are 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene which are excellent in transparency, especially good. It is 3,3'-diaminodiphenylanthracene.

Specific examples of the monohydric alcohol used in the present invention include methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, 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, Terpineol, dimethylbenzylmethanol, ethyl lactate, glycidol, 3-ethyl-3-hydroxymethyloxetane, and the like.

Preferred among these monohydric alcohols are isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyl oxetane. Considering a polyester-polyproline copolymer formed by mixing these monohydric alcohols, a copolymer with an N-substituted maleimide and a monomer having an oxirane group, or an N-substituted maleate The compatibility of the imide with the oxetane group-containing monomer and the epoxy curing agent, or the coating property of the final product thermosetting resin composition on the color filter, More preferably, benzyl alcohol is used in the monohydric alcohol.

Specific examples of the monoamine containing ruthenium used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyldimethoxydecane. , 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutyldimethoxydecane, p-aminobenzene Trimethoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl methyl dimethoxy decane, p-aminophenyl methyl diethoxy decane, m-aminophenyl trimethoxy Decane and m-aminophenylmethyldiethoxydecane, and the like. Among these monoamines containing ruthenium, preferred are 3-aminopropyltriethoxydecane and p-aminophenyltrimethoxydecane, and the coating film of 3-aminopropyltriethoxydecane has good acid resistance, and thus Especially good.

Specific examples of the reaction solvent for obtaining the polymerization reaction of the polyester-polyglycolic acid copolymer include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and diethyl ethylene. Alcohol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, N- Methyl-2-pyrrolidone and N,N-dimethylacetamide. Preferred among these reaction solvents are propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, diethylene glycol methyl ethyl ether and N-methyl-2-pyrrolidone.

These reaction solvents may be used singly or as a mixed solvent of two or more kinds. Further, in the case of a ratio of 30% by weight or 30% by weight or less, other solvents may be used in addition to the above-mentioned reaction solvent.

The polyester compound of the present invention can be produced from tetracarboxylic dianhydride and a polyvalent hydroxy compound.

Here, a more preferred polyester compound is a polyester-polyglycolic acid copolymer. The polyester-polyglycolic acid copolymer is produced by reacting tetracarboxylic dianhydride (X mole), diamine (Y mole) and polyvalent hydroxy compound (Z mole) in the above reaction solvent. In this case, it is preferred that X, Y and Z are determined by the ratio between the following formulas (1) and (2). When it is in this range, since the solubility with respect to the polyester-polyamide copolymer of a solvent is high, the coating property of a composition improves, and the cured film which is excellent in flatness is obtained.

0.2≦Z/Y≦8.0.........(1) 0.2≦(Y+Z)/X≦5.0.........(2)

The relationship of the formula (1) is preferably 0.7≦Z/Y≦7.0, more preferably 1.0≦Z/Y≦5.0. Further, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) / X ≦ 4.0, more preferably 0.6 ≦ (Y + Z) / X ≦ 2.0.

When the polyester-polyproline copolymer used in the present invention has an acid anhydride group at the molecular terminal, the above-mentioned monohydric alcohol may be added and reacted as needed. The addition of a monohydric alcohol-polyamido acid copolymer not only improves the copolymer with N-substituted maleimine and a monomer having an oxocyclo group or N-substituted maleimide The compatibility of the copolymer of the oxetane group-containing monomer and the epoxy curing agent improves the coatability of the thermosetting resin composition of the present invention containing the same.

Further, when the monoamine containing ruthenium is reacted with a polyester-polyglycine copolymer having an acid anhydride group at the molecular terminal, the acid resistance of the obtained coating film is improved. Further, the monool and the monoamine containing ruthenium may be simultaneously reacted with the polyester-polyglycolic acid copolymer.

When 100 parts by weight or more of the reaction solvent is used per 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. It is preferred to carry out the reaction 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 preferably added. It is allowed to react at 10 to 40 ° C for 0.1 to 6 hours. Further, the monohydric alcohol can be added at any time during the reaction.

The order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound may be simultaneously added to a reaction solvent; after dissolving a diamine and a polyhydric hydroxy compound in a reaction solvent, tetracarboxylic dianhydride is added; After the reaction of the anhydride with the polyvalent hydroxy compound, the diamine is added to the copolymer; or the tetracarboxylic dianhydride is reacted with the diamine in advance, and then the polyvalent hydroxy compound is added to any of the copolymers. The polyester-polyamine copolymer obtained has a weight average molecular weight of preferably from 1,000 to 200,000, more preferably from 2,000 to 150,000. The foreign matter characteristic, the higher the molecular weight, the better; the lower the molecular weight, the better, relative to the solubility of the solvent.

In order to increase the weight average molecular weight of the polyester-polyglycine copolymer, a compound having three or more acid anhydride groups may be added for the synthesis reaction. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer.

The polyester-polyamine copolymer thus synthesized contains a structural unit composed of the above formulas (1) and (2), and the terminal is derived from a tetracarboxylic dianhydride, a diamine or a polyvalent hydroxy compound as a raw material. An acid anhydride group, an amine group or a hydroxyl group, or an additive other than these compounds constitutes the terminal. In the formulae (1) and (2), R ¹ is a tetracarboxylic dianhydride residue, 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.

[Second component: N-substituted maleimide copolymer]

The N-substituted maleimide copolymer used in the present invention can be used as long as it has good compatibility with the other components forming the thermosetting polymer composition of the present invention, and is not particularly limited. The copolymer of N-substituted maleimide and a monomer having an oxocyclo group or a monomer having an oxetanyl group, N-substituted maleimide and oxygen may be mentioned. a heterocyclic ethylenic monomer or a copolymer of an oxetane group monomer with another monomer, an N-substituted maleimide and a monomer having an oxirane group or having an oxo group a mixture of a cyclobutane monomer and a mixture of an alicyclic epoxy resin or a bisphenol A epoxy resin, or an N-substituted maleimide and a monomer having an oxirane group or A copolymer of a monomer having an oxetane group and another monomer, a mixture of an alicyclic epoxy resin or a bisphenol A epoxy resin, or the like. Among these N-substituted maleimide copolymers, a copolymer of an N-substituted maleimide and a monomer having an oxirane group is particularly preferable because of excellent transparency and foreign matter characteristics.

Specific examples of the N-substituted maleimide used in the present invention include N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide. Particularly preferred are N-phenylmaleimide and N-cyclohexylmaleimide.

Specific examples of the monomer having an oxirane group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and a 3,4-epoxy ring of (meth)acrylic acid. Hexyl methyl ester. Among these oxirane-based monomers, glycidyl methacrylate is preferred as a cured film having good foreign matter properties.

Specific examples of the monomer having an oxetane group include 3-(methacryloxymethyl)-3-ethyloxetane and 3-(acryloxymethyl). 3-ethyloxetane, 3-(methacryloxymethyl)-2-trichloromethyloxetane, 3-(methacryloxymethyl)-2 -phenyloxetane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trichloromethyloxetane Alkane, 4-acetoxystyrene and 3-ethyl-3-hydroxymethyloxetane compounds and 4-(1-ethoxyethoxy)styrene and -ethyl-3-hydroxyl A compound of oxetane.

Specific examples of the other monomer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) 2-hydroxypropyl acrylate, styrene, methyl styrene, chloromethyl styrene, and the like. Among these other monomers, methyl (meth)acrylate and benzyl (meth)acrylate which are excellent in compatibility of the obtained copolymer with the polyester-polyglycine copolymer of the present invention are more preferable. N-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and styrene.

Specific examples of the alicyclic epoxy resin or the bisphenol A epoxy resin include Epikote 807, Epikote 815, Epikote 825, Epikote 827, Epikote 828, Epikote 190P, and Epikote 191P (above trade name, oiled Shell Epoxy) (manufacturing company), Epikote 1001, Epikote 1002, Epikote 1004AF, Epikote 1256 (above trade name, Japan Epoxy Resins Co., Ltd.), araldite CY177, Araldite CY184 (above trade name, Ciba-Geigy (share company)), CELL 2021, CELL 3000 and EHPE-3150 (above trade name, DAICEL Chemical Industry (stock company) ( DAICEL CHEMICAL INDUSTRIES, LTD.)). Copolymer of N-substituted maleimide and monomer having oxirane epoxy or N-substituted maleimide and monomer having oxetanyl group used in the present invention The copolymer may be used in combination of two or more kinds. Mixing a copolymer of N-substituted maleimide having a molecular weight of less than 10,000 and a monomer having an oxirane group or N-substituted maleimide and a monomer having an oxetane group Copolymer, copolymer with N-substituted maleimide having a molecular weight of 10,000 or more and a monomer having an oxirane group or N-substituted maleimide and having an oxetane group In the case of a copolymer of a monomer, if the molecular weight is 10,000 or more, a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide has The copolymer of the oxetane monomer is a copolymer of N-substituted maleimine and a monomer having an oxirane group or N-substituted maleimide and has an oxygen It is preferred that the total amount of the copolymer of the cyclobutane monomer is 5 wt%, and the foreign matter characteristics are good.

When the ratio of the oxirane group-containing monomer to the copolymer of the other monomer is 30% by mole or more based on the oxirane group, the chemical resistance is excellent, which is preferable. More preferably, the monomer having an oxoyl group is 50 mol% or more.

The polymer of the monomer having an oxirane group, or the copolymer of the monomer having an oxirane group and another monomer, preferably having a weight average molecular weight of 3,000 to 1,000,000, more preferably It is 50,000 to 500,000. The reason for this is that the higher the molecular weight, the better the foreign matter characteristics, and the lower the molecular weight, the better the solubility to the solvent.

When the ratio of the oxetane group-containing monomer to the copolymer of the other monomer is 30% by mole or more, the oxirane group is excellent in chemical resistance. More preferably, the monomer having an oxoyl group is 50 mol% or more.

The polymer of the monomer having an oxetane group, or the copolymer of a monomer having an oxetane group and another monomer, preferably having a weight average molecular weight of 3,000 to 1,000,000, more preferably It is 50,000 to 500,000. The reason for this is that the higher the molecular weight, the better the foreign matter characteristics, and the lower the molecular weight, the better the solubility to the solvent.

[Third component: solvent]

The solvent of the polymer composition used in the present invention can be used as it is in the reaction solvent used in the polymerization reaction in the synthesis of the polyester-polyglycolic acid copolymer. Further, if necessary, after the reaction is carried out, one of the reaction solvents is partially evaporated, and a new solvent may be added. The solid content of the above thermosetting polymer composition is selected according to the film thickness of the coating film, and generally it is contained in the range of 5 to 40% by weight in the polymer composition.

The thermosetting polymer composition of the present invention has 20 to 400 parts by weight of the N-substituted maleimide copolymer with respect to 100 parts by weight of the polyester-polyglycolic acid copolymer. When the N-substituted maleimide copolymer is in this range, the balance between flatness, heat resistance, chemical resistance, adhesion, and foreign matter characteristics is good. Further, it is further preferred if the N-substituted maleimide copolymer is in the range of 50 to 200 parts by weight.

[Other ingredients]

In order to improve heat resistance and chemical resistance, it is effective to add an epoxy curing agent to the thermosetting polymer composition of the present invention. As the epoxy curing agent, for example, an acid anhydride-based curing agent, a polyamine-based curing agent, a polyphenol-based curing agent, and a catalyst-type curing agent are preferably an acid anhydride-based curing agent in view of coloring and heat resistance.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. An aromatic polycarboxylic acid anhydride such as phthalic anhydride or trimellitic anhydride, or a styrene-maleic anhydride copolymer. Among these acid anhydride-based hardeners, hexahydrotrimellitic anhydride and trimellitic anhydride are particularly preferable in view of the balance between heat resistance and solubility in a solvent.

When an epoxy hardener is added for the purpose of improving heat resistance and chemical resistance, the ratio of the N-substituted maleimide copolymer to the epoxy hardener is preferably relative to the N-substituted maleimide The oxirane group or oxetane group contained in the copolymer is added to the carboxylic anhydride group or the carboxylic acid group of the epoxy curing agent to make it 0.05 to 2 equivalents. At this time, the carboxylic anhydride group is calculated in binary. When a carboxylic anhydride group or a carboxylic acid group is added so as to be 0.1 to 1.5 times equivalent, the chemical resistance is further improved, which is more preferable.

The thermosetting polymer composition of the present invention may contain other components than those described above, as long as the object of the present invention is not impaired. As such other components, a coupling agent and a surfactant are mentioned.

The coupling agent is for improving the adhesion to the substrate, and is preferably 100 parts by weight of the solid component of the thermosetting polymer composition (the component remaining after removing the solvent from the polymer composition) Add 1 to 30 parts by weight of a coupling agent and use it.

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

Specific examples thereof include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like. A titanate such as decane-based, acetalkoxy aluminum diisopropylate or the like, and a titanate such as tetraisopropanol bis(dioctylphosphoric acid) titanate. Among these coupling agents, 3-glycidoxypropyltrimethoxysilane has a large effect of improving the adhesion, and therefore is preferable.

The surfactant is used to increase the wettability, homogenization property, or coating property of the underlayer substrate, and is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the thermosetting polymer composition. As the surfactant, a ruthenium-based surfactant, a propylene-based surfactant, a fluorine-based surfactant, or the like can be used. Specific examples include Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, and Byk-370 (above trade name, BYK-Chemie (manufactured by the company)) , Byk-354, Byk-358 and Byk-361 (above trade name, BYK-Chemie (manufactured by the company)) and other acrylic systems, DFX-18,ftergent 250 and ffergent 251 (above trade name, NEOS (stock company) system).

[Method of forming a cured film]

The thermosetting polymer composition of the present invention can be obtained by mixing a polyester compound, an N-substituted maleimide copolymer, and a solvent, and optionally adding an epoxy according to the purpose of the purpose. The hardener, coupling agent and surfactant are mixed and dissolved evenly.

When the thermosetting polymer composition prepared as described above is applied onto the surface of the substrate and the solvent is removed by heating, a coating film can be formed. The thermosetting polymer composition is applied to the surface of the substrate, and the coating film can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. The coating film is then heated (prebaked) with a hot plate or a heating furnace. The heating conditions vary depending on the type of each component and the mixing ratio, and are usually 70 to 120 ° C, 5 to 15 minutes in the case of a heating furnace, and 1 to 5 minutes in the case of a hot plate. Thereafter, in order to harden the coating film, heat treatment is 180 to 250 ° C, preferably 200 to 240 ° C for heat treatment, heat treatment for 30 to 90 minutes in the case of a heating furnace, and heat treatment for 5 to 30 minutes in the case of a heating plate. Thereby, a cured film can be obtained.

The cured film thus obtained is, when heated, 1) dehydrated and cyclized to form a quinone bond of the polyamido acid of the polyester-polyamide copolymer, and 2) a polyester-polyamide copolymer The carboxylic acid is reacted with an epoxy (oxiranyl or oxetane) of an N-substituted maleimide copolymer to be polymerized, and 3) an N-substituted maleimide copolymer Since the epoxy reacts with the epoxy curing agent and is highly polymerized, it is very tough, and is excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance.

Then, the synthesis examples, examples, and comparative examples of the present invention will be specifically described, but the present invention is not limited by these examples.

A polyester-polyaminic acid copolymer solution containing a copolymer of a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound was synthesized as follows.

Here, the viscosity shown below was measured at 25 ° C using an E-type viscometer (trade name: VISCONIC END, manufactured by Tokyo Instruments Co., Ltd.).

(Synthesis Example 1)

After replacing the 500 ml flask equipped with a thermometer and a stirring blade with nitrogen, 92.99 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as "ODPA"), 27.01 was charged. g of 1,4-butanediol and 280 g of dehydrated purified methyl 3-methoxypropionate (hereinafter referred to as "MMP"), heated to 130 ° C in an oil bath, and stirred for 4 hours, Cooling, thereby obtaining a 30% solution of a pale yellow transparent polyester compound. The viscosity of the solution is 65 mPa. s. The weight average molecular weight was 7,600 as determined by GPC.

(Synthesis Example 2)

The 500 ml flask equipped with a thermometer and a stirring blade was replaced with nitrogen, and then charged with 13.03 g of 3,3'-diaminodiphenyl hydrazine (hereinafter referred to as "DDS") and 14.19 g of 1,4-. After the butanediol, 280 g of the dehydrated MMP was charged, and the mixture was stirred at room temperature to dissolve DDS and 1,4-butanediol. Thereafter, 81.42 g of ODPA and 11.35 g of benzyl alcohol were charged. The mixture was heated to 130 ° C in an oil bath, stirred for 4 hours, and then cooled to 30 ° C to obtain a 30% solution of a pale yellow transparent polyester-polyamine copolymer. The viscosity of the solution is 20 mPa. s. The weight average molecular weight was 3,400 as determined by GPC.

(Synthesis Example 3)

After replacing the 500 ml flask equipped with a thermometer and a stirring blade with nitrogen, 81.42 g of ODPA, 14.19 g of 1,4-butanediol, and 11.35 g of benzyl alcohol were charged, and then 217.18 g of dehydrated refined MMP was charged. The mixture was heated to 130 ° C in an oil bath and stirred for 2 hours. Then, it was cooled to 30 ° C, and 13.03 g of DDS and 62.82 g of dehydrated MMP were charged, and stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C in an oil bath, and after stirring for 1 hour, it was cooled to 30 ° C to obtain a 30% solution of a pale yellow transparent polyester-polyamide copolymer. The viscosity of the solution is 27 mPa. s. The weight average molecular weight was 4,000 as determined by GPC.

(Synthesis Example 4)

A 500 ml flask equipped with a thermometer and a stirring blade was replaced with nitrogen, and then charged with 16.95 ODPA and 51.55 g of a styrene-maleic anhydride copolymer (styrene/maleic anhydride = 1/1 (mole ratio). After the weight average molecular weight of 1,800), 3.28 g of 1,4-butanediol, and 19.70 g of benzyl alcohol, 137.22 g of dehydrated refined propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was added to the oil. The bath was warmed to 130 ° C and stirred for 2 hours. Then, the mixture was cooled to 30 ° C, and 4.523 g of DDS and 86.78 g of dehydrated purified PGMEA were charged, and the mixture was stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C in an oil bath and stirred for 1 hour, and then cooled to 30 ° C to obtain a 30% solution of a pale yellow transparent polyester-polyamide copolymer. The viscosity of the solution is 36 mPa. s. The weight average molecular weight was 48,000 as determined by GPC.

[Example 1]

After replacing the 1,000 ml flask with the stirring blade with nitrogen, the flask was charged with 250 g of the polyester compound solution obtained in Synthesis Example 1, and 75 g of N-phenylmaleimide/ Glycidyl methacrylate copolymer (mole ratio 30:70, weight average molecular weight 80,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane and 0.95 g of Byk-344 ( Trade name: BYK-Chemie (manufactured by the company), 518 g of dehydrated MMP, and stirred at room temperature for 5 hours to be uniformly dissolved. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution (hereinafter referred to as a coating liquid). Then, the coating liquid was spin-coated on the glass substrate at 600 rpm for 10 seconds, and then prebaked on a hot plate which had been warmed to 80 ° C for 2 minutes to form a coating film. Thereafter, the coating film was cured by heating in an oven which had been warmed to 230 ° C for 40 minutes to obtain a cured film having a film thickness of 1.5 μm. The cured film obtained in this manner was evaluated for foreign material properties, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, transparency, and flatness characteristics. The results of these evaluations are shown in Table 1.

[Evaluation method]

Foreign matter characteristics: A chromium substrate was placed on a diffuser of a glass bead spacer, and a glass bead spacer having a diameter of 20 μm was spread so as to have a ratio of 3 to 5 pieces/cm ² . The coating liquid was spin-coated on the substrate at 600 rpm for 10 seconds, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a coating film. Thereafter, the film was cured by heating at 220 ° C for 30 minutes in an oven to obtain a cured film having a film thickness of 1.5 μm. The surface of the cured film was observed at 50 times using a differential interference type microscope (trade name: AFX-IIA, manufactured by Nikon Co., Ltd.), and the diameter of the film protruding portion around the glass bead spacer was measured. The unit is μm.

Heat resistance: After the obtained glass substrate with a cured film was further heated at 250 ° C for 1 hour, the residual film ratio after heating with respect to the film thickness before heating and the transmittance at 400 nm after heating were measured.

The residual film rate after heating is 99% or more, and the case where the transmittance at 400 nm after heating is 99% or more is referred to as "A+"; the transmittance of less than 99% and 98% or more is recorded as "A". When the transmittance is less than 98%, it is recorded as "B". Further, the residual film rate after heating was 97% or more, and the case where the transmittance at 400 nm after heating was 98% or more was recorded as "A", and the transmittance was less than 98% as "B". Further, when the residual film ratio after heating is less than 97%, it is referred to as "B".

Alkali resistance: The obtained glass substrate with a cured film was immersed in a 5% sodium hydroxide aqueous solution at 30 ° C for 30 minutes (hereinafter, abbreviated as NaOH treatment), and then measured with respect to the film thickness before the treatment. Residual film rate after treatment and transmittance before and after treatment. The residual film ratio after the treatment was 95% or more, and the case where the transmittance at 400 nm after the treatment was 99% or more was referred to as "A". The residual film ratio after the treatment was less than 95%, or the case where the transmittance after the treatment was less than 99% was referred to as "B".

Acid resistance: The obtained glass substrate with a cured film was subjected to immersion treatment at 50 ° C for 15 minutes in a mixed solution (weight ratio) containing 36% hydrochloric acid / 60% nitric acid / water = 40 / 20 / 40 ( Hereinafter, after simply referred to as mixed acid treatment, the residual film ratio after the treatment with respect to the film thickness before the treatment and the transmittance before and after the treatment were measured. The residual film ratio after the treatment was 95% or more, and the case where the transmittance at 400 nm after the treatment was 99% or more was referred to as "A". The residual film ratio after the treatment was less than 95%, or the case where the transmittance after the treatment was less than 99% was referred to as "B".

Solvent resistance: The obtained glass substrate with a cured film was immersed in N-methyl-2-pyrrolidone at 40 ° C for 30 minutes (hereinafter, abbreviated as NMP treatment), and then measured and treated. The residual film ratio after the treatment of the front film thickness and the transmittance before and after the treatment. The residual film ratio after the treatment was 95% or more, and the case where the transmittance at 400 nm after the treatment was 99% or more was referred to as "A". The residual film ratio after the treatment was less than 95%, or the case where the transmittance after the treatment was less than 99% was referred to as "B".

Adhesion: The obtained glass substrate with a cured film was subjected to a 24-hour pressure cooker test (hereinafter, abbreviated as PCT treatment) at 120 ° C, 100%, and 0.2 MPa, and the cured film was peeled off by a tape. The square test (JIS-K-5400) and counted the remaining number. When the residual number /100 is 100/100, it is marked as "A", and when it is less than or equal to 99/100, it is recorded as "B".

Sputter resistance: In the obtained glass substrate with a cured film, in order to obtain a resistance value of 10 Ω/cm ² , when the ITO film is formed on the cured film by sputtering at 240 ° C, the presence or absence of the film is checked. Wrinkles are produced. In the case of no wrinkles, it is referred to as "A", and the case where wrinkles are generated is referred to as "B".

Transparency: In the obtained glass substrate with a cured film, the spectrophotometer (trade name: MICRO COLOR ANALYZER TC-1800M, manufactured by Tokyo Electrochrome Technology Center Co., Ltd.) was used to measure only the light wavelength of the cured film at 400 nm. Transmittance. When the transmittance is 99% or more, it is marked as "A", and when it is less than 99%, it is recorded as "B".

Flatness: The coating liquid was spin-coated on a glass substrate at 600 rpm for 10 seconds, and then placed in a vacuum dryer and dried under vacuum at 666.6 Pascal for 2 minutes. The surface of the dried film on the glass substrate thus obtained was observed at 50 times using a differential interference type microscope (trade name; AFX-IIA, manufactured by Nikon Co., Ltd.), and the surface was smoothed as "A", and it was observed. When the surface is uneven, it is marked as "B".

[Embodiment 2]

After replacing the 1,000 ml flask with the stirring blade with nitrogen, the flask was charged with 250 g of the polyester-polyproline copolymer solution obtained in Synthesis Example 2, and 75 g of N-phenyl group. Maleidin/glycidyl methacrylate copolymer (mole ratio 30:70, weight average molecular weight 80,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane and 0.95 Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.) and 518 g of dehydrated MMP were stirred at room temperature for 5 hours to be uniformly dissolved. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.

[Example 3]

After replacing a 1,000 ml flask equipped with a stirring blade with nitrogen, the flask was charged with 250 g of a polyester-polyproline copolymer solution obtained in Synthesis Example 3, and 75 g of N-benzene. Kamalimide/glycidyl methacrylate copolymer (mol ratio 30:70, weight average molecular weight 80,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxydecane and 0.95 Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.) and 518 g of dehydrated MMP were stirred at room temperature for 5 hours to be uniformly dissolved. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.

[Example 4]

After replacing a 1,000 ml flask equipped with a stirring blade with nitrogen, the flask was charged with 250 g of a polyester-polyproline copolymer solution obtained in Synthesis Example 3, and 75 g of N-benzene. Kamalimide imine/n-butyl methacrylate/glycidyl methacrylate copolymer (mol ratio 30:10:60, weight average molecular weight 40,000), 15 g of trimellitic anhydride, 8.25 g of 3-shrinkage Glyceroxypropyltrimethoxysilane and 0.95 g of Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.), 318 g of dehydrated PGMEA, and 200 g of dehydrated diethylene glycol methyl ether. Stir at room temperature for 5 hours and dissolve evenly. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.

(Comparative Example 1)

The 500 ml separable flask with the stirring blade was replaced with nitrogen, and after charging 4.85 g of DDS and 43.22 g of 3-aminopropyltriethoxysilane, 197 g of dehydrated refined MMP was charged into the chamber. Stirring was carried out under temperature to dissolve DDS and 3-aminopropyltriethoxydecane. Thereafter, the flask was cooled in an ice bath, and when the temperature of the content liquid was 10 ° C, 36.36 g of ODPA was charged. After the temperature rise caused by the exothermic reaction was stopped, the ice bath was removed and stirred at room temperature for 8 hours to obtain a pale yellow transparent ruthenium-containing lysine solution. The viscosity of the solution is 12 mPa. s.

100 g of the above-mentioned hydrazine-containing polyaminic acid solution and 30 g of Epikote 191P (trade name; manufactured by Oiled Shell Epoxy Co., Ltd.) were placed in a 500 ml separable flask equipped with a stirring blade. 16.95 g of trimellitic anhydride, 3.85 g of 3-glycidoxypropyltrimethoxydecane and 172.4 g of dehydrated refined MMP were stirred at room temperature to uniformly dissolve. Then, 0.17 g of Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition. Solution. Then, the cured film obtained by the same method as in Example 1 was subjected to comparative evaluation of foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and transparency. Sexuality and flatness characteristics. The results of these evaluations are shown in Table 1.

(Comparative Example 2)

A 1,000 ml flask equipped with a stirring blade was replaced with nitrogen, and 250 g of the polyester compound solution obtained in Synthesis Example 1 and 75 g of benzyl methacrylate/methacrylic acid glycidyl glycol copolymer were charged into the flask. (mole ratio 30:70, weight average molecular weight 100,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxydecane, 0.95 g of Byk-344 (trade name; Byk-Chemie ( The joint-stock company) and 518 g of dehydrated MMP were stirred at room temperature for 5 hours to be uniformly dissolved. The membrane was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.

(Comparative Example 3)

A 1,000 ml flask equipped with a stirring blade was replaced with nitrogen, and 250 g of the polyester-polyproline copolymer solution obtained in Synthesis Example 2, 75 g of benzyl methacrylate/methacrylic acid was placed in the flask. Glycidyl ester copolymer (mole ratio 30:70, weight average molecular weight 100,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane, 0.95 g of Byk-344 (trade name; Byk-Chemie (manufactured by the company) and 518 g of dehydrated MMP, and stirred at room temperature for 5 hours to be uniformly dissolved. The membrane was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.

(Comparative Example 4)

A 1,000 ml flask equipped with a stirring blade was replaced with nitrogen, and 250 g of the polyester-polyproline copolymer solution obtained in Synthesis Example 3, 75 g of benzyl methacrylate/methyl group was placed in the flask. Glycidyl acrylate copolymer (mole ratio 30:70, weight average molecular weight 100,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane, 0.95 g of Byk-344 (trade name) ; Byk-Chemie (manufactured by the company) and 518 g of dehydrated MMP, stirred at room temperature for 5 hours to dissolve evenly. The membrane was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.

As shown in the results of Table 1, the cured films obtained from the thermosetting polymer compositions having N-phenylmaleimide/glycidyl methacrylate copolymers of Examples 1 to 4 are known. The foreign matter has good properties and is excellent in heat resistance. It is expected that the cured film obtained from the ruthenium-containing phthalic acid composition of Comparative Example 1 (refer to Patent Document 1) has poor foreign matter characteristics or alkali resistance, and is used as a color filter protective film. low. It is also conceivable that the cured films obtained from the thermosetting polymer compositions using benzyl methacrylate/glycidyl methacrylate copolymer of Comparative Examples 2 to 4 are inferior in heat resistance as compared with the examples. And does not function as a color filter protective film.

The cured film obtained from the thermosetting polymer composition of the present invention is excellent in foreign matter characteristics and heat resistance, and is excellent in characteristics such as sputter resistance and transparency. A protective film of various optical materials such as a filter, an LED 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 (24)

A thermosetting polymer composition comprising a polyester compound, an N-substituted maleimide copolymer, and a solvent; wherein the polyester compound is obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound with the following a compound of the structural unit represented by the formula (2); the N-substituted maleimide copolymer is a copolymer of an N-substituted maleimide and a monomer having an oxirane group or an N-substituted horse a copolymer of a quinone imine and a monomer having an oxetane group, R ¹ is a tetracarboxylic dianhydride residue, and R ³ is a residue of a polyvalent hydroxy compound. The thermosetting polymer composition according to claim 1, wherein the polyester compound is a polyester-polylysine obtained by reacting using a tetracarboxylic dianhydride, a polyvalent hydroxy compound, and a diamine. a copolymer; a polyester compound is a compound having a structural unit represented by the following formulas (1) and (2), R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a residue of a polyvalent hydroxy compound. The thermosetting polymer composition according to claim 2, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(trimellitic acid ester) One or more compounds; the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-g a compound of one or more of a diol and 1,8-octanediol; the diamine is selected from the group consisting of 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy) One or more compounds of phenyl]anthracene. The thermosetting polymer composition according to claim 2, wherein the copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide The copolymer with the oxetane-containing monomer is a two-component copolymer selected from N-phenylmaleimide/glycidyl methacrylate, N-phenylmaleimide/A a two-component copolymer of methyl glycidyl acrylate, a three-component copolymer of N-phenylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-phenylmaleimide Three-component copolymer of glycidyl methacrylate/n-butyl methacrylate, N-phenylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of N-phenylmaleimide/glycidyl methacrylate/styrene three-component copolymer. The thermosetting polymer composition according to claim 2, wherein the copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide The copolymer with the oxetane-containing monomer is a two-component copolymer selected from N-cyclohexylmaleimide/glycidyl methacrylate, N-cyclohexylmaleimide/A Two-component copolymer of methyl glycidyl acrylate, three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-cyclohexylmaleimide Three-component copolymer of glycidyl methacrylate/n-butyl methacrylate, N-cyclohexylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of N-cyclohexylmaleimide/glycidyl methacrylate/styrene three-component copolymer. The thermosetting polymer composition according to claim 2, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; the polyvalent hydroxy compound is 1, 4-butanediol; diamine is 3,3'-diaminodiphenylphosphonium; copolymer of N-substituted maleimide with a monomer having an oxocyclo group or N-substituted Malay The copolymer of a quinone imine and a monomer having an oxetane group is a three-component copolymer of N-phenylmaleimide/n-butyl methacrylate/glycidyl methacrylate or an N-ring. a three-component copolymer of hexamyl imine/n-butyl methacrylate/glycidyl methacrylate; the solvent is methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, and diethyl phthalate a solvent of one of the alcohol methyl ethers. The thermosetting polymer composition according to claim 2, wherein the polyester compound is a polyester-polymer obtained by reacting using a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine, and a monohydric alcohol. Proline copolymer. The thermosetting polymer composition according to claim 7, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(trimellitic acid) ester One or more compounds; the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-g a compound of one or more of a diol and 1,8-octanediol; the diamine is selected from the group consisting of 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy) One or more compounds of phenyl]anthracene; the monohydric alcohol is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyl Oxetane. The thermosetting polymer composition according to claim 7, wherein the copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide The copolymer with the oxetane-containing monomer is a two-component copolymer selected from N-phenylmaleimide/glycidyl methacrylate, N-phenylmaleimide/A a two-component copolymer of methyl glycidyl acrylate, a three-component copolymer of N-phenylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-phenylmaleimide Three-component copolymer of glycidyl methacrylate/n-butyl methacrylate, N-phenylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of N-phenylmaleimide/glycidyl methacrylate/styrene three-component copolymer. The thermosetting polymer composition according to claim 7, wherein the copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide The copolymer with the oxetane-containing monomer is a two-component copolymer selected from N-cyclohexylmaleimide/glycidyl methacrylate, N-cyclohexylmaleimide/A Two-component copolymer of methyl glycidyl acrylate, three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-cyclohexylmaleimide Three-component copolymer of glycidyl methacrylate/n-butyl methacrylate, N-cyclohexylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of N-cyclohexylmaleimide/glycidyl methacrylate/styrene three-component copolymer. The thermosetting polymer composition according to claim 7, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; the polyvalent hydroxy compound is 1, 4-butanediol; diamine is 3,3'-diaminodiphenylanthracene; monohydric alcohol is benzyl alcohol; copolymer of N-substituted maleimide and monomer having oxirane group Or the copolymer of N-substituted maleimide and a monomer having an oxetane group is a three component of N-phenylmaleimide/n-butyl methacrylate/glycidyl methacrylate. a copolymer or a three-component copolymer of N-cyclohexylmaleimide/n-butyl methacrylate/glycidyl methacrylate; the solvent is methyl 3-methoxypropionate, propylene glycol monomethyl ether a solvent of one of an acid ester and diethylene glycol methyl ethyl ether. The thermosetting polymer composition according to claim 7, wherein the polyester compound is reacted by using a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine, a monohydric alcohol, and a monoamine containing ruthenium. A polyester-polyamide copolymer obtained. The thermosetting polymer composition according to any one of claims 2 to 12, wherein the polyester-polyglycolic acid copolymer is further subjected to a styrene-maleic anhydride copolymer. The polyester-polyproline copolymer obtained by the reaction. The thermosetting polymer composition according to any one of claims 1 to 12, further comprising an epoxy hardener. The thermosetting polymer composition according to claim 14, wherein the epoxy hardener is trimellitic anhydride. The thermosetting polymer composition according to any one of claims 1 to 12, wherein the polyester compound has a weight average molecular weight of 1,000 to 200,000. The thermosetting polymer composition according to any one of claims 1 to 12, wherein the copolymer of the N-substituted maleimide and the monomer having an oxirane group Alternatively, the copolymer of the N-substituted maleimide and the oxetane-containing monomer may have a weight average molecular weight of 3,000 to 1,000,000. A cured film obtained by heating the thermosetting polymer composition according to any one of claims 1 to 17. A color filter using a cured film as described in claim 18 of the patent application as a protective film. A liquid crystal display element using the color filter as described in claim 19 of the patent application. A solid-state image pickup element using the color filter described in claim 19 of the patent application. A liquid crystal display element using the cured film as described in claim 18 of the patent application as a transparent insulating film formed between the TFT and the transparent electrode. A liquid crystal display element using the cured film as described in claim 18 of the patent application as a transparent insulating film formed between the transparent electrode and the alignment film. An LED illuminator using a cured film as described in claim 18 of the patent application as a protective film.