JP4779670B2 - Thermosetting polymer composition - Google Patents

Description

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

  In a manufacturing process of an element such as a liquid crystal display element, various chemical treatments such as an organic solvent, an acid, and an alkaline solution are performed. Further, when the wiring electrode is formed by sputtering, the surface may be locally heated to a high temperature. Therefore, a surface protective film may be provided on the surface of an element such as a liquid crystal display element for the purpose of preventing deterioration, damage, or alteration. These protective films are required to have various characteristics that can withstand the chemical treatment and local heat treatment in the manufacturing process as described above. Specifically, chemical resistance such as solvent resistance, acid resistance, and alkali resistance, water resistance, heat resistance, adhesion to underlying substrates such as glass, transparency, scratch resistance, coatability, flatness, long-term Light resistance or the like is required so as not to change coloration or the like. In particular, when used as a color filter protective film in recent years, foreign matter characteristics have come to be regarded as important. The term “foreign matter characteristics” as used herein refers to a phenomenon in which foreign matters are easily noticeable. This is because when the polymer composition is applied to a substrate on which foreign matter is present and dried, the film thickness around the foreign matter is disturbed. As a result, the reflected light around the foreign matter is disturbed and is larger than the actual size of the foreign matter. This is a phenomenon that occurs because the shape is visually observed. “Excellent foreign material properties” means that such a phenomenon is unlikely to occur and foreign materials are not conspicuous. The foreign matter characteristics greatly affect the yield at the time of manufacturing the color filter.

As a protective film material excellent in these characteristics, there is a silicon-containing polyamic acid composition (see Patent Document 1). This composition is an excellent composition excellent in solvent resistance, acid resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, coatability, and flatness. There is a disadvantage of being inferior. Furthermore, in recent years, it has been found that the decomposition gas generated from the protective film during the heating process at the time of manufacturing the liquid crystal panel deteriorates the display quality of the liquid crystal panel, and further heat resistance is required for the protective film. From this point of view, the silicon-containing polyamic acid composition did not have sufficient heat resistance.
JP-A-9-291150

  The object of the present invention is to solve the drawbacks of the above-mentioned composition, and have characteristics such as solvent resistance, acid resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, coatability, and flatness. An object of the present invention is to provide a cured film that is excellent in alkali resistance and foreign matter characteristics and is excellent in heat resistance, and a polymer composition that provides the cured film while being satisfied.

As a result of various studies to solve the above problems, the present inventors have found that a polyester compound obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound as the first component, and an N-substituted maleimide as the second component It has been found that the above object can be achieved by a cured film obtained by heat-curing a copolymer composition containing a copolymer and a solvent as the third component, and the present invention has been completed. Here, the N-substituted maleimide copolymer of the second component is a copolymer of a monomer having N-substituted maleimide and oxiranyl, or a copolymer of a monomer having N-substituted maleimide and oxetanyl.
The present invention has the following configuration.

Ｒ^１はテトラカルボン酸二無水物残基であり、Ｒ^３は多価ヒドロキシ化合物残基である。 1. A thermosetting polymer composition comprising a polyester compound, an N-substituted maleimide copolymer and a solvent. Here, the polyester compound is obtained by reacting with tetracarboxylic dianhydride and a polyvalent hydroxy compound, and is a compound having a structural unit represented by the following formula (2). The N-substituted maleimide copolymer is N -A copolymer of a monomer having a substituted maleimide and oxiranyl or a copolymer of a monomer having an N-substituted maleimide and oxetanyl.

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

Ｒ^１はテトラカルボン酸二無水物残基であり、Ｒ^２はジアミン残基であり、Ｒ^３は多価ヒドロキシ化合物残基である。 2. Item 2. The thermosetting polymer according to item 1, wherein the polyester compound is a polyester-polyamic acid copolymer obtained by reacting with a tetracarboxylic dianhydride, a polyvalent hydroxy compound, and a diamine. Composition. Here, the polyester compound is a compound having structural units 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 polyvalent hydroxy compound residue.

3. Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- (bis (3,4-dicarboxyphenyl)) one or more compounds selected from hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate), wherein the polyvalent hydroxy compound is ethylene glycol, propylene glycol, One or more compounds selected from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol; Selected from 3'-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone The thermosetting polymer composition according to claim 2 is one or more compounds.

4). Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a two-component copolymer of N-phenylmaleimide / glycidyl methacrylate, N-phenylmaleimide / methylglycidyl methacrylate Two-component copolymer, N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate three-component copolymer, N-phenylmaleimide / glycidyl methacrylate / n-butyl methacrylate three-component copolymer, N-phenylmaleimide / 2-hydroxy Claims 1 to 3 which are one or more compounds selected from a three-component copolymer of ethyl methacrylate / glycidyl methacrylate and a three-component copolymer of N-phenylmaleimide / glycidyl methacrylate / styrene The thermosetting polymer composition according to any one.

5. Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a binary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate, N-cyclohexylmaleimide / methylglycidyl methacrylate Two-component copolymer, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / benzyl methacrylate, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / n-butyl methacrylate, N-cyclohexylmaleimide / 2-hydroxy Selection from ternary copolymer of ethyl methacrylate / glycidyl methacrylate and ternary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / styrene The thermosetting polymer composition according to any one of claim 1 to 3 is one or more compounds.

6). The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the polyvalent hydroxy compound is 1,4-butanediol, and the diamine is 3,3′-diaminodiphenyl. Three-component copolymer of N-phenylmaleimide / n-butylmethacrylate / glycidylmethacrylate, which is a sulfone copolymer of a monomer having N-substituted maleimide and oxiranyl, or a copolymer of a monomer having N-substituted maleimide and oxetanyl Or a ternary copolymer of N-cyclohexylmaleimide / n-butyl methacrylate / glycidyl methacrylate, and the solvent is any one of methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, and diethylene glycol methyl ethyl ether. The thermosetting polymer composition according to any one of claims 1 to 5 is a solvent containing.

7). Item 3. The thermosetting polymer according to item 1 or 2, wherein the polyester compound is a polyester-polyamic acid copolymer obtained by reacting with a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine, and a monohydric alcohol. Composition.

8). Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- (bis (3,4-dicarboxyphenyl)) one or more compounds selected from hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate), wherein the polyvalent hydroxy compound is ethylene glycol, propylene glycol, One or more compounds selected from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol; Selected from 3'-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone Item 8. The thermosetting of Item 7, wherein the monohydric alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyloxetane. Polymer composition.

9. Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a two-component copolymer of N-phenylmaleimide / glycidyl methacrylate, N-phenylmaleimide / methylglycidyl methacrylate Two-component copolymer, N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate three-component copolymer, N-phenylmaleimide / glycidyl methacrylate / n-butyl methacrylate three-component copolymer, N-phenylmaleimide / 2-hydroxy Item 7 which is one or more compounds selected from a ternary copolymer of ethyl methacrylate / glycidyl methacrylate and a ternary copolymer of N-phenylmaleimide / glycidyl methacrylate / styrene The thermosetting polymer composition according to 8.

10. Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a binary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate, N-cyclohexylmaleimide / methylglycidyl methacrylate Two-component copolymer, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / benzyl methacrylate, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / n-butyl methacrylate, N-cyclohexylmaleimide / 2-hydroxy Selection from ternary copolymer of ethyl methacrylate / glycidyl methacrylate and ternary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / styrene The thermosetting polymer composition according to claim 7 or 8 is one or more compounds.

11. The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the polyvalent hydroxy compound is 1,4-butanediol, and the diamine is 3,3′-diaminodiphenyl. N-phenylmaleimide / n-butyl methacrylate, which is a sulfone, a monohydric alcohol is benzyl alcohol, and a copolymer of a monomer having N-substituted maleimide and oxiranyl or a monomer having N-substituted maleimide and oxetanyl / Glycidyl methacrylate ternary copolymer or N-cyclohexylmaleimide / n-butyl methacrylate / glycidyl methacrylate ternary copolymer, solvent is methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, diethylene The thermosetting polymer composition according to any one of claims 1 to 5 is a solvent containing any one of the recall methyl ethyl ether.

12 Any one of Items 1 to 11 in which the polyester compound is a polyester-polyamic acid copolymer obtained by reacting a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine, a monohydric alcohol, and a silicon-containing monoamine. The thermosetting polymer composition according to item.

13. Item 13. The thermosetting polymer according to any one of Items 1 to 12, wherein the polyester-polyamic acid copolymer is a polyester-polyamic acid copolymer obtained by further reacting with a styrene-maleic anhydride copolymer. Combined composition.

14 Item 14. The thermosetting polymer composition according to any one of items 1 to 13, further comprising an epoxy curing agent.

15. Item 15. The thermosetting polymer composition according to any one of Items 14 to 14, wherein the epoxy curing agent is trimellitic anhydride.

16. Item 16. The thermosetting polymer composition according to any one of Items 1 to 15, wherein the polyester compound has a weight average molecular weight of 1,000 to 200,000.

17. Any one of Items 1 to 16 wherein the weight average molecular weight of the copolymer of the monomer having N-substituted maleimide and oxiranyl or the copolymer of the monomer having N-substituted maleimide and oxetanyl is 3,000 to 1,000,000. The thermosetting polymer composition according to one item.

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

19. Item 21. A color filter using the cured film according to Item 18 as a protective film.

20. Item 20. A liquid crystal display device using the color filter according to Item 19.

21. Item 20. A solid-state imaging device using the color filter according to Item 19.

22. Item 19. A liquid crystal display device using the cured film according to Item 18 as a transparent insulating film formed between a TFT and a transparent electrode.

23. Item 19. A liquid crystal display device using the cured film according to Item 18 as a transparent insulating film formed between the transparent electrode and the alignment film.

24. Item 20. An LED light emitter using the cured film according to Item 18 as a protective film.

  The thermosetting polymer composition of the present invention is excellent in foreign matter characteristics, and the yield is improved when used as a color filter protective film. 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. Is well-balanced in terms of properties, coating properties, and flatness, and is very practical. In particular, it is useful as a protective film for a color filter produced by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

[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 and polyester-polyamic acid copolymer. A preferred polyester compound is a polyester-polyamic acid copolymer. The polyester-polyamic 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 general formula (1) or / and (2). In the case of a polyester compound obtained by reacting tetracarboxylic dianhydride and a polyvalent hydroxy compound, it has a structural unit of the general formula (2). In the case of a polyester compound obtained by reacting tetracarboxylic dianhydride, a polyvalent hydroxy compound and a diamine, it has structural units of general formulas (1) and (2).

  Specific examples of the tetracarboxylic dianhydride used in the present invention include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride and 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride. Anhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2,2 ′ , 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoro Professional Dianhydrides, aromatic tetracarboxylic dianhydrides such as ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.), cyclobutane tetracarboxylic dianhydride , Cycloaliphatic tetracarboxylic dianhydrides such as methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride, and ethanetetracarboxylic dianhydride and butane Mention may be made of aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides.

  Among these, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride give resins having good transparency Product, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.) 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride are particularly preferable.

  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, 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-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-nonanediol, 1 , 9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecane Diol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine, and triethanolamine, SEO-2 (trade name, Nikka Chemical Co., Ltd.), SKY CHDM, Rikabinol HB Name, manufactured by New Japan Chemical Co., Ltd.), and the like.

  Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, SEO-2, SKY CHDM , And Ricabinol HB are preferred, and 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are particularly preferred because of their good solubility in solvents.

  Specific examples of the diamine used in the present invention include 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, and bis [4- (4-aminophenoxy) phenyl. ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) ) Phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, etc. Can be mentioned. Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone that give a resin having good transparency are preferable, and 3,3′-diaminodiphenylsulfone is particularly preferable.

  Specific examples of the monohydric alcohol used in the present invention include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, 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, dimethylbenzyl carbinol, ethyl lactate, glycidol 3-ethyl-3-hydroxymethyloxy Mention may be made of the Tan and the like.

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are preferable. When a polyester-polyamic acid copolymer formed using these, a copolymer of a monomer having N-substituted maleimide and oxiranyl, or a copolymer of a monomer having N-substituted maleimide and oxetanyl and an epoxy curing agent are mixed In view of the compatibility of the above and the applicability of the thermosetting resin composition, which is the final product, on the color filter, it is more preferable to use benzyl alcohol as the monohydric alcohol.

  Specific examples of the silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-amino. Butyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenyl Mention may be made of methyldiethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylmethyldiethoxysilane and the like. Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane are preferable, and 3-aminopropyltriethoxysilane is particularly preferable because of good acid resistance of the coating film.

Specific examples of the reaction solvent used in the polymerization reaction for obtaining the polyester-polyamic acid copolymer include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol. Examples thereof include monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, diethylene glycol methyl ethyl ether, and N-methyl-2-pyrrolidone are preferable.
These reaction solvents can be used alone or as a mixture of two or more. Moreover, if it is a ratio of 30 weight% or less, in addition to the said reaction solvent, another solvent can also be mixed and used.

The polyester compound used in the present invention can be produced from a tetracarboxylic dianhydride and a polyvalent hydroxy compound.
Here, a more preferable polyester compound is a polyester-polyamic acid copolymer. In the method for producing a polyester-polyamic acid copolymer, tetracarboxylic dianhydride (X mol), diamine (Y mol), and polyvalent hydroxy compound (Z mol) are reacted in the reaction solvent. At this time, it is preferable that X, Y, and Z are determined at such a ratio that the relationship of the following formulas (1) and (2) is established. If it is this range, the solubility of the polyester-polyamic acid copolymer with respect to a solvent is high, therefore the applicability | paintability of a composition improves, As a result, the cured film excellent in flatness can be 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, and more preferably 1.0 ≦ Z / Y ≦ 5.0. Further, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) /X≦4.0, and more preferably 0.6 ≦ (Y + Z) /X≦2.0.

  When the polyester-polyamic acid copolymer used in the present invention has an acid anhydride group at the molecular end, the above-described monohydric alcohol can be added and reacted as necessary. A polyester-polyamic acid copolymer to which a monohydric alcohol has been added is a copolymer of a monomer having N-substituted maleimide and oxiranyl or a copolymer of a monomer having N-substituted maleimide and oxetanyl and an epoxy curing agent. While solubility is improved, the applicability | paintability of the thermosetting resin composition of this invention containing them is improved.

  Moreover, when the silicon-containing monoamine described above is reacted with a polyester-polyamic acid copolymer having an acid anhydride group at the molecular end, the acid resistance of the obtained coating film is improved. Furthermore, the monohydric alcohol and the silicon-containing monoamine can be simultaneously reacted with the polyester-polyamic acid copolymer.

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

  The order of adding the reaction raw materials to the reaction system is not particularly particular. That is, a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound are simultaneously added to the reaction solvent. After the diamine and the polyvalent hydroxy compound are dissolved in the reaction solvent, the tetracarboxylic dianhydride is added. After reacting acid dianhydride and polyvalent hydroxy compound in advance, diamine is added to the copolymer, or after reacting tetracarboxylic dianhydride and diamine in advance, polyhydric hydroxy is added to the copolymer. Any method such as adding a compound can be used. The weight average molecular weight of the obtained polyester-polyamic acid copolymer is preferably 1,000 to 200,000, and more preferably 2,000 to 150,000. This is because a higher molecular weight is preferable for foreign matter characteristics and a lower molecular weight is more preferable for solubility in a solvent.

  In order to increase the weight average molecular weight of the polyester-polyamic acid copolymer, a compound having three or more acid anhydride groups may be added to perform a synthesis reaction. Specific examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer.

The polyester-polyamic acid copolymer synthesized in this way contains structural units consisting of the above formulas (1) and (2), and the terminal thereof is a tetracarboxylic dianhydride, diamine or polyvalent hydroxy compound as a raw material. An acid anhydride group derived from the above, amino or hydroxy, or an additive other than these compounds constitutes the terminal. In the formulas (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 polyvalent hydroxy compound residue, 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 is not particularly limited as long as it has good compatibility with other components forming the thermosetting polymer composition of the present invention. Copolymer of substituted maleimide and oxiranyl-containing monomer or oxetanyl-containing monomer, N-substituted maleimide and oxiranyl-containing monomer or oxetanyl-containing monomer and other monomer, N-substituted maleimide and oxiranyl-containing Monomer or copolymer of oxetanyl-containing monomer and alicyclic epoxy resin or bisphenol A type epoxy resin, or N-substituted maleimide and oxiranyl-containing monomer or oxetanyl-containing monomer and other monomers Coalescence and alicyclic epoxy resin or Mixture of scan phenol A type epoxy resins, and the like. Among these, a copolymer of an N-substituted maleimide and a monomer having oxiranyl is particularly preferable because it is excellent in transparency and foreign matter characteristics.

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

  Specific examples of the monomer having oxiranyl include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. Among these, glycidyl methacrylate is preferable because it can provide a cured film having good foreign matter characteristics.

  Specific examples of the monomer having oxetanyl include 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane. 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, p-acetoxystyrene and 3-ethyl-3-hydroxy Mention may be made of compounds of methyl oxetane and compounds of p- (1-ethoxyethoxy) styrene and 3-ethyl-3-hydroxymethyl oxetane.

  Specific examples of other monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene and the like can be mentioned. . Among these, methyl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, and the resulting copolymer have excellent compatibility with the polyester-polyamic acid copolymer used in the present invention, More preferred are 2-hydroxyethyl (meth) acrylate and styrene.

  Specific examples of the alicyclic epoxy resin or bisphenol A type epoxy resin include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, and Epicoat 191P (trade names, manufactured by Yuka Shell Epoxy Co., Ltd.) ), Epicoat 1001, Epicoat 1002, Epicoat 1004AF, Epicoat 1256 (above trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Araldite CY177, Araldite CY184 (above trade name, manufactured by Ciba Geigy Japan, Inc.), Celoxide 2021, Celoxide 3000 , And EHPE-3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.). The copolymer of the monomer having N-substituted maleimide and oxiranyl epoxy or the monomer having N-substituted maleimide and oxetanyl used in the present invention may be used in combination of two or more. Copolymer of N-substituted maleimide having a molecular weight of less than 10,000 and a monomer having oxiranyl or a copolymer of a monomer having N-substituted maleimide and oxetanyl and a monomer having a molecular weight of 10,000 or more and a monomer having oxiranyl When a polymer or a copolymer of N-substituted maleimide and a monomer having oxetanyl is used in combination, it has a copolymer of N-substituted maleimide having a molecular weight of 10,000 or more and a monomer having oxiranyl or N-substituted maleimide and oxetanyl. When the copolymer of the monomer is 5% by weight or more of the copolymer of the monomer having N-substituted maleimide and oxiranyl or the copolymer of the monomer having N-substituted maleimide and oxetanyl, the foreign matter characteristics are good. preferable.

  The proportion of the copolymer of the monomer having oxiranyl and the other monomer is preferably 30% by mole or more of the monomer having oxiranyl because the chemical resistance is excellent. It is more preferable that the monomer having oxiranyl is 50 mol% or more.

The molecular weight of the polymer of the monomer having oxiranyl or the copolymer of the monomer having oxiranyl and another monomer is preferably 3,000 to 1,000,000 in terms of weight average molecular weight, and preferably 50,000 to 500,000. More preferred. This is because the foreign matter characteristics are better as the molecular weight is higher, and the solubility in the solvent is better as the molecular weight is lower.
The proportion of the copolymer of the monomer having oxetanyl and another monomer is preferably 30% by mole or more of the monomer having oxetanyl because the chemical resistance is excellent. It is more preferable that the monomer having oxiranyl is 50 mol% or more.
The molecular weight of the polymer of the monomer having oxetanyl or the copolymer of the monomer having oxetanyl and another monomer is preferably 3,000 to 1,000,000 in terms of weight average molecular weight, and preferably 50,000 to 500,000. More preferred. This is because the foreign matter characteristics are better as the molecular weight is higher, and the solubility in the solvent is better as the molecular weight is lower.

[Third component: solvent]
As the solvent used in the polymer composition of the present invention, the reaction solvent used in the polymerization reaction when synthesizing the polyester-polyamic acid copolymer can be used as it is. If necessary, after the reaction, a part of the reaction solvent may be evaporated or a new solvent may be added. The solid content of the thermosetting polymer composition is selected depending on the film thickness of the coating film, but is generally contained in the polymer composition in the range of 5 to 40% by weight.

  In the thermosetting polymer composition of the present invention, the N-substituted maleimide copolymer is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester-polyamic acid copolymer. When the N-substituted maleimide copolymer is in this range, the balance of flatness, heat resistance, chemical resistance, adhesion, and foreign matter characteristics is good. The N-substituted maleimide copolymer is more preferably 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. Examples of the epoxy curing agent include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, and a catalyst type curing agent, and an acid anhydride curing agent is preferable from the viewpoint of coloring and heat resistance.

  Specific examples of acid anhydride-based curing agents include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride and other aliphatic dicarboxylic anhydrides, phthalic anhydride Examples thereof include aromatic polyvalent carboxylic acid anhydrides such as acid and trimellitic anhydride, and styrene-maleic anhydride copolymers. Among these, hexahydro trimellitic anhydride and trimellitic anhydride are particularly preferable from the viewpoint of balance between heat resistance and solubility in solvents.

  The ratio of the N-substituted maleimide copolymer and the epoxy curing agent when adding an epoxy curing agent for the purpose of improving heat resistance and chemical resistance is relative to oxiranyl or oxetanyl contained in the N-substituted maleimide copolymer. The carboxylic acid anhydride group or carboxylic acid group which is an epoxy curing agent is preferably added in an amount of 0.05 to 2 times equivalent. At this time, the carboxylic acid anhydride group is calculated as divalent. The addition of a carboxylic acid anhydride group or a carboxylic acid group in an amount of 0.1 to 1.5 times the equivalent is further preferred because the chemical resistance is further improved.

The thermosetting polymer composition according to the present invention may contain other components other than those described above, if necessary, as long as the object of the present invention is not impaired. Examples of such other components include a coupling agent and a surfactant.
The coupling agent is used to improve the adhesion to the substrate, and is 100 parts by weight of the solid content of the thermosetting polymer composition (the remaining component excluding the solvent from the polymer composition). It is preferable to add 1 to 30 parts by weight based on the weight.

As the coupling agent, silane-based, aluminum-based and titanate-based compounds can be used.
Specifically, silanes such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane, aluminum such as acetoalkoxyaluminum diisopropylate And titanate systems such as tetraisopropyl bis (dioctyl phosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

  The surfactant is used to improve wettability, leveling property, or coating property to the base substrate, and 0.01 to 1 part by weight is added to 100 parts by weight of the thermosetting polymer composition. Used. As the surfactant, a silicon surfactant, an acrylic surfactant, a fluorine surfactant, or the like is used. Specifically, silicon systems such as Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, and Byk-370 (above trade names, manufactured by BYK Chemie Co., Ltd.) , Byk-354, ByK-358, and Byk-361 (above trade names, manufactured by Big Chemie Co., Ltd.) and the like, DFX-18, Aftergent 250, and Aftergent 251 (above trade names, Neos ( Product)).

[Method for forming cured film]
In the thermosetting polymer composition of the present invention, a polyester compound, an N-substituted maleimide copolymer and a solvent are mixed, and depending on the intended properties, an epoxy curing agent, a coupling agent and a surfactant are further required. It can be obtained by selectively adding them and mixing and dissolving them uniformly.
A coating film can be formed by applying the thermosetting polymer composition prepared as described above to the substrate surface and removing the solvent by heating. Application of the thermosetting polymer composition to the substrate surface can form a coating film by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. Next, this coating film is heated (prebaked) with a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 120 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Thereafter, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 240 ° C. for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

When the cured film thus obtained is heated, 1) the polyamic acid portion of the polyester-polyamic acid copolymer is dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester-polyamic acid copolymer is It reacts with the epoxy (oxiranyl or oxetanyl) of the N-substituted maleimide copolymer to increase the molecular weight, and 3) The epoxy of the N-substituted maleimide copolymer reacts with the epoxy curing agent to increase the molecular weight. Therefore, it is very tough and excellent in transparency, heat resistance, chemical resistance, flatness, adhesion and sputtering resistance.
Next, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.
A polyester-polyamic acid copolymer solution comprising a copolymer of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound was synthesized as shown below.

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

(Synthesis Example 1)
A 500 ml flask equipped with a thermometer and a stirring blade was purged with nitrogen, and then 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as “ODPA”) 92.99 g, 1,4 -27.01 g of butanediol and 280 g of dehydrated and purified methyl 3-methoxypropionate (hereinafter abbreviated as “MMP”) were charged, heated to 130 ° C. in an oil bath, stirred for 4 hours, and then cooled to light yellow transparent A 30% solution of the polyester compound was obtained. The viscosity of this solution was 65 mPa · s. The weight average molecular weight measured by GPC was 7,600.

(Synthesis Example 2)
A 500 ml flask equipped with a thermometer and stirring blades was purged with nitrogen, and then charged with 13.3 g of 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as “DDS”) and 14.19 g of 1,4-butanediol. Thereafter, 280 g of dehydrated and purified MMP was charged and 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 added. 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-polyamic acid copolymer. The viscosity of this solution was 20 mPa · s. The weight average molecular weight measured by GPC was 3,400.

(Synthesis Example 3)
A 500 ml flask equipped with a thermometer and a stirring blade was purged with nitrogen, and then 81.42 g of ODPA, 14.19 g of 1,4-butanediol and 11.35 g of benzyl alcohol were added, and 217.18 g of dehydrated and purified MMP was added. The mixture was heated to 130 ° C. with an oil bath and stirred for 2 hours. After cooling to 30 ° C., 13.03 g of DDS and 62.82 g of dehydrated and purified MMP were charged and stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C. in an oil bath, stirred for 1 hr, and then cooled to 30 ° C. to obtain a 30% solution of a pale yellow transparent polyester-polyamic acid copolymer. The viscosity of this solution was 27 mPa · s. The weight average molecular weight measured by GPC was 4,000.

(Synthesis Example 4)
A 500 ml flask equipped with a thermometer and stirring blades was purged with nitrogen, and then ODPA 16.95 g, styrene / maleic anhydride copolymer (styrene / maleic anhydride = 1/1 (molar ratio), weight average molecular weight 1,800 ) After charging 51.55 g, 3.28 g of 1,4-butanediol and 19.70 g of benzyl alcohol, 137.22 g of dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”) was added to the oil bath. At 130 ° C. and stirred for 2 hr. After cooling to 30 ° C., 4.523 g of DDS and 86.78 g of dehydrated and purified PGMEA were charged and stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C. in an oil bath, stirred for 1 hr, and then cooled to 30 ° C. to obtain a 30% solution of a pale yellow transparent polyester-polyamic acid copolymer. The viscosity of this solution was 36 mPa · s. The weight average molecular weight measured by GPC was 48,000.

  A 1,000 ml flask equipped with a stirring blade was purged with nitrogen, and 250 g of the polyester compound solution obtained in Synthesis Example 1 and an N-phenylmaleimide / glycidyl methacrylate copolymer (molar ratio 30:70, weight average molecular weight) were placed in the flask. 80,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxypropyltrimethoxysilane 8.25 g, Byk-344 (trade name; manufactured by Big Chemie) 0.95 g, dehydrated and purified MMP518 g, room temperature The mixture was stirred for 5 hours and dissolved uniformly. This mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution (hereinafter sometimes referred to as a coating solution). Next, this coating solution was spin coated on a glass substrate at 600 rpm for 10 seconds, and then prebaked on a hot plate heated to 80 ° C. for 2 minutes to form a coating film. Thereafter, the coating film was cured by heating in an oven heated to 230 ° C. for 40 minutes to obtain a cured film having a thickness of 1.5 μm. The cured film thus obtained was subjected to comparative evaluation of characteristics regarding foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, transparency, and flatness. These evaluation results are shown in Table 1.

[Evaluation methods]
Foreign material characteristics: A chromium substrate was set on a spreader of bead spacers, and bead spacers having a diameter of 20 μm were spread at a rate of 3 to 5 pieces / cm ² . The coating solution was spin-coated on this substrate at 600 rpm for 10 seconds, and then pre-baked 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 220 ° C. for 30 minutes to obtain a cured film having a thickness of 1.5 μm. The surface of this cured film was observed at a magnification of 50 using a differential interference microscope (trade name; AFX-IIA, manufactured by Nikon Co., Ltd.), and the diameter of the portion where the film around the bead spacer was raised was measured. The unit is μm.

Heat resistance: After the obtained glass substrate with a cured film was reheated at 250 ° C. for 1 hour, the remaining film ratio after heating with respect to the film thickness before heating and the transmittance at 400 nm after heating were measured.
“A +” when the residual film rate after heating is 99% or more and the transmittance at 400 nm after heating is 99% or more, “A” when the transmittance is less than 99% and 98% or more, and the transmittance Of less than 98% was designated as “B”. Further, the case where the remaining film rate after heating was 97% or more and the transmittance at 400 nm after heating was 98% or more was designated as “A”, and the transmittance less than 98% was designated as “B”. Moreover, when the remaining film rate after heating was less than 97%, it was set as “B”.

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

  Acid resistance: The obtained glass substrate with a cured film was immersed in a mixed solution (weight ratio) composed of 36% hydrochloric acid / 60% nitric acid / water = 40/20/40 at 50 ° C. for 15 minutes (hereinafter referred to as mixed acid treatment). After abbreviation), the remaining film ratio after the treatment and the transmittance before and after the treatment with respect to the film thickness before the treatment were measured. The case where the remaining film rate after the treatment was 95% or more and the transmittance at 400 nm after the treatment was 99% or more was designated as “A”. The case where the residual film rate after the treatment was less than 95% or the transmittance after the treatment was less than 99% was defined as “B”.

  Solvent resistance: After 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”), after the treatment for the film thickness before the treatment The remaining film rate and the transmittance before and after the treatment were measured. The case where the remaining film rate after the treatment was 95% or more and the transmittance at 400 nm after the treatment was 99% or more was designated as “A”. The case where the residual film rate after the treatment was less than 95% or the transmittance after the treatment was less than 99% was defined as “B”.

  Adhesiveness: The obtained cured film-coated glass substrate was subjected to a pressure cooker test (hereinafter abbreviated as PCT treatment) for 24 hours under conditions of 120 ° C., 100%, and 0.2 MPa, and then the tape was peeled off from the cured film The Goban eye test (JIS-K-5400) was performed and the remaining number was counted. The case where the remaining number / 100 is 100/100 is “A”, and the case where it is 99/100 or less is “B”.

Sputtering resistance: When the ITO film was formed on the cured film by sputtering at 240 ° C. so that a resistance value of 10 Ω / cm ² was obtained in the obtained glass substrate with a cured film, the presence or absence of wrinkling of the film I investigated. The case where there was no wrinkle was designated as “A”, and the case where wrinkle occurred was designated as “B”.

  Transparency: In the obtained glass substrate with a cured film, a spectrophotometer (trade name: MICRO COLOR ANALYZER TC-1800M, manufactured by Tokyo Denshoku Technical Center) transmits only the cured film at a wavelength of 400 nm. Was measured. The case where the transmittance was 99% or more was designated as “A”, and the case where the transmittance was less than 99% was designated as “B”.

  Flatness: The coating solution was spin-coated on a glass substrate at 600 rpm for 10 seconds, then placed in a vacuum dryer and vacuum-dried at 666.6 Pascals for 2 minutes. The dried film on the glass substrate thus obtained was observed with a differential interference microscope (trade name; AFX-IIA, manufactured by Nikon) at a magnification of 50 times. The case where irregularities were observed on the surface was defined as “B”.

  A 1,000-ml flask equipped with a stirring blade was purged with nitrogen, and 250 g of the polyester-polyamic acid copolymer solution obtained in Synthesis Example 2 and an N-phenylmaleimide / glycidyl methacrylate copolymer (molar ratio 30: 70, weight average molecular weight 80,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxypropyltrimethoxysilane 8.25 g, Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) 0.95 g, dehydrated and purified 518 g of prepared MMP was stirred and stirred at room temperature for 5 hours to dissolve uniformly. This mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Next, with respect to the cured film obtained by the same method as in Example 1, foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputter resistance, transparency, and flatness The characteristics were compared and evaluated. These evaluation results are shown in Table 1.

  A 1,000-ml flask equipped with a stirring blade was purged with nitrogen, and 250 g of the polyester-polyamic acid copolymer solution obtained in Synthesis Example 3 and an N-phenylmaleimide / glycidyl methacrylate copolymer (molar ratio 30: 70, weight average molecular weight 80,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxypropyltrimethoxysilane 8.25 g, Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) 0.95 g, dehydrated and purified 518 g of prepared MMP was stirred and stirred at room temperature for 5 hours to dissolve uniformly. This mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Next, with respect to the cured film obtained by the same method as in Example 1, foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputter resistance, transparency, and flatness The characteristics were compared and evaluated. These evaluation results are shown in Table 1.

  A 1,000 ml flask with a stirring blade was purged with nitrogen, and 250 g of the polyester-polyamic acid copolymer solution obtained in Synthesis Example 3 was added to the flask, and N-phenylmaleimide / n-butyl methacrylate / glycidyl methacrylate copolymer. (Molar ratio 30:10:60, weight average molecular weight 40,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxypropyltrimethoxysilane 8.25 g, Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) ) 0.95 g, 318 g of dehydrated and purified PGMEA and 200 g of deethylene purified diethylene glycol methyl ethyl ether were charged and stirred at room temperature for 5 hours to dissolve uniformly. This mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Next, with respect to the cured film obtained by the same method as in Example 1, foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputter resistance, transparency, and flatness The characteristics were compared and evaluated. These evaluation results are shown in Table 1.

(Comparative Example 1)
A 500 ml separable flask equipped with a thermometer and a stirring blade was purged with nitrogen, and then 4.85 g of DDS and 43.22 g of 3-aminopropyltriethoxysilane were added, and 197 g of dehydrated and purified MMP was added and stirred at room temperature. , DDS and 3-aminopropyltriethoxysilane were dissolved. Thereafter, the flask was cooled in an ice bath, and 36.36 g of ODPA was added when the temperature of the content liquid reached 10 ° C. When the temperature increase due to the exothermic reaction stopped, the ice bath was removed and the mixture was stirred at room temperature for 8 hours to obtain a pale yellow transparent silicon-containing polyamic acid solution. The viscosity of this solution was 12 mPa · s.
In a 500-ml separable flask purged with nitrogen with a stirring blade, 100 g of the above-mentioned silicon-containing polyamic acid solution, 30 g of Epicoat 191P (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), 16.95 g of trimellitic anhydride, 3- 3.85 g of glycidoxypropyltrimethoxysilane and 172.4 g of dehydrated and purified MMP were charged and stirred at room temperature to be uniformly dissolved. Next, 0.17 g of Byk-344 (trade name; manufactured by Big Chemie Co., Ltd.) was added, stirred at room temperature for 1 hour, filtered through a membrane filter having a pore size of 0.2 μm, and a thermosetting polymer composition solution. Got. Next, with respect to the cured film obtained by the same method as in Example 1, foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputter resistance, transparency, and flatness The characteristics were compared and evaluated. These evaluation results are shown in Table 1.

(Comparative Example 2)
A 1,000 ml flask equipped with a stirring blade was purged with nitrogen, and 250 g of the polyester compound solution obtained in Synthesis Example 1 and a benzyl methacrylate / glycidyl methacrylate copolymer (molar ratio 30:70, weight average molecular weight 100,000) were placed in the flask. ) 75 g, trimellitic anhydride 15 g, 3-glycidoxypropyltrimethoxysilane 8.25 g, Byk-344 (trade name; manufactured by Big Chemie) 0.95 g, dehydrated and purified MMP518 g, charged at room temperature for 5 hr Stir to dissolve evenly. This mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Next, with respect to the cured film obtained by the same method as in Example 1, foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputter resistance, transparency, and flatness The characteristics were compared and evaluated. These evaluation results are shown in Table 1.

(Comparative Example 3)
A 1,000 ml flask equipped with a stirring blade was purged with nitrogen, and 250 g of the polyester-polyamic acid copolymer solution obtained in Synthesis Example 2 and a benzyl methacrylate / glycidyl methacrylate copolymer (molar ratio 30:70, Weight average molecular weight 100,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxypropyltrimethoxysilane 8.25 g, Byk-344 (trade name; manufactured by Big Chemie) 0.95 g, dehydrated and purified MMP 518 g The mixture was stirred and stirred for 5 hours at room temperature to dissolve uniformly. This mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Next, with respect to the cured film obtained by the same method as in Example 1, foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputter resistance, transparency, and flatness The characteristics were compared and evaluated. These evaluation results are shown in Table 1.

(Comparative Example 4)
A 1,000-ml flask equipped with a stirring blade was purged with nitrogen, and 250 g of the polyester-polyamic acid copolymer solution obtained in Synthesis Example 3 and a benzyl methacrylate / glycidyl methacrylate copolymer (molar ratio 30:70, Weight average molecular weight 100,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxypropyltrimethoxysilane 8.25 g, Byk-344 (trade name; manufactured by Big Chemie) 0.95 g, dehydrated and purified MMP 518 g The mixture was stirred and stirred for 5 hours at room temperature to dissolve uniformly. This mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Next, with respect to the cured film obtained by the same method as in Example 1, foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputter resistance, transparency, and flatness The characteristics were compared and evaluated. These evaluation results are shown in Table 1.

  As is clear from the results shown in Table 1, the cured film obtained from the thermosetting polymer composition using the N-phenylmaleimide / glycidyl methacrylate copolymer of Examples 1 to 4 has good foreign matter characteristics. It can be seen that the heat resistance is also excellent. The cured film obtained from the silicon-containing polyamic acid composition of Comparative Example 1 (see Patent Document 1) has poor foreign matter characteristics and alkali resistance, and a decrease in yield is expected when used as a color filter protective film. Moreover, the cured film obtained from the thermosetting polymer composition using the benzyl methacrylate / glycidyl methacrylate copolymer of Comparative Examples 2 to 4 has poor heat resistance as compared with the Examples, and as a color filter protective film. Expected to play no role.

  The cured film obtained from the thermosetting polymer composition of the present invention is excellent not only in foreign matter characteristics and heat resistance, but also in characteristics as an optical material such as spatter resistance and transparency. It can be used as protective films for various optical materials such as LED light-emitting elements and light-receiving elements, and transparent insulating films formed between TFTs and transparent electrodes and between transparent electrodes and alignment films.

Claims (24)

A thermosetting polymer composition comprising a polyester compound, an N-substituted maleimide copolymer and a solvent. Here, the polyester compound is a compound obtained by reacting with a tetracarboxylic dianhydride and a polyvalent hydroxy compound and having a structural unit represented by the following formula (2), and the N-substituted maleimide copolymer is: N- copolymer der of a monomer having a copolymer or N- substituted maleimide and oxetanyl monomer having substituted maleimide and oxiranyl Ri, N- substituted maleimide, N- phenylmaleimide, N- cyclohexyl maleimide, N- benzyl Maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, or N-butylmaleimide, and the monomer having oxiranyl is glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, or 3,4-epoxy Cyclohexylmethyl (meta Monomers that are acrylates and have oxetanyl include 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane , 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, or 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, the thermosetting polymer composition of the present invention The product is 100 parts by weight of the N-substituted maleimide copolymer with respect to 100 parts by weight of the polyester compound, and the N-substituted maleimide copolymer is 20 to 400 parts by weight with respect to 100 parts by weight of the polyester-polyamic acid copolymer. Part of the heat of the present invention. Solvent used for the reduction polymer composition comprises in the range of 95 to 60 wt% in the thermosetting polymer composition.

R ¹ is a tetracarboxylic dianhydride residue and R ³ is a polyvalent hydroxy compound residue. The thermosetting polymer according to claim 1, wherein the polyester compound is a polyester-polyamic acid copolymer obtained by reacting with a tetracarboxylic dianhydride, a polyvalent hydroxy compound, and a diamine. Combined composition. Here, the polyester compound is a compound having structural units 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 polyvalent hydroxy compound residue.   Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- (bis (3,4-dicarboxyphenyl)) one or more compounds selected from hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate), wherein the polyvalent hydroxy compound is ethylene glycol, propylene glycol, One or more compounds selected from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol; Selected from 3'-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone The thermosetting polymer composition according to claim 2 is one or more compounds.   Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a two-component copolymer of N-phenylmaleimide / glycidyl methacrylate, N-phenylmaleimide / methylglycidyl methacrylate Two-component copolymer, N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate three-component copolymer, N-phenylmaleimide / glycidyl methacrylate / n-butyl methacrylate three-component copolymer, N-phenylmaleimide / 2-hydroxy 2. One or more compounds selected from a ternary copolymer of ethyl methacrylate / glycidyl methacrylate and a ternary copolymer of N-phenylmaleimide / glycidyl methacrylate / styrene. Any thermosetting polymer composition according to one of 3.   Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a binary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate, N-cyclohexylmaleimide / methylglycidyl methacrylate Two-component copolymer, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / benzyl methacrylate, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / n-butyl methacrylate, N-cyclohexylmaleimide / 2-hydroxy Selection from ternary copolymer of ethyl methacrylate / glycidyl methacrylate and ternary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / styrene The thermosetting polymer composition according to any one of claims 1 to 3 is one or more compounds.   The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the polyvalent hydroxy compound is 1,4-butanediol, and the diamine is 3,3′-diaminodiphenyl. Three-component copolymer of N-phenylmaleimide / n-butylmethacrylate / glycidylmethacrylate, which is a sulfone copolymer of a monomer having N-substituted maleimide and oxiranyl, or a copolymer of a monomer having N-substituted maleimide and oxetanyl Or a ternary copolymer of N-cyclohexylmaleimide / n-butyl methacrylate / glycidyl methacrylate, and the solvent is any one of methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, and diethylene glycol methyl ethyl ether. The thermosetting polymer composition according to any one of claims 1 to 5 is a solvent containing.   The thermosetting heavy resin according to claim 1 or 2, wherein the polyester compound is a polyester-polyamic acid copolymer obtained by reacting with a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine and a monohydric alcohol. Combined composition.   Tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- (bis (3,4-dicarboxyphenyl)) one or more compounds selected from hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate), wherein the polyvalent hydroxy compound is ethylene glycol, propylene glycol, One or more compounds selected from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol; Selected from 3'-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone The heat according to claim 7, wherein the monohydric alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyloxetane. Curable polymer composition.   Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a two-component copolymer of N-phenylmaleimide / glycidyl methacrylate, N-phenylmaleimide / methylglycidyl methacrylate Two-component copolymer, N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate three-component copolymer, N-phenylmaleimide / glycidyl methacrylate / n-butyl methacrylate three-component copolymer, N-phenylmaleimide / 2-hydroxy 8. One or more compounds selected from a ternary copolymer of ethyl methacrylate / glycidyl methacrylate and a ternary copolymer of N-phenylmaleimide / glycidyl methacrylate / styrene. Other thermosetting polymer composition according to 8.   Copolymer of monomer having N-substituted maleimide and oxiranyl or copolymer of monomer having N-substituted maleimide and oxetanyl is a binary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate, N-cyclohexylmaleimide / methylglycidyl methacrylate Two-component copolymer, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / benzyl methacrylate, three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / n-butyl methacrylate, N-cyclohexylmaleimide / 2-hydroxy Selection from ternary copolymer of ethyl methacrylate / glycidyl methacrylate and ternary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / styrene The thermosetting polymer composition according to claim 7 or 8 is one or more compounds.   The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, the polyvalent hydroxy compound is 1,4-butanediol, and the diamine is 3,3′-diaminodiphenyl. N-phenylmaleimide / n-butyl methacrylate, which is a sulfone, a monohydric alcohol is benzyl alcohol, and a copolymer of a monomer having N-substituted maleimide and oxiranyl or a monomer having N-substituted maleimide and oxetanyl / Glycidyl methacrylate ternary copolymer or N-cyclohexylmaleimide / n-butyl methacrylate / glycidyl methacrylate ternary copolymer, solvent is methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, diethylene The thermosetting polymer composition according to any one of claims 1 to 5 is a solvent containing any one of the recall methyl ethyl ether.   12. The polyester-polyamic acid copolymer obtained by reacting the polyester compound with a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine, a monohydric alcohol and a silicon-containing monoamine. 2. A thermosetting polymer composition according to item 1.   The thermosetting according to any one of claims 1 to 12, wherein the polyester-polyamic acid copolymer is a polyester-polyamic acid copolymer obtained by further reacting with a styrene-maleic anhydride copolymer. Polymer composition.   Furthermore, an epoxy curing agent is included, The thermosetting polymer composition as described in any one of Claims 1-13 characterized by the above-mentioned.   The thermosetting polymer composition according to claim 14, wherein the epoxy curing agent is trimellitic anhydride.   The thermosetting polymer composition according to any one of claims 1 to 15, wherein the polyester compound has a weight average molecular weight of 1,000 to 200,000.   The weight average molecular weight of the copolymer of the monomer having N-substituted maleimide and oxiranyl or the copolymer of the monomer having N-substituted maleimide and oxetanyl is 3,000 to 1,000,000. The thermosetting polymer composition according to claim 1.   The cured film obtained by heating the thermosetting polymer composition as described in any one of Claims 1-17.   A color filter using the cured film according to claim 18 as a protective film.   A liquid crystal display device using the color filter according to claim 19.   A solid-state imaging device using the color filter according to claim 19.   A liquid crystal display element using the cured film according to claim 18 as a transparent insulating film formed between a TFT and a transparent electrode.   A liquid crystal display device using the cured film according to claim 18 as a transparent insulating film formed between a transparent electrode and an alignment film.   The LED light-emitting body which used the cured film of Claim 18 as a protective film.