KR101128489B1 - Thermosetting polymer composition - Google Patents

Abstract

The present invention is excellent in adhesiveness, transparency, acid resistance, coating property, flatness, light resistance and foreign matter characteristics to substrates such as solvent resistance, acid resistance, alkali resistance, water resistance or glass, and excellent cured film also in heat resistance. And a polymer composition for imparting such a cured film. A thermosetting polymer composition comprising a polyester compound obtained by reacting a tetracarboxylic dianhydride and a polyhydroxy compound, an N-substituted maleimide copolymer, and a solvent is provided. Here, the N-substituted maleimide copolymer is a copolymer of a monomer containing N-substituted maleimide and oxilanyl or a copolymer of a monomer containing N-substituted maleimide and oxetanyl.

Description

 Thermosetting Polymer Composition {THERMOSETTING POLYMER COMPOSITION}

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

In the manufacturing process of elements, such as a liquid crystal display element, various chemical treatments, such as an organic solvent, an acid, an alkali solvent, are performed. In addition, when the wiring electrode is formed by sputtering, the surface may be locally treated at a high temperature. For this reason, a surface protective film may be arrange | positioned on the surface of elements, such as a liquid crystal display element, for the purpose of preventing deterioration, damage, or alteration. As such a protective film, all the characteristics which can withstand the chemical | medical treatment of a manufacturing process mentioned above and local heat processing are calculated | required. Specifically, adhesion to underlying substrates such as chemical resistance, water resistance, heat resistance and glass such as solvent resistance, acid resistance and alkali resistance, transparency, scratch resistance, coating property, flatness and coloring over a long period of time Light resistance and the like are required so that there is no alteration of the back. In particular, when it is used as a color filter protective film in recent years, foreign material characteristics are important. Here, the foreign material characteristic means a phenomenon in which the foreign material becomes easily visible. This is because when the polymer composition is applied and dried on a substrate in which foreign matter is present, the film is disturbed after the film around the foreign material, and as a result, the reflected light around the foreign material is disturbed, and thus it is observed in a shape that is larger than the actual size of the foreign material. It is a phenomenon that occurs. The excellent foreign material characteristic means that the foreign material is inconspicuous so that such a phenomenon hardly occurs. The foreign material characteristic greatly influences the yield in manufacturing the color filter.

As a protective film material excellent in the above-mentioned characteristic, there exists a silicone containing polyimide acid composition. Such silicone-containing polyimide acid compositions are disclosed in Japanese Patent Laid-Open No. 9-291150. The composition is adhesiveness to the substrate, such as solvent resistance, acid resistance, water resistance, glass, transparency. Although it is a composition excellent in coatability and flatness, it has a drawback of weak alkali resistance and foreign material characteristics. In addition, since it has recently been found that the decomposition gas generated from the protective film in the heating process during liquid crystal panel manufacture lowers the display quality of the liquid crystal panel, the protective film is required to have further heat resistance. From this point of view, the silicone-containing polyimide acid composition did not have sufficient heat resistance.

The present invention has been made to solve the drawbacks of the above-described conventional composition, the object of the present invention satisfies characteristics such as solvent resistance, acid resistance, water resistance, adhesion to the substrate, such as glass, transparency, coating properties and flatness The present invention provides a cured film excellent in alkali resistance and foreign matter characteristics and further excellent in heat resistance and a polymer composition for forming such a cured film.

MEANS TO SOLVE THE PROBLEM The present inventors examined variously in order to solve the above-mentioned problem, and, as a result, the polyester compound which can be obtained by making tetracarboxylic dianhydride and a polyhydroxy compound react with a 1st component, and N-substituted maleimide air as a 2nd component The present invention was completed by discovering that the above-mentioned object of the present invention can be achieved by a cured film obtained by heating and curing a polymer composition comprising a solvent as a coalescence and a third component. Here, the N-substituted maleimide copolymer of the second component is a copolymer of a monomer containing N-substituted maleimide and oxiranyl or a copolymer of a monomer containing N-substituted maleimide and oxetanyl.

1. A thermosetting polymer composition comprising a polyester compound, an N-substituted maleimide copolymer, and a solvent. Here, a polyester compound is a compound which can be obtained by making tetracarboxylic dianhydride and a polyhydroxy compound react, and has a structural unit represented by following formula (1), The N-substituted maleimide copolymer is N-substituted maleimide and oxiranyl It is a copolymer of the monomer containing or a copolymer containing N-substituted maleade and oxetanyl.

In Chemical Formula 1, R ¹ is a tetracarboxylic dianhydride residue, and R ³ is a polyhydroxy compound residue.

2. Thermosetting polymer composition, characterized in that the polyester compound is a polyester-polyamine acid copolymer obtained by reacting with tetracarboxylic dianhydride, polyhydric hydroxy compound and diamine. Here, a polyether compound is a compound which has a structural unit represented by following formula (2) and (3).

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

3. Tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2,2- (bis ( 3,4-dicarboxyphenyl)) hexafluoropropane anhydride and at least one compound selected from ethylene glycol bis (unhydrotrimerate), the polyhydroxy compound is ethylene glycol, propylene glycol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol, diamine having 3,3'-diaminodiphenylsulfone, bis The thermosetting polymer composition according to claim 2, which is at least one compound selected from (4- (3-aminoperoxy) phenyl) sulfone.

4. Two-component copolymer of N-phenylmaleimide / glycidyl methacrylate in which a copolymer of a monomer comprising N-substituted maleimide and oxiranyl or a monomer copolymer comprising N-substituted maleimide and oxetanyl Copolymer, bicomponent copolymer of N-phenylmaleimide / methylglycidyl methacrylate, tricomponent copolymer of N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate, N-phenylmaleimide / 3-component copolymer of glycidyl methacrylate / n-butyl methacrylate, 3-component copolymer of N-phenylmaleimide / 2-hydroxyethyl methacrylate / glycidyl methacrylate and N-phenylmaleic The thermosetting polymer composition according to any one of claims 1 to 3, which is at least one compound selected from three-component copolymers of mid / glycidyl methacrylate / styrene.

5. A copolymer of a monomer containing N-substituted maleimide and oxiranyl or a copolymer of a monomer containing N-substituted maleimide and oxetanyl is selected from N-cyclohexylmaleimide / glycidyl methacrylate. Binary copolymer, Binary copolymer of N-cyclohexylmaleimide / methylglycidyl methacrylate, Binary copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / benzyl methacrylate , 3-component copolymer of N-cyclohexyl maleimide / glycidyl methacrylate / n-butyl methacrylate, N-cyclohexyl maleimide / 2-hydroxyethyl methacrylate / glycidyl methacryl Thermosetting according to any one of claims 1 to 3, which is at least one compound selected from a three-component copolymer of rate and a three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / styrene. Polymer composition.

6. Tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, polyhydric hydroxy compound is 1,4-butanediol, diamine is 3,3'- diaminodiphenyl sulfone The compound is a monomer copolymer comprising N-substituted maleimide and oxiranyl or a monomer copolymer comprising N-substituted maleimide and oxetanyl is N-phenylmaleimide / n-butylmethacrylate / glycidyl. 3-component copolymer of methacrylate or 3-component copolymer of N-cyclohexyl maleimide / n-butyl methacrylate / glycidyl methacrylate, and a solvent is methyl 3-methoxypropionate and propylene glycol monomethyl The thermosetting polymer composition according to any one of claims 1 to 5, which is a solvent containing any one of ether acetate and diethylene glycol methyl ethyl ether.

7. The thermosetting polymer composition according to claim 1 or 2, wherein the polyester compound is a polyester-polyamine acid copolymer obtainable by reacting with a tetracarboxylic dianhydride, a polyhydroxy compound, a diamine and a monohydric alcohol.

8. Tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2,2- (bis ( 3,4-dicarboxyphenyl)) hexafluoropropane anhydride and at least one compound selected from ethylene glycol bis (unhydrotrimerate), the polyhydroxy compound is ethylene glycol, propylene glycol, 1,4-butanediol, At least one compound selected from 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol, wherein the diamine is 3,3'-diaminodiphenylsulfone, bis ( At least one compound selected from 4- (3-aminophenoxy) phenyl) sulfone, and the monohydric alcohol is isopropyl alcohol, aryl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl Thermosetting polymer composition according to claim 7 which is 3-hydroxymethyloxetane .

9. A copolymer of a monomer comprising N-substituted maleade and oxiranyl or a copolymer comprising N-substituted maleade and oxetanyl is a two-component copolymer of N-phenylmaleimide / glycidyl methacrylate. , Two-component copolymer of N-phenylmaleimide / methylglycidyl methacrylate, three-component copolymer of N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate N-phenylmaleimide / glycid 3-component copolymer of dimethyl methacrylate / n-butyl methacrylate, 3-component copolymer of N-phenylmaleimide / 2-hydroxyethyl methacrylate / glycidyl methacrylate and N-phenylmaleimide / The thermosetting polymer composition according to claim 7 or 8, which is at least one compound of a three component copolymer of glycidyl methacrylate / styrene.

10. The copolymer of the monomer containing N-substituted maleimide and oxiranyl or the copolymer of the monomer containing N-substituted maleimide and oxetanyl is 2 of N-cyclohexylmaleimide / glycidyl methacrylate. Component copolymer, 2-component copolymer of N-cyclohexyl maleimide / methylglycidyl methacrylate, 3-component copolymer of N-cyclohexyl maleimide / glycidyl methacrylate / benzyl methacrylate, N- Tricomponent copolymer of dichlorohexyl maleimide / glycidyl methacrylate / n-butyl methacrylate, tricomponent of N-cyclohexyl maleimide / 2-hydroxyethyl methacrylate / glycidyl methacrylate The thermosetting polymer composition according to claim 7 or 8, which is at least one compound selected from a copolymer and a three-component copolymer of N-cyclohexylmaleimide / glycidyl methacrylate / styrene.

11. Tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, polyhydroxy compound is 1,4-butanediol, diamine is 3,3'-diaminodiphenylsulfone The monohydric alcohol is benzyl alcohol, the copolymer of a monomer containing N-substituted maleimide and oxiranyl or the copolymer of a monomer containing N-substituted maleimide and oxetanyl is N-phenylmaleimide / n 3-component copolymers of butyl methacrylate / glycidyl methacrylate or 3-component copolymers of N-cyclohexyl maleimide / n-butyl methacrylate / glycidyl methacrylate, and the solvent is 3-methacrylate. The thermosetting polymer composition according to any one of claims 1 to 5, which is a solvent containing any one of methyl oxypropionate, propylene glycol monomethyl ether acetate, and diethylene glycol methyl ethyl ether.

12. The compound of claims 1 to 11, wherein the polyester compound is a polyester-polyamic acid copolymer obtained by reacting with a tetracarboxylic dianhydride, a polyhydroxy compound, a diamine, a monohydric alcohol and a silicone-containing monoamine. Thermosetting polymer composition according to any one of the preceding.

13. The thermosetting polymer composition 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 a styrene-maleic anhydride copolymer.

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

15. The thermosetting polymer composition according to claim 14, wherein the epoxy curing agent is trimellitic anhydride.

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

17. Claims 1 to 2, wherein the weight average molecular weight of the copolymer of the monomer containing N-substituted maleimide and oxiranyl or the copolymer of the monomer containing N-substituted maleimide and oxetanyl is about 3,000 to 1,000,000. The thermosetting polymer composition according to claim 16.

18. Cured film obtained by heating the thermosetting polymer composition according to any one of claims 1 to 17.

19. A color filter comprising the cured film according to claim 18 as a protective film.

20. A liquid crystal display device comprising the color filter according to claim 19.

21. A solid-state imaging device comprising the color filter according to claim 19.

22. A liquid crystal display device comprising the cured film according to claim 18 as a transparent insulating film formed between the thin film transistor (TFT) and the transparent electrode.

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

24. A light emitting diode (LED) light emitting body comprising the cured film according to claim 18 as a protective film.

The thermosetting polymer composition which concerns on this invention is excellent in a foreign material characteristic, and when used as a color filter protective film, a yield improves. Moreover, the cured film obtained by heating the thermosetting polymer composition which concerns on this invention is balanced in adhesiveness, transparency, applicability | paintability, and flatness with respect to the base substrate, such as heat resistance, alkali resistance, acid resistance, solvent resistance, water resistance, glass, etc. It is quite practical. In particular, it is useful as a protective film of the color filter manufactured by the dyeing method, the pigment dispersion method, the electrodeposition method, and the printing method. It can also be used as a protective film and a transparent insulating film of various optical materials.

Hereinafter, the thermosetting polymer composition and the cured film obtained by heat curing the same according to exemplary embodiments of the present invention will be described in detail, but the present invention is not limited or limited by the following examples.

First component: polyester compound

The polyester compound used for this invention is a compound obtained by making tetracarboxylic dianhydride and a polyhydroxy compound react. Specific examples of such polyester compounds include polyesters and polyester-polyamic acid copolymers. Preferably, the polyester compound is a polyester-polyamic acid copolymer. Polyester-polyamic acid copolymers are obtained by reacting tetracarboxylic dianhydrides, polyhydroxy compounds and diamines.

The polyester compound used in the present invention has a structural unit represented by the following formula (4) and / or formula (5). The polyester compound obtained by making tetracarboxylic dianhydride and a polyhydroxy compound react has a structural unit of following General formula (5). The polyester compound obtained by making tetracarboxylic dianhydride, a polyhydroxy compound, and diamine react, has a structural unit of Formula (4) and Formula (5).

Specific examples of the tetracarboxylic dianhydride used in the present invention include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3 , 3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylsulfontetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylethertetra Carboxylic dianhydride, 2,3,3 ', 4'-diphenylethertetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, and ethylene glycol bis ( Aromatic tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methyl cyclobutane tetra, such as anhydrotrimerate) (brand name; TMEG-100, Nippon Chemical Co., Ltd. product) And aliphatic tetracarboxylic dianhydrides such as cyclic dianhydrides, cyclopentane tetracarboxylic dianhydrides and cyclohexane tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides such as ethanetetracarboxylic dianhydrides and butanetetracarboxylic dianhydrides. .

3,3 ', 4,4'- diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride which gives resin with good transparency among the above-mentioned substance, 2, 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimerate) (trade name; TMEG-100, manufactured by Nippon Eika Co., Ltd.) are preferred. And 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride and the like are particularly preferred.

Specific examples of the polyhydroxy compound used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of about 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetra Propylene glycol, polypropylene glycol having a molecular weight of about 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-heptane Diol, 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-nonantriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1, 2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, Pentaerythritol, bisphenol A (brand name), bisphenol S (brand name), bisphenol F (brand name), diethanolamine and triethanolamine, SEO-2 (brand name, product of Ilhwa Chemical Co., Ltd.), SKY CHDM, ricabinol HB ( The following brand name, the product of Nippon Ewha Co., Ltd.) etc. are mentioned.

Among the substances mentioned above, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, SEO-2, SKY CHDM And ribabinol HB are preferred, and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like 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, 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, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, and the like. Of these materials, 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone, which give a resin having good transparency, are preferable, and 3,3'-diaminodiphenyl is preferred. Sulfon is particularly preferred.

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, di Propylene Glycol Monoethyl Ether, Dipropylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monoethyl Ether, Phenol, Borneol, Maltol, Linarool , Terpineol, dimethylbenzylcarbonol, ethyl lactate, glycidol, 3-ethyl-3-hydroxymethyloxetane, and the like.

Among the aforementioned materials, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, 3-ethyl-3-hydroxyoxetane and the like are preferable. Polyester-polyamic acid copolymers which can be formed using these materials, copolymers of monomers comprising N-substituted maleimide and oxiranyl or copolymers of monomers comprising N-substituted maleimide and oxetanyl, and In consideration of the compatibility when the epoxy curing agent is mixed and the applicability on the color filter of the thermosetting resin composition which is the final product, benzyl alcohol is more preferably used as the monovalent alcohol.

Specific examples of the silicone-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4 -Aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethicone Oxysilane, p-aminophenylmethyl diethoxysilane, m-aminophenyl trimethoxysilane, m-aminophenylmethyl diethoxysilane, etc. are mentioned. Among these materials, 3-aminopropyltriethoxysilane, p-aminophenyltrimethoxysilane, and the like are preferred, and 3-aminopropyltriethoxysilane is particularly preferred because of good acid resistance of the coating film.

Specific examples of the reaction solvent used in the polymerization reaction for obtaining the polyester-polyamine acid copolymer include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, and ethylene. Glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, N-methyl-2-pyrrolidone, N, N-methylacetamide, etc. Can be. Among these materials, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, diethylene glycol methyl ethyl ether, N-methyl-2-pyrrolidone and the like are preferable.

As these reaction solvents, it can be used individually or as a mixed solvent of 2 or more types. Moreover, if it is the ratio of about 30 weight% or less, you may mix and use other solvent other than the said reaction solvent.

The polyester compound used for this invention can be manufactured from tetracarboxylic dianhydride and a polyhydroxy compound.

Here, more preferably, the polyester compound is a polyester-polyamine acid copolymer. In the method for producing a polyester-polyamine acid copolymer, tetracarboxylic dianhydride (X mole), diamine (Y mole) and a polyhydroxy compound (Z mole) are reacted in the reaction solvent. At this time, X, Y, and Z are preferably set at a ratio such that the relationship between the equations (1) and (2) holds. If it is such a range, the solubility of the polyester polyamic-acid copolymer with respect to the said solvent is high, the coating property of a composition will improve by this, and the cured film excellent in flatness can be obtained as a result.

0.2 ≤ Z / Y ≤ 8.0

0.2 ≤ (Y + Z) / X ≤ 5.0

In Equation 1, preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.0 ≦ Z / Y ≦ 5.0. In formula (2), 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 for this invention has an acid anhydride group at the terminal of a molecule | numerator, it can react by adding the above-mentioned monohydric alcohol as needed. The polyester-polyamic acid copolymer to which monohydric alcohol is added is a copolymer of a monomer containing N-substituted maleimide and oxiranyl or a copolymer of a monomer containing N-substituted maleimide and oxetanyl and an epoxy curing agent. At the same time as compatibility with the improved, the coating property of the thermosetting resin composition of the present invention containing them is improved.

Moreover, the acid resistance of the coating film obtained by making the above-mentioned silicone containing monoamine react with the polyester polyamic-acid copolymer which has an acid anhydride group at a molecular terminal improves. The monohydric alcohol and the silicone-containing monoamine can also be reacted with the polyester-polyamine acid copolymer at the same time.

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

There is no particular limitation on the order of addition of the reaction raw materials to the reaction system. That is, a method of simultaneously adding a tetracarboxylic dianhydride, a diamine and a polyhydroxy compound to the reaction solvent, a method of dissolving the diamine and a polyhydroxy compound in the reaction solvent, and then adding a tetracarboxylic dianhydride, tetracarboxylic acid Any method may be used, such as reacting the anhydride and the polyhydroxy compound again, and then adding diamine to the copolymer, or adding the polyhydroxy compound to the copolymer after reacting the tetracarboxylic dianhydride and the diamine again. have. It is preferable that it is about 1,000-200,000, and, as for the weight average molecular weight of the obtained polyester polyamic-acid copolymer, it is more preferable that it is about 2,000-150,000. It is because a high molecular weight grade is preferable for a foreign material characteristic, and a low molecular weight grade is preferable for solubility to a solvent.

In order to raise the weight average molecular weight of a polyester polyamic-acid copolymer, the compound which has three or more acid anhydride groups may be added and a synthetic reaction may be performed. Specific examples of the compound having three or more acid anhydride groups include styrene-maleic anhydride copolymers.

The polyester-polyamic acid copolymer synthesized according to the above includes a structural unit according to Chemical Formulas 4 and 5, and an end thereof is an acid anhydride group derived from a tetracarboxylic dianhydride, a diamine or a polyhydroxy compound as a raw material. , Amino or hydroxy, and additives other than these compounds constitute the terminal. In the formulas (4) and (5), R ¹ is a tetracarboxylic dianhydride residue, and preferably an organic group having about 2 to 30 carbon atoms. R ² is a diamine residue, and preferably an organic group having about 2 to 30 carbon atoms. In addition, R <^3> is a polyhydric hydroxy compound residue, Preferably it is an organic group of about 2-20 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 compatibility with other components forming the thermosetting polymer composition according to the present invention is good, but preferably, N-substituted maleimide and oxiranyl are used. N-substituted maleimide and copolymer with monomer containing oxetanyl or monomer containing oxetanyl and other monomer, N-substituted maleimide and oxiranyl copolymer A mixture of a copolymer containing a monomer containing a monomer or oxetanyl and an alicyclic epoxy resin or bisphenol A epoxy resin, or a monomer or oxetanyl containing N-substituted maleimide and oxiranyl The mixture of the copolymer with another monomer, alicyclic epoxy resin, or bisphenol-A epoxy resin, etc. are mentioned. have. Of these materials, copolymers of monomers containing N-substituted maleimide with oxiranyl are particularly preferred because of their excellent transparency and foreign material properties.

As a specific example of N-substituted maleimide used for this invention, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide And N-butyl maleimide. Particularly preferred are N-phenylmaleimide, N-cyclohexylmaleimide and the like.

Specific examples of the monomer having oxiranyl include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. Among these materials, glycidyl methacrylate is preferable because a cured film having good foreign material properties can be obtained.

As a specific example of the monomer which has the said oxetanyl, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacrylo) Yloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacrylo) Yloxymethyl) -4-trifluoromethyloxetane, p-acetoxystyrene and 3-ethyl-3-hydroxymethyloxetane, p- (1-ethoxyethoxy) styrene and 3-ethyl- The compound of 3-hydroxymethyl oxetane, etc. are mentioned.

As a specific example of another monomer, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acryl Rate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, Methyl styrene, chloromethyl styrene, etc. are mentioned. Among these materials, the copolymer obtained is methyl (meth) acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, having excellent compatibility with the polyester-polyamic acid copolymer used in the present invention, It is more preferable that it is 2-hydroxyethyl (meth) acrylate, styrene, etc.

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 according to the present invention. Examples of the epoxy curing agent include an acid anhydride curing agent, a polyamine curing agent, a polyphenol curing agent, a catalyst curing agent, and the like, but an acid anhydride curing agent is preferable in terms 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 hexahydrotrimeric anhydride, phthalic anhydride, and trimellitic anhydride. Aromatic polyhydric carboxylic anhydride, a styrene maleic anhydride copolymer, etc. are mentioned. Among these substances, hexahydrotrimethane anhydride, trimellitic anhydride, and the like are particularly preferable in view of the balance of heat resistance and solubility in solvents.

For the purpose of improving the heat resistance and chemical resistance, the ratio of the N-substituted maleimide copolymer and the epoxy curing agent in the case of adding an epoxy curing agent is epoxy to the oxiranyl or oxetanyl contained in the N-substituted maleimide copolymer. It is preferable to add so that the carboxylic anhydride group or carboxylic acid group which is a hardening | curing agent may be equivalent about about 0.05-2 times. At this time, a carboxylic anhydride group calculates bivalently. It is more preferable if the carboxylic anhydride group or the carboxyl group is added so as to have an equivalent of about 0.1 to 1.5 times because the chemical resistance is further improved.

The thermosetting polymer composition which concerns on this invention may contain components other than the component mentioned above as needed in the range which does not impair the objective of this invention. As such another component, a coupling agent, surfactant, etc. are mentioned.

The coupling agent is used to improve adhesion to the substrate, and it is preferable to add about 1 to 30 parts by weight based on 100 parts by weight of the solid content of the thermosetting polymer composition (the remaining components except the solvent from the polymer composition). Do.

As said coupling agent, compounds, such as a silane type, aluminum type, titanate type, can be used.

More specifically, Silanes, such as 3-glycid oxy propyl dimethyl ethoxysilane, 3-glycid oxy propyl methyl diethoxysilane, and 3-glycid oxy propyl trimethoxysilane, acetalkoxy aluminum diisopropylate, etc. And titanate systems such as aluminum series and tetraisopropylbis (dioctylphosphite) titanate. Among these materials, 3-glycidoxy propyltrimethoxysilane is preferred because of its large effect of improving adhesion.

The surfactant is used to improve the wettability, leveling property or applicability to the underlying substrate, and is used by adding about 0.01 to 1 part by weight based on 100 parts by weight of the thermosetting polymer composition. As said surfactant, silicone type surfactant, acrylic type surfactant, fluorine type surfactant, etc. are used. Specifically, silicones such as Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344 or Byk-370 (above trade names, products of BYK-Chemie Co., Ltd.), Byk- Acrylic system such as 354, Byk-358 or Byk-361 (above brand name, product of BYK-Chemie), DFX-18, aftergent 250 or aftergent 251 (above brand name, product of Neos Co., Ltd.) ), And the like.

Manufacturing method of cured film

In the thermosetting polymer composition according to the present invention, a polyester compound, an N-substituted maleimide copolymer, and a solvent are mixed, and an epoxy curing agent, a coupling agent, and a surfactant are further selected and added as necessary according to the desired properties, These can be obtained by mixing and dissolving these uniformly.

The coating film can be formed by apply | coating the thermosetting polymer composition prepared as mentioned above to a base surface, and removing a solvent by heating. Application of the thermosetting polymer composition to the substrate surface can form a coating film by a known method such as spin coating, roll coating, dipping and slit coating. Next, the coating film is heated (prebaked) with a hot plate or an oven or the like. Heating conditions vary depending on the type and blending ratio of each component, but are usually heated at a temperature of about 70 to 120 ° C. for about 5 to 15 minutes in an oven and about 1 to 5 minutes in a hot plate. Thereafter, in order to cure the coating film, at a temperature of about 180 to 250 ° C., preferably at a temperature of about 200 to 240 ° C., about 30 to 90 minutes in an oven and about 5 to 30 minutes in a hot plate. A cured film can be obtained by heat processing.

In the cured film obtained as described above, when heated, 1) the polyamic acid portion of the polyester-polyamic acid copolymer is dehydrated to form an imide bond, and 2) the polyester-polyamic acid copolymer Since the carboxylic acid reacts with the epoxy (oxyranyl or oxetanyl) of the N-substituted maleimide copolymer to high molecular weight, and 3) the epoxy and the epoxy curing agent of the N-substituted maleimide copolymer react with the high molecular weight, It is very tough and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion and sputter resistance.

Hereinafter, the present invention will be described in detail by synthesis examples, experimental examples and comparative examples, but the present invention is not limited or limited by the following experimental examples.

A polyester-polyamic acid copolymer solution consisting of a copolymer of tetracarboxylic dianhydride, diamine and polyhydroxy compound was synthesized as shown below.

Here, the viscosity shown below was measured at the temperature of 25 degreeC using the E-type viscosity meter (brand name; VISCONIC END, the product of Tokyo Co., Ltd.).

Synthesis Example 1

After replacing a 500 ml flask with a thermometer and a stirring blade with nitrogen, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as "ODPA") 92.99 g, 1,4 -27.01 g of butanediol and 280 g of dehydrated and purified 3-methoxypropionate methyl (hereinafter referred to as "MMP") were added, heated to a temperature of 130 ° C in an oil bath, stirred for 4 hours, and cooled to give a pale yellow transparent poly. A 30% solution of ester compound was obtained. The viscosity of the solution was 65 mPa · s. The weight average molecular weight measured by GPC was 7600.

Synthesis Example 2

After nitrogen replacement of a 500 ml flask with a thermometer and a stirring blade, 13.03 g of 3,3'-diaminodiphenyl sulfone (hereinafter referred to as "DDS") and 14.19 g of 1,4-butanediol were added thereto. 280 g of dehydrated and purified MMP was added 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 thereto. It heated to the temperature of 130 degreeC in the oil bath, stirred for 4 hours, and then cooled to the temperature of 30 degreeC, and obtained the 30% solution of the 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 3400.

Synthesis Example 3

Nitrogen-substituted 500 ml flask with a thermometer and agitating blades was added, followed by 81.42 g of ODPA, 14.19 g of 1,4-butanediol, and 11.35 g of benzyl alcohol. Then, 217.18 g of dehydrated and purified MMP was added thereto. It heated to the temperature of ° C and stirred for 2 hours. Thereafter, after cooling to a temperature of 30 ° C., 13.03 g of DDS and 62.82 g of dehydrated and purified MMP were added thereto, and the mixture was stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C. in an oil bath, stirred for 1 hour, and then cooled to 30 ° C. to obtain a 30% solution of a pale yellow transparent polyester-polyamine acid copolymer. The viscosity of this solution was 27 mPa * s. The weight average molecular weight measured by GPC was 4000.

Synthesis Example 4

51.55 g of ODPA, styrene-maleic anhydride copolymer (styrene / maleic anhydride = 1/1 (molar ratio), weight average molecular weight 1800) after nitrogen-substituting a 500 mL flask with a thermometer and a stirring blade. After adding 3.28 g of 4-butanediol and 19.70 g of benzyl alcohol, 137.22 g of dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was added thereto, and the mixture was heated to 130 ° C in an oil bath and stirred for 2 hours. . Then, it cooled to 30 degreeC, 4.523g of DDS and 86.78g of dehydrated PGMEA were put, and it stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C in an oil bath, stirred for 1 hour, cooled to 30 ° C, and a 30% solution of a pale yellow transparent polyester-polyamine acid copolymer was obtained. The viscosity of this solution was 36 mPa * s. The weight average molecular weight measured by GPC was 48000.

Experimental Example 1

A 1000 ml flask with agitating blades was nitrogen-substituted, and 250 g of the polyester compound solution obtained in Synthesis Example 1, N-phenylmaleimide / glycidyl methacrylate copolymer (molar ratio of 30:70, weight) was added to the flask. 75 g of average molecular weight 80,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxy propyl trimethoxysilane, 0.95 g of Byk-344 (trade name, manufactured by BYK-Chemie), and 518 g of dehydrated and purified MMP were added thereto. It stirred for 5 hours at room temperature, and dissolved uniformly. This mixed solution was filtered with a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution (hereinafter sometimes referred to as a coating liquid). Next, the coating liquid was spin coated on the glass substrate at 600 rpm for 10 seconds, and then prebaked for 2 minutes on a hot plate heated to 80 ° C to form a coating film. Then, the coating film was hardened by heating for 40 minutes in the oven heated to 230 degreeC, and the cured film which has a film thickness of 1.5 micrometers was obtained. About the cured film obtained in this way, the characteristic was compared with respect to the foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Assessment Methods

Foreign material characteristics: The chromium substrate was provided in the spreader of the beads spacer, and the 20 micrometers diameter beads spacer was scattered so that it might become the ratio of 3-5 pieces / cm <^2> . The coating solution was spin coated on the substrate at 600 rpm for 10 seconds, and then prebaked at 80 ° C. for 3 minutes on a hot plate 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 film thickness of 1.5 μm. The cured film was observed at 50 times the surface using a differential interference type microscope (trade name; AFX-IIA, manufactured by Nikon Corporation) to measure the diameter of the portion in which the film around the beads spacer was swollen. The unit is μm.

Heat resistance: After the obtained glass substrate with a cured film was reheated at 250 degreeC for 1 hour, the residual film rate after heating with respect to the film thickness before heating, and the transmittance | permeability in 400 nm after heating were measured. When the residual film rate after heating is 99% or more and the transmittance at 400 nm after heating is 99% or more, "A" for the transmittance is less than 99% and 98% or more for "A", and the transmittance is less than 98% for "B". Marked as. In addition, "A" and the transmittance | permeability of less than 98% were represented by "B" when the residual film rate after heating is 97% or more, and the transmittance | permeability in 400 nm after heating is 98% or more. In addition, when the residual film ratio after heating is less than 97%, it represented with "B".

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

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

Solvent resistance: After the obtained glass substrate with a cured film was immersed in N-methyl-2-pyrrolidone for 30 minutes at 40 degreeC (hereafter, NMP process), the residual film rate after the process with respect to the film thickness before a process And the transmittance before and after treatment. The case where the residual film ratio after the treatment is 95% or more and the transmittance at 400 nm after the treatment is 99% or more is indicated by "A". The case where the residual film rate after the treatment is less than 95% or the transmittance after the treatment is less than 99% is indicated by "B".

Adhesiveness: After the pressure cooker test (hereinafter, referred to as PCT treatment) was performed for 24 hours on the obtained glass substrate with a cured film at 120 ° C., 100%, and 0.2 MPa, adhesion of the cured film by peeling off the tape. Sex test (JIS-K-5400) was performed to count the remaining water. The case where the remaining number / 100 is 100/100 is represented by "A" and the case where 99/100 or less is represented by "B".

Sputter resistance: In the obtained glass substrate with a cured film, when the ITO film was formed on the cured film by 240 degreeC by the sputter | spatter so that the resistance value of 10 ohm / cm <^2> might be obtained, the presence or absence of wrinkles of a film was investigated. The case where there is no wrinkle is represented by "A", and the case where wrinkles arise is represented by "B".

Transparency: In the obtained glass substrate with a cured film, the transmittance | permeability in the wavelength of 400 nm of the light of a cured film only was measured with the spectrophotometer (brand name; MICRO COLOR ANALYZER TC-1800M, the product of the Tokyo Electrotechnical Technology Center). . The case where the transmittance | permeability is 99% or more is represented by "A", and the case where it is less than 99% is represented by "B".

Flatness: The coating solution was spin-coated on the glass substrate at 600 rpm for 10 seconds, then placed in a vacuum dryer and vacuum dried at 666.6 Pa for 2 minutes. The dried film on the glass substrate thus obtained was observed at 50 times the surface using a differential interference type microscope (trade name; AFX-IIA, manufactured by Nikon Corporation), and the surface was observed to have a smooth surface "A", and irregularities were observed on the surface. In the case of "B".

Experimental Example 2

The 1000 ml flask with a stirring blade was nitrogen-substituted, and 250 g of polyester-polyamine acid copolymer solutions obtained in Synthesis Example 2 and the N-phenylmaleimide / glycidyl methacrylate copolymer (30:70) were added to the flask. Molar ratio, weight average molecular weight 80,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxy propyl trimethoxysilane 8.25 g, Byk-344 (trade name, product of BYK-Chemie Co., Ltd.) 0.95 g, dehydrated MMP 518g was added, it stirred at room temperature for 5 hours, and it melt | dissolved uniformly. This mixed solution was filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution. Next, the cured film obtained by the same method as Experimental Example 1 compared and evaluated the characteristic with respect to a foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Experimental Example 3

A 1000 ml flask with agitated vanes was nitrogen-substituted, and 250 g of polyester-polyamine acid copolymer solution obtained in Synthesis Example 3 and N-phenylmaleimide / glycidyl methacrylate copolymer (30:70) Molar ratio, weight average molecular weight 80,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxy propyl trimethoxysilane 8.25 g, Byk-344 (trade name, product of BYK-Chemie Co., Ltd.) 0.95 g, dehydrated 518 g of MMP was added, and the mixture was stirred at room temperature for 5 hours to uniformly dissolve. This mixed solution was filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution. Next, the cured film obtained by the same method as Experimental Example 1 compared and evaluated the characteristic with respect to a foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Example 4

The 1000 ml flask with the stirring blade was nitrogen-substituted, and 250 g of polyester-polyamine acid copolymer solutions and N-phenylmaleimide / n-butyl methacrylate / glycidyl methacryl obtained in Synthesis Example 3 were added to the flask. 75 g of a rate copolymer (molar ratio 30:10:60, weight average molecular weight 40,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxy propyl trimethoxysilane, Byk-344 (brand name, BYK-Chemie Co., Ltd.) Product) 0.95g, 318g of dehydrated and purified PGMEA, and 200g of dehydrated and purified diethylene glycol methylethyl ether were added, and it stirred for 5 hours and made it melt | dissolve uniformly at room temperature. This mixed solution was filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution. Next, the cured film obtained by the same method as Experimental Example 1 compared and evaluated the characteristic with respect to a foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Comparative Example 1

After nitrogen-substituting a 500 ml separate flask with a thermometer and a stirring blade, 4.85 g of DDS and 43.22 g of 3-aminopropyltriethoxysilane were added thereto, followed by adding 197 g of dehydrated and purified MMP, followed by stirring at room temperature. And 3-aminopropyltriethoxysilane. Thereafter, the flask was cooled in an ice bath, and 36.36 g of ODPA was added when the temperature of the solution reached 10 ° C. When the temperature rise by the exothermic reaction stopped, the ice bath was removed and stirred at room temperature for 8 hours to obtain a pale yellow transparent silicone-containing polyamic acid solution. The viscosity of this solution was 12 mPa * s.

In a 500 ml separate flask equipped with a nitrogen wing with a stirring blade, 100 g of a silicon-containing polyamic acid solution, 30 g of Epicoat 191P (trade name, manufactured by Emulsified Shell Epoxy Co., Ltd.), 16.95 g of anhydrous trimellitic acid, 3-glycol 3.85 g of seed oxypropyl trimethoxysilane and 172.4 g of dehydrated and purified MMP were added thereto, stirred at room temperature, and dissolved homogeneously. Next, 0.17 g of Byk-344 (trade name, manufactured by BYK-Chemie Co., Ltd.) was added thereto, stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution. Next, the cured film obtained by the same method as Experimental Example 1 compared and evaluated the characteristic with respect to a foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Comparative Example 2

A 1000 ml flask with agitating blades was nitrogen-substituted, 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) were added to the flask. 100,000 g), 75 g of trimellitic anhydride, 15 g of 3-glycidoxy propyltrimethoxysilane, 0.95 g of Byk-344 (trade name, manufactured by BYK-Chemie), and 518 g of dehydrated and purified MMP were added thereto. The mixture was stirred for 5 hours and dissolved uniformly. This mixed solution was filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution. Next, the cured film obtained by the same method as Experimental Example 1 compared and evaluated the characteristic with respect to a foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Comparative Example 3

A 1000 ml flask with agitating blades was nitrogen-substituted, and 250 g of the polyester-polyamic acid copolymer solution obtained in Synthesis Example 2 and the benzyl methacrylate / glycidyl methacrylate copolymer (molar ratio 30:70) were added to the flask. , Weight average molecular weight 100,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxy propyl trimethoxysilane 8.25 g, Byk-344 (trade name, product of BYK-Chemie Co., Ltd.) 0.95 g, dehydrated MMP 518 g Was added, and stirred at room temperature for 5 hours to dissolve uniformly. This mixed solution was filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution. Next, the cured film obtained by the same method as Experimental Example 1 compared and evaluated the characteristic with respect to a foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Comparative Example 4

A 1000 ml flask with agitated vanes was nitrogen-substituted, and 250 g of the polyester-polyamine acid copolymer solution obtained in Synthesis Example 3 and the benzyl methacrylate / glycidyl methacrylate copolymer (molar ratio 30:70) were added to the flask. , Weight average molecular weight 100,000) 75 g, trimellitic anhydride 15 g, 3-glycidoxy propyl trimethoxysilane 8.25 g, Byk-344 (trade name, product of BYK-Chemie Co., Ltd.) 0.95 g, dehydrated MMP 518 g Was added, and stirred at room temperature for 5 hours to dissolve uniformly. This mixed solution was filtered through a membrane filter having a pore diameter of 0.2 µm to obtain a thermosetting polymer composition solution. Next, the cured film obtained by the same method as Experimental Example 1 compared and evaluated the characteristic with respect to a foreign material characteristic, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesiveness to a glass substrate, sputter resistance, transparency, and flatness. These evaluation results are shown in Table 1 below.

Item

Experimental example

Comparative Example One 2 3 4 One 2 3 4 Foreign substance characteristic [μm] 70 86 82 68 196 66 80 77 Heat resistance A + A A + A A B B B Alkali resistance A A A A B A A A Acid resistance A A A A A A A A Solvent resistance A A A A A A A A Adhesion A A A A A A A A Sputter resistance A A A A A A A A Transparency A A A A A A A A Flatness A A A A A B A A

As can be seen from the results shown in Table 1, the cured film obtained from the thermosetting polymer composition using the N-phenylmaleimide / glycidyl methacrylate copolymer according to Experimental Example 1 to Experimental Example 4 has good foreign material properties and heat resistance. It can be seen that it is excellent. The cured film obtained from the silicone containing polyamic-acid composition (refer Japanese Unexamined-Japanese-Patent No. 9-291105) which concerns on the comparative example 1 has bad foreign material characteristics and alkali resistance, and the fall of a yield is anticipated when used as a color filter protective film. In addition, the cured film obtained from the thermosetting polymer composition using the benzyl methacrylate / glycidyl methacrylate copolymer according to Comparative Examples 2 to 4 has poor heat resistance as compared with the experimental examples, and serves as a color filter protective film. It is not expected.

The thermosetting polymer composition which concerns on this invention is excellent in a foreign material characteristic, and when used as a color filter protective film, a yield improves. In addition, the cured film obtained by heating the thermosetting polymer composition which concerns on this invention is balanced in adhesiveness, transparency, applicability | paintability, and flatness with respect to the base substrate, such as heat resistance, alkali resistance, acid resistance, solvent resistance, water resistance, glass, etc. It is quite practical. It is especially useful as a protective film of the color filter manufactured by the dyeing method, the pigment dispersion method, the electrodeposition method, and the printing method. It can also be used as a protective film and a transparent insulating film of various optical materials. In addition, the cured film obtained from the thermosetting polymer composition according to the present invention has excellent properties as an optical material such as sputter resistance and transparency, as well as foreign material characteristics and heat resistance, and a light emitting device such as a color filter and a light emitting diode (LED); It can be used as a protective film, such as various optical materials, such as a light receiving element, a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode, or between a transparent electrode and an orientation film.

Although described above with reference to preferred embodiments of the present invention, those skilled in the art various modifications and changes of the present invention without departing from the spirit and scope of the invention described in the claims below It will be appreciated that it can be changed.

Claims (24)

Polyester compounds, N-substituted maleimide copolymers and solvents, The polyester compound is a compound obtained by reacting using tetracarboxylic dianhydride and a polyhydroxy compound and having a structural unit represented by the following formula (1), wherein the N-substituted maleimide copolymer is N- substituted maleade and oxy A copolymer of a monomer containing ranyl or a copolymer containing N-substituted maleade and oxetanyl,  N-substituted maleimide is N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, or N-butylmaleimide ,  The monomer having an oxiranyl is glycidyl (meth) acrylate, methylglycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate,  The monomer which has the said oxetanyl is 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxy Methyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, or 2- (methacryloyl Oxymethyl) -4-trifluoromethyloxetane, A thermosetting polymer composition comprising 100 parts by weight of N-substituted maleimide copolymer based on 100 parts by weight of the polyester compound. [Formula 1]

Wherein R ¹ is a tetracarboxylic dianhydride residue and R ³ is a polyhydroxy compound. The polyester-polyamic acid copolymer according to claim 1, wherein the polyester compound is obtained by reacting with a tetracarboxylic dianhydride, a polyhydroxy compound, and a diamine, The polyester compound is a thermosetting polymer composition, characterized in that the compound comprising a structural unit according to the formula (2) and formula (3).        [Formula 2]

(3)

Wherein R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyhydroxy compound residue. The method of claim 2, wherein the tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2, At least one compound selected from the group consisting of 2- (bis (3,4-dicarboxyphenyl)) hexafluoropropane anhydride and ethylene glycol bis (unhydrotrimerate), wherein the polyhydroxy compound is ethylene glycol, propylene At least one compound selected from the group consisting of glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol, wherein the diamine is 3, A thermosetting compound polymer composition, characterized in that at least one compound selected from the group consisting of 3'-diaminodiphenylsulfone and bis (4-3 aminophenoxy) phenyl) sulfone. The copolymer of the monomer of N-substituted maleimide and oxiranyl or the monomer copolymer of N-substituted maleimide and oxetanyl is N-phenylmaleimide / glycidyl meta. Two-component copolymer of acrylate, two-component copolymer of N-phenylmaleimide / methylglycidyl methacrylate, three-component copolymer of N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate, 3-component copolymer of N-phenylmaleimide / glycidyl methacrylate / n-butyl methacrylate, 3-component air of N-phenylmaleimide / 2-hydroxyethyl methacrylate / glycidyl methacrylate A thermosetting polymer composition characterized in that it is at least one compound selected from the group consisting of a copolymer and a three-component copolymer of N-phenylmaleimide / glycidyl methacrylate / styrene. The copolymer of the monomer containing N-substituted maleimide and oxiranyl or the copolymer of monomer containing N-substituted maleimide and oxetanyl is N-cyclohexyl maleimide / glycol. Bicomponent copolymer of cyl methacrylate, Bicomponent copolymer of N-cyclohexyl maleimide / methylglycidyl methacrylate, N-cyclohexyl maleimide / glycidyl methacrylate / benzyl methacryl 3-component copolymer of rate, 3-component copolymer of N-cyclohexyl maleimide / glycidyl methacrylate / n-butyl methacrylate, N-cyclohexyl maleimide / 2-hydroxyethyl methacrylate Among the thermosetting, characterized in that at least one compound selected from the group consisting of a three-component copolymer of / glycidyl methacrylate and a three-component copolymer of N-cyclohexyl maleimide / glycidyl methacrylate / styrene Body composition. 3. The tetracarboxylic dianhydride according to claim 2, wherein the tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, the polyhydroxy compound is 1,4-butanediol, and the diamine is 3,3 '-Diaminodiphenyl sulfone compound, the copolymer of the monomer containing N- substituted maleimide and oxiranyl or the monomer copolymer containing N-substituted maleimide and oxetanyl is N-phenylmaleimide / 3-component copolymer of n-butyl methacrylate / glycidyl methacrylate or 3-component copolymer of N-cyclohexyl maleimide / n-butyl methacrylate / glycidyl methacrylate, and the solvent A thermosetting polymer bath characterized in that it is a solvent containing any one selected from the group consisting of methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate and diethylene glycol methylethyl ether. Water. The thermosetting polymer composition according to claim 2, wherein the polyester compound is a polyester-polyamine acid copolymer obtained by reacting with a tetracarboxylic dianhydride, a polyhydroxy compound, a diamine and a monohydric alcohol. The tetracarboxylic dianhydride according to claim 7, wherein the tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 2 , 2- (bis (3,4-dicarboxyphenyl)) hexafluoropropane anhydride and at least one compound selected from the group consisting of ethylene glycol bis (unhydrotrimerate), the polyhydroxy compound is ethylene glycol, At least one compound selected from the group consisting of propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol, wherein the diamine is 3 At least one compound selected from the group consisting of 3'-diaminodiphenylsulfone and bis (4- (3-aminophenoxy) phenyl) sulfone, wherein the monohydric alcohol is isopropyl alcohol, aryl alcohol, benzyl alcohol, Roxyethyl methacrylate, propylene Recall monoethyl ether or 3-ethyl-3-hydroxymethyl-oxetanes of the thermosetting compound The polymer composition according to claim. The method of claim 7, wherein the copolymer of the monomer containing N- substituted maleimide and oxiranyl or the copolymer of the monomer containing N-substituted maleimide and oxetanyl is N-phenylmaleimide / glycidyl. 2-component copolymer of methacrylate, 2-component copolymer of N-phenylmaleimide / methylglycidyl methacrylate, 3-component copolymer of N-phenylmaleimide / glycidyl methacrylate / benzyl methacrylate , 3-component copolymer of N-phenylmaleimide / glycidyl methacrylate / n-butyl methacrylate, 3-component of N-phenylmaleimide / 2-hydroxyethyl methacrylate / glycidyl methacrylate A thermosetting polymer composition, characterized in that it is at least one compound selected from the group consisting of a copolymer and a three-component copolymer of N-phenylmaleimide / glycidyl methacrylate / styrene. The method of claim 7, wherein the copolymer of the monomer containing N-substituted maleimide and oxiranyl or the copolymer of the monomer containing N-substituted maleimide and oxetanyl is N-cyclohexylmaleimide / gly Bicomponent copolymer of cyl methacrylate, Bicomponent copolymer of N-cyclohexyl maleimide / methylglycidyl methacrylate, N-cyclohexyl maleimide / glycidyl methacrylate / benzyl methacryl 3-component copolymer of rate, 3-component copolymer of N-cyclohexyl maleimide / glycidyl methacrylate / n-butyl methacrylate, N-cyclohexyl maleimide / 2-hydroxyethyl methacrylate Among the thermosetting, characterized in that at least one compound selected from the group consisting of a three-component copolymer of / glycidyl methacrylate and a three-component copolymer of N-cyclohexyl maleimide / glycidyl methacrylate / styrene Body composition. 8. The method of claim 7, wherein the tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, the polyhydroxy compound is 1,4-butanediol, and the diamine is 3,3 '-Diaminodiphenyl sulfone, the monohydric alcohol is benzyl alcohol, a copolymer of a monomer containing the N- substituted maleimide and oxiranyl or a copolymer containing the N- substituted maleimide and oxetanyl Trivalent copolymer of N-phenylmaleimide / n-butyl methacrylate / glycidyl methacrylate or tricomponent of N-cyclohexyl maleimide / n-butyl methacrylate / glycidyl methacrylate And a solvent containing any one selected from the group consisting of methyl methoxypropionate, propylene glycol monomethyl ether acetate, and diethylene glycol methyl ethyl ether. The thermosetting polymer composition. The thermosetting polymer composition according to claim 7, wherein the polyester compound is a polyester-polyamine acid copolymer obtained by reacting with a tetracarboxyanhydride, a polyhydroxy compound, a diamine, a monohydric alcohol, and a silicone-containing monoamine. The thermosetting polymer composition according to claim 2, wherein the polyester-polyamic acid copolymer is also a polyester-polyamic acid copolymer obtained by reacting a styrene-maleic anhydride copolymer. The thermosetting polymer composition according to claim 1, further comprising an epoxy curing agent. The thermosetting polymer composition according to claim 14, wherein the epoxy curing agent is trimellitic anhydride. The thermosetting polymer composition according to claim 1, wherein the polyester compound has a weight average molecular weight of 1,000 to 200,000. The method of claim 1, wherein the weight average molecular weight of the copolymer of the monomer containing N- substituted maleimide and oxiranyl or the copolymer of the monomer containing N-substituted maleimide and oxetanyl is 3,000 to 1,000,000 Thermosetting polymer composition characterized by. The cured film obtained by heating the thermosetting polymer composition of any one of Claims 1-17. A color filter comprising the cured film according to claim 18 as a protective film. A liquid crystal display device comprising the color filter according to claim 19. A solid-state image sensor comprising the color filter according to claim 19. A liquid crystal display device comprising the cured film according to claim 18 as a transparent insulating film formed between the thin film transistor (TFT) and the transparent electrode. A liquid crystal display device comprising the cured film according to claim 18 as a transparent insulating film formed between the transparent electrode and the alignment electrode film. A light emitting diode (LED) light emitting body comprising the cured film according to claim 18 as a protective film.