TWI401278B - Thermosetting polymer composition - Google Patents
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- TWI401278B TWI401278B TW095107372A TW95107372A TWI401278B TW I401278 B TWI401278 B TW I401278B TW 095107372 A TW095107372 A TW 095107372A TW 95107372 A TW95107372 A TW 95107372A TW I401278 B TWI401278 B TW I401278B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D41/00—Electrical control of supply of combustible mixture or its constituents
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Description
本發明是有關於一種熱硬化性(Thermosetting)聚合物組成物,及藉由加熱、硬化該熱硬化性聚合物組成物而獲得之硬化膜。The present invention relates to a thermosetting polymer composition and a cured film obtained by heating and hardening the thermosetting polymer composition.
於液晶顯示元件等元件之製造步驟中,存有有機溶劑、酸、鹼溶液等各種藥品處理。而且,藉由濺鍍法將配線電極進行成膜時,表面被局部地加熱至高溫。因此,有時於液晶顯示元件等元件之表面設置保護膜以防止劣化、損傷及變質。要求這些保護膜具有可耐如上所述之製造步驟中之藥品處理或者局部加熱處理之各特性。具體而言,要求具有耐溶劑性、耐酸性、耐鹼性等耐藥品性、耐水性、耐熱性、與玻璃等底層基板之密著性、透明性、耐傷性、塗布性、平坦性、經過長時間後著色等不變質之耐光性等。尤其是,近年來使用為彩色濾光片保護膜之情形時,異物特性得以重視。於此,所謂異物特性,指異物易變明顯之現象。這種現象是由於下述原因所產生之現象:於存在有異物之基板上塗布、乾燥聚合物組成物時,異物周圍之膜厚產生不均勻,其結果,異物周圍之反射光錯亂,而產生因為目視成較實際異物大小更大之形狀的現象。所謂優異之異物特性,是指如此之現象難以發生,且異物不明顯。異物特性對彩色濾光片製造時之良率產生較大影響。In the manufacturing steps of components such as liquid crystal display elements, various chemical treatments such as an organic solvent, an acid, and an alkali solution are present. Further, when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Therefore, a protective film may be provided on the surface of an element such as a liquid crystal display element to prevent deterioration, damage, and deterioration. These protective films are required to have various properties that are resistant to the drug treatment or the local heat treatment in the manufacturing steps as described above. Specifically, it is required to have chemical resistance such as solvent resistance, acid resistance, and alkali resistance, water resistance, heat resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, coating property, flatness, and Light resistance, etc., which are not deteriorated after a long time. In particular, in the case where a color filter protective film is used in recent years, foreign matter characteristics are taken into consideration. Here, the term "foreign matter property" refers to a phenomenon in which foreign matter is easily changed. This phenomenon is caused by the following phenomenon: when the polymer composition is applied and dried on a substrate having foreign matter, the film thickness around the foreign matter is uneven, and as a result, the reflected light around the foreign matter is disordered. Because it looks like a larger shape than the actual foreign matter. The so-called excellent foreign matter characteristics mean that such a phenomenon is difficult to occur and the foreign matter is not obvious. The foreign matter characteristics have a large influence on the yield of the color filter.
作為具有優異之這些特性之保護膜材料,存有含矽之聚醯胺酸組成物(參照專利文獻1)。該組成物為具有優異之耐溶劑性、耐酸性、耐水性、與玻璃等底層基板之密著性、透明性、塗布性、平坦性的優良組成物,但其具有耐鹼性、異物特性較差之缺點。進而,近年來,已確知於製造液晶面板時之加熱步驟中自保護膜所產生之分解氣體使液晶面板之顯示品位下降,要求保護膜具有更好之耐熱性。從此觀點看來,含矽聚醯胺酸組成物之耐熱性並不充分。As a protective film material having such excellent properties, a polyamine composition containing ruthenium is present (see Patent Document 1). This composition is an excellent composition having excellent solvent resistance, acid resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, coatability, and flatness, but it has poor alkali resistance and poor foreign matter characteristics. The shortcomings. Further, in recent years, it has been confirmed that the decomposition gas generated from the protective film in the heating step in the production of the liquid crystal panel lowers the display quality of the liquid crystal panel, and the protective film is required to have better heat resistance. From this point of view, the heat resistance of the ruthenium-containing lysine composition is not sufficient.
[專利文獻1]日本專利特開平9-291150號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-291150
本發明之目的在於提供一種解決上述組成物之缺點者,即滿足耐溶劑性、耐酸性、耐水性、與玻璃等底層基板之密著性、透明性、塗布性、平坦性等特性,且具有優異的耐鹼性或者異物特性,進而具有優異的耐熱性之硬化膜,及製成該硬化膜之聚合物組成物。An object of the present invention is to provide a solution to the disadvantages of the above-mentioned composition, that is, to satisfy solvent resistance, acid resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, coating properties, flatness, and the like, and A cured film having excellent resistance to alkali or foreign matter, and further having excellent heat resistance, and a polymer composition obtained as the cured film.
本發明者們,為了解決上述問題點而進行各種研究,其結果發現藉由加熱硬化含有將四羧酸二酐及多元羥基化合物進行反應而獲得之聚酯化合物作為第一成分,N-取代馬來醯亞胺共聚物作為第二成分及溶劑作為第三成分之聚合物組成物而獲得之硬化膜,可達成上述目的,從而完成本發明。於此,第二成分之N-取代馬來醯亞胺共聚物是N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物。The inventors of the present invention conducted various studies to solve the above problems, and as a result, it has been found that a polyester compound obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound as a first component, N-substituted horse, is cured by heat curing. The above object can be attained by the above-described object, which is a cured film obtained by using a ruthenium imine copolymer as a second component and a solvent as a polymer component of the third component, thereby completing the present invention. Here, the N-substituted maleimide copolymer of the second component is a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide and a copolymer of a monomer having an oxetane group.
本發明具有以下構成。The present invention has the following constitution.
1.一種熱硬化性聚合物組成物,包括聚酯化合物、N-取代馬來醯亞胺共聚物及溶劑。於此,聚酯化合物是使用四羧酸二酐及多元羥基化合物進行反應所獲得的、具有以下述式(2)所表示之結構單元之化合物;N-取代馬來醯亞胺共聚物是N-取代馬來醯亞胺與具有氧雜環乙烷基之單體之共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體之共聚物。A thermosetting polymer composition comprising a polyester compound, an N-substituted maleimide copolymer, and a solvent. Here, the polyester compound is a compound having a structural unit represented by the following formula (2) obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound; the N-substituted maleimide copolymer is N a copolymer of a substituted maleimide and a monomer having an oxirane group or a copolymer of an N-substituted maleimide and a monomer having an oxetane group.
R1 是四羧酸二酐殘基,R3 是多元羥基化合物殘基。R 1 is a tetracarboxylic dianhydride residue, and R 3 is a residue of a polyvalent hydroxy compound.
2.如1中所述之熱硬化性聚合物組成物,其中聚酯化合物是藉由使用四羧狻二酐、多元羥基化合物及二胺進行反應而獲得之聚酯-聚醯胺酸共聚物。於此,聚酯化合物是具有以下述式(1)及(2)所表示之結構單元的化合物。2. The thermosetting polymer composition according to 1, wherein the polyester compound is a polyester-polyproline copolymer obtained by reacting using tetracarboxylic phthalic anhydride, a polyvalent hydroxy compound and a diamine. . Here, the polyester compound is a compound having a structural unit represented by the following formulas (1) and (2).
R1 是四羧酸二酐殘基,R2 是二胺殘基,R3 是多元羥基化合物殘基。R 1 is a tetracarboxylic dianhydride residue, R 2 is a diamine residue, and R 3 is a residue of a polyvalent hydroxy compound.
3.如2中所述之熱硬化性聚合物組成物,其中四羧酸二酐是選自3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐及乙二醇雙(偏苯三甲酸酯)中之一種或一種以上之化合物;多元羥基化合物是選自乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇及1,8-辛二醇中之一種或一種以上之化合物;二胺是選自3,3'-二胺基二苯基碸、雙[4-(3-胺基苯氧基)苯基]碸中之一種或一種以上之化合物。3. The thermosetting polymer composition according to 2, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(p-benzoate) One or more compounds; the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol And one or more compounds of 1,8-octanediol; the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium, bis[4-(3-aminophenoxy)phenyl One or more compounds of the formula.
4.如1至3中任一項所述之熱硬化性聚合物組成物,其中N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物是選自N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯之二成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸甲基縮水甘油酯之二成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯/甲基丙烯酸苄酯之三成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯/甲基丙烯酸正丁酯之三成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸2-羥基乙酯/甲基丙烯酸縮水甘油酯之三成分共聚物及N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯/苯乙烯之三成分共聚物中之一種或一種以上之化合物。4. The thermosetting polymer composition according to any one of 1 to 3, wherein a copolymer of N-substituted maleimide and a monomer having an oxocyclo group or N-substituted Malay The copolymer of quinone and a monomer having an oxetane group is a two-component copolymer selected from N-phenylmaleimide/glycidyl methacrylate, N-phenyl Malaya A two-component copolymer of amine/methyl methacrylate methyl glycidyl ester, a three-component copolymer of N-phenyl maleimide/glycidyl methacrylate/benzyl methacrylate, N-phenyl Malay a three-component copolymer of phthalimide/glycidyl methacrylate/n-butyl methacrylate, N-phenylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate One or more compounds of the component copolymer and the three-component copolymer of N-phenylmaleimide/glycidyl methacrylate/styrene.
5.如1至3中任一項所述之熱硬化性聚合物組成物,其中N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物是選自N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯之二成分共聚物、N-環己基馬來醯亞胺/甲基丙烯酸甲基縮水甘油酯之二成分共聚物、N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯/甲基丙烯酸苄酯之三成分共聚物、N-環己基馬來醯亞股/甲基丙烯酸縮水甘油酯/甲基丙烯酸正丁酯之三成分共聚物、N-環己基馬來醯亞胺/甲基丙烯酸2-羥基乙酯/甲基丙烯酸縮水甘油酯之三成分共聚物及N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯/苯乙烯之三成分共聚物中之一種或一種以上之化合物。5. The thermosetting polymer composition according to any one of 1 to 3, wherein a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted Malay The copolymer of a quinone imine and a monomer having an oxetane group is a two-component copolymer selected from N-cyclohexylmaleimide/glycidyl methacrylate, N-cyclohexylmalaya A two-component copolymer of amine/methyl methacrylate methyl glycidyl ester, a three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-cyclohexylmalay三Asian stock / glycidyl methacrylate / n-butyl methacrylate copolymer, N-cyclohexylmaleimide / 2-hydroxyethyl methacrylate / glycidyl methacrylate One or more compounds of the component copolymer and the three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/styrene.
6.如1至5中任一項所述之熱硬化性聚合物組成物,其中四羧酸二酐是3,3',4,4'-二苯醚四羧酸二酐;多元羥基化合物是1,4-丁二醇;二胺是3,3'-二胺基二苯基碸;N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物是N-苯基馬來醯亞胺/甲基丙烯酸正丁酯/甲基丙烯酸縮水甘油酯之三成分共聚物或者N-環己基馬來醯亞胺/甲基丙烯酸正丁酯/甲基丙烯酸縮水甘油酯之三成分共聚物;溶劑是含有3-甲氧基丙酸甲酯、丙二醇單甲醚乙酸酯、二乙二醇甲乙醚之其中之一的溶劑。6. The thermosetting polymer composition according to any one of 1 to 5, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; a polyvalent hydroxy compound Is 1,4-butanediol; the diamine is 3,3'-diaminodiphenylanthracene; a copolymer of N-substituted maleimide and a monomer having an oxirane group or N- a copolymer of substituted maleimide and a monomer having an oxetane group is a three-component copolymer of N-phenylmaleimide/n-butyl methacrylate/glycidyl methacrylate or a three-component copolymer of N-cyclohexylmaleimide/n-butyl methacrylate/glycidyl methacrylate; the solvent is methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, A solvent of one of diethylene glycol methyl ethyl ether.
7.如1或者2中所述之熱硬化性聚合物組成物,其中聚酯化合物是藉由使用四羧酸二酐、多元羥基化合物、二胺及一元醇進行反應而獲得之聚酯-聚醯胺酸共聚物。7. The thermosetting polymer composition according to 1 or 2, wherein the polyester compound is a polyester-polymer obtained by reacting using a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a diamine and a monohydric alcohol. Proline copolymer.
8.如7中所述之熱硬化性聚合物組成物,其中四羧酸二酐是選自3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐及乙二醇雙(偏苯三甲酸)酯中之一種或一種以上之化合物;多元羥基化合物乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇及1,8-辛二醇中之一種或一種以上之化合物;二胺是選自3,3'-二胺基二苯基碸、雙[4-(3-胺基苯氧基)苯基]碸中之一種或一種以上之化合物;一元醇是選自異丙醇、烯丙醇、苯甲醇、甲基丙烯酸羥乙酯、丙二醇單乙醚或者3-乙基-3-羥甲基氧雜環丁烷。8. The thermosetting polymer composition according to 7, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(trimellitic acid) ester One or more compounds; a polyhydric hydroxy compound ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1, One or more compounds of 8-octanediol; the diamine is selected from the group consisting of 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene One or more compounds; the monohydric alcohol is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyl oxetane .
9.如7或者8中所述之熱硬化性聚合物組成物,其中,N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物是選自N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯之二成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸甲基縮水甘油酯之二成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯/甲基丙烯酸苄酯之三成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯/甲基丙烯酸正丁酯之三成分共聚物、N-苯基馬來醯亞胺/甲基丙烯酸2-羥基乙酯/甲基丙烯酸縮水甘油酯之三成分共聚物及N-苯基馬來醯亞股/甲基丙烯酸縮水甘油酯/苯乙烯之三成分共聚物中之一種或一種以上之化合物。9. The thermosetting polymer composition according to 7 or 8, wherein a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted Malayan The copolymer of an amine and a monomer having an oxetane group is a two-component copolymer selected from N-phenylmaleimide/glycidyl methacrylate, N-phenylmaleimide/ Two-component copolymer of methyl glycidyl methacrylate, three-component copolymer of N-phenylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-phenyl Malaya Three-component copolymer of amine/glycidyl methacrylate/n-butyl methacrylate, N-phenylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of the three-component copolymer of N-phenyl maleate subunit/glycidyl methacrylate/styrene.
10.如7或者8中所述之熱硬化性聚合物組成物,其中N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物是選自N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯之二成分共聚物、N-環己基馬來醯亞胺/甲基丙烯酸甲基縮水甘油酯之二成分共聚物、N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯/甲基丙烯酸苄酯之三成分共聚物、N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯/甲基丙烯酸正丁酯之三成分共聚物、N-環己基馬來醯亞胺/甲基丙烯酸2-羥基乙酯/甲基丙烯酸縮水甘油酯之三成分共聚物及N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯/苯乙烯之三成分共聚物中之一種或一種以上之化合物。10. The thermosetting polymer composition according to 7 or 8, wherein a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide The copolymer with the oxetane-containing monomer is a two-component copolymer selected from N-cyclohexylmaleimide/glycidyl methacrylate, N-cyclohexylmaleimide/A Two-component copolymer of methyl glycidyl acrylate, three-component copolymer of N-cyclohexylmaleimide/glycidyl methacrylate/benzyl methacrylate, N-cyclohexylmaleimide Three-component copolymer of glycidyl methacrylate/n-butyl methacrylate, N-cyclohexylmaleimide/2-hydroxyethyl methacrylate/glycidyl methacrylate And one or more compounds of N-cyclohexylmaleimide/glycidyl methacrylate/styrene three-component copolymer.
11.如1至5中任一項所述之熱硬化性聚合物組成物,其中四羧酸二酐是3,3',4,4'-二苯醚四羧酸二酐;多元羥基化合物是1,4-丁二醇;二胺是3,3'-二胺基二苯基碸;一元醇是苯甲醇;N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物是N-苯基馬來醯亞胺/甲基丙烯酸正丁酯/甲基丙烯酸縮水甘油酯之三成分共聚物或者N-環己基馬來醯亞胺/甲基丙烯酸正丁酯/甲基丙烯酸縮水甘油酯之三成分共聚物;溶劑是含有3-甲氧基丙酸甲酯、丙二醇單甲醚乙酸酯、二乙二醇甲乙醚之其中之一的溶劑。The thermosetting polymer composition according to any one of 1 to 5, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride; a polyvalent hydroxy compound Is 1,4-butanediol; diamine is 3,3'-diaminodiphenylphosphonium; monohydric alcohol is benzyl alcohol; N-substituted maleimide and monomer having oxirane Copolymer or copolymer of N-substituted maleimide and oxetane-containing monomer is N-phenylmaleimide/n-butyl methacrylate/glycidyl methacrylate a three-component copolymer or a three-component copolymer of N-cyclohexylmaleimide/n-butyl methacrylate/glycidyl methacrylate; the solvent is methyl 3-methoxypropionate, propylene glycol alone a solvent of one of methyl ether acetate and diethylene glycol methyl ether.
12.如1至11中任一項所述之熱硬化性聚合物組成物,其中聚酯化合物是藉由使用四羧酸二酐、多元羥基化合物、二股、一元醇及含矽之單胺進行反應而獲得之聚酯一聚醯胺酸共聚物。The thermosetting polymer composition according to any one of 1 to 11, wherein the polyester compound is produced by using a tetracarboxylic dianhydride, a polyvalent hydroxy compound, a divalent, a monohydric alcohol, and a monoamine containing ruthenium. A polyester-polyglycolic acid copolymer obtained by the reaction.
13.如1至12中任一項所述之熱硬化性聚合物組成物,其中聚酯-聚醯胺酸共聚物是進而使苯乙烯-馬來酸酐共聚物亦進行反應而獲得之聚酯-聚醯胺酸共聚物。The thermosetting polymer composition according to any one of 1 to 12, wherein the polyester-polyglycolic acid copolymer is a polyester obtained by further reacting a styrene-maleic anhydride copolymer. - Polyproline copolymer.
14.如1至13中任一項所述之熱硬化性聚合物組成物,更包括環氧硬化劑。14. The thermosetting polymer composition according to any one of 1 to 13, further comprising an epoxy hardener.
15.如14中任一項所述之熱硬化性聚合物組成物,其中環氧硬化劑是偏苯三酸酐。The thermosetting polymer composition according to any one of the preceding claims, wherein the epoxy hardener is trimellitic anhydride.
16.如1至15中任一項所述之熱硬化性聚合物組成物,其中聚酯化合物之重量平均分子量為1,000至200,000。The thermosetting polymer composition according to any one of 1 to 15, wherein the polyester compound has a weight average molecular weight of 1,000 to 200,000.
17.如1至16中任一項所述之熱硬化性聚合物組成物,其中N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物的重量平均分子量為3,000至1,000,000。The thermosetting polymer composition according to any one of 1 to 16, wherein a copolymer of N-substituted maleimide and a monomer having an oxocyclo group or N-substituted Malay The copolymer of the quinoneimine and the monomer having an oxetane group has a weight average molecular weight of 3,000 to 1,000,000.
18.一種硬化膜,其是藉由加熱如1至17中任一項所述之熱硬化性聚合物組成物而獲得的。A cured film obtained by heating the thermosetting polymer composition according to any one of 1 to 17.
19.一種彩色濾光片,其使用如18中所述之硬化膜作為保護膜。A color filter using a cured film as described in 18 as a protective film.
20.一種液晶顯示元件,其使用有如19中所述之彩色濾光片。20. A liquid crystal display element using a color filter as described in 19.
21.一種固體攝像元件,其使用有如19中所述之彩色濾光片。A solid-state image pickup element using a color filter as described in 19.
22.一種液晶顯示元件,其使用如18中所述之硬化膜作為形成於TFT與透明電極間之透明絕緣膜。A liquid crystal display element using a cured film as described in 18 as a transparent insulating film formed between a TFT and a transparent electrode.
23.一種液晶顯示元件,其使用如18中所述之硬化膜作為形成於透明電極與配向膜間之透明絕緣膜。A liquid crystal display element using a cured film as described in 18 as a transparent insulating film formed between a transparent electrode and an alignment film.
24.一種LED發光體,其使用有如18中所述之硬化膜作為保護膜。An LED illuminator using a cured film as described in 18 as a protective film.
本發明之熱硬化性聚合物組成物具有優異的異物特性,於使用為彩色濾光片保護膜之情形時,良率得以提高。又,藉由加熱本發明之熱硬化性聚合物組成物而獲得之硬化膜是耐熱性、耐鹼性、耐酸性、耐溶劑性、耐水性、與玻璃等底層基板之密著性、透明性、塗布性、平坦性平衡且實用性高。尤其是可用作藉由染色法、顏料分散法、電鍍法及印刷法而製造之彩色濾光片保護膜。又,可使用為各種光學材料之保護膜及透明絕緣膜。The thermosetting polymer composition of the present invention has excellent foreign matter characteristics, and when used as a color filter protective film, the yield is improved. Further, the cured film obtained by heating the thermosetting polymer composition of the present invention has heat resistance, alkali resistance, acid resistance, solvent resistance, water resistance, adhesion to an underlying substrate such as glass, and transparency. The coating property and flatness are balanced and the utility is high. In particular, it can be used as a color filter protective film produced by a dyeing method, a pigment dispersion method, an electroplating method, and a printing method. Further, a protective film and a transparent insulating film which are various optical materials can be used.
本發明中所使用之聚酯化合物是藉由將四羧酸二酐及多元羥基化合物進行反應而獲得之化合物。聚酯化合物之具體例是聚酯、聚酯-聚醯胺酸共聚物。較好的聚酯化合物是聚酯-聚醯胺酸共聚物。聚酯-聚醯胺酸共聚物藉由將四羧酸二酐、多元羥基化合物及二胺進行反應而獲得。The polyester compound used in the present invention is a compound obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound. Specific examples of the polyester compound are polyester, polyester-polyglycolic acid copolymer. A preferred polyester compound is a polyester-polyglycolic acid copolymer. The polyester-polyglycolic acid copolymer is obtained by reacting a tetracarboxylic dianhydride, a polyvalent hydroxy compound, and a diamine.
於本發明中所使用之聚酯化合物,具有以通式(1)或/及(2)所表示之結構單元。於將四羧酸二酐及多元羥基化合物進行反應而獲得之聚酯化合物之情形時,含有通式(2)之結構單元。於將四羧酸二酐、多元羥基化合物及二胺進行反應而獲得之聚酯化合物之情形時,含有通式(1)及(2)之結構單元。The polyester compound used in the present invention has a structural unit represented by the formula (1) or / and (2). In the case of a polyester compound obtained by reacting a tetracarboxylic dianhydride and a polyvalent hydroxy compound, the structural unit of the formula (2) is contained. In the case of a polyester compound obtained by reacting a tetracarboxylic dianhydride, a polyvalent hydroxy compound, and a diamine, the structural unit of the formula (1) and (2) is contained.
作為本發明中所使用之四羧酸二酐之具體例,可列舉3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、2,2',3,3'-二苯基碸四羧酸二酐、2,3,3',4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯醚四羧酸二酐、2,2',3,3'-二苯醚四羧酸二酐、2,3,3',4'-二苯醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐及乙二醇雙(偏苯三甲酸酯)(商品名:TMEG-100、新日本理化(股份公司)製造)等芳香族四羧酸二酐、環丁烷四羧酸二酐、甲基環丁烷四羧酸二酐、環戊烷四羧酸二酐及環己烷四羧酸二酐等脂環式四羧酸二酐及乙烷四羧酸二酐及丁烷四羧酸二酐等脂肪族四羧酸二酐。Specific examples of the tetracarboxylic dianhydride used in the present invention include 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2,2',3,3'-diphenyl. Ketone tetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2, 2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-diphenyl Ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[ Aromatic four such as bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(trimellitic acid ester) (trade name: TMEG-100, manufactured by Nippon Chemical and Chemical Co., Ltd.) An alicyclic tetracarboxylic acid such as a carboxylic acid dianhydride, a cyclobutane tetracarboxylic dianhydride, a methylcyclobutane tetracarboxylic dianhydride, a cyclopentane tetracarboxylic dianhydride, and a cyclohexane tetracarboxylic dianhydride An aliphatic tetracarboxylic dianhydride such as an anhydride, ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride.
這些四羧酸二酐中較好的是,可製成透明性良好之樹脂的3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、乙二醇雙(偏苯三甲酸酯)(商品名:TMEG-100,新日本理化(股份公司)製造),尤其好的是3,3',4,4'-二苯醚四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐。Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4, 4', which can be made into a resin having good transparency, is preferred. -diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(p-benzoate) (trade name: TMEG- 100, manufactured by New Japan Physical and Chemical (stock company), especially good 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylfluorene Carboxylic dianhydride.
作為本發明中所使用之多元羥基化合物之具體例,可列舉乙二醇、二乙二醇、三乙二醇、四乙二醇、分子量為1,000以下之聚乙二醇、丙二醇、二丙二醇、三丙二醇、四丙二醇、分子量為1,000以下之聚丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,5-戊二醇、2,4-戊二醇、1,2,5-戊三醇、1,2-己二醇、1,6-己二醇、2,5-己二醇、1,2,6-己三醇、1,2-庚二醇、1,7-庚二醇、1,2,7-庚三醇、1,2-辛二醇、1,8-辛二醇、3,6-辛二醇、1,2,8-辛三醇、1,2-壬二醇、1,9-壬二醇、1,2,9-壬三醇、1,2-癸二醇、1,10-癸二醇、1,2,10-癸三醇、1,2-十二烷二醇、1,12-十二烷二醇、丙三醇、三羥甲基丙烷、季戊四醇、二季戊四醇、雙酚A(商品名)、雙酚S(商品名)、雙酚F(商品名)、二乙醇胺及三乙醇胺、SEO-2(商品名,日華化學(股份公司)製),SKY CHDM,RIKABINOL()HB(以上為商品名,新日本理化(股份公司)製造)等。Specific examples of the polyvalent hydroxy compound used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, and the like. Tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5- Pentandiol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2, 6-hexanetriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3, 6-octanediol, 1,2,8-octanetriol, 1,2-decanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-nonanediol, 1,2,10-nonanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylolpropane, pentaerythritol, Dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine and triethanolamine, SEO-2 (trade name, manufactured by Rihua Chemical Co., Ltd.), SKY CHDM, RIKABINOL ( ) HB (the above is the trade name, manufactured by New Japan Physical and Chemical Co., Ltd.).
這些多元羥基化合物中較好的是乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、SEO-2、SKY CHDM及RIKABINOL()HB,因1,4-丁二醇、1,5-戊二醇及1,6-己二醇溶解對於溶劑之溶解性良好,故而尤其好。Preferred among these polyvalent hydroxy compounds are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8. -octanediol, SEO-2, SKY CHDM and RIKABINOL ( HB, because 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are excellent in solubility in a solvent, and therefore are particularly preferable.
作為於本發明中使用之二胺之具體例,可列舉4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、3,4'-二胺基二苯基碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、雙[3-(4-胺基苯氧基)苯基]碸、[4-(4-胺基苯氧基)苯基][3-(4-胺基苯氧基)苯基]碸、[4-(3-胺基苯氧基)苯基][3-(4-胺基苯氧基)苯基]碸及2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷等。這些二胺中較好的是可製成透明性良好之樹脂的3,3'-二胺基二苯基碸及雙[4-(3-胺基苯氧基)苯基]碸,尤其好的是3,3'-二胺基二苯基碸。Specific examples of the diamine used in the present invention include 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, and 3,4'-diaminodiyl. Phenylhydrazine, bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]indole, bis[3-(4-aminobenzene) Oxy)phenyl]indole, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]indole, [4-(3-aminophenoxy) Phenyl][3-(4-aminophenoxy)phenyl]anthracene and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and the like. Preferred among these diamines are 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene which are excellent in transparency, especially good. It is 3,3'-diaminodiphenylanthracene.
作為本發明所使用之一元醇之具體例,可列舉甲醇、乙醇、1-丙醇、異丙醇、烯丙醇、苯甲醇、甲基丙烯酸羥乙酯、丙二醇單乙醚、丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單甲醚、乙二醇單乙醚、乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單乙醚、酚、冰片、麥芽酚、芳樟醇、松油醇、二甲基苄基甲醇、乳酸乙酯、縮水甘油、3-乙基-3-羥甲基氧雜環丁烷等。Specific examples of the monohydric alcohol used in the present invention include methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and propylene glycol monomethyl ether. Dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, linalool, Terpineol, dimethylbenzylmethanol, ethyl lactate, glycidol, 3-ethyl-3-hydroxymethyloxetane, and the like.
這些一元醇中較好的是異丙醇、烯丙醇、苯甲醇、甲基丙烯酸羥乙酯、丙二醇單乙醚、3-乙基-3-羥甲基氧雜環丁烷。考慮到混合使用這些一元醇而生成之聚酯-聚醯胺酸共聚物、與N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物、及環氧硬化劑之情形時之相溶性,或者於最終製品熱硬化性樹脂組成物之於彩色濾光片上之塗布性,更好的是使用一元醇中之苯甲醇。Preferred among these monohydric alcohols are isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyl oxetane. Considering a polyester-polyproline copolymer formed by mixing these monohydric alcohols, a copolymer with an N-substituted maleimide and a monomer having an oxirane group, or an N-substituted maleate The compatibility of the imide with the oxetane group-containing monomer and the epoxy curing agent, or the coating property of the final product thermosetting resin composition on the color filter, More preferably, benzyl alcohol is used in the monohydric alcohol.
作為本發明中所使用之含矽之單胺的具體例,可列舉3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-胺丙基甲基二甲氧矽烷、3-胺丙基甲基二乙氧基矽烷、4-胺丁基三甲氧基矽烷、4-胺丁基三乙氧基矽烷、4-胺丁基甲基二乙氧基矽烷、對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、對胺基苯基甲基二甲氧矽烷、對胺基苯基甲基二乙氧基矽烷、間胺基苯基三甲氧基矽烷及間胺基苯基甲基二乙氧基矽烷等。這些含矽之單胺中較好的是3-胺丙基三乙氧基矽烷及對胺基苯基三甲氧基矽烷,3-胺丙基三乙氧基矽烷之塗膜耐酸性良好,故而特別好。Specific examples of the monoamine containing ruthenium used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyldimethoxydecane. , 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutyldimethoxydecane, p-aminobenzene Trimethoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl methyl dimethoxy decane, p-aminophenyl methyl diethoxy decane, m-aminophenyl trimethoxy Decane and m-aminophenylmethyldiethoxydecane, and the like. Among these monoamines containing ruthenium, preferred are 3-aminopropyltriethoxydecane and p-aminophenyltrimethoxydecane, and the coating film of 3-aminopropyltriethoxydecane has good acid resistance, and thus Especially good.
作為用於獲得聚酯-聚醯胺酸共聚物之聚合反應之反應溶劑的具體例,可列舉二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲乙醚、二乙二醇單乙醚乙酸酯、乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、環己酮、N-甲基-2-吡咯酮及N,N-二甲基乙醯胺等。這些反應溶劑中較好的是丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、二乙二醇甲乙醚及N-甲基-2-吡咯酮。Specific examples of the reaction solvent for obtaining the polymerization reaction of the polyester-polyglycolic acid copolymer include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and diethyl ethylene. Alcohol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, N- Methyl-2-pyrrolidone and N,N-dimethylacetamide. Preferred among these reaction solvents are propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, diethylene glycol methyl ethyl ether and N-methyl-2-pyrrolidone.
這些反應溶劑可單獨使用或者使用為2種以上之混合溶劑。又,若為30重量%或30重量%以下之比例,則除上述反應溶劑以外亦可混合其它溶劑使用。These reaction solvents may be used singly or as a mixed solvent of two or more kinds. Further, in the case of a ratio of 30% by weight or 30% by weight or less, other solvents may be used in addition to the above-mentioned reaction solvent.
本發明之聚酯化合物可自四羧酸二酐及多元羥基化合物而製造。The polyester compound of the present invention can be produced from tetracarboxylic dianhydride and a polyvalent hydroxy compound.
於此,更好的聚酯化合物是聚酯-聚醯胺酸共聚物。聚酯-聚醯胺酸共聚物之製造方法是使四羧酸二酐(X莫耳),二胺(Y莫耳)及多元羥基化合物(Z莫耳)於上述反應溶劑中進行反應。此時較好的是X、Y及Z由彼等之間以滿足下述式(1)及式(2)之關係之比例定而決定。若為該範圍,則相對於溶劑之聚酯-聚醯胺酸共聚物之溶解性高,因此,組成物之塗布性提高,結果可獲得平坦性優異之硬化膜。Here, a more preferred polyester compound is a polyester-polyglycolic acid copolymer. The polyester-polyglycolic acid copolymer is produced by reacting tetracarboxylic dianhydride (X mole), diamine (Y mole) and polyvalent hydroxy compound (Z mole) in the above reaction solvent. In this case, it is preferred that X, Y and Z are determined by the ratio between the following formulas (1) and (2). When it is in this range, since the solubility with respect to the polyester-polyamide copolymer of a solvent is high, the coating property of a composition improves, and the cured film which is excellent in flatness is obtained.
0.2≦Z/Y≦8.0………(1) 0.2≦(Y+Z)/X≦5.0………(2)0.2≦Z/Y≦8.0.........(1) 0.2≦(Y+Z)/X≦5.0.........(2)
(1)式之關係,較好的是0.7≦Z/Y≦7.0,更好的是1.0≦Z/Y≦5.0。又,(2)式之關係,較好的是0.5≦(Y+Z)/X≦4.0,更好的是0.6≦(Y+Z)/X≦2.0。The relationship of the formula (1) is preferably 0.7≦Z/Y≦7.0, more preferably 1.0≦Z/Y≦5.0. Further, the relationship of the formula (2) is preferably 0.5 ≦ (Y + Z) / X ≦ 4.0, more preferably 0.6 ≦ (Y + Z) / X ≦ 2.0.
本發明中所使用之聚酯-聚醯胺酸共聚物,於分子末端具有酸酐基之情形時,根據需要,可添加上述之一元醇使之進行反應。添加有一元醇之聚酯-聚醯胺酸共聚物不僅可改善與N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物及環氧硬化劑之相溶性,且可改善含有彼等之本發明之熱硬化性樹脂組成物之塗布性。When the polyester-polyproline copolymer used in the present invention has an acid anhydride group at the molecular terminal, the above-mentioned monohydric alcohol may be added and reacted as needed. The addition of a monohydric alcohol-polyamido acid copolymer not only improves the copolymer with N-substituted maleimine and a monomer having an oxocyclo group or N-substituted maleimide The compatibility of the copolymer of the oxetane group-containing monomer and the epoxy curing agent improves the coatability of the thermosetting resin composition of the present invention containing the same.
又,若使上述含矽之單胺與於分子末端具有酸酐基之聚酯-聚醯胺酸共聚物進行反應,則所獲得之塗膜之耐酸性得到改善。進而,亦可使一元醇與含有矽之單胺同時與聚酯-聚醯胺酸共聚物進行反應。Further, when the monoamine containing ruthenium is reacted with a polyester-polyglycine copolymer having an acid anhydride group at the molecular terminal, the acid resistance of the obtained coating film is improved. Further, the monool and the monoamine containing ruthenium may be simultaneously reacted with the polyester-polyglycolic acid copolymer.
若相對於四羧酸二酐、二胺及多元羥基化合物之總和100重量份使用100重量份或100重量份以上之反應溶劑,則反應平穩進行,故而較好。較好的是於40℃至200℃下,使之反應0.2至20小時。於使含矽之單胺進行反應之情形時,四羧酸二酐與二胺及多元羥基化合物之反應結束後,將反應液冷卻至小於等於40℃後,添加含矽之單胺,較好的是於10至40℃下,使之反應0.1至6小時。又,一元醇可於反應之任一時刻進行添加。When 100 parts by weight or more of the reaction solvent is used per 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine and the polyvalent hydroxy compound, the reaction proceeds smoothly, which is preferable. It is preferred to carry out the reaction at 40 ° C to 200 ° C for 0.2 to 20 hours. When the reaction of the monoamine containing ruthenium is carried out, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the monoamine containing ruthenium is preferably added. It is allowed to react at 10 to 40 ° C for 0.1 to 6 hours. Further, the monohydric alcohol can be added at any time during the reaction.
將反應原料添加至反應系統之順序,並無特別限定。即,可使用將四羧酸二酐與二胺及多元羥基化合物同時添加至反應溶劑;使二胺及多元羥基化合物溶解於反應溶劑中後,添加四羧酸二酐;預先使四羧酸二酐與多元羥基化合物進行反應後,添加二胺至其共聚物中;或者預先使四羧酸二酐與二胺進行反應後,添加多元羥基化合物至其共聚物中等任一之方法。所獲得之聚酯-聚醯胺酸共聚物之重量平均分子量較好的是1,000至200,000,更好的是2,000至150,000。異物特性,分子量越高越好;相對於溶劑之溶解性,分子量越低越好。The order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound may be simultaneously added to a reaction solvent; after dissolving a diamine and a polyhydric hydroxy compound in a reaction solvent, tetracarboxylic dianhydride is added; After the reaction of the anhydride with the polyvalent hydroxy compound, the diamine is added to the copolymer; or the tetracarboxylic dianhydride is reacted with the diamine in advance, and then the polyvalent hydroxy compound is added to any of the copolymers. The polyester-polyamine copolymer obtained has a weight average molecular weight of preferably from 1,000 to 200,000, more preferably from 2,000 to 150,000. The foreign matter characteristic, the higher the molecular weight, the better; the lower the molecular weight, the better, relative to the solubility of the solvent.
為了提高聚酯-聚醯胺酸共聚物之重量平均分子量,亦可添加具有三個以上酸酐基之化合物進行合成反應。作為具有三個以上酸酐基之化合物之具體例,可列舉苯乙烯-馬來酸酐共聚物。In order to increase the weight average molecular weight of the polyester-polyglycine copolymer, a compound having three or more acid anhydride groups may be added for the synthesis reaction. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer.
如此而合成之聚酯-聚醯胺酸共聚物含有由前記式(1)及(2)所構成的結構單元,其末端是來源自作為原料之四羧酸二酐、二胺或者多元羥基化合物的酸酐基、胺基或者羥基,或者這些化合物以外之添加物構成該末端。式(1)及(2)中,R1 為四羧酸二酐殘基,較好的是碳數為2至30之有機基。R2 為二胺殘基,較好的是碳數為2至30之有機基。R3 為多元羥基化合物殘基,較好的是碳數為2至20之有機基。The polyester-polyamine copolymer thus synthesized contains a structural unit composed of the above formulas (1) and (2), and the terminal is derived from a tetracarboxylic dianhydride, a diamine or a polyvalent hydroxy compound as a raw material. An acid anhydride group, an amine group or a hydroxyl group, or an additive other than these compounds constitutes the terminal. In the formulae (1) and (2), R 1 is a tetracarboxylic dianhydride residue, preferably an organic group having 2 to 30 carbon atoms. R 2 is a diamine residue, preferably an organic group having 2 to 30 carbon atoms. R 3 is a residue of a polyvalent hydroxy compound, preferably an organic group having 2 to 20 carbon atoms.
本發明中所使用之N-取代馬來醯亞胺共聚物,只要其與形成本發明之熱硬化性聚合物組成物之其它成分之相溶性較好就可以使用,而無特別限定,較好的是,可列舉N-取代馬來醯亞胺與具有氧雜環乙烷基之單體或者具有氧雜環丁烷基之單體的共聚物、N-取代馬來醯亞胺與具有氧雜環乙烷基之單體或者具有氧雜環丁烷基之單體與其它單體的共聚物、N-取代馬來醯亞胺與具有氧雜環乙烷基之單體或者具有氧雜環丁烷基之單體的共聚物與脂環式環氧樹脂或者雙酚A型環氧樹脂之混合體、或者N-取代馬來醯亞胺與具有氧雜環乙烷基之單體或者具有氧雜環丁烷基之單體與其它單體的共聚物與脂環式環氧樹脂或者雙酚A型環氧樹脂之混合體等。這些N-取代馬來醯亞胺共聚物中,N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物藉由優異的透明性與異物特性,故而尤其好。The N-substituted maleimide copolymer used in the present invention can be used as long as it has good compatibility with the other components forming the thermosetting polymer composition of the present invention, and is not particularly limited. The copolymer of N-substituted maleimide and a monomer having an oxocyclo group or a monomer having an oxetanyl group, N-substituted maleimide and oxygen may be mentioned. a heterocyclic ethylenic monomer or a copolymer of an oxetane group monomer with another monomer, an N-substituted maleimide and a monomer having an oxirane group or having an oxo group a mixture of a cyclobutane monomer and a mixture of an alicyclic epoxy resin or a bisphenol A epoxy resin, or an N-substituted maleimide and a monomer having an oxirane group or A copolymer of a monomer having an oxetane group and another monomer, a mixture of an alicyclic epoxy resin or a bisphenol A epoxy resin, or the like. Among these N-substituted maleimide copolymers, a copolymer of an N-substituted maleimide and a monomer having an oxirane group is particularly preferable because of excellent transparency and foreign matter characteristics.
作為本發明中所使用之N-取代馬來醯亞胺之具體例,可列舉N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-丙基馬來醯亞胺、N-丁基馬來醯亞胺。尤其好的是N-苯基馬來醯亞胺及N-環己基馬來醯亞胺。Specific examples of the N-substituted maleimide used in the present invention include N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide. Particularly preferred are N-phenylmaleimide and N-cyclohexylmaleimide.
作為具有氧雜環乙烷基之單體之具體例,可列舉(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯及(甲基)丙烯酸3,4-環氧基環己基甲酯。這些具有氧雜環乙烷基之單體中,甲基丙烯酸縮水甘油酯可製成異物特性良好之硬化膜,故而較好。Specific examples of the monomer having an oxirane group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and a 3,4-epoxy ring of (meth)acrylic acid. Hexyl methyl ester. Among these oxirane-based monomers, glycidyl methacrylate is preferred as a cured film having good foreign matter properties.
作為具有氧雜環丁烷基之單體之具體例,可列舉3-(甲基丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-三氯甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-苯基氧雜環丁烷、2-(甲基丙烯醯氧基甲基)氧雜環丁烷、2-(甲基丙烯醯氧基甲基)-4-三氯甲基氧雜環丁烷、4-乙酸基苯乙烯與3-乙基-3-羥甲基氧雜環丁烷之化合物及4-(1-乙氧基乙氧基)苯乙烯與-乙基-3-羥甲基氧雜環丁烷之化合物。Specific examples of the monomer having an oxetane group include 3-(methacryloxymethyl)-3-ethyloxetane and 3-(acryloxymethyl). 3-ethyloxetane, 3-(methacryloxymethyl)-2-trichloromethyloxetane, 3-(methacryloxymethyl)-2 -phenyloxetane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trichloromethyloxetane Alkane, 4-acetoxystyrene and 3-ethyl-3-hydroxymethyloxetane compounds and 4-(1-ethoxyethoxy)styrene and -ethyl-3-hydroxyl A compound of oxetane.
作為其它單體之具體例,可列舉(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、苯乙烯、甲基苯乙烯及氯甲基苯乙烯等。這些其它單體中,更好的是所獲得之共聚物與本發明之聚酯-聚醯胺酸共聚物之相溶性優異之(甲基)丙烯酸甲酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-羥基乙酯及苯乙烯。Specific examples of the other monomer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) ) 2-hydroxypropyl acrylate, styrene, methyl styrene, chloromethyl styrene, and the like. Among these other monomers, methyl (meth)acrylate and benzyl (meth)acrylate which are excellent in compatibility of the obtained copolymer with the polyester-polyglycine copolymer of the present invention are more preferable. N-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and styrene.
作為脂環式環氧樹脂或者雙酚A型環氧樹脂之具體例,可列舉Epikote 807、Epikote 815、Epikote 825、Epikote 827、Epikote 828、Epikote 190P、Epikote 191P(以上商品名、油化Shell Epoxy(股份公司)製)、Epikote 1001、Epikote 1002、Epikote 1004AF、Epikote 1256(以上商品名、日本環氧樹脂(股份公司)(Japan Epoxy Resins Co.,Ltd.)製)、愛牢達(araldite)CY177、愛牢達CY184(以上商品名、日本汽巴嘉基(Ciba-Geigy)(股份公司)製)、CELL 2021、CELL 3000及EHPE-3150(以上商品名、DAICEL化學工業(股份公司)(DAICEL CHEMICAL INDUSTRIES,LTD.)製)等。本發明中所使用之N-取代馬來醯亞胺與具有氧雜環乙烷基環氧之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物亦可混合2種或者2種以上使用。混合使用分子量不足1萬之N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物,與分子量為大於等於1萬之N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物之情形時,若分子量大於等於1萬之N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物為大於等於N-取代馬來醯亞胺與具有氧雜環乙烷基之單體的共聚物或者N-取代馬來醯亞胺與具有氧雜環丁烷基之單體的共聚物全體之5重量%,則其異物特性良好,故而較好。Specific examples of the alicyclic epoxy resin or the bisphenol A epoxy resin include Epikote 807, Epikote 815, Epikote 825, Epikote 827, Epikote 828, Epikote 190P, and Epikote 191P (above trade name, oiled Shell Epoxy) (manufacturing company), Epikote 1001, Epikote 1002, Epikote 1004AF, Epikote 1256 (above trade name, Japan Epoxy Resins Co., Ltd.), araldite CY177, Araldite CY184 (above trade name, Ciba-Geigy (share company)), CELL 2021, CELL 3000 and EHPE-3150 (above trade name, DAICEL Chemical Industry (stock company) ( DAICEL CHEMICAL INDUSTRIES, LTD.)). Copolymer of N-substituted maleimide and monomer having oxirane epoxy or N-substituted maleimide and monomer having oxetanyl group used in the present invention The copolymer may be used in combination of two or more kinds. Mixing a copolymer of N-substituted maleimide having a molecular weight of less than 10,000 and a monomer having an oxirane group or N-substituted maleimide and a monomer having an oxetane group Copolymer, copolymer with N-substituted maleimide having a molecular weight of 10,000 or more and a monomer having an oxirane group or N-substituted maleimide and having an oxetane group In the case of a copolymer of a monomer, if the molecular weight is 10,000 or more, a copolymer of N-substituted maleimide and a monomer having an oxirane group or N-substituted maleimide has The copolymer of the oxetane monomer is a copolymer of N-substituted maleimine and a monomer having an oxirane group or N-substituted maleimide and has an oxygen It is preferred that the total amount of the copolymer of the cyclobutane monomer is 5 wt%, and the foreign matter characteristics are good.
具有氧雜環乙烷基之單體與其它單體的共聚物之比例,若具有氧雜環乙烷基之單體為大於等於30莫耳%,則耐藥品性優異,故而較好。更好的是具有氧雜環乙烷基之單體為大於等於50莫耳%。When the ratio of the oxirane group-containing monomer to the copolymer of the other monomer is 30% by mole or more based on the oxirane group, the chemical resistance is excellent, which is preferable. More preferably, the monomer having an oxoyl group is 50 mol% or more.
具有氧雜環乙烷基之單體之聚合物,或者具有氧雜環乙烷基之單體與其它單體之共聚物的分子量,較好的是重量平均分子量為3,000至1,000,000,更好的是50,000至500,000。其原因在於分子量越高則異物特性越好,分子量越低則對於溶劑之溶解性越好。The polymer of the monomer having an oxirane group, or the copolymer of the monomer having an oxirane group and another monomer, preferably having a weight average molecular weight of 3,000 to 1,000,000, more preferably It is 50,000 to 500,000. The reason for this is that the higher the molecular weight, the better the foreign matter characteristics, and the lower the molecular weight, the better the solubility to the solvent.
具有氧雜環丁烷基之單體與其它單體之共聚物之比例,若具有氧雜環丁烷基之單體為大於等於30莫耳%,則耐藥品性優異,故而較好。更好的是具有氧雜環乙烷基之單體為大於等於50莫耳%。When the ratio of the oxetane group-containing monomer to the copolymer of the other monomer is 30% by mole or more, the oxirane group is excellent in chemical resistance. More preferably, the monomer having an oxoyl group is 50 mol% or more.
具有氧雜環丁烷基之單體之聚合物,或者具有氧雜環丁烷基之單體與其它單體之共聚物的分子量,較好的是重量平均分子量為3,000至1,000,000,更好的是50,000至500,000。其原因在於分子量越高則異物特性越好,分子量越低則對於溶劑之溶解性越好。The polymer of the monomer having an oxetane group, or the copolymer of a monomer having an oxetane group and another monomer, preferably having a weight average molecular weight of 3,000 to 1,000,000, more preferably It is 50,000 to 500,000. The reason for this is that the higher the molecular weight, the better the foreign matter characteristics, and the lower the molecular weight, the better the solubility to the solvent.
作為於本發明中所使用之聚合物組成物之溶劑,可直接使用於合成聚酯-聚醯胺酸共聚物時之聚合反應中所使用的反應溶劑。進而根據必要,進行反應後,使反應溶劑之一部分蒸發,亦可追加新溶劑。上述熱硬化性聚合物組成物之固體成分,應根據塗膜之膜厚加以選擇,一般而言,其於該聚合物組成物中含有5至40重量%之範圍。The solvent of the polymer composition used in the present invention can be used as it is in the reaction solvent used in the polymerization reaction in the synthesis of the polyester-polyglycolic acid copolymer. Further, if necessary, after the reaction is carried out, one of the reaction solvents is partially evaporated, and a new solvent may be added. The solid content of the above thermosetting polymer composition is selected according to the film thickness of the coating film, and generally it is contained in the range of 5 to 40% by weight in the polymer composition.
本發明之熱硬化性聚合物組成物,相對於100重量份之聚酯-聚醯胺酸共聚物,N-取代馬來醯亞胺共聚物是20至400重量份。N-取代馬來醯亞胺共聚物若為該範圍,則平坦性、耐熱性、耐藥品性、密著性、異物特性之平衡良好。若N-取代馬來醯亞胺共聚物為50至200重量份之範圍,則進而較好。The thermosetting polymer composition of the present invention has 20 to 400 parts by weight of the N-substituted maleimide copolymer with respect to 100 parts by weight of the polyester-polyglycolic acid copolymer. When the N-substituted maleimide copolymer is in this range, the balance between flatness, heat resistance, chemical resistance, adhesion, and foreign matter characteristics is good. Further, it is further preferred if the N-substituted maleimide copolymer is in the range of 50 to 200 parts by weight.
為了提高耐熱性、耐藥品性,有效的是於本發明之熱硬化性聚合物組成物中添加環氧硬化劑。作為環氧硬化劑,例如酸酐系硬化劑、聚胺系硬化劑、聚酚系硬化劑及觸媒型硬化劑等,考慮到著色及耐熱性之方面,較好的是酸酐系硬化劑。In order to improve heat resistance and chemical resistance, it is effective to add an epoxy curing agent to the thermosetting polymer composition of the present invention. As the epoxy curing agent, for example, an acid anhydride-based curing agent, a polyamine-based curing agent, a polyphenol-based curing agent, and a catalyst-type curing agent are preferably an acid anhydride-based curing agent in view of coloring and heat resistance.
作為酸酐系硬化劑之具體例,可列舉馬來酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、六氫偏苯三酸酐等脂肪族二羧酸酐,苯二甲酸酐、偏苯三酸酐等芳香族多元羧酸酐,苯乙烯-馬來酸酐共聚物等。考慮到耐熱性與對於溶劑之溶解性之平衡之方面,這些酸酐系硬化劑之中,尤其好的是六氫偏苯三酸酐、偏苯三酸酐。Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. An aromatic polycarboxylic acid anhydride such as phthalic anhydride or trimellitic anhydride, or a styrene-maleic anhydride copolymer. Among these acid anhydride-based hardeners, hexahydrotrimellitic anhydride and trimellitic anhydride are particularly preferable in view of the balance between heat resistance and solubility in a solvent.
以提高耐熱性、耐藥品性為目的添加環氧硬化劑情形時,N-取代馬來醯亞胺共聚物與環氧硬化劑之比率,較好的是相對於N-取代馬來醯亞胺共聚物中所含有之氧雜環乙烷基或者氧雜環丁烷基,添加環氧硬化劑之羧酸酐基或者羧酸基使之成為0.05至2倍當量。此時,羧酸酐基以二元計算。若添加羧酸酐基或者羧酸基使之成為0.1至1.5倍當量時,耐藥品性進一步得以提高,故而更好。When an epoxy hardener is added for the purpose of improving heat resistance and chemical resistance, the ratio of the N-substituted maleimide copolymer to the epoxy hardener is preferably relative to the N-substituted maleimide The oxirane group or oxetane group contained in the copolymer is added to the carboxylic anhydride group or the carboxylic acid group of the epoxy curing agent to make it 0.05 to 2 equivalents. At this time, the carboxylic anhydride group is calculated in binary. When a carboxylic anhydride group or a carboxylic acid group is added so as to be 0.1 to 1.5 times equivalent, the chemical resistance is further improved, which is more preferable.
本發明之熱硬化性聚合物組成物,於不損及本發明目的之範圍內,亦可根據需要含有上述以外之其它成分。作為該其它成分,可列舉偶合劑、界面活性劑。The thermosetting polymer composition of the present invention may contain other components than those described above, as long as the object of the present invention is not impaired. As such other components, a coupling agent and a surfactant are mentioned.
偶合劑是用於提高與基板之密著性者,較好的是,相對於上述熱硬化性聚合物組成物之固體成分100重量份(自該聚合物組成物中除去溶劑後殘存之成分),添加1至30重量份偶合劑而加以使用。The coupling agent is for improving the adhesion to the substrate, and is preferably 100 parts by weight of the solid component of the thermosetting polymer composition (the component remaining after removing the solvent from the polymer composition) Add 1 to 30 parts by weight of a coupling agent and use it.
作為偶合劑,可使用矽烷系、鋁系及鈦酸酯系之化合物。As the coupling agent, a compound of a decane type, an aluminum type, and a titanate type can be used.
具體而言,可列舉3-縮水甘油氧基丙基二甲基乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷及3-縮水甘油氧基丙基三甲氧矽烷等矽烷系、乙醯烷氧基二異丙醇鋁(acetalkoxy aluminum diisopropylate)等鋁系及四異丙醇雙(二辛基磷酸)鈦酸酯等鈦酸酯系。這些偶合劑中,3-縮水甘油氧基丙基三甲氧矽烷提高密著性的效果較大,故而較好。Specific examples thereof include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like. A titanate such as decane-based, acetalkoxy aluminum diisopropylate or the like, and a titanate such as tetraisopropanol bis(dioctylphosphoric acid) titanate. Among these coupling agents, 3-glycidoxypropyltrimethoxysilane has a large effect of improving the adhesion, and therefore is preferable.
界面活性劑是用於提高底層基板之浸潤性、勻化性、或者塗布性者,相對於上述熱硬化性聚合物組成物100重量份,添加使用0.01至1重量份。作為界面活性劑,可使用矽系界面活性劑、丙烯系界面活性劑及氟系界面活性劑等。具體而言,可列舉Byk-300,Byk-306,Byk-335,Byk-310,Byk-341,Byk-344及Byk-370(以上商品名,BYK-Chemie(股份公司)製)等矽系,Byk-354,Byk-358及Byk-361(以上商品名,BYK-Chemie(股份公司)製)等丙烯基系,DFX-18,ftergent 250及ftergent 251(以上商品名,NEOS(股份公司)製)。The surfactant is used to increase the wettability, homogenization property, or coating property of the underlayer substrate, and is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the thermosetting polymer composition. As the surfactant, a ruthenium-based surfactant, a propylene-based surfactant, a fluorine-based surfactant, or the like can be used. Specific examples include Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, and Byk-370 (above trade name, BYK-Chemie (manufactured by the company)) , Byk-354, Byk-358 and Byk-361 (above trade name, BYK-Chemie (manufactured by the company)) and other acrylic systems, DFX-18,ftergent 250 and ffergent 251 (above trade name, NEOS (stock company) system).
本發明之熱硬化性聚合物組成物,可通過下述之方式獲得:混合聚酯化合物、N-取代馬來醯亞胺共聚物及溶劑,根據作為目的之特性,進而根據需要選擇添加環氧硬化劑、偶合劑及界面活性劑,將彼等混合溶解均勻。The thermosetting polymer composition of the present invention can be obtained by mixing a polyester compound, an N-substituted maleimide copolymer, and a solvent, and optionally adding an epoxy according to the purpose of the purpose. The hardener, coupling agent and surfactant are mixed and dissolved evenly.
若將如上所述調製之熱硬化性聚合物組成物塗布於基體表面,並藉由加熱除去溶劑,則可形成塗膜。向基體表面塗布熱硬化性聚合物組成物,可藉由旋塗法、滾筒塗裝法、浸漬法及隙縫塗佈法等先前眾所周知之方法形成塗膜。繼而以加熱板,或者加熱爐等加熱(預烘烤)該塗膜。加熱條件根據各成分之種類及配合比例不同而不同,通常為70至120℃,若為加熱爐,則為5至15分鐘,若為加熱板,則為1至5分鐘。其後,為使塗膜硬化而加熱處理180至250℃,較好的是加熱處理200至240℃,若為加熱爐則加熱處理30至90分鐘,若為加熱板則加熱處理5至30分鐘,藉此可獲得硬化膜。When the thermosetting polymer composition prepared as described above is applied onto the surface of the substrate and the solvent is removed by heating, a coating film can be formed. The thermosetting polymer composition is applied to the surface of the substrate, and the coating film can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method. The coating film is then heated (prebaked) with a hot plate or a heating furnace. The heating conditions vary depending on the type of each component and the mixing ratio, and are usually 70 to 120 ° C, 5 to 15 minutes in the case of a heating furnace, and 1 to 5 minutes in the case of a hot plate. Thereafter, in order to harden the coating film, heat treatment is 180 to 250 ° C, preferably 200 to 240 ° C for heat treatment, heat treatment for 30 to 90 minutes in the case of a heating furnace, and heat treatment for 5 to 30 minutes in the case of a heating plate. Thereby, a cured film can be obtained.
如此而所獲得之硬化膜,於加熱時,1)聚酯-聚醯胺酸共聚物之聚醯胺酸部分脫水環化形成醯亞胺鍵,2)聚酯-聚醯胺酸共聚物之羧酸與N-取代馬來醯亞胺共聚物之環氧(氧雜環乙烷基或者氧雜環丁烷基)反應而高分子量化,以及3)N-取代馬來醯亞胺共聚物之環氧與環氧硬化劑反應而高分子量化,故而非常堅韌,且透明性、耐熱性、耐藥品性、平坦性、密著性及耐濺鍍性優異。The cured film thus obtained is, when heated, 1) dehydrated and cyclized to form a quinone bond of the polyamido acid of the polyester-polyamide copolymer, and 2) a polyester-polyamide copolymer The carboxylic acid is reacted with an epoxy (oxiranyl or oxetane) of an N-substituted maleimide copolymer to be polymerized, and 3) an N-substituted maleimide copolymer Since the epoxy reacts with the epoxy curing agent and is highly polymerized, it is very tough, and is excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, and sputtering resistance.
繼而,藉由本發明之合成例、實施例及比較例加以具體說明,但本發明並不受這些實施例任何限制。Then, the synthesis examples, examples, and comparative examples of the present invention will be specifically described, but the present invention is not limited by these examples.
如下所述合成含有四羧酸二酐、二胺、多元羥基化合物之共聚物的聚酯-聚醯胺酸共聚物溶液。A polyester-polyaminic acid copolymer solution containing a copolymer of a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound was synthesized as follows.
於此,以下所表示之黏度使用E型黏度計(商品名:VISCONIC END,(股份公司)東京計器製造)於25℃下進行測定。Here, the viscosity shown below was measured at 25 ° C using an E-type viscometer (trade name: VISCONIC END, manufactured by Tokyo Instruments Co., Ltd.).
將附有溫度計、攪拌葉片之500 ml之燒瓶以氮氣置換之後,裝入92.99 g之3,3',4,4'-二苯醚四羧酸二酐(以下簡稱為「ODPA」)、27.01 g之1,4-丁二醇及280 g之脫水精製之3-甲氧基丙酸甲酯(以下簡稱為「MMP」),以油浴加溫至130℃,並攪拌4小時後,進行冷卻,藉此獲得淡黃色透明之聚酯化合物之30%溶液。該溶液之黏度為65 mPa.s。以GPC測定其重量平均分子量為7,600。After replacing the 500 ml flask equipped with a thermometer and a stirring blade with nitrogen, 92.99 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as "ODPA"), 27.01 was charged. g of 1,4-butanediol and 280 g of dehydrated purified methyl 3-methoxypropionate (hereinafter referred to as "MMP"), heated to 130 ° C in an oil bath, and stirred for 4 hours, Cooling, thereby obtaining a 30% solution of a pale yellow transparent polyester compound. The viscosity of the solution is 65 mPa. s. The weight average molecular weight was 7,600 as determined by GPC.
將附有溫度計、攪拌葉片之500 ml之燒瓶以氮氣置換之後,裝入13.03 g之3,3'-二胺基二苯基碸(以下簡稱為「DDS」)、14.19 g之1,4-丁二醇之後,裝入280g之脫水精製之MMP,於室溫下進行攪拌,使DDS、1,4-丁二醇溶解。其後,投入81.42 g之ODPA、11.35 g之苯甲醇。以油浴加溫至130℃,並攪拌4小時後冷卻至30℃,獲得淡黃色透明之聚酯-聚醯胺酸共聚物之30%溶液。該溶液之黏度為20 mPa.s。以GPC測定其重量平均分子量為3,400。The 500 ml flask equipped with a thermometer and a stirring blade was replaced with nitrogen, and then charged with 13.03 g of 3,3'-diaminodiphenyl hydrazine (hereinafter referred to as "DDS") and 14.19 g of 1,4-. After the butanediol, 280 g of the dehydrated MMP was charged, and the mixture was stirred at room temperature to dissolve DDS and 1,4-butanediol. Thereafter, 81.42 g of ODPA and 11.35 g of benzyl alcohol were charged. The mixture was heated to 130 ° C in an oil bath, stirred for 4 hours, and then cooled to 30 ° C to obtain a 30% solution of a pale yellow transparent polyester-polyamine copolymer. The viscosity of the solution is 20 mPa. s. The weight average molecular weight was 3,400 as determined by GPC.
將附有溫度計、攪拌葉片之500 ml之燒瓶以氮氣置換之後,裝入81.42 g之ODPA、14.19 g之1,4-丁二醇、11.35 g之苯甲醇之後,裝入217.18 g之脫水精製MMP,以油浴加溫至130℃,並攪拌2小時後。繼而冷卻至30℃,裝入13.03 g之DDS、62.82 g之脫水精製MMP,並於室溫下攪拌2小時。其後以油浴加溫至130℃,並攪拌1小時後,冷卻至30℃,獲得淡黃色透明之聚酯-聚醯胺酸共聚物之30%溶液。該溶液之黏度為27 mPa.s。以GPC測定其重量平均分子量為4,000。After replacing the 500 ml flask equipped with a thermometer and a stirring blade with nitrogen, 81.42 g of ODPA, 14.19 g of 1,4-butanediol, and 11.35 g of benzyl alcohol were charged, and then 217.18 g of dehydrated refined MMP was charged. The mixture was heated to 130 ° C in an oil bath and stirred for 2 hours. Then, it was cooled to 30 ° C, and 13.03 g of DDS and 62.82 g of dehydrated MMP were charged, and stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C in an oil bath, and after stirring for 1 hour, it was cooled to 30 ° C to obtain a 30% solution of a pale yellow transparent polyester-polyamide copolymer. The viscosity of the solution is 27 mPa. s. The weight average molecular weight was 4,000 as determined by GPC.
將附有溫度計、攪拌葉片之500 ml之燒瓶以氮氣置換之後,裝入16.95之ODPA、51.55g之苯乙烯-馬來酸酐共聚物(苯乙烯/馬來酸酐=1/1(莫耳比),重量平均分子量1,800)、3.28g之1,4-丁二醇、19.70g之苯甲醇之後,裝入137.22g之脫水精製丙二醇單甲醚乙酸酯(以下簡稱為「PGMEA」),以油浴加溫至130℃,並攪拌2小時。繼而冷卻至30℃,裝入4.523g之DDS、86.78g之脫水精製PGMEA,於室溫下攪拌2小時。其後以油浴加溫至130℃並攪拌1小時後,將其冷卻至30℃,獲得淡黃色透明之聚酯-聚醯胺酸共聚物之30%溶液。該溶液之黏度為36 mPa.s。以GPC測定其重量平均分子量為48,000。A 500 ml flask equipped with a thermometer and a stirring blade was replaced with nitrogen, and then charged with 16.95 ODPA and 51.55 g of a styrene-maleic anhydride copolymer (styrene/maleic anhydride = 1/1 (mole ratio). After the weight average molecular weight of 1,800), 3.28 g of 1,4-butanediol, and 19.70 g of benzyl alcohol, 137.22 g of dehydrated refined propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was added to the oil. The bath was warmed to 130 ° C and stirred for 2 hours. Then, the mixture was cooled to 30 ° C, and 4.523 g of DDS and 86.78 g of dehydrated purified PGMEA were charged, and the mixture was stirred at room temperature for 2 hours. Thereafter, the mixture was heated to 130 ° C in an oil bath and stirred for 1 hour, and then cooled to 30 ° C to obtain a 30% solution of a pale yellow transparent polyester-polyamide copolymer. The viscosity of the solution is 36 mPa. s. The weight average molecular weight was 48,000 as determined by GPC.
將附有攪拌葉片之1,000 ml之燒瓶以氮氣置換後,於該燒瓶中裝入於合成例1中所獲得之250 g之聚酯化合物溶液、75 g之N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物(莫耳比30:70,重量平均分子量8萬)、15 g之偏苯三酸酐、8.25 g之3-縮水甘油氧基丙基三甲氧矽烷及0.95 g之Byk-344(商品名:BYK-Chemie(股份公司)製)、518g之脫水精製MMP,於室溫下攪拌5小時,使之均勻溶解。以孔徑為0.2 μm之薄膜過濾器過濾該混合溶液,獲得熱硬化性聚合物組成物溶液(以下,稱之為塗布液)。繼而,該塗布液以600 rpm之轉速旋塗於玻璃基板上10秒鐘後,於已溫熱至80℃之加熱板上預烘烤2分鐘,形成塗膜。其後藉由已溫熱至230℃之烘箱加熱40分鐘硬化塗膜,獲得膜厚1.5 μm之硬化膜。關於如此所獲得之硬化膜,比較評價異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。After replacing the 1,000 ml flask with the stirring blade with nitrogen, the flask was charged with 250 g of the polyester compound solution obtained in Synthesis Example 1, and 75 g of N-phenylmaleimide/ Glycidyl methacrylate copolymer (mole ratio 30:70, weight average molecular weight 80,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane and 0.95 g of Byk-344 ( Trade name: BYK-Chemie (manufactured by the company), 518 g of dehydrated MMP, and stirred at room temperature for 5 hours to be uniformly dissolved. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution (hereinafter referred to as a coating liquid). Then, the coating liquid was spin-coated on the glass substrate at 600 rpm for 10 seconds, and then prebaked on a hot plate which had been warmed to 80 ° C for 2 minutes to form a coating film. Thereafter, the coating film was cured by heating in an oven which had been warmed to 230 ° C for 40 minutes to obtain a cured film having a film thickness of 1.5 μm. The cured film obtained in this manner was evaluated for foreign material properties, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, transparency, and flatness characteristics. The results of these evaluations are shown in Table 1.
異物特性:將鉻基板設置於玻璃珠間隔件之散佈器上,散佈直徑為20 μm之玻璃珠間隔件使之以成為3至5個/cm2 之比例。以600 rpm旋塗塗布液於該基板10秒鐘後,於加熱板上以80℃預烘烤3分鐘形成塗膜。其後,以烘箱於220℃下加熱30分鐘,藉此硬化塗膜,獲得膜厚為1.5 μm之硬化膜。使用微分干涉型顯微鏡(商品名:AFX-IIA,(股份公司)Nikon製造)以50倍觀察該硬化膜之表面,測定玻璃珠間隔件周圍的膜突起部分之直徑。單位為μm。Foreign matter characteristics: A chromium substrate was placed on a diffuser of a glass bead spacer, and a glass bead spacer having a diameter of 20 μm was spread so as to have a ratio of 3 to 5 pieces/cm 2 . The coating liquid was spin-coated on the substrate at 600 rpm for 10 seconds, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a coating film. Thereafter, the film was cured by heating at 220 ° C for 30 minutes in an oven to obtain a cured film having a film thickness of 1.5 μm. The surface of the cured film was observed at 50 times using a differential interference type microscope (trade name: AFX-IIA, manufactured by Nikon Co., Ltd.), and the diameter of the film protruding portion around the glass bead spacer was measured. The unit is μm.
耐熱性:將所獲得之附有硬化膜之玻璃基板於250℃下再加熱1小時後,測定相對於加熱前膜厚的加熱後之殘膜率及加熱後之400 nm之透過率。Heat resistance: After the obtained glass substrate with a cured film was further heated at 250 ° C for 1 hour, the residual film ratio after heating with respect to the film thickness before heating and the transmittance at 400 nm after heating were measured.
將加熱後之殘膜率為大於等於99%,且加熱後之400 nm之透過率為大於等於99%之情形記為「A+」;透過率不足99%大於等於98%記為「A」,透過率不足98%時記為「B」。又,將加熱後之殘膜率大於等於97%,且加熱後之400 nm之透過率大於等於98%之情形記為「A」,透過率不足98%記為「B」。又,加熱後之殘膜率不足97%之情形時記為「B」。The residual film rate after heating is 99% or more, and the case where the transmittance at 400 nm after heating is 99% or more is referred to as "A+"; the transmittance of less than 99% and 98% or more is recorded as "A". When the transmittance is less than 98%, it is recorded as "B". Further, the residual film rate after heating was 97% or more, and the case where the transmittance at 400 nm after heating was 98% or more was recorded as "A", and the transmittance was less than 98% as "B". Further, when the residual film ratio after heating is less than 97%, it is referred to as "B".
耐鹼性:將所獲得之附有硬化膜之玻璃基板於5%氫氧化鈉水溶液中於30℃下實施浸漬處理30分鐘(以下,簡稱為NaOH處理)後,測定相對於處理前膜厚的處理後之殘膜率以及處理前後之透過率。處理後之殘膜率為大於等於95%,且處理後之400 nm之透過率為大於等於99%之情形記為「A」。處理後之殘膜率不足95%,或者處理後之透過率不足99%之情形記為「B」。Alkali resistance: The obtained glass substrate with a cured film was immersed in a 5% sodium hydroxide aqueous solution at 30 ° C for 30 minutes (hereinafter, abbreviated as NaOH treatment), and then measured with respect to the film thickness before the treatment. Residual film rate after treatment and transmittance before and after treatment. The residual film ratio after the treatment was 95% or more, and the case where the transmittance at 400 nm after the treatment was 99% or more was referred to as "A". The residual film ratio after the treatment was less than 95%, or the case where the transmittance after the treatment was less than 99% was referred to as "B".
耐酸性:將所獲得之附有硬化膜之玻璃基板,於含有36%鹽酸/60%硝酸/水=40/20/40之混合液(重量比)中於50℃下施加浸漬處理15分鐘(以下,簡稱為混酸處理)後,測定相對於處理前膜厚的處理後之殘膜率及處理前後之透過率。處理後之殘膜率為大於等於95%,且處理後之400 nm之透過率為大於等於99%之情形記為「A」。處理後之殘膜率不足95%,或者處理後之透過率不足99%之情形記為「B」。Acid resistance: The obtained glass substrate with a cured film was subjected to immersion treatment at 50 ° C for 15 minutes in a mixed solution (weight ratio) containing 36% hydrochloric acid / 60% nitric acid / water = 40 / 20 / 40 ( Hereinafter, after simply referred to as mixed acid treatment, the residual film ratio after the treatment with respect to the film thickness before the treatment and the transmittance before and after the treatment were measured. The residual film ratio after the treatment was 95% or more, and the case where the transmittance at 400 nm after the treatment was 99% or more was referred to as "A". The residual film ratio after the treatment was less than 95%, or the case where the transmittance after the treatment was less than 99% was referred to as "B".
耐溶劑性:將所獲得之附有硬化膜之玻璃基板,於N-甲基-2-吡咯酮中於40℃下進行浸漬處理30分鐘(以下,簡稱為NMP處理)後,測定相對於處理前膜厚的處理後之殘膜率及處理前後之透過率。處理後之殘膜率為大於等於95%,且處理後之400 nm之透過率為大於等於99%之情形記為「A」。處理後之殘膜率不足95%,或者處理後之透過率不足99%之情形記為「B」。Solvent resistance: The obtained glass substrate with a cured film was immersed in N-methyl-2-pyrrolidone at 40 ° C for 30 minutes (hereinafter, abbreviated as NMP treatment), and then measured and treated. The residual film ratio after the treatment of the front film thickness and the transmittance before and after the treatment. The residual film ratio after the treatment was 95% or more, and the case where the transmittance at 400 nm after the treatment was 99% or more was referred to as "A". The residual film ratio after the treatment was less than 95%, or the case where the transmittance after the treatment was less than 99% was referred to as "B".
密著性:關於所獲得之附有硬化膜之玻璃基板,於120℃、100%及0.2 MPa之條件下實行24小時壓力鍋試驗(以下,簡稱為PCT處理)後,進行以膠帶剝離硬化膜的方格試驗(JIS-K-5400)並計數殘存數。殘存數/100為100/100之情形時記為「A」,小於等於99/100之情形時記為「B」。Adhesion: The obtained glass substrate with a cured film was subjected to a 24-hour pressure cooker test (hereinafter, abbreviated as PCT treatment) at 120 ° C, 100%, and 0.2 MPa, and the cured film was peeled off by a tape. The square test (JIS-K-5400) and counted the remaining number. When the residual number /100 is 100/100, it is marked as "A", and when it is less than or equal to 99/100, it is recorded as "B".
耐濺鍍性:所獲得之附有硬化膜之玻璃基板中,以獲得10 Ω/cm2 之電阻值之方式,藉由濺鍍於240℃下於硬化膜上形成ITO膜時,檢查膜有無褶皺產生。無褶皺之情形時記為「A」,產生褶皺之情形記為「B」。Sputter resistance: In the obtained glass substrate with a cured film, in order to obtain a resistance value of 10 Ω/cm 2 , when the ITO film is formed on the cured film by sputtering at 240 ° C, the presence or absence of the film is checked. Wrinkles are produced. In the case of no wrinkles, it is referred to as "A", and the case where wrinkles are generated is referred to as "B".
透明性:於所獲得之附有硬化膜之玻璃基板中,以分光光度計(商品名:MICRO COLOR ANALYZER TC-1800M,東京電色技術中心有限公司製造)僅測定硬化膜之光波長400 nm之透過率。透過率大於等於99%之情形時記為「A」,不足99%之情形時記為「B」。Transparency: In the obtained glass substrate with a cured film, the spectrophotometer (trade name: MICRO COLOR ANALYZER TC-1800M, manufactured by Tokyo Electrochrome Technology Center Co., Ltd.) was used to measure only the light wavelength of the cured film at 400 nm. Transmittance. When the transmittance is 99% or more, it is marked as "A", and when it is less than 99%, it is recorded as "B".
平坦性:於玻璃基板上以600 rpm之轉速旋塗塗布液10秒鐘後,裝入真空乾燥器以666.6帕斯卡真空乾燥2分鐘。使用微分干涉型顯微鏡(商品名;AFX-IIA,(股份公司)Nikon製造)於50倍下觀察如此所獲得之玻璃基板上乾燥膜之表面,表面平滑之情形時記為「A」,觀測到表面凹凸之情形時記為「B」。Flatness: The coating liquid was spin-coated on a glass substrate at 600 rpm for 10 seconds, and then placed in a vacuum dryer and dried under vacuum at 666.6 Pascal for 2 minutes. The surface of the dried film on the glass substrate thus obtained was observed at 50 times using a differential interference type microscope (trade name; AFX-IIA, manufactured by Nikon Co., Ltd.), and the surface was smoothed as "A", and it was observed. When the surface is uneven, it is marked as "B".
將附有攪拌葉片之1,000 ml之燒瓶以氮氣置換後,於該燒瓶中裝入於合成例2中所獲得之250 g之聚酯-聚醯胺酸共聚物溶液、75 g之N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物(莫耳比30:70,重量平均分子量8萬)、15 g之偏苯三酸酐、8.25 g之3-縮水甘油氧基丙基三甲氧矽烷及0.95 g之Byk-344(商品名;Byk-Chemie(股份公司)製)、518 g之脫水精製MMP,於室溫下攪拌5小時,使之均勻溶解。將該混合溶液以孔徑為0.2 μm之薄膜過濾器進行過濾,獲得熱硬化性聚合物組成物溶液。繼而,對根據與實施例1同樣之方法所獲得之硬化膜,比較評價其異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。After replacing the 1,000 ml flask with the stirring blade with nitrogen, the flask was charged with 250 g of the polyester-polyproline copolymer solution obtained in Synthesis Example 2, and 75 g of N-phenyl group. Maleidin/glycidyl methacrylate copolymer (mole ratio 30:70, weight average molecular weight 80,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane and 0.95 Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.) and 518 g of dehydrated MMP were stirred at room temperature for 5 hours to be uniformly dissolved. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.
將附有攪拌葉片之1,000 ml之燒瓶以氮氣置換後,於該燒瓶中裝入於合成例3中所獲得之250 g之聚酯-聚醯胺酸共聚物溶液溶液、75 g之N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物(莫耳比30:70,重量平均分子量8萬)、15g之偏苯三酸酐、8.25 g之3-縮水甘油氧基丙基三甲氧矽烷及0.95 g之Byk-344(商品名;Byk-Chemie(股份公司)製)、518g之脫水精製之MMP,於室溫下攪拌5小時,使之均勻溶解。將該混合溶液以孔徑為0.2 μm之薄膜過濾器進行過濾,獲得熱硬化性聚合物組成物溶液。繼而,對根據與實施例1同樣之方法所獲得之硬化膜,比較評價其異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。After replacing a 1,000 ml flask equipped with a stirring blade with nitrogen, the flask was charged with 250 g of a polyester-polyproline copolymer solution obtained in Synthesis Example 3, and 75 g of N-benzene. Kamalimide/glycidyl methacrylate copolymer (mol ratio 30:70, weight average molecular weight 80,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxydecane and 0.95 Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.) and 518 g of dehydrated MMP were stirred at room temperature for 5 hours to be uniformly dissolved. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.
將附有攪拌葉片之1,000 ml之燒瓶以氮氣置換後,於該燒瓶中裝入於合成例3中所獲得之250 g之聚酯-聚醯胺酸共聚物溶液溶液、75 g之N-苯基馬來醯亞胺/甲基丙烯酸正丁酯/甲基丙烯酸縮水甘油酯共聚物(莫耳比30:10:60,重量平均分子量4萬)、15 g之偏苯三酸酐、8.25 g之3-縮水甘油氧基丙基三甲氧矽烷及0.95 g之Byk-344(商品名;Byk-Chemie(股份公司)製)、318g之脫水精製之PGMEA、200 g之脫水精製之二乙二醇甲乙醚,於室溫下攪拌5小時,均勻溶解。將該混合溶液以孔徑為0.2 μm之薄膜過濾器進行過濾,獲得熱硬化性聚合物組成物溶液。繼而,對根據與實施例1同樣之方法所獲得之硬化膜,比較評價其異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。After replacing a 1,000 ml flask equipped with a stirring blade with nitrogen, the flask was charged with 250 g of a polyester-polyproline copolymer solution obtained in Synthesis Example 3, and 75 g of N-benzene. Kamalimide imine/n-butyl methacrylate/glycidyl methacrylate copolymer (mol ratio 30:10:60, weight average molecular weight 40,000), 15 g of trimellitic anhydride, 8.25 g of 3-shrinkage Glyceroxypropyltrimethoxysilane and 0.95 g of Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.), 318 g of dehydrated PGMEA, and 200 g of dehydrated diethylene glycol methyl ether. Stir at room temperature for 5 hours and dissolve evenly. The mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.
將附有攪拌葉片之500ml之可分離性燒瓶以氮氣置換後,裝入4.85 g之DDS及43.22 g之3-胺丙基三乙氧基矽烷後,裝入197 g之脫水精製MMP,於室溫下進行攪拌,使DDS及3-胺丙基三乙氧基矽烷進行溶解。其後,將燒瓶以冰浴進行冷卻,內容液之溫度為10℃時,投入36.36 g之ODPA。若發熱反應所引起之溫度上升停止後,移出冰槽,於室溫下攪拌8小時,獲得淡黃色透明之含矽聚醯胺酸溶液。該溶液之黏度為12 mPa.s。The 500 ml separable flask with the stirring blade was replaced with nitrogen, and after charging 4.85 g of DDS and 43.22 g of 3-aminopropyltriethoxysilane, 197 g of dehydrated refined MMP was charged into the chamber. Stirring was carried out under temperature to dissolve DDS and 3-aminopropyltriethoxydecane. Thereafter, the flask was cooled in an ice bath, and when the temperature of the content liquid was 10 ° C, 36.36 g of ODPA was charged. After the temperature rise caused by the exothermic reaction was stopped, the ice bath was removed and stirred at room temperature for 8 hours to obtain a pale yellow transparent ruthenium-containing lysine solution. The viscosity of the solution is 12 mPa. s.
於附有攪拌葉片之氮氣置換之500 ml可分離性燒瓶中,裝入100 g之上述含矽聚醯胺酸溶液、30 g之Epikote 191P(商品名;油化Shell Epoxy(股份公司)製)、16.95 g之偏苯三酸酐、3.85 g之3-縮水甘油氧基丙基三甲氧矽烷及172.4 g之脫水精製MMP,於室溫下攪拌,使之均勻溶解。繼而,投入0.17 g之Byk-344(商品名;Byk-Chemie(股份公司)製),於室溫下攪拌1小時,以孔徑為0.2 μm之薄膜過濾器過濾,獲得熱硬化性聚合物組成物溶液。繼而,對根據與實施例1同樣之方法所獲得之硬化膜,比較評價異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。100 g of the above-mentioned hydrazine-containing polyaminic acid solution and 30 g of Epikote 191P (trade name; manufactured by Oiled Shell Epoxy Co., Ltd.) were placed in a 500 ml separable flask equipped with a stirring blade. 16.95 g of trimellitic anhydride, 3.85 g of 3-glycidoxypropyltrimethoxydecane and 172.4 g of dehydrated refined MMP were stirred at room temperature to uniformly dissolve. Then, 0.17 g of Byk-344 (trade name; manufactured by Byk-Chemie Co., Ltd.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition. Solution. Then, the cured film obtained by the same method as in Example 1 was subjected to comparative evaluation of foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and transparency. Sexuality and flatness characteristics. The results of these evaluations are shown in Table 1.
以氮氣置換附有攪拌葉片之1,000 ml燒瓶,於該燒瓶中裝入250 g之於合成例1中所獲得之聚酯化合物溶液,75 g之甲基丙烯酸苄酯/甲基丙烯酸縮水甘油脂共聚物(莫耳比30:70,重量平均分子量10萬),15 g之偏苯三酸酐,8.25 g之3-縮水甘油氧基丙基三甲氧矽烷、0.95 g之Byk-344(商品名;Byk-Chemie(股份公司)製)及518 g之脫水精製MMP,於室溫下攪拌5小時,使之均勻溶解。以孔徑為0.2 μm之薄膜過濾器過濾,獲得熱硬化性聚合物組成物溶液。繼而,對根據與實施例1同樣之方法所獲得之硬化膜,比較評價其異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。A 1,000 ml flask equipped with a stirring blade was replaced with nitrogen, and 250 g of the polyester compound solution obtained in Synthesis Example 1 and 75 g of benzyl methacrylate/methacrylic acid glycidyl glycol copolymer were charged into the flask. (mole ratio 30:70, weight average molecular weight 100,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxydecane, 0.95 g of Byk-344 (trade name; Byk-Chemie ( The joint-stock company) and 518 g of dehydrated MMP were stirred at room temperature for 5 hours to be uniformly dissolved. The membrane was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.
以氮氣置換附有攪拌葉片之1,000 ml燒瓶,於該燒瓶中裝入250 g之於合成例2所獲得之聚酯-聚醯胺酸共聚物溶液,75g之甲基丙烯酸苄酯/甲基丙烯酸縮水甘油酯共聚物(莫耳比30:70,重量平均分子量10萬),15 g之偏苯三酸酐,8.25 g之3-縮水甘油氧基丙基三甲氧矽烷、0.95 g之Byk-344(商品名;Byk-Chemie(股份公司)製)及518 g之脫水精製MMP,於室溫下攪拌5小時,使之均勻溶解。以孔徑為0.2 μm之薄膜過濾器過濾,獲得熱硬化性聚合物組成物溶液。繼而,對根據與實施例1同樣之方法所獲得之硬化膜,比較評價其異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。A 1,000 ml flask equipped with a stirring blade was replaced with nitrogen, and 250 g of the polyester-polyproline copolymer solution obtained in Synthesis Example 2, 75 g of benzyl methacrylate/methacrylic acid was placed in the flask. Glycidyl ester copolymer (mole ratio 30:70, weight average molecular weight 100,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane, 0.95 g of Byk-344 (trade name; Byk-Chemie (manufactured by the company) and 518 g of dehydrated MMP, and stirred at room temperature for 5 hours to be uniformly dissolved. The membrane was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.
以氮氣置換附有攪拌葉片之1,000 ml燒瓶,於該燒瓶中裝入250 g之於合成例3所獲得之聚酯-聚醯胺酸共聚物溶液,75 g之甲基丙烯酸苄酯/甲基丙烯酸縮水甘油酯共聚物(莫耳比30:70,重量平均分子量10萬),15 g之偏苯三酸酐,8.25 g之3-縮水甘油氧基丙基三甲氧矽烷、0.95 g之Byk-344(商品名;Byk-Chemie(股份公司)製)及518 g之脫水精製MMP,於室溫下攪拌5小時,使之均勻溶解。以孔徑為0.2 μm之薄膜過濾器過濾,獲得熱硬化性聚合物組成物溶液。繼而,對根據與實施例1同樣之方法所獲得之硬化膜,比較評價其異物特性、耐熱性、耐鹼性、耐酸性、耐溶劑性、與玻璃基板之密著性、耐濺鍍性、透明性、平坦性特性。將這些評價結果表示於表一。A 1,000 ml flask equipped with a stirring blade was replaced with nitrogen, and 250 g of the polyester-polyproline copolymer solution obtained in Synthesis Example 3, 75 g of benzyl methacrylate/methyl group was placed in the flask. Glycidyl acrylate copolymer (mole ratio 30:70, weight average molecular weight 100,000), 15 g of trimellitic anhydride, 8.25 g of 3-glycidoxypropyltrimethoxy decane, 0.95 g of Byk-344 (trade name) ; Byk-Chemie (manufactured by the company) and 518 g of dehydrated MMP, stirred at room temperature for 5 hours to dissolve evenly. The membrane was filtered through a membrane filter having a pore size of 0.2 μm to obtain a thermosetting polymer composition solution. Then, the cured film obtained by the same method as in Example 1 was evaluated for its foreign matter characteristics, heat resistance, alkali resistance, acid resistance, solvent resistance, adhesion to a glass substrate, sputtering resistance, and Transparency and flatness characteristics. The results of these evaluations are shown in Table 1.
如自表一所表示之結果可知實施例1至4之從使用有N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物之熱硬化性聚合物組成物所獲得之硬化膜,異物特性良好、且耐熱性亦優良。可預想的,比較例1之自含矽聚醯胺酸組成物(參照專利文獻1)所獲得之硬化膜異物特性或者耐鹼性較差,且使用為彩色濾光片保護膜之情形時良率低下。又可預想的,比較例2至4之從使用有甲基丙烯酸苄酯/甲基丙烯酸縮水甘油酯共聚物之熱硬化性聚合物組成物所獲得之硬化膜,與實施例相比較耐熱性較差,且起不到作為彩色濾光片保護膜之作用。As shown in the results of Table 1, the cured films obtained from the thermosetting polymer compositions having N-phenylmaleimide/glycidyl methacrylate copolymers of Examples 1 to 4 are known. The foreign matter has good properties and is excellent in heat resistance. It is expected that the cured film obtained from the ruthenium-containing phthalic acid composition of Comparative Example 1 (refer to Patent Document 1) has poor foreign matter characteristics or alkali resistance, and is used as a color filter protective film. low. It is also conceivable that the cured films obtained from the thermosetting polymer compositions using benzyl methacrylate/glycidyl methacrylate copolymer of Comparative Examples 2 to 4 are inferior in heat resistance as compared with the examples. And does not function as a color filter protective film.
從本發明之熱硬化性聚合物組成物所獲得之硬化膜,不僅異物特性及耐熱性優異,且耐濺鍍性及透明性等光學材料之特性亦優異之觀點來看,其可用作彩色濾光片、LED發光元件及受光元件等各種光學材料等之保護膜,及TFT與透明電極之間及透明電極與配向膜之間所形成之透明絕緣膜。The cured film obtained from the thermosetting polymer composition of the present invention is excellent in foreign matter characteristics and heat resistance, and is excellent in characteristics such as sputter resistance and transparency. A protective film of various optical materials such as a filter, an LED light-emitting element, and a light-receiving element, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.
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JP2005205264A (en) * | 2004-01-20 | 2005-08-04 | Hamamatsu Photonics Kk | Method and apparatus for redispersing fine particle and vessel containing liquid to be treated |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105086316A (en) * | 2014-05-15 | 2015-11-25 | 捷恩智株式会社 | Thermosetting compositions, harden film, color filter, liquid crystal displaying element, solid camera shooting element and light emitting diode illuminant |
CN105086316B (en) * | 2014-05-15 | 2018-01-30 | 捷恩智株式会社 | Thermosetting composition, cured film, colored filter, liquid crystal display cells, solid-state imager and LED illuminant heart |
Also Published As
Publication number | Publication date |
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KR20060099417A (en) | 2006-09-19 |
KR101128489B1 (en) | 2012-03-27 |
JP2006282995A (en) | 2006-10-19 |
JP4779670B2 (en) | 2011-09-28 |
TW200631992A (en) | 2006-09-16 |
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