TWI544006B - 難燃化之脂環式聚醯亞胺樹脂組成物及其薄壁成型體 - Google Patents
難燃化之脂環式聚醯亞胺樹脂組成物及其薄壁成型體 Download PDFInfo
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- TWI544006B TWI544006B TW101122238A TW101122238A TWI544006B TW I544006 B TWI544006 B TW I544006B TW 101122238 A TW101122238 A TW 101122238A TW 101122238 A TW101122238 A TW 101122238A TW I544006 B TWI544006 B TW I544006B
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- alicyclic
- polyimine resin
- resin composition
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- 229920001721 polyimide Polymers 0.000 title claims description 65
- 239000009719 polyimide resin Substances 0.000 title claims description 46
- 230000015572 biosynthetic process Effects 0.000 title description 9
- 238000000465 moulding Methods 0.000 title description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 133
- 239000011347 resin Substances 0.000 claims description 76
- 229920005989 resin Polymers 0.000 claims description 76
- 239000000203 mixture Substances 0.000 claims description 54
- -1 4-cyanophenoxy group Chemical group 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 22
- 239000011342 resin composition Substances 0.000 claims description 22
- 239000004642 Polyimide Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
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- 238000000034 method Methods 0.000 description 15
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- 229910052707 ruthenium Inorganic materials 0.000 description 12
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 5
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 4
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
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- 238000002329 infrared spectrum Methods 0.000 description 4
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- 239000010452 phosphate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000004060 quinone imines Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
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- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- KRPRVQWGKLEFKN-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine Chemical compound NCCCOCCCN KRPRVQWGKLEFKN-UHFFFAOYSA-N 0.000 description 2
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- YJOAIOIVLVUPST-UHFFFAOYSA-N 4-(4-amino-2-methoxyphenyl)-3-methoxyaniline Chemical group COC1=CC(N)=CC=C1C1=CC=C(N)C=C1OC YJOAIOIVLVUPST-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 2
- WJMQNPAEXWNWMD-UHFFFAOYSA-N 4-[9-(4-aminophenyl)-10h-anthracen-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2CC2=CC=CC=C21 WJMQNPAEXWNWMD-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
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- XQBSPQLKNWMPMG-UHFFFAOYSA-N bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O XQBSPQLKNWMPMG-UHFFFAOYSA-N 0.000 description 2
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- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
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- LMXQEKNFTHKIMN-UHFFFAOYSA-N 2-(1,3-dimethoxy-2-methoxycarbonyl-1,3-dioxopropan-2-yl)heptanoic acid Chemical compound COC(=O)C(C(CCCCC)C(=O)O)(C(=O)OC)C(=O)OC LMXQEKNFTHKIMN-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- DVXYMCJCMDTSQA-UHFFFAOYSA-N 3-[2-(3-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC(N)=CC=1C(C)(C)C1=CC=CC(N)=C1 DVXYMCJCMDTSQA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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Description
本發明係關於聚醯亞胺樹脂組成物及其薄壁成型體。
一般而言,聚醯亞胺樹脂係以芳香族四羧酸酐與芳香族二胺作為原料,將利用該等之縮合反應合成之聚醯胺酸進行閉環反應而得到的耐熱性樹脂。如此的全芳香族聚醯亞胺樹脂具有分子鏈剛直性、共振安定化、由於強化學鍵而對於熱分解有優異耐性,且對於如氧化或水解之化學變化具有高耐久性,且機械特性及電特性優異。此外,全芳香族聚醯亞胺樹脂有柔軟性,所以在電、電子、汽車及航太產業等領域廣泛使用於當作膜、塗覆劑、成形零件及絕緣材料。但全芳香族聚醯亞胺樹脂由於會著色為淡黃色至紅褐色,所以不適於當作電腦或行動電話設備等的基板所使用的玻璃及陶瓷之代替材料。
開發兼具可撓性與耐熱性及機械強度的透明高耐熱性樹脂之技術為當務之急。就滿足如此的要求的材料,無色透明性聚醯亞胺受到期待。就具有高耐熱性與透明性之聚醯亞胺樹脂,有人報告在重複結構單元中導入有全氟烷基之氟化聚醯亞胺樹脂(參照專利文獻1及專利文獻2)。該等聚醯亞胺樹脂本身欠缺溶劑可溶性,因此當將保存安定性差的聚醯胺酸進行澆鑄而形成膜後,由於在350℃之高溫進行加熱醯亞胺化,並形成膜或塗膜時會有由於熱處理條件而著色為黃色,無法獲得足夠透明性的缺點。
另一方面,就於膜成形不需高溫處理的溶劑可溶性之透明聚醯亞胺樹脂而言,有人報告:以4價之脂環式四羧酸及其衍生物與2
價之二胺當作構成成分之脂環式聚醯亞胺樹脂、或以4價之四羧酸及其衍生物與2價之脂環式二胺當作構成成分之脂環式聚醯亞胺樹脂。例如有人針對由以1,2,4,5-環己烷四羧酸二酐及具有特定結構之二胺製備的聚醯亞胺樹脂溶液製作玻璃轉移溫度300℃以上且透明且著色少之膜之方法進行了揭示(參照專利文獻3)。
但是脂環式聚醯亞胺樹脂雖能藉由將脂環式成分或脂肪族成分導入聚醯亞胺樹脂而賦予溶劑溶解性,但相反地會有容易燃燒的缺點。從安全上之觀點,作為電‧電子零件之密封材料、保護膜材料、絕緣材料等的用途受到限制。又,使用於當作電腦或行動電話設備等之顯示器基板或太陽能電池等基板時,也要求難燃性。
為了對於樹脂賦予難燃性,一般使用鹵素系難燃劑、銻系難燃劑、不含鹵素及銻之難燃劑當作複合化的難燃劑。
鹵素系難燃劑,在鹵素化合物中由於游離的鹵素,會有樹脂組成物之耐候性或電特性低落之問題、樹脂在高溫暴露時熱分解而產生鹵化氫造成環境污染之問題等多的讓人顧慮的材料。
銻系難燃劑之代表例可列舉氧化銻。通常添加當作難燃助劑之氧化銻,據指出會有致癌性,對於人體之安全性被視為問題。
由上述背景,需求不使用鹵素化合物及銻化合物之難燃性樹脂組成物。
不含鹵素之難燃劑,可列舉氫氧化鎂或氫氧化鋁等無機金屬水合物、聚磷酸銨等磷酸鹽類等。但是該等難燃劑為了獲得足夠的難燃效果需要大量添加,有導致透明性下降之虞。又,該等難燃劑難以對於樹脂均勻複合化,有導致機械特性低落之虞。
又,該等由於含有離子成分,所以有時會損及聚醯亞胺樹脂所具有的良好的絕緣特性。
作為對於含有選自於脂肪族化合物成分、脂環族化合物成分、或雙酚化合物之環氧烷加成物成分中之至少一種溶劑溶解性賦予成分的聚醯亞胺系樹脂賦予難燃性的方法,據報告有使環狀苯氧基磷腈化合物複合化的方法(參照專利文獻4)。專利文獻4之實施例中,為了僅添加磷氮化合物而賦予相當於UL94規格之V-0的難燃性,相對於聚醯亞胺樹脂100質量份添加了磷腈化合物30質量份的量(參照實施例1),為了降低磷腈化合物之添加量,摻合了氣凝膠等難燃助劑。如此的磷腈化合物之添加量之增加或難燃助劑之摻合,會有損及無色透明性、耐熱性、電絕緣性等特性之虞,實用性不佳。
【先前技術文獻】
【專利文獻】
【專利文獻1】日本特開平8-143666號公報
【專利文獻2】日本特開平8-225645號公報
【專利文獻3】日本特開2003-168800號公報
【專利文獻4】日本特開2002-235001號公報
本發明之目的在於提供不含鹵素系難燃劑、銻系難燃劑、無機金屬水合物、磷酸鹽類等難燃劑而可難燃化,且透明性、耐熱性、絕緣特性也優異的脂環式聚醯亞胺樹脂組成物及其薄壁成型體。
本案發明人等為了解決上述課題努力探討,結果發現:藉由相對於具有特定結構之脂環式聚醯亞胺樹脂100質量份將氰基改性環狀苯氧基磷腈化合物1~13質量份予以複合化,可獲得透明性、
耐熱性及絕緣特性優異且經難燃化之脂環式聚醯亞胺樹脂組成物。再者,發現:可獲得由上述脂環式聚醯亞胺樹脂組成物構成之薄壁成型體,其係使將上述脂環式聚醯亞胺樹脂組成物溶於有機溶劑而成之溶液流延後進行加熱,而獲得全光線穿透率高、霧度值低之薄壁成型體,乃完成本發明。
亦即本發明,係一種相對於具有以下列通式(1)表示之結構單元之脂環式聚醯亞胺樹脂(A)100質量份含有下列通式(2)表示之氰基改性環狀苯氧基磷腈化合物(B)1~13質量份之脂環式聚醯亞胺樹脂組成物;及一種薄壁成型體,係由該脂環式聚醯亞胺樹脂組成物構成之薄壁成型體,其係將使該脂環式聚醯亞胺樹脂組成物溶於有機溶劑而製得脂環式聚醯亞胺樹脂組成物溶液,並使所得之脂環式聚醯亞胺樹脂組成物溶液流延後加熱而得到。
(式(1)中,R1為碳數4~16之4價之脂環式烴基,R2為選自於碳數2~28之2價之脂肪族烴基、及碳數6~27之2價之芳香族烴基中之至少1種基團。)
(式(2)中,n為3或4之整數。X各自獨立,為苯氧基或4-氰基苯氧基,於多數之X之中的25%以上為4-氰基苯氧基,也可所有的X均為4-氰基苯氧基。)
依照本發明,能不使用對於人體及環境之影響有所顧慮的鹵素化合物或氧化銻化合物等難燃劑,而可獲得難燃性、透明性、耐熱性、絕緣特性優異之脂環式聚醯亞胺樹脂組成物及其薄壁成型體。
【實施發明之形態】
本發明之脂環式聚醯亞胺樹脂(A)具有下列通式(1)表示之重複單元。
式(1)式中,R1為碳數4~16之4價之脂環式烴基。R2為選自於碳數2~28之2價之脂肪族烴基、及碳數6~27之2價之芳香族烴基中之至少1種基。R2也可含硫醚基、磺醯基、亞磺醯基、羰基、甲氧基、酯基、醚基、氟基等。R2之碳數2~28之2價之脂肪族烴基,可為經由伸芳基而連結成之脂肪族烴基。
R1之碳數4~16之4價之脂環族烴基,為碳數6~12之4價之脂環式烴基較佳,更佳為從於之後具體例示之脂環式四羧酸或其衍生物而來之脂環式烴基,又更佳為從以下列通式(3)表示之構成單元所含之環己烷而來之基。
式(3)中,R2與前述同。
前述通式(1)及(3)之R2之碳數2~28之2價之脂肪族烴基,例如從於後具體例示之脂肪族二胺去除2個胺基而得之基。同樣,R2之碳數6~27之2價之芳香族烴基,例如從於後具體例示之芳香族二胺去除2個胺基而得之基。
前述通式(1)及(3)之R2,較佳為碳數6~27之2價之芳香族烴基且具有鍵結於R2之氮原子係直接鍵結在R2之芳香環之結構較佳。
脂環式聚醯亞胺樹脂(A),係藉由將具有碳數4~16之4價之脂環式烴基之脂環式四羧酸或其衍生物,與從具有碳數2~28之2價之脂肪族烴基之脂肪族二胺、及具有碳數6~27之2價之芳香族烴基之芳香族二胺選出之至少1種二胺,於有機溶劑中在醯亞胺化觸媒之存在下反應而合成。
脂環式四羧酸或其衍生物,例如脂環式四羧酸、脂環式四羧酸酯類、脂環式四羧酸二酐等。其中,脂環式四羧酸二酐為較佳。
具有碳數4~16之4價之脂環式烴基之脂環式四羧酸二酐,例如:1,2,4,5-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、雙環[2.2.1]庚烷四羧酸二酐、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、雙環[2.2.2]辛烷-2,3,5,6-四羧酸二酐、3,3’,4,4’-二環己基四羧酸二酐等。其中,1,2,4,5-環己烷四羧酸二酐為較佳。該等脂環式四羧酸二酐,可以單獨使用或將二種以上混合使用,但宜單獨使用1,2,4,5-環己烷四羧酸二酐較佳。
具碳數4~16之4價之脂環式烴基之四羧酸,例如:1,2,4,5-環戊烷四羧酸、1,2,4,5-環己烷四羧酸、雙環[2.2.1]庚烷四羧酸、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸、雙環[2.2.2]辛烷-2,3,5,6-四羧酸、3,3’,4,4’-二環己基四羧酸等。
具有碳數4~16之4價之脂環式烴基之四羧酸酯類,例如:1,2,4,5-環己烷四羧酸甲酯、1,2,4,5-環己烷四羧酸二甲酯、1,2,4,5-環己烷四羧酸三甲酯、1,2,4,5-環己烷四羧酸四甲酯、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸甲酯、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二甲酯、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸三甲酯、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸四甲酯、雙環[2.2.1]庚烷四羧酸甲酯、雙環[2.2.1]庚烷四羧酸二甲酯、雙環[2.2.1]庚烷四羧酸三甲酯、雙環[2.2.1]庚烷四羧酸四甲酯、雙環[2.2.2]辛烷-2,3,5,6-四羧酸甲酯、雙環[2.2.2]辛烷-2,3,5,6-四羧酸二甲酯、雙環[2.2.2]辛烷-2,3,5,6-四羧酸三甲酯、雙環[2.2.2]辛烷-2,3,5,6-四羧酸四甲酯、3,3’,4,4’-二環己基四羧酸甲酯、3,3’,4,4’-二環己基四羧酸二甲酯、3,3’,4,4’-二環己基四羧酸三甲酯、3,3’,4,4’-二環己基四羧酸四甲酯等。
前述脂肪族二胺、及前述芳香族二胺,係以下列通式(4)表示。
H2N-R2-NH2 (4)
式(4)中,R2與前述同。亦即,前述脂肪族二胺,具有在碳數2~28之2價之脂肪族烴基直接鍵結有2個胺基的結構。碳數2~28之2價之脂肪族烴基,也可為經由伸芳基而連結之脂肪族烴基。
前述芳香族二胺,具有在碳數6~27之2價之芳香族烴基直接鍵結有2個胺基之結構。
前述脂肪族二胺及前述芳香族二胺,也可各於骨架中含有硫醚基、磺醯基、亞磺醯基、羰基、甲氧基、酯基、醚基、氟基。
前述脂肪族二胺不特別限定,可為直鏈狀或分支鏈狀之脂肪族二胺,也可為含有脂環結構之脂肪族二胺。直鏈狀或分支鏈狀之脂肪族二胺,例如乙二胺、四亞甲基二胺、對亞二甲苯二胺、六亞甲基二胺、2,5-二甲基六亞甲基二胺、三甲基六亞甲基二胺、聚乙二醇雙(3-胺基丙基)醚、聚丙二醇雙(3-胺基丙基)醚、間亞二甲苯二胺、矽氧烷二胺等。含有脂環結構之脂肪族二胺,例如4,4-二胺基二環己基甲烷、異佛爾酮二胺、降莰烷二胺、1,3-雙(胺基甲基)環己烷、1,3-二胺基環己烷、1,4-二胺基環己烷、雙環己基二胺等。該等二胺可以單獨使用或將二種以上混合使用。
前述芳香族二胺不特別限定,例如4,4’-二胺基二苯醚、3,4’-二胺基二苯醚、4,4’-二胺基二苯基甲烷、1,3-苯二胺、1,4-苯二胺、4,4’-二胺基-3,3’-二甲基聯苯、4,4’-二胺基-2,2’-二甲基聯苯、4,4’-二胺基-2,2’-二甲氧基聯苯、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯、4,4’-二胺基二苯基硫醚、4,4’-二胺基二苯基碸、4,4’-二胺基二苯基酮、9,9-雙(4-胺基苯基)茀、1,1-雙[4-(4-胺基苯氧基)苯基]環己烷、2,2-雙(3-胺基苯基)丙烷、2,2-雙(4-胺基苯基)丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-雙(3-胺基-α,α-二甲基苄基)苯、1,3-雙(4-胺基-α,α-二甲基苄基)苯、1,4-雙(3-胺基-α,α-二甲基苄基)苯、1,4-雙(4-胺基-α,α-二甲基苄基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-雙(3-胺基苯氧基)聯苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[4-(3-胺基苯氧基)苯基]酮、雙[4-(4-胺基苯氧基)苯基]酮、雙[4-(3-胺基苯氧基)苯基]硫醚、雙[4-(4-胺基苯氧基)苯基]硫醚、雙[4-(3-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸等。該等二胺,可以單獨使用或將二種以上混合使用。
上述二胺之中,從可獲得高耐熱性之聚醯亞胺之觀點,前述芳香族二胺為較佳。前述芳香族二胺之中,從高分子量化容易且耐熱性優異之觀點,1,4-雙(4-胺基-α,α-二甲基苄基)苯、4,4’-雙(4-胺基苯氧基)聯苯、9,9-雙(4-胺基苯基)茀、4,4’-二胺基二苯醚、4,4’-二胺基-2,2’-二甲氧基聯苯、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯為較佳。
本發明之脂環式聚醯亞胺樹脂(A)之製造時使用之有機溶劑,宜為含有從由環狀醚、環狀酮、環狀酯、醯胺、及脲構成之群組中選出之至少1種結構的溶劑為較佳。具體例不特別限定,較佳為含有從γ-丁內酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、二甲基亞碸、六甲基磷醯胺、環戊酮、環己酮、1,3-二氧戊環(dioxolane)、1,4-二烷、四甲基脲、四氫呋喃等非質子性極性有機溶劑選出之至少一種。其中,從γ-丁內酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺及N-甲基-2-吡咯烷酮選出之一種以上更佳。
脂環式聚醯亞胺樹脂(A)之製造時使用之醯亞胺化觸媒,可使用三乙胺、三丙胺、三丁胺、吡啶、喹啉、異喹啉、α-甲基吡啶、β-甲基吡啶、N,N-二甲基苯胺、N,N-二乙基苯胺等3級胺、或巴豆酸、苯甲酸、甲基苯甲酸、羥基苯甲酸、苯磺酸、對甲苯磺酸等酸類,但使用3級胺較佳。
以下舉脂環式聚醯亞胺樹脂(A)之製造方法之例,但製造方法不限於下列例。
於30℃以下之溫度將使二胺溶於有機溶劑而得之溶液與脂肪族四羧酸或其衍生物混合,於4~30℃之溫度使反應,獲得聚醯胺酸溶液。於上述聚醯胺酸溶液中添加醯亞胺化觸媒,邊將生成水餾出到系外邊進行脫水醯亞胺化反應,獲得脂環式聚醯亞胺樹脂(A)之溶液。
二胺與脂環式四羧酸或其衍生物之莫耳比(二胺/脂肪族四羧酸或其衍生物),為0.95~1.05之範圍較佳,尤佳為0.99~1.01之範圍。二胺與脂環式四羧酸或其衍生物之莫耳比若為0.95以上、或1.05以下,高分子量化會充分進行,能防止薄壁成型體變脆。
醯亞胺化觸媒與二胺之理想莫耳比(醯亞胺化觸媒/二胺),為0.01~1.0之範圍較佳,0.05~0.5之範圍更佳。醯亞胺化觸媒與二胺之莫耳比若為0.01以上,由於醯亞胺化觸媒之觸媒作用,醯亞胺化反應會充分進行,若為1.0以下,容易去除醯亞胺化觸媒本身,不僅能防止由後述脂環式聚醯亞胺樹脂組成物構成之薄壁成型體之著色,也能防止脂環式聚醯亞胺樹脂之溶解性下降。
脫水醯亞胺化反應中,係將以水為主成分之餾去液利用安裝在反應槽上部的蒸氣冷卻塔及與其卡合的餾去液儲留裝置去除到反應系外。反應溫度通常為160~200℃之範圍,較佳為170~190℃之範圍,更佳為180~190℃之範圍。若為160℃以上,醯亞胺化及高分子量化會充分進行,若為200℃以下,當溶液黏度顯著增加時,可防止反應容器之壁面發生樹脂焦化附著等不良現象。又,視情形,也可使用甲苯、二甲苯等共沸脫水劑。反應壓力通常為常壓,但視需要也可於加壓進行反應。反應溫度之保持時間必須至少1小時以上,更佳為3小時以上。若少於1小時,醯亞胺化及高分子量化有未充分進行之虞。反應時間無特別上限,但通常於3~10小時之範圍進行。
上述步驟中,相對於含有有機溶劑之總質量份,脂環式聚醯亞胺樹脂之固體成分濃度較佳為20質量%以上50質量%以下,更佳為30質量%以上40質量%以下。若為20質量%以上,聚醯亞胺樹脂之固有黏度會適度上升,高分子量化會充分進行,所以能防止薄
壁成型體變脆。又,若為50質量%以下,可壓抑隨著聚醯亞胺樹脂之固有黏度之上升造成聚醯亞胺樹脂溶液之黏度過度上升,且能均勻攪拌,所以能防止樹脂之焦化附著。溶於上述有機溶劑之溫度,至少為20℃以上較理想,較佳為30℃~100℃之溫度範圍。若為20℃以上,具有適當溶液黏度,所以操作性提高。
對於上述脂環式聚醯亞胺樹脂溶液混合過量甲醇並攪拌,獲得脂環式聚醯亞胺樹脂之沉澱物。將上述沉澱物過濾後於真空下加熱,獲得白色粉末狀之脂環式聚醯亞胺樹脂(A)。
又,上述製造方法中,醯亞胺化觸媒也可在添加脂環式四羧酸或其衍生物以前加入。於此情形,一般而言不須保持在形成聚醯胺酸之反應條件即室溫附近至其以下之溫度,能立即開始加熱並進行脫水醯亞胺化。
本發明使用之氰基改性環狀苯氧基磷腈化合物(B),為下列通式(2)表示氰基苯酚取代環狀磷腈或氰基苯酚‧苯酚混合取代環狀磷腈。
(式(2)中,n為3或4之整數。X各自獨立,為苯氧基或4-氰基苯氧基,於多數的X之中25%以上為4-氰基苯氧基,也可全部的X均為4-氰基苯氧基。)
上述氰基改性環狀苯氧基磷腈化合物,對於後述有機溶劑的溶解度高,且對於脂環式聚醯亞胺樹脂(A)也顯示良好的互溶性,所
以能對於薄壁成型體賦予足夠的透明性。又,由於具有經氰基改性之取代基,故比起習知的環狀苯氧基磷腈化合物,於高溫時之質量減少小,高溫可靠性優異,不僅如此,不易損及樹脂成型體之介電特性。又,由於單位質量的含氮比率高,以少量添加即能發揮優異的難燃性。是以,將氰基改性環狀苯氧基磷腈化合物予以複合化而得之脂環式聚醯亞胺樹脂組成物及其薄壁成型體,透明性優異,而且耐熱性及機械強度也不易降低。
上述通式(2)中,鍵結於磷原子之所有X之中,4-氰基苯氧基的比例為25~100%,35~75%更佳,45~55%又更佳。
氰基改性環狀苯氧基磷腈化合物,可使用合成品也可使用市售品。市售品,例如:Rabitle FP-300(以上為伏見製藥工業社(股)製、商品名)等。氰基改性環狀苯氧基磷腈化合物,可以單獨使用1種也可併用2種以上。
本發明之脂環式聚醯亞胺樹脂組成物中,氰基改性環狀苯氧基磷腈化合物之摻合量,相對於脂環式聚醯亞胺樹脂100質量份必須為1~13質量份,1~10質量份較佳。氰基改性環狀苯氧基磷腈化合物之摻合量若超過13質量份,於後述由脂環式聚醯亞胺樹脂組成物構成之薄壁成型體,玻璃轉移溫度會下降且有損耐熱性。又,上述薄壁成型體中,會導致全光線穿透率下降及霧度值上升,透明性下降。且機械強度有時會下降。摻合量少於1質量份時,難燃性受損,不實用。
上述脂環式聚醯亞胺樹脂組成物,除了氰基改性環狀苯氧基磷腈化合物以外,在不妨礙本發明之效果之範圍,也可含有分子量大的縮合型磷酸酯類或環狀有機磷化合物等。縮合型磷酸酯類或環狀有機磷化合物等之具體例,例如間苯二酚雙(苯基)磷酸酯、間苯二
酚雙(2,6-二-二甲苯基)磷酸酯、雙酚A雙(二苯基)磷酸酯、雙酚A雙(二甲苯酚基)磷酸酯、9,10-二氫-9-氧雜-10-磷氮菲-10-氧化物(三光(股)、商品名:HCA)等,但不限於該等。
又,上述脂環式聚醯亞胺樹脂組成物,視需要在保持透明性之範圍內,也可含有公知的添加劑,例如2,6-二第三丁基-4-甲基苯酚、2-(1-甲基環己基)-4,6-二甲基苯酚、2,2-亞甲基雙-(4-乙基-6-第三甲基苯酚)、4,4’-硫雙-(6-第三丁基-3-甲基苯酚)等抗氧化劑、2,2’-二羥基-4-甲氧基二苯基酮、2-(2’-羥基-4’-正辛氧基苯基)苯并三唑、對第三丁基苯基水楊酸酯等紫外線吸收劑、碳酸鈣、滑石、二氧化矽、玻璃纖維、碳纖維等充填劑及各種界面活性劑。
又,上述脂環式聚醯亞胺樹脂組成物,也可含有至少含有1種選自於環狀醚、環狀酮、環狀酯、醯胺、及脲構成之群組中之結構的有機溶劑。具體例不特別限定,也可含從γ-丁內酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、二甲基亞碸、六甲基磷醯胺、環戊酮、環己酮、1,3-二氧戊環(dioxolane)、1,4-二烷、四甲基脲、四氫呋喃等非質子性極性有機溶劑選出之至少1種。其中,從γ-丁內酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺及N-甲基-2-吡咯烷酮選出之至少1種更佳。
本發明之由脂環式聚醯亞胺樹脂組成物構成之薄壁成型體,依下列方法製造。
步驟(1):製備包含脂環式聚醯亞胺樹脂(A)、氰基改性環狀苯氧基磷腈化合物(B)與有機溶劑的3種成分的脂環式聚醯亞胺樹脂組成物溶液。
步驟(2):將該溶液擠製或塗佈於支持體上成膜狀後,將該溶液加熱,並使有機溶劑揮發,製造由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。
步驟(1)之製備包含脂環式聚醯亞胺樹脂(A)、氰基改性環狀苯氧基磷腈化合物(B)與有機溶劑之3種成分的脂環式聚醯亞胺樹脂組成物溶液的方法,可採以下任一方法:混合使脂環式聚醯亞胺樹脂(A)溶於有機溶劑而得之脂環式聚醯亞胺樹脂溶液(A’)、以及氰基改性環狀苯氧基磷腈化合物(B)之方法;或將氰基改性環狀苯氧基磷腈化合物(B)預先溶解或膨潤於能與脂環式聚醯亞胺樹脂(A)均勻混合之有機溶劑而得之(B’)與前述溶液(A’)混合之方法。該步驟(1)中,混合時之溫度為20~90℃較佳。於任一方法混合後均以在利用混練機等進行機械剪切下進行攪拌為重要。
步驟(1)獲得之脂環式聚醯亞胺樹脂組成物溶液中之固體成分濃度,為10~50質量%較佳,20~40質量%更佳。若為10質量%以上,能防止保持薄壁成型體之厚度變得困難、或去除有機溶劑需費時長時間的不利。又,若為50質量%以下,可防止由於脂環式聚醯亞胺樹脂組成物溶液之流動性變差導致的薄壁成型體形成困難的不利現象。
步驟(2)中,支持體之材質不特別限定,可使用玻璃基板、不銹鋼製基板,此外也可使用如聚對苯二甲酸乙二醇酯或聚萘二甲酸乙二醇酯之有機高分子之膜。
步驟(2)中,就在上述支持體上擠製或塗佈成膜狀並形成塗佈層之方法,可使用公知方法。例如:利用模具擠製之流延法、利用塗抹器(applicator)、塗佈機等之方法。
其次,在熱板上或乾燥爐中,將該塗佈層於120℃以下之溫度加熱約30~60分鐘使有機溶劑揮發,直到具自支持性。其次將其從支持體剝除,將端部利用金屬製夾子或拉幅機固定。其次,於氮氣
流下或減壓下,以不發生殘留有機溶劑之突沸之方式,於限制膜收縮的狀態至少升溫到有機溶劑的沸點,較佳為至少升溫到比有機溶劑之沸點高5~10℃的溫度,,於該溫度進行乾燥及回火處理,藉此去除殘留溶劑,獲得薄壁成型體。
上述薄壁成型體中所含之有機溶劑之含有率宜少於1質量%較佳。有機溶劑之含有率若少於1質量%,可防止由於可塑化的作用導致薄壁成型品之玻璃轉移溫度下降而發生熱變形等不良現象,可防止由於高溫曝露時溶劑氧化分解等造成著色。
上述薄壁成型體之壁厚,從成型方法之觀點,為1μm~1mm較佳,10~500μm更佳,30~300μm又更佳。
上述薄壁成型體,膜厚100μm之全光線穿透率為88%以上較佳,89%以上更佳。全光線穿透率若為88%以上,當作電腦或行動電話設備等的顯示器基板或太陽能電池等的基板使用時,透明性足夠。
上述薄壁成型體,於膜厚100μm之霧度值為1.3以下較佳,1.0以下更佳。霧度值若為1.3以下,當作為電腦或行動電話設備等的顯示器基板或太陽能電池等的基板使用時的透明性足夠。
上述薄壁成型體之耐熱指標即玻璃轉移溫度,為240℃以上較佳。上述薄壁成形體之玻璃轉移溫度若為240℃以上,可確保足夠耐熱性。當形成作為電腦、行動電話設備等的顯示器基板的透明導電層時,為了降低導電層的絕緣電阻、提高電子移動度,需進行250℃以上的熱處理。又,當在各種電‧電子零件中當作可撓性金屬張疊層體之絕緣基板使用時,需要更高耐熱性。從上述觀點,上述薄壁成形體之玻璃轉移溫度為250℃以上較佳,更佳為270℃以
上。上述薄壁成形體之玻璃轉移溫度若為250℃以上,能防止於焊接步驟發生不良現象。
本發明之由脂環式聚醯亞胺樹脂組成物構成之薄壁成型體,發揮優良的透明性、耐熱性、絕緣特性及難燃性,適於作為以光學材料為首的電‧電子零件的密封材料、保護膜材料、絕緣材料。又,將上述方法獲得之脂環式聚醯亞胺樹脂組成物溶液塗佈在光電變換元件之上,之後使有機溶劑揮發,可藉此形成耐熱性優異、具有高折射率的樹脂密封部,可獲得優異的光電變換裝置。又,發光二極體用密封樹脂有時為了將發光波長變換為可見區域等目的會混合螢光材料等。本發明之脂環式聚醯亞胺樹脂,當與各種螢光材料混合時,混合性、分散性、安定性優異,所以當作發光二極用之密封材料為理想。
【實施例】
以下舉實施例具體說明本發明。惟本發明不限於該等實施例。
各製造例獲得之脂環式聚醯亞胺樹脂(A)及各實施例及比較例獲得之由脂環式聚醯亞胺樹脂組成物構成之薄壁成型體之物性,係以下列所示方法測定。
<對數黏度測定>
將製造例1~4獲得的脂環式聚醯亞胺樹脂溶液投入無水甲醇,使固體析出,去除未反應單體之後,過濾後於80℃進行12小時真空乾燥,將獲得之聚醯亞胺樹脂0.1g溶於N-甲基-2-吡咯烷酮20mL,使用Cannon-Fenske黏度計測定於30℃的對數黏度。對數黏度(μ)依下式求取。
μ=ln(ts/t0)/C
t0:溶劑之流動時間
ts:稀薄高分子溶液之流動時間
C:0.5g/dL
<玻璃轉移溫度>
脂環式聚醯亞胺樹脂組成物之耐熱性,係利用SII Technology(股)製示差熱分析裝置(型號DSC-6220),於氮氣氛圍下以10℃/分的速度升溫到400℃,並測定玻璃轉移溫度。
<全光線穿透率及霧度值>
使用脂環式聚醯亞胺樹脂組成物之薄壁成型品,依「JIS K7105透明度試驗法」,使用日本電色工業(股)製色差‧濁度測定器(型號COH-400)求取作為評價無色性、透明性之指標的全光線穿透率及霧度值。
<表面電阻率>
脂環式聚醯亞胺樹脂組成物之薄壁成型品之絕緣特性,係於23℃/50%RH環境下使用Advantest(股)製微小電流計(型號R-8340),測定表面電阻率以進行評價。
<難燃性評價>
將由脂環式聚醯亞胺樹脂組成物構成的厚度約0.1mm的薄壁成型品切成50mm×200mm,捲成直徑12.7mm、長度200mm的筒狀,製作依據UL94VTM規格的試驗片,並實施垂直燃燒試驗。
(參考例)
<1,2,4,5-環己烷四羧酸二酐之合成>
於內容積5公升之赫史持合金(Hastelloy)製(HC22)高壓釜中放入苯均四酸552g、於活性碳載持銠(Rh)之觸媒(ne-chemcat(股)製)200g、水1656g,邊攪拌邊將反應容器內進行取代,設定反應器之氫氣壓力為5.0MPa,升溫至60℃。保持氫氣壓力為5.0MPa的
狀態反應2小時。將反應容器內之氫氣取代為氮氣,從高壓釜抽出反應液,將該反應液過濾並分離觸媒。將過濾液以旋轉蒸發器於減壓下蒸發水並濃縮,使結晶析出後,將析出的結晶於室溫進行固液分離,並乾燥獲得1,2,4,5-環己烷四羧酸481g(產率85.0%)。接著,將獲得之1,2,4,5-環己烷四羧酸481g與乙酸酐4000g裝入5公升之玻璃製可分離燒瓶,於攪拌狀態將反應容器內進行氮氣取代。於氮氣氣體氛圍下升溫到溶劑的回流溫度,使溶劑回流10分鐘。邊攪拌邊冷卻至室溫,並使結晶析出。將析出之結晶進行固液分離,乾燥獲得一次結晶。再將分離母液以旋轉蒸發器於減壓下濃縮,使結晶析出。將該結晶進行固液分離,乾燥獲得二次結晶。合併一次結晶、二次結晶,獲得1,2,4,5-環己烷四羧酸二酐375g(酸酐化的產率為96.6%)。
關於製造例使用之四羧酸二酐與二胺、及實施例與比較例使用之難燃劑,如以下所示。
<四羧酸二酐>
H-PMDA:1,2,4,5-環己烷四羧酸二酐
<二胺>
BisAP:1,4-雙(4-胺基-α,α-二甲基苄基)苯
BAPB:4,4’-雙(4-胺基苯氧基)聯苯
BAFL:9,9-雙(4-胺基苯基)茀
DCHM:4,4-二胺基二環己基甲烷
<難燃劑>
B1:氰基改性環狀苯氧基磷腈化合物[伏見製藥所(股)製、商品名Rabitle FP-300(於前述通式(2),n為3及4之混合物,全部的X之中,4-氰基苯氧基比例為50%。)〕
B2:磷酸三苯酯(大八化學工業(股)製、商品名TPP)
B3:間苯二酚雙(苯基)磷酸酯(大八化學工業(股)製、商品名CR-733S)
B4:苯氧基磷腈化合物(大塚化學(股)製、商品名SPS-100)
(製造例1)
<脂環式聚醯亞胺樹脂(A1)之合成>
於配備溫度計、攪拌器、氮氣導入管、附有分餾器之冷卻管的500mL的5口燒瓶,裝入1,4-雙(4-胺基-α,α-二甲基苄基)苯24.18g(0.07莫耳)及4,4’-雙(4-胺基苯氧基)聯苯11.07g(0.03莫耳)、當作溶劑之SP值12.6之γ-丁內酯68.19g及、SP值10.8之N,N-二甲基乙醯胺17.25g使溶解,使用冰水浴冷卻至5℃。保持在同溫的狀態,一次加入1,2,4,5-環己烷四羧酸二酐22.45g(0.1莫耳)及當作醯亞胺化觸媒之三乙胺0.51g(0.005莫耳)。滴加結束後,升溫到180℃,在持續餾去餾去液的狀態進行5小時回流,結束反應,以空氣冷卻使內溫成為120℃之後,加入作為稀釋溶劑之N,N-二甲基乙醯胺143.7g,於攪拌狀態進行冷卻,獲得固體成分濃度20質量%之脂環式聚醯亞胺樹脂溶液(A1’)。將上述溶液之一部分注入1L之甲醇,使聚合物沉澱,進行過濾、甲醇洗滌後,於100℃之真空乾燥機中乾燥24小時,獲得白色粉末(脂環式聚醯亞胺樹脂A1)。測定該粉末之IR光譜,結果觀察到醯亞胺基特有的1704、1770cm-1的吸收。測定脂環式聚醯亞胺樹脂(A1)之對數黏度之結果為1.05。
(製造例2)
<脂環式聚醯亞胺樹脂(A2)之合成>
於配備溫度計、攪拌器、氮氣導入管、附有分餾器之冷卻管之500mL之5口燒瓶中,加入4,4’-雙(4-胺基苯氧基)聯苯36.89g(0.1莫耳)、作為溶劑之SP值12.6之γ-丁內酯71.18g及、SP值10.8之N,N-二甲基乙醯胺17.79g使溶解,使用冰水浴冷卻至5℃。保持在同溫狀態,一次加入1,2,4,5-環己烷四羧酸二酐22.45g(0.1莫耳)及當作醯亞胺化觸媒之三乙胺0.51g(0.005莫耳)。滴加結束後,升溫到180℃,於持續餾去餾去液的狀態進行5小時回流,結束反應,
以空氣冷卻至內溫成為120℃後,加入作為稀釋溶劑之N,N-二甲基乙醯胺134.7g,於攪拌狀態進行冷卻,獲得固體成分濃度20質量%之脂環式聚醯亞胺樹脂溶液(A2’)。上述溶液之質量為278.26g、又,餾去液總質量為3.66g。將上述溶液之一部分注入1L之甲醇,使聚合物沉澱,進行過濾、甲醇洗滌後,於100℃之真空乾燥機中進行24小時乾燥,獲得白色粉末(脂環式聚醯亞胺樹脂(A2))。測定該粉末之IR光譜,觀察到醯亞胺基特有之1705、1768cm-1之吸收。測定脂環式聚醯亞胺樹脂(A2)之對數黏度,結果為1.24。
(製造例3)
<脂環式聚醯亞胺樹脂(A3)之合成>
於配備溫度計、攪拌器、氮氣導入管、附有分餾器之冷卻管之500mL之5口燒瓶中,加入9,9-雙(4-胺基苯基)茀27.95g(0.08莫耳)及4,4’-雙(4-胺基苯氧基)聯苯7.38g(0.02莫耳)、作為溶劑之SP值12.6之γ-丁內酯69.31g及、SP值10.8之N,N-二甲基乙醯胺17.33g使溶解,使用冰水浴冷卻至5℃。保持在同溫狀態,一次加入1,2,4,5-環己烷四羧酸二酐22.45g(0.1莫耳)及當作醯亞胺化觸媒之三乙胺0.51g(0.005莫耳)。滴加結束後,升溫到180℃,於持續餾去餾去液的狀態進行5小時回流,結束反應,以空氣冷卻至內溫成為120℃後,加入作為稀釋溶劑之N,N-二甲基乙醯胺130.7g,於攪拌狀態進行冷卻,獲得固體成分濃度20質量%之脂環式聚醯亞胺樹脂溶液(A3’)。上述溶液之質量為270.26g、又,餾去液總質量為4.35g。將上述溶液之一部分注入1L之甲醇,使聚合物沉澱,進行過濾、甲醇洗滌後,於100℃之真空乾燥機中進行24小時乾燥,獲得白色粉末(脂環式聚醯亞胺樹脂(A3))。測定該粉末之IR光譜,觀察到醯亞胺基特有之1704、1771cm-1之吸收。測定脂環式聚醯亞胺樹脂(A3)之對數黏度,結果為1.16。
(製造例4)
<脂環式聚醯亞胺樹脂(A4)之合成>
於配備溫度計、攪拌器、氮氣導入管、附有分餾器之冷卻管之500mL之5口燒瓶中,加入4,4-二胺基二環己基甲烷21.14g(0.1莫耳)與作為有機溶劑之SP值11.3之N-甲基-2-吡咯烷酮54.54g及SP值10.8之N,N-二甲基乙醯胺13.60g使溶解,使用冰水浴冷卻至5℃。保持在同溫狀態,一次加入1,2,4,5-環己烷四羧酸二酐22.62g(0.1莫耳)及當作醯亞胺化觸媒之三乙胺0.50g(0.005莫耳)。滴加結束後,升溫到130℃,藉由攪拌約30分鐘,生成的塊狀的鹽均勻溶解。之後,升溫到180℃,於持續餾去餾去液之狀態進行6小時回流,結束反應,進行空氣冷卻使內溫成為120℃後,加入作為稀釋溶劑之N,N-二甲基乙醯胺113.4g,於攪拌狀態進行冷卻,獲得濃度20質量%之脂環式聚醯亞胺樹脂溶液(A4’)。上述溶液之質量為223.82g,又,餾去液總質量為3.54g。將上述溶液之一部分注入1L之甲醇,使聚合物沉澱,進行過濾、甲醇洗滌後,於100℃之真空乾燥機中進行24小時乾燥,獲得白色粉末(脂環式聚醯亞胺樹脂(A4))。測定該粉末之IR光譜,觀察到醯亞胺基特有之1691、1764cm-1之吸收。測定脂環式聚醯亞胺樹脂(A4)之對數黏度,結果為0.86。
(實施例1)
對於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),於室溫添加作為難燃劑之氰基改性環狀苯氧基磷腈化合物(B1),使相對於聚醯亞胺樹脂固體成分100質量份之含量為3質量份,於70℃之條件攪拌混合2小時,獲得脂環式聚醯亞胺樹脂組成物溶液。溶液之濃度為20.48質量%。獲得之脂環式聚醯亞胺樹脂組成物溶液,使用1000μm的刮刀澆鑄在均勻塗有塑膠脫模劑(PELICOAT)的玻璃基板上。將其於熱板在100℃保持60分鐘,使溶劑揮發,藉此獲得具有自支持性之無色透明的一次乾燥膜。將該膜固定在不銹鋼框,於200℃進行3小時真空乾燥,去除殘留溶劑,獲得膜厚97μm
之由透明的脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0。結果如表1所示。
(實施例2)
對於製造例2獲得之脂環式聚醯亞胺樹脂溶液(A2’),於室溫添加作為難燃劑之氰基改性環狀苯氧基磷腈化合物(B1),使相對於聚醯亞胺樹脂固體成分100質量份之含量為5質量份,於70℃之條件攪拌混合2小時,獲得脂環式聚醯亞胺樹脂組成物溶液。溶液之濃度為20.79質量%。
其次,使用前述獲得之脂環式聚醯亞胺樹脂組成物溶液,除此以外與實施例1以同樣方法,獲得膜厚101μm之透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0。結果如表1所示。
(實施例3)
對於製造例3獲得之脂環式聚醯亞胺樹脂溶液(A3’),於室溫添加作為難燃劑之氰基改性環狀苯氧基磷腈化合物(B1),使相對於聚醯亞胺樹脂固體成分100質量份之含量為3質量份,於70℃之條件攪拌混合2小時,獲得脂環式聚醯亞胺樹脂組成物溶液。溶液之濃度為20.48質量%。
其次,使用前述獲得之脂環式聚醯亞胺樹脂組成物溶液,除此以外與實施例1以同樣方法,獲得膜厚100μm之透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0。結果如表1所示。
(實施例4)
對於製造例4獲得之脂環式聚醯亞胺樹脂溶液(A4’),於室溫添加作為難燃劑之氰基改性環狀苯氧基磷腈化合物(B1),使相對於聚醯亞胺樹脂固體成分100質量份之含量為10質量份,於70℃之條件攪拌混合2小時,獲得脂環式聚醯亞胺樹脂組成物溶液。溶液之濃度為21.57質量%。
其次,使用前述獲得之脂環式聚醯亞胺樹脂組成物溶液,除此以外與實施例1以同樣方法,獲得膜厚102μm之透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0。結果如表1所示。
(實施例5)
對於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),於室溫添加作為難燃劑之氰基改性環狀苯氧基磷腈化合物(B1),使相對於聚醯亞胺樹脂固體成分100質量份之含量為10質量份,於70℃之條件攪拌混合2小時,獲得脂環式聚醯亞胺樹脂組成物溶液。溶液之濃度為21.57質量%。
其次,使用前述獲得之脂環式聚醯亞胺樹脂組成物溶液,除此以外與實施例1以同樣方法,獲得膜厚105μm之無色透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0。結果如表1所示。
(實施例6)
對於製造例4獲得之脂環式聚醯亞胺樹脂溶液(A4’),於室溫添加作為難燃劑之氰基改性環狀苯氧基磷腈化合物(B1),使相對於聚醯亞胺樹脂固體成分100質量份之含量為5質量份,於70℃之條件攪拌混合2小時,獲得脂環式聚醯亞胺樹脂組成物溶液。溶液
之濃度為20.79質量%。
其次,使用前述獲得之脂環式聚醯亞胺樹脂組成物溶液,除此以外與實施例1以同樣方法,獲得膜厚104μm之透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0。結果如表1所示。
(比較例1)
於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),於室溫添加作為難燃劑之磷酸三苯酯(B2),使相對於聚醯亞胺樹脂固體成分100質量份之含量為3質量份,除此以外與實施例1以同樣方法,獲得膜厚118μm之透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗,結果完全燃燒,相當於UL規格外。結果如表2所示。
(比較例2)
對於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),添加作為難燃劑之磷酸三苯酯(B2),使相對於聚醯亞胺樹脂固體成分100質量份之含量為20質量份,除此以外與實施例1以同樣方法,獲得膜厚103μm之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率,結果,與實施例1比較,全光線穿透率下降,霧度值大幅升高。又,實施燃燒性試驗之結果,相當於UL規格VTM-1。結果如表2所示。
(比較例3)
對於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),添加作為難燃劑之間苯二酚雙(苯基)磷酸酯(B3),使相對於聚醯亞胺樹脂
固體成分100質量份之含量為20質量份,除此以外與實施例1以同樣方法,獲得膜厚98μm之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率,結果,與實施例1比較,全光線穿透率下降,霧度值大幅升高。又,實施燃燒性試驗之結果,相當於UL規格VTM-1。結果如表2所示。
(比較例4)
對於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),添加作為難燃劑之苯氧基磷腈(B4),使相對於聚醯亞胺樹脂固體成分100質量份之含量為3質量份,除此以外與實施例1以同樣方法,獲得膜厚105μm之透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-1。結果如表2所示。
(比較例5)
對於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),添加作為難燃劑之苯氧基磷腈(B4),使相對於聚醯亞胺樹脂固體成分100質量份之含量為20質量份,除此以外與實施例1以同樣方法,獲得膜厚109μm之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0,但是相較於實施例1,玻璃轉移溫度大幅降低,全光線穿透率下降,霧度值上升。結果如表2所示。
(比較例6)
對於製造例1獲得之脂環式聚醯亞胺樹脂溶液(A1’),添加作為難燃劑之氰基改性環狀苯氧基磷腈化合物(B1),使相對於聚醯亞
胺樹脂固體成分100質量份之含量為20質量份,除此以外與實施例1以同樣方法,獲得膜厚111μm之透明之由脂環式聚醯亞胺樹脂組成物構成的薄壁成型體。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,相當於UL規格VTM-0,但是相較於實施例1,玻璃轉移溫度大幅降低。結果如表2所示。
(比較例7)~(比較例10)
如表3所示,由脂環式聚醯亞胺樹脂組成物構成之薄壁成型體,除未添加難燃劑以外係以與實施例1同樣的方法獲得。求取該等之全光線穿透率及霧度值,並測定玻璃轉移溫度、表面電阻率。又,實施燃燒性試驗之結果,結果完全燃燒,相當於UL規格外。結果如表3。
【產業利用性】
依照本發明,可不使用對於人體及環境之影響有顧慮的鹵素化合物或氧化銻化合物等難燃劑而提供難燃性、透明性、耐熱性、絕緣特性優異之脂環式聚醯亞胺樹脂組成物及其薄壁成型體,並使用於當作透明性或難燃性為必要的各種電性‧電子零件之密封材料、保護膜材料、絕緣材料。具體例,宜使用在電腦、行動電話設備等的顯示器基板、太陽能電池等的絕緣基板、發光二極體用之密封材料等用途。
Claims (4)
- 一種脂環式聚醯亞胺樹脂組成物,其相對於具有以下列通式(1)表示之結構單元之脂環式聚醯亞胺樹脂(A)100質量份,含有以下列通式(2)表示之氰基改性環狀苯氧基磷腈化合物(B)1~13質量份;
- 如申請專利範圍第1項之脂環式聚醯亞胺樹脂組成物,其中,該脂環式聚醯亞胺樹脂(A)係具有以下列通式(3)表示之結構單元之聚醯亞胺樹脂;
- 如申請專利範圍第1或2項之脂環聚醯亞胺樹脂組成物,其中,於上式(1)及(3),R2為碳數6~27之2價之芳香族烴基,且鍵結於R2之氮原子係直接鍵結於R2之芳香環。
- 一種薄壁成型體,其係由如申請專利範圍第1至3項中任一項之脂環式聚醯亞胺樹脂組成物構成,藉由將該脂環式聚醯亞胺樹 脂組成物溶解於有機溶劑製得脂環式聚醯亞胺樹脂組成物溶液,並使所製得之脂環式聚醯亞胺樹脂組成物溶液流延後加熱而獲得。
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