JPH01279966A - Polyimide resin composition - Google Patents
Polyimide resin compositionInfo
- Publication number
- JPH01279966A JPH01279966A JP63109082A JP10908288A JPH01279966A JP H01279966 A JPH01279966 A JP H01279966A JP 63109082 A JP63109082 A JP 63109082A JP 10908288 A JP10908288 A JP 10908288A JP H01279966 A JPH01279966 A JP H01279966A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- bis
- group
- aminophenoxy
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title abstract description 21
- 239000009719 polyimide resin Substances 0.000 title description 5
- 239000004642 Polyimide Substances 0.000 claims abstract description 33
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 23
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 23
- 239000011342 resin composition Substances 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 abstract description 7
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 125000002723 alicyclic group Chemical group 0.000 abstract 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004963 Torlon Substances 0.000 description 2
- 229920003997 Torlon® Polymers 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- JFEXPVDGVLNUSC-UHFFFAOYSA-N 3-(3-aminophenyl)sulfanylaniline Chemical compound NC1=CC=CC(SC=2C=C(N)C=CC=2)=C1 JFEXPVDGVLNUSC-UHFFFAOYSA-N 0.000 description 1
- QHWXZLXQXAZQTO-UHFFFAOYSA-N 3-(3-aminophenyl)sulfinylaniline Chemical compound NC1=CC=CC(S(=O)C=2C=C(N)C=CC=2)=C1 QHWXZLXQXAZQTO-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-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
- ZKGYNWLJTGAEGS-UHFFFAOYSA-N 3-(4-aminophenyl)sulfanylaniline Chemical compound C1=CC(N)=CC=C1SC1=CC=CC(N)=C1 ZKGYNWLJTGAEGS-UHFFFAOYSA-N 0.000 description 1
- HDGMNVDCJJQDKD-UHFFFAOYSA-N 3-(4-aminophenyl)sulfinylaniline Chemical compound C1=CC(N)=CC=C1S(=O)C1=CC=CC(N)=C1 HDGMNVDCJJQDKD-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- ZDBWYUOUYNQZBM-UHFFFAOYSA-N 3-(aminomethyl)aniline Chemical compound NCC1=CC=CC(N)=C1 ZDBWYUOUYNQZBM-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- NQZOFDAHZVLQJO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 NQZOFDAHZVLQJO-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- MITHMOYLTXMLRB-UHFFFAOYSA-N 4-(4-aminophenyl)sulfinylaniline Chemical compound C1=CC(N)=CC=C1S(=O)C1=CC=C(N)C=C1 MITHMOYLTXMLRB-UHFFFAOYSA-N 0.000 description 1
- BFWYZZPDZZGSLJ-UHFFFAOYSA-N 4-(aminomethyl)aniline Chemical compound NCC1=CC=C(N)C=C1 BFWYZZPDZZGSLJ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- CRWSMXYQAJWFQC-UHFFFAOYSA-N [4-[4-[3-(4-aminophenoxy)benzoyl]phenoxy]phenyl]-[3-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(C(=O)C=2C=CC(OC=3C=CC(=CC=3)C(=O)C=3C=C(OC=4C=CC(N)=CC=4)C=CC=3)=CC=2)=C1 CRWSMXYQAJWFQC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GBASTSRAHRGUAB-UHFFFAOYSA-N ethylenetetracarboxylic dianhydride Chemical compound O=C1OC(=O)C2=C1C(=O)OC2=O GBASTSRAHRGUAB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は成形用樹脂組成物に関する。更に詳しくは、耐
熱性、耐薬品性、機械的強度などにすぐれ、かつ成形加
工性にすぐれたポリイミド系の成形用樹脂組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding resin composition. More specifically, the present invention relates to a polyimide-based molding resin composition that has excellent heat resistance, chemical resistance, mechanical strength, etc., and excellent moldability.
従来からポリイミドはその高耐熱性に加え、力学的強度
、寸法安定性が優れ、難燃性、電気絶縁性などを併せ持
つために、電気電子機器、宇宙航空用機器、輸送機器な
どの分野で使用されており、今後共耐熱性が要求される
分野に広（用いられることが期待されている。Polyimide has traditionally been used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment due to its high heat resistance, excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation properties. It is expected that it will be widely used in fields where heat resistance is required in the future.
従来価れた特性を示すポリイミドが種々開発されている
。Various polyimides have been developed that exhibit superior properties.
しかしながら耐熱性に優れていても、明瞭なガラス転移
温度を有しないために、成形材料として用いる場合に焼
結成形などの手法を用いて加工しなければならないとか
、また加工性は優れているが、ガラス転移温度が低く、
しかもハロゲン化炭化水素に可溶で、耐熱性、耐溶荊性
の面からは満足がゆかないとか、性能に一長一短があっ
た。However, even if it has excellent heat resistance, it does not have a clear glass transition temperature, so it must be processed using methods such as sintering when used as a molding material, and although it has excellent processability, it does not have a clear glass transition temperature. , low glass transition temperature,
Moreover, it is soluble in halogenated hydrocarbons, and its performance has both advantages and disadvantages, such as being unsatisfactory in terms of heat resistance and molten metal resistance.
本発明の目的は、ポリイミドが本来有する優れた特性に
加え、さらに耐熱性、および／または機械的強度が向上
したポリイミド系樹脂組成物を得ることにある。An object of the present invention is to obtain a polyimide resin composition that has improved heat resistance and/or mechanical strength in addition to the excellent properties inherently possessed by polyimide.
本発明者らは前記問題点を解決するために鋭意、研究を
行なった結果、ポリイミドと特定量の芳香族ポリアミド
イミドとよりなるポリイミド系樹脂組成物が特に前記目
的に存効であることを見出し、本発明を完成した。The present inventors conducted intensive research to solve the above-mentioned problems and found that a polyimide-based resin composition composed of polyimide and a specific amount of aromatic polyamide-imide is particularly effective for the above-mentioned purpose. , completed the invention.
本発明者はさきに機械的性質、熱的性質、電気的性質、
耐溶剤性などにすぐれ、かつ耐熱性を有するポリイミド
として
（式中、Ｒは炭素数２以上の脂肪族基、環式脂肪族基、
単環式芳香族基、縮合多環式芳香族基、芳香族基が直接
または架橋員により相互に連結された非縮合多環式芳香
族基から成る群より選ばれた４価の基を表す、）
で表わされる繰り返し単位を有する樹脂を見出した（特
開昭６２−０７６０９５号）。The inventor first described mechanical properties, thermal properties, electrical properties,
As a polyimide having excellent solvent resistance and heat resistance (wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. , ) was discovered (Japanese Patent Application Laid-Open No. 62-076095).
本発明の目的は、これらのポリイミドが本来有する機械
的、熱的および電気的特性や耐溶剤性を損なうことなく
、さらにその耐熱性、機械的強度を向上させたポリイミ
ド系樹脂組成物を提供することにある。An object of the present invention is to provide a polyimide resin composition that has improved heat resistance and mechanical strength without impairing the mechanical, thermal and electrical properties and solvent resistance inherent to these polyimides. There is a particular thing.
すなわち本発明は、式
（式中Ｒは前と同じ）
で表わされる繰り返し単位を存するポリイミド９９．９
〜５０重量％と芳香族ポリアミドイミド０．１〜５０重
量％とからなる樹脂組成物である。That is, the present invention provides a polyimide 99.9 having a repeating unit represented by the formula (wherein R is the same as before)
50% by weight and 0.1 to 50% by weight of aromatic polyamideimide.
本発明で使用されるポリイミドは、ジアミン成分として
式
で表わされるエーテルジアミン、即ち、ビス〔４−（３
−（４−アミノフェノキシ）ベンゾイル）フェニル〕エ
ーテルを使用したものであり、これと一種以上のテトラ
カルボン酸二無水物とを反応させて得られるポリアミド
酸を、イミド化して得られる。好ましくは有機溶剤中で
行なう。The polyimide used in the present invention is an ether diamine represented by the formula as a diamine component, that is, bis[4-(3
-(4-Aminophenoxy)benzoyl)phenyl]ether is used, and is obtained by imidizing a polyamic acid obtained by reacting this with one or more types of tetracarboxylic dianhydride. Preferably it is carried out in an organic solvent.
この時用いられるテトラカルボン酸二無水物は、式 （式中Ｒは前に同じ） で表わされるテトラカルボン酸二無水物である。The tetracarboxylic dianhydride used at this time has the formula (R in the formula is the same as before) It is a tetracarboxylic dianhydride represented by
即ち、使用されるテトラカルボン酸二無水物としては、
エチレンテトラカルボン酸二無水物、ブタンテトラカル
ボン酸に無水物、シクロペンタンテトラカルボン酸二無
水物、ピロメリット酸二無水物、３，３°、４．４’
−ベンゾフェノンテトラカルボン酸二無水物、２．２’
、３．３°−ベンゾフェノンテトラカルボン酸二無水
物、３．３″、４．４°−ビフェニルテトラカルボン酸
二無水物、２．２’、３．３’−ビフェニルテトラカル
ボン酸二無水物、２．２−ビス（３，４−ジカルボキシ
フェニル）プロパンニ無水物、２．２−ビス（２．３−
ジカルボキシフェニル）プロパンニ無水物、ビス（３，
４−ジカルボキシフェニル）エーテルジアミン、ビス（
３，４−ジカルボキシフェニル）スルホンニ無水物、１
．１−ビス（２，３−ジカルボキシフェニル）エタンニ
無水物、ビス（２，３−ジカルボキシフェニル）メタン
ニ無水物、ビス（３，４−ジカルボキシフェニル）メタ
ンニ無水物、４．４″−（Ｐ−フェニレンジオキシ）シ
フタル酸二無水物、４．４′−（ｍ−フェニレンジオキ
シ）シフタル酸二無水物、２．３，６．７−ナフタレン
テトラカルボン酸二無水物、１．４，５．８−ナフタレ
ンテトラカルボン酸二無水物、１．２，５．６−ナフタ
レンテトラカルボン酸二無水物、１．２，３．４−ベン
ゼンテトラカルボン酸二無水物、３゜４．９．１０−ペ
リレンテトラカルボン酸二無水物、２゜３．６．７−ア
ントラセンテトラカルボン酸二無水物、１．２，７．８
−フェナントレンテトラカルボン酸二無水物などであり
、これらテトラカルボン酸二無水物は単独あるいは２種
以上混合して用いられる。That is, the tetracarboxylic dianhydride used is:
Ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3°, 4.4'
-benzophenonetetracarboxylic dianhydride, 2.2'
, 3.3°-benzophenonetetracarboxylic dianhydride, 3.3″, 4.4°-biphenyltetracarboxylic dianhydride, 2.2′, 3.3′-biphenyltetracarboxylic dianhydride, 2.2-bis(3,4-dicarboxyphenyl)propanihydride, 2.2-bis(2.3-
dicarboxyphenyl)propanihydride, bis(3,
4-dicarboxyphenyl)ether diamine, bis(
3,4-dicarboxyphenyl)sulfone dianhydride, 1
．． 1-Bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4.4″-( P-phenylenedioxy)cyphthalic dianhydride, 4.4'-(m-phenylenedioxy)cyphthalic dianhydride, 2.3,6.7-naphthalenetetracarboxylic dianhydride, 1.4, 5.8-Naphthalenetetracarboxylic dianhydride, 1.2,5.6-naphthalenetetracarboxylic dianhydride, 1.2,3.4-benzenetetracarboxylic dianhydride, 3°4.9. 10-perylenetetracarboxylic dianhydride, 2゜3.6.7-anthracenetetracarboxylic dianhydride, 1.2,7.8
-phenanthrenetetracarboxylic dianhydride, etc., and these tetracarboxylic dianhydrides may be used alone or in combination of two or more.
なお、本発明の組成物に用いられる熱可塑性ポリイミド
は、前記のエーテルジアミンを原料として用いられるポ
リイミドであるが、このポリイミドの良好な物性を損な
わない範囲内で他のジアミンを混合使用して得られるポ
リイミドも本発明の組成物に用いることができる。The thermoplastic polyimide used in the composition of the present invention is a polyimide using the above-mentioned ether diamine as a raw material, but it may be obtained by mixing other diamines within a range that does not impair the good physical properties of this polyimide. Polyimides that can be used in the compositions of the present invention can also be used.
混合して用いることのできるジアミンとしては、例えば
ｍ−フェニレンジアミン、Ｏ−フェニレンジアミン、ｐ
−フェニレンジアミン、ｍ−アミノベンジルアミン、ｐ
−アミノベンジルアミン、ビス（３−アミノフェニル）
エーテル、（３−アミノフェニル）（４−アミノフェニ
ル）エーテル、ビス（４−アミノフェニル）エーテル、
ビス（３−アミノフェニル）スルフィド、（３−アミノ
フェニル）（４−アミノフェニル）スルフィド、ビス（
４−アミノフェニル）スルフィド、ビス（３−アミノフ
ェニル）スルホキシド、（３−アミノフェニル）（４−
アミノフェニル）スルホキシド、ビス（４−アミノフェ
ニル）スルホキシド、ビス（３−アミノフェニル）スル
ホン、（３−アミノフェニル）（４−アミノフェニル）
スルホン、ビス（４−アミノフェニル）スルホン、３．
３°−ジアミノベンゾフェノン、３．４′−ジアミノベ
ンゾフェノン、４，４°−ジアミノベンゾフェノン、ビ
ス（４−（３−アミノフェノキシ）フェニルコメタン、
ビス（４−（４−アミノフェノキシ）フェニルコメタン
、１，１−ビス（４−（３−アミノフェノキシ）フェニ
ル〕エタン、１．１−ビス（４−（４−アミノフェノキ
シ）フェニル〕エタン、１．２−ビス（４−（３−アミ
ノフェノキシ）フェニル〕エタン、１．２−ビス（４−
（４−アミノフェノキシ）フェニル〕エタン、２．２−
ビス（４−（３−アミノフェノキシ）フェニル〕プロパ
ン、２Ｉ２−ビス〔４−（４−アミノフェノキシ）フェ
ニル〕プロパン、２．２−ヒス（４−（３−アミノフェ
ノキシ）フェニルコブタン、２．２−ビス（４−（４−
アミノフェノキシ）フェニルコブタン、２．２−ビス（
４−（３−アミノフェノキシ）フェニル） −１，１，
１，３，３，３−ヘキサフルオロプロパン、２．２−ビ
ス（４−（４−アミノフェノキシ）フェニル） −１，
１，１，３，３，３−ヘキサフルオロプロパン、１．３
−ビス（３−アミノフェノキシ）ベンゼン、１．３−ビ
ス（４−アミノフェノキシ）ベンゼン、１．４−ビス（
３−アミノフェノキシ）ベンゼン、１．４−ビス（４−
アミノフェノキシ）ベンゼン、４．４°−ビス（３−ア
ミノフェノキシ）ビフェニル、４．４°−ビス（４−ア
ミノフェノキシ）ビフェニル、ビス（４−（３−アミノ
フェノキシ）フェニルコケトン、ビス（４−（４−アミ
ノフェノキシ）フェニルコケトン、ビス〔４−（３−ア
ミノフェノキシ）フェニルフスルフィド、ビス（４−（
４−アミノフェノキシ）フェニルフスルフィド、ビス（
４−（３−アミノフェノキシ）フェニル〕スルホキシド
、ビス（４−（４−アミノフェノキシ）フ二ニル〕スル
ホキシド、ビス（４−（３−アミノフェノキシ）フェニ
ル〕スルホン、ビス（４−（４−アミノフェノキシ）フ
ェニル〕スルホン、ビス（４−（３−アミノフェノキシ
）フェニル〕エーテル、ビス（４−（４−アミノフェノ
キシ）フェニル〕エーテルなどが挙げられる。Examples of diamines that can be used in combination include m-phenylenediamine, O-phenylenediamine, and p-phenylenediamine.
-phenylenediamine, m-aminobenzylamine, p
-aminobenzylamine, bis(3-aminophenyl)
ether, (3-aminophenyl)(4-aminophenyl) ether, bis(4-aminophenyl) ether,
Bis(3-aminophenyl) sulfide, (3-aminophenyl)(4-aminophenyl) sulfide, bis(
4-aminophenyl) sulfide, bis(3-aminophenyl) sulfoxide, (3-aminophenyl)(4-
aminophenyl) sulfoxide, bis(4-aminophenyl) sulfoxide, bis(3-aminophenyl) sulfone, (3-aminophenyl)(4-aminophenyl)
Sulfone, bis(4-aminophenyl)sulfone, 3.
3°-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4°-diaminobenzophenone, bis(4-(3-aminophenoxy)phenylcomethane,
Bis(4-(4-aminophenoxy)phenylcomethane, 1,1-bis(4-(3-aminophenoxy)phenyl)ethane, 1,1-bis(4-(4-aminophenoxy)phenyl)ethane, 1.2-bis(4-(3-aminophenoxy)phenyl)ethane, 1.2-bis(4-
(4-aminophenoxy)phenyl]ethane, 2.2-
Bis(4-(3-aminophenoxy)phenyl)propane, 2I2-bis[4-(4-aminophenoxy)phenyl]propane, 2.2-His(4-(3-aminophenoxy)phenylcobutane), 2. 2-bis(4-(4-
aminophenoxy)phenylcobutane, 2,2-bis(
4-(3-aminophenoxy)phenyl) -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl) -1,
1,1,3,3,3-hexafluoropropane, 1.3
-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(
3-aminophenoxy)benzene, 1,4-bis(4-
aminophenoxy)benzene, 4.4°-bis(3-aminophenoxy)biphenyl, 4.4°-bis(4-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenylkoketone, bis(4 -(4-aminophenoxy)phenylkoketone, bis[4-(3-aminophenoxy)phenyl fusulfide, bis(4-(
4-aminophenoxy) phenyl fusulfide, bis(
4-(3-aminophenoxy)phenyl]sulfoxide, bis(4-(4-aminophenoxy)phynyl)sulfoxide, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(4-amino Examples include phenoxy)phenyl]sulfone, bis(4-(3-aminophenoxy)phenyl)ether, and bis(4-(4-aminophenoxy)phenyl)ether.
本発明で使用される芳香族ポリアミドイミドは主鎖の繰
り返し単位中にイミドとアミドの結合をもつものであり
、
下記−数式
（式中、Ａｒはすくなくともつのベンゼン環を含む３価
の芳香族基、Ｚは２価の有機基を示す）で表わされる繰
り返し単位を有する芳香族ポリアミドイミドである。The aromatic polyamide-imide used in the present invention has imide and amide bonds in the repeating unit of the main chain, and has the following formula (where Ar is a trivalent aromatic group containing at least one benzene ring). , Z represents a divalent organic group).
本発明において特に好ましい芳香族ポリアミドイミドは
、式、
および式、
で表わされる繰り返し単位を有する芳香族ポリアミドイ
ミドである。A particularly preferred aromatic polyamide-imide in the present invention is an aromatic polyamide-imide having repeating units represented by the following formulas:
これらの芳香族ポリアミドイミドは、例えば米国アモコ
社よりトーロン（ＴＯＲＬＯＮ ）の商標名で、また東
し社よりは芳香族ポリアミドイミドのＴｌ−１０００シ
リーズまたはＴＩ−５０００のシリーズの商標名で市販
されている。These aromatic polyamideimides are commercially available, for example, from Amoco Corporation in the United States under the trade name TORLON, and from Toshisha Co., Ltd. under the trade name Tl-1000 series or TI-5000 series of aromatic polyamideimides. There is.
本発明の成形用樹脂組成物は前記ポリイミド９９．９〜
５０重量％、芳香族ポリアミドイミドが０．１〜５０重
量％の範囲にあり、その合計が１００３１１％であるよ
うに調整される。The molding resin composition of the present invention comprises the polyimide 99.9 to 99.9.
50% by weight, aromatic polyamideimide in the range of 0.1 to 50% by weight, and the total amount is adjusted to be 100311%.
本発明のポリイミド／芳香族ポリアミドイミド複合樹脂
系において芳香族ポリアミドイミドによる耐熱性および
／または機械的強度の向上効果は少量でも認められ、そ
の組成割合の下限は０．１重量％であるが、好ましくは
、０．５重量％以上である。In the polyimide/aromatic polyamide-imide composite resin system of the present invention, the effect of improving heat resistance and/or mechanical strength by the aromatic polyamide-imide is recognized even in small amounts, and the lower limit of its composition ratio is 0.1% by weight. Preferably, it is 0.5% by weight or more.
また芳香族ポリアミドイミドは通常の熱可塑性樹脂に比
べて非常に高い熔融粘度を有するため、該組成物中の芳
香族ポリアミドイミドの量を余り多くするとポリイミド
の有する優れた成形加工性を維持できなくなり、また破
断伸度も低下し好ましくない、そのため芳香族ポリアミ
ドイミドの組成割合には上限があり、５０重量％以下が
良い。Furthermore, since aromatic polyamide-imide has a much higher melt viscosity than ordinary thermoplastic resins, if the amount of aromatic polyamide-imide in the composition is too large, the excellent moldability of polyimide cannot be maintained. Moreover, the elongation at break also decreases, which is undesirable.Therefore, there is an upper limit to the composition ratio of the aromatic polyamide-imide, which is preferably 50% by weight or less.
本発明による組成物を混合調製するにあたっては、通常
公知の方法により製造できるが、例えば次に示す方法な
どは好ましい方法である。The composition according to the present invention can be mixed and prepared by commonly known methods, but the following methods are preferred, for example.
（１）ポリイミド粉末と芳香族ポリアミドイミド粉末を
乳鉢、ヘンシェルミキサー、ドラムブレンダー、タンブ
ラーブレンダー、ポールミルリボンブレンダーなどを利
用して予備混練し粉状とする。(1) Preliminarily kneading polyimide powder and aromatic polyamideimide powder using a mortar, Henschel mixer, drum blender, tumbler blender, Pall mill ribbon blender, etc. to form a powder.
（２）ポリイミド粉末をあらかじめ有Ｓ溶媒に溶解ある
いは懸濁させ、この溶液あるいは懸濁液に芳香族ポリア
ミドイミドを添加し、均一に分散または溶解させた後、
溶媒を除去し、粉状とする。(2) Polyimide powder is dissolved or suspended in an S-containing solvent in advance, aromatic polyamide-imide is added to this solution or suspension, and the aromatic polyamide-imide is uniformly dispersed or dissolved.
Remove the solvent and grind to powder.
（３）本発明のポリイミドの前駆体であるポリアミド酸
の有ｉ溶剤溶液中に、芳香族ポリアミドイミドを溶解ま
たは懸濁させた後、１００〜４００’Ｃに加熱処理する
か、または通常用いられるイミド化剤を用いて化学イミ
ド化した後、溶剤を除去して粉状とする。(3) After dissolving or suspending the aromatic polyamide-imide in a solvent solution of polyamic acid, which is a precursor of the polyimide of the present invention, the aromatic polyamide-imide is heated to 100 to 400'C, or a conventional method is used. After chemical imidization using an imidization agent, the solvent is removed to form a powder.
二のようにして得られた粉状ポリイミド系樹脂組成物は
、そのまま各種成形用途、すなわち射出成形、圧縮成形
、トランスファー成形、押出成形などに用いられるが、
溶融ブレンドしてから用いるのはさらに好ましい方法で
ある。ことに前記組成物を混合調製するに当り、粉末同
志、ペレット同志、あるいは粉末とベレットを混合溶融
するのも、簡易で有効な方法である。The powdered polyimide resin composition obtained in step 2 can be used as it is for various molding purposes, such as injection molding, compression molding, transfer molding, and extrusion molding.
A more preferred method is to use the mixture after melt blending. In particular, when preparing the composition by mixing, it is a simple and effective method to mix and melt powders, pellets, or powders and pellets.
溶融ブレンドには通常のゴムまたはプラスチック類を溶
融ブレンドするのに用いられる装置、例えば熱ロール、
バンバリーミキサ−、ブラベンダー、押出機などを利用
することができる。溶融温度は配合系が溶融可能な温度
以上で、かつ配合系が熱分解し始める温度以下に設定さ
れるが、その温度は通常２８０〜４２０℃、好ましくは
３００〜４００℃である。Melt blending involves equipment used to melt blend conventional rubbers or plastics, such as hot rolls,
A Banbury mixer, Brabender, extruder, etc. can be used. The melting temperature is set above the temperature at which the blended system can be melted and below the temperature at which the blended system begins to thermally decompose, and the temperature is usually 280 to 420°C, preferably 300 to 400°C.
本発明の樹脂組成物の成形方法としては、均一熔融ブレ
ンド体を成形し、かつ生産性の高い成形方法である射出
成形または押出成形が好適であるが、その他のトランス
ファー成形、圧縮成形、焼結成形、押出しフィルム成形
などを通用してもなんら差し支えない。As a method for molding the resin composition of the present invention, injection molding or extrusion molding, which is a molding method that molds a homogeneous melt blend and has high productivity, is suitable, but other methods such as transfer molding, compression molding, and sinter molding are suitable. There is no problem in using shapes, extrusion film molding, etc.
なお本発明の樹脂組成物に対して固体潤滑剤、例えば二
硫化モリブデン、グラファイト、窒化ホウ酸、−酸化鉛
、鉛粉などを一種以上添加す・ることができる、また補
強側、例えばガラス繊維、炭素繊維、芳香族ポリアミド
繊維、炭化ケイ素繊維、チタン酸カリウム繊維、ガラス
ピーズを一種以上添加することもできる。In addition, one or more solid lubricants such as molybdenum disulfide, graphite, boric acid nitride, lead oxide, lead powder, etc. may be added to the resin composition of the present invention, and reinforcing materials such as glass fibers may be added to the resin composition of the present invention. , carbon fibers, aromatic polyamide fibers, silicon carbide fibers, potassium titanate fibers, and glass peas.
なお本発明の樹脂組成物に対して、本発明の目的をそこ
なわない範囲で、酸化防止剤、熱安定剤、紫外線吸収剤
、難燃剤、難燃助剤、帯電防止剤、滑剤、着色材、など
の通常の添加剤を一種以上添加することができる。In addition, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants, and colorants may be added to the resin composition of the present invention within a range that does not impair the purpose of the present invention. One or more conventional additives such as , etc. can be added.
以下本発明を合成例、実施例および比較例によりさらに
詳細に説明する。The present invention will be explained in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples.
合成例−１
かきまぜ機、還流冷却器および窒素導入管を備えた反応
容器に、ビス（４−＋３− （４−アミノフェノキシ）
ベンゾイル）フェニル〕エーテル５゜９２ｋｇ （１０
モル）と、Ｎ、Ｎ−ジメチルアセトアミド１８．８ｋｇ
を装入し、室温で窒素雰囲気下にとロメリット酸二無水
物２．１４ｋｇ （９，８モル）を、溶液温度の上昇に
注意しながら加え、室温で約２４時間かきまぜポリアミ
ドイミド酸溶液を得た。Synthesis Example-1 Bis(4-+3-(4-aminophenoxy)
benzoyl)phenyl]ether 5゜92kg (10
mol) and 18.8 kg of N,N-dimethylacetamide
2.14 kg (9.8 mol) of romellitic dianhydride was added under a nitrogen atmosphere at room temperature, taking care not to increase the solution temperature, and the mixture was stirred at room temperature for about 24 hours to obtain a polyamideimide acid solution. Ta.
このポリアミド酸溶液に、Ｎ、Ｎ−ジメチルアセトアミ
ド５．３７ｋｇ加え、室温、窒素雰囲気下でかきまぜな
がら４．０８ｋｇ （４０モル）のトリエチルアミンお
よび６．０３ｋｇ （６０モル）の無水酢酸を滴下した
。To this polyamic acid solution, 5.37 kg of N,N-dimethylacetamide was added, and 4.08 kg (40 mol) of triethylamine and 6.03 kg (60 mol) of acetic anhydride were added dropwise while stirring at room temperature under a nitrogen atmosphere.
さらに室温で約２４時間かききまぜた後、この溶液を激
しくかきまぜている水２５０２中に排出した。After approximately 24 hours of additional stirring at room temperature, the solution was drained into vigorously stirred water 2502.
得られた析出物をろ別し、メタノールで洗浄した後、１
５０℃で２４時間減圧乾燥して、７．４７ｋｇ （収率
的９７．０％）の淡黄色ポリイミド粉末を得た。The obtained precipitate was filtered, washed with methanol,
It was dried under reduced pressure at 50° C. for 24 hours to obtain 7.47 kg (yield: 97.0%) of pale yellow polyimide powder.
このポリイミド粉の対数粘度は０．８６ｄ１／ ｇであ
った。ここに対数粘度はポリイミド粉末０．５ｇをｐ−
クロロフェノールとフェノールの混合溶媒（Ｐ−クロロ
フェノール：フェノール−９０：１帽１比） １００
ｇに加熱溶解し、３５゛Ｃに冷却して測定した値である
。The logarithmic viscosity of this polyimide powder was 0.86 d1/g. Here, the logarithmic viscosity is p-
Mixed solvent of chlorophenol and phenol (P-chlorophenol:phenol-90:1 ratio) 100
This is the value measured after heating and dissolving the solution at 35°C.
またこの粉末のＤＳＣ測定によるガラス転移温度は２３
５°Ｃであった。Furthermore, the glass transition temperature of this powder according to DSC measurement is 23
It was 5°C.
実施例−１〜４
合成例−１〜６で得られたポリイミド粉末と、芳香族ポ
リアミドイミド粉末であって、市販されているトーロン
４２０３Ｌ （ＴＯＲＬＯＮ ４２０３Ｌ ｉ米国３Ｎ
Ｂ社商標）を表−１のように各種の組成でトライブレン
ドした後、熔融混練しながら押し出す操作を行なって均
一配合ペレットを得た。Examples 1 to 4 The polyimide powders obtained in Synthesis Examples 1 to 6 and the aromatic polyamideimide powder, commercially available TORLON 4203L (US 3N
B Company Trademark) was tri-blended with various compositions as shown in Table 1, and then an extrusion operation was performed while melt-kneading to obtain uniformly blended pellets.
次に、上記で得た均一配合ペレットを射出成形Ｉｌ（ア
ープルグ社製 アーブルグオールラウンドＡ−２２０）
を用い、バレル温度３８０〜４００°Ｃ１金型温度２０
０℃で射出成形し、試験片を作成して、試験片の物理的
、熱的性質を測定した。Next, the uniformly mixed pellets obtained above were injection molded (Aburg All Round A-220 manufactured by Aburg Co., Ltd.).
Barrel temperature: 380-400°C 1 mold temperature: 20°C
Test pieces were prepared by injection molding at 0°C, and the physical and thermal properties of the test pieces were measured.
結果を表−１に示す。The results are shown in Table-1.
なお６表には最低射出成形圧力も併せて記す。Table 6 also shows the minimum injection molding pressure.
表中引張強度及び破断伸度はＡＳＴＭ Ｄ−６３８、曲
げ強度及び曲げ弾性率はＡＳＴＭ Ｄ−７９０、アイゾ
ツト衝撃値はＡＳＴＭ Ｄ−２５６、熱変形温度はＡＳ
ＴＭ Ｄ−６４８に拠比較例−１〜２
本発明の範囲外の組成物を用い、実施例１〜４と同様の
操作で得られた成形物の物理的、熱的性質を測定した結
果を、併せて表−１に比較例−１〜２として示す。In the table, tensile strength and elongation at break are ASTM D-638, flexural strength and flexural modulus are ASTM D-790, Izod impact value is ASTM D-256, and heat distortion temperature is ASTM
Comparative Examples 1 to 2 Based on TM D-648 The results of measuring the physical and thermal properties of molded products obtained by the same operations as Examples 1 to 4 using compositions outside the scope of the present invention are , are also shown in Table 1 as Comparative Examples 1 and 2.
合成例−２〜５
各種ジアミンと、各種テトラカルボン酸二無水物との組
み合わせにより、合成例−１と同様に行ない、各種ポリ
イミド粉末を得た０表−２にポリイミド合成条件と、生
成ポリイミド粉末の対数粘度を示す。Synthesis Examples 2 to 5 Various polyimide powders were obtained by combining various diamines and various tetracarboxylic dianhydrides in the same manner as in Synthesis Example 1.Table 2 shows the polyimide synthesis conditions and the resulting polyimide powders. The logarithmic viscosity of
実施例−５〜１４、及び比較例−３〜６合成例−２〜５
で得られたポリイミド粉を用い、実施例−１〜４と同様
に均一配合ペレットを得、次いで同様に射出成形し、成
形物の物理的、熱的性質を測定した。Examples-5 to 14 and Comparative Examples-3 to 6 Synthesis Examples-2 to 5
Uniformly blended pellets were obtained in the same manner as in Examples 1 to 4 using the polyimide powder obtained in , and then injection molded in the same manner as above, and the physical and thermal properties of the molded products were measured.
本発明の範囲内の組成物の結果を実施例−５〜１４に、
範囲外の組成物を比較例−３〜６として、併せて表−３
〜４に示す。The results of compositions within the scope of the present invention are shown in Examples-5 to 14.
Compositions outside the range are shown in Table 3 as Comparative Examples 3 to 6.
- Shown in 4.
本発明の方法によればポリイミドが本来有する優れた特
性に加え、著しく耐熱製および／または機械的強度が向
上したポリイミド系樹脂組成物が提供される。According to the method of the present invention, a polyimide-based resin composition is provided which has significantly improved heat resistance and/or mechanical strength in addition to the excellent properties inherently possessed by polyimide.
特許出願人 三井東圧化学株式会社
手続主甫正書 １発）
平成１年１月１７日
特許庁長官 吉 １）文 毅 殿
１、事件の表示
昭和６３年特許願第 １０９０８２ 号２、発明の名
称
ポリイミド系樹脂組成物
３、補正をする者
事件との関係 特許出願人
住所 東京都千代田区霞が関三丁目２番５号４、補正に
より増加する発明の数 零（］）明細書第６頁第３行
目に「好ましくは有８１溶剤中で行う、」とあるのを削
除する。Patent Applicant: Mitsui Toatsu Chemical Co., Ltd. Proceeding Officer 1) January 17, 1999 Director General of the Patent Office Yoshi 1) Moon Takeshi 1, Indication of the Case Patent Application No. 109082 of 1988 2, Invention Name: Polyimide Resin Composition 3, Relationship with the case of the person making the amendment Patent applicant address: 3-2-5-4 Kasumigaseki, Chiyoda-ku, Tokyo Number of inventions increased by the amendment: 0 (]) Page 6 of the specification In the third line, the statement "preferably carried out in a 81-containing solvent" is deleted.
（２）明細書第１１頁第４行目にｒＡｒはすくなくとも
つのベンゼンＪとあるのを「Ａｒはすくなくとも１つの
ベンゼンＪに訂正する。(2) On page 11, line 4 of the specification, the statement that rAr means at least one benzene J is corrected to read ``Ar means at least one benzene J.
〔３）明細書第１９頁表−１の実施例−１，熱変形温度
の欄に記載の数字ｒ２６１Ｊとあるのをｒ２０６ 、に
訂正する。[3) The number r261J in the heat distortion temperature column of Example-1 in Table-1 on page 19 of the specification has been corrected to r206.
（４）明細書１９頁表−１の実施例−４９曲げ弾性率の
欄に記載の数字ｒ ２８５００ Ｊとあるのをｒ ３８
５００ノに訂正する。(4) The number written in the flexural modulus column of Example 49 in Table 1 on page 19 of the specification is r 28500 J, and is r 38
Corrected to 500 no.
Claims (1)
単環式芳香族基、縮合多環式芳香族基、芳香族基が直接
または架橋員により相互に連結された非縮合多環式芳香
族基から成る群より選ばれた４価の基を表わす。） で表わされる繰り返し単位を有するポリイミド９９．９
〜５０重量％と芳香族ポリアミドイミド０．１〜５０重
量％とからなる樹脂組成物。(1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is an aliphatic group with 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. . ) Polyimide 99.9 having a repeating unit represented by
A resin composition comprising ~50% by weight and 0.1-50% by weight of aromatic polyamideimide.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10908288A JPH0676553B2 (en) | 1988-05-06 | 1988-05-06 | Polyimide resin composition |
| US07/341,810 US4987197A (en) | 1988-05-06 | 1989-04-24 | Polyimide/polyamideimide resin composition |
| AU33858/89A AU598972B2 (en) | 1988-05-06 | 1989-04-28 | Polyimide resin composition |
| KR1019890006030A KR920004193B1 (en) | 1988-05-06 | 1989-05-04 | Polyimide resin compositions |
| DE8989304477T DE68905225T2 (en) | 1988-05-06 | 1989-05-04 | POLYIMIA RESIN COMPOSITION. |
| EP89304477A EP0341052B1 (en) | 1988-05-06 | 1989-05-04 | Polyimide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10908288A JPH0676553B2 (en) | 1988-05-06 | 1988-05-06 | Polyimide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01279966A true JPH01279966A (en) | 1989-11-10 |
| JPH0676553B2 JPH0676553B2 (en) | 1994-09-28 |
Family
ID=14501141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10908288A Expired - Fee Related JPH0676553B2 (en) | 1988-05-06 | 1988-05-06 | Polyimide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676553B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711792A (en) * | 1993-06-24 | 1995-01-13 | Nippon Sogo Jiyuuseikatsu Kk | Multi-story type parking device |
-
1988
- 1988-05-06 JP JP10908288A patent/JPH0676553B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0676553B2 (en) | 1994-09-28 |
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