WO2016147997A1 - ポリイミド樹脂 - Google Patents
ポリイミド樹脂 Download PDFInfo
- Publication number
- WO2016147997A1 WO2016147997A1 PCT/JP2016/057511 JP2016057511W WO2016147997A1 WO 2016147997 A1 WO2016147997 A1 WO 2016147997A1 JP 2016057511 W JP2016057511 W JP 2016057511W WO 2016147997 A1 WO2016147997 A1 WO 2016147997A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyimide resin
- group
- carbon atoms
- mol
- formula
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 239
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 231
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 105
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 45
- 125000003118 aryl group Chemical group 0.000 claims abstract description 31
- 150000004985 diamines Chemical class 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 27
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 239000004642 Polyimide Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000000470 constituent Substances 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 89
- -1 aliphatic diamine Chemical class 0.000 description 73
- 239000000835 fiber Substances 0.000 description 50
- 239000000243 solution Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 49
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 39
- 239000000843 powder Substances 0.000 description 33
- 239000002904 solvent Substances 0.000 description 32
- 239000002131 composite material Substances 0.000 description 29
- 239000002657 fibrous material Substances 0.000 description 29
- 238000005259 measurement Methods 0.000 description 26
- 238000000465 moulding Methods 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 17
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 230000032683 aging Effects 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 229920005575 poly(amic acid) Polymers 0.000 description 15
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- 239000004917 carbon fiber Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 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 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 238000009998 heat setting Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003856 thermoforming Methods 0.000 description 5
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 4
- DZDVMKLYUKZMKK-UHFFFAOYSA-N 7-methyloctan-1-amine Chemical compound CC(C)CCCCCCN DZDVMKLYUKZMKK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000000149 argon plasma sintering 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
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 4
- 150000003949 imides Chemical group 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003303 reheating Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229920006259 thermoplastic polyimide Polymers 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
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- 230000020169 heat generation Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 2
- UKVQTDPWSWISPM-UHFFFAOYSA-N 3-methylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound CC1=C(C(O)=O)C(C(O)=O)=CC(C(O)=O)=C1C(O)=O UKVQTDPWSWISPM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- LJQFHDUFUVMPSP-UHFFFAOYSA-N 8-methylnonan-1-amine Chemical compound CC(C)CCCCCCCN LJQFHDUFUVMPSP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
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- 239000011304 carbon pitch Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 238000001641 gel filtration chromatography Methods 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
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- 229920002239 polyacrylonitrile Polymers 0.000 description 2
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- 125000005579 tetracene group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- QUMDOMSJJIFTCA-UHFFFAOYSA-N 1,1,2-tribromoethane Chemical compound BrCC(Br)Br QUMDOMSJJIFTCA-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- CBDSAGQXGRIBSI-UHFFFAOYSA-N 1,2-diethynylcyclohexa-3,5-diene-1,2-diamine Chemical compound C#CC1(N)C=CC=CC1(N)C#C CBDSAGQXGRIBSI-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
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- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Natural products CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier 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
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 230000026683 transduction Effects 0.000 description 1
- 238000010361 transduction Methods 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- HHPPHUYKUOAWJV-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCC1CO1 HHPPHUYKUOAWJV-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
-
- 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
- C08G73/1075—Partially aromatic polyimides
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
Definitions
- the present invention relates to a thermoplastic polyimide resin.
- Polyimide resin is a useful engineering plastic that has high thermal stability, high strength, and high solvent resistance due to molecular chain rigidity, resonance stabilization, and strong chemical bonding, and is applied in a wide range of fields. Moreover, since the polyimide resin which has crystallinity can further improve the heat resistance, intensity
- Patent Document 1 Highly heat-resistant resin Vespel (registered trademark) or the like is known as a polyimide molding material (Patent Document 1), but it is difficult to mold because of its extremely low fluidity even at high temperatures, and it is difficult for a long time under high temperature and high pressure conditions. Since it is necessary to perform molding, it is disadvantageous in terms of cost. On the other hand, if the resin has a melting point and is flowable at a high temperature like a crystalline resin, it can be molded easily and inexpensively.
- thermoplastic polyimide resins having thermoplasticity have been reported.
- Thermoplastic polyimide resins are excellent in moldability in addition to the heat resistance inherent in polyimide resins. Therefore, the thermoplastic polyimide resin can be applied to a molded body used in a harsh environment where nylon or polyester, which are general-purpose thermoplastic resins, cannot be applied.
- Aurum registered trademark
- Non-patent Document 1 thermoplastic polyimide resins
- One method of improving the moldability of the polyimide resin is a method of using a long-chain aliphatic diamine as a raw material diamine (Non-patent Document 2).
- Non-patent Document 2 a method of using a long-chain aliphatic diamine as a raw material diamine.
- the rigidity of the polyimide resin is lowered, and the melting point is lowered.
- the glass transition temperature also decreases with a decrease in the melting point, and particularly the strength decreases at high temperatures.
- Patent Documents 5 and 6 polyimide resins having both moldability and heat resistance and compositions containing the polyimide resins have been developed.
- An object of the present invention is to provide a novel polyimide resin which is excellent in molding processability and heat resistance, and particularly excellent in heat aging resistance.
- the present inventors have found that a polyimide resin having specific specific polyimide constituent units combined at a specific ratio and having a specific group at the terminal can solve the above-mentioned problems. That is, the present invention includes a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2). There is provided a polyimide resin having a content ratio of the repeating structural unit of the formula (1) to 20 to 70 mol% and a chain aliphatic group having 5 to 14 carbon atoms at the terminal.
- R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
- R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
- X 1 And X 2 each independently represents a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
- the polyimide resin of the present invention is excellent in moldability, heat resistance and heat aging resistance. For example, even when a film containing the polyimide resin is stored for several days in a high temperature environment of 200 ° C. or higher, the decrease in molecular weight retention is small and the mechanical strength (toughness) of the film is maintained.
- the polyimide resin is used in applications requiring heat aging resistance, such as gears, tubes and pipes used in automobiles, sliding members used in copiers, industrial piping, electronic members, coating materials, etc. Preferably used.
- the polyimide resin of the present invention includes a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the repeating structural unit of the formula (1) and the repeating of the formula (2).
- the content ratio of the repeating structural unit of the formula (1) with respect to the total of the structural units is 20 to 70 mol%, and has a chain aliphatic group having 5 to 14 carbon atoms at the terminal.
- R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
- R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
- X 1 And X 2 each independently represents a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
- the polyimide resin of the present invention is formed by combining specific different polyimide structural units in the above-mentioned specific ratio, and has a predetermined group at the end, so that it has excellent moldability and heat resistance, and further has heat aging resistance. It will be excellent.
- R 1 is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure.
- the alicyclic hydrocarbon structure means a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated. It may be a ring or a polycycle.
- Examples of the alicyclic hydrocarbon structure include, but are not limited to, cycloalkane rings such as cyclohexane ring, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane ring, and bicycloalkene rings such as norbornene. Do not mean.
- a cycloalkane ring is preferable, a cycloalkane ring having 4 to 7 carbon atoms is more preferable, and a cyclohexane ring is more preferable.
- R 1 has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms.
- R 1 contains at least one alicyclic hydrocarbon structure, and preferably contains 1 to 3 alicyclic hydrocarbon structures.
- R 1 is preferably a divalent group represented by the following formula (R1-1) or (R1-2).
- M 11 and m 12 are each independently an integer of 0 to 2, preferably 0 or 1.
- m 13 to m 15 are each independently an integer of 0 to 2, preferably 0. Or 1.
- R 1 is particularly preferably a divalent group represented by the following formula (R1-3).
- the positional relationship between the two methylene groups with respect to the cyclohexane ring may be cis or trans, and the ratio of cis to trans is Any value is acceptable.
- X 1 is a C 6-22 tetravalent group containing at least one aromatic ring.
- the aromatic ring may be a single ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
- X 1 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
- X 1 contains at least one aromatic ring, preferably 1 to 3 aromatic rings.
- X 1 is preferably a tetravalent group represented by any of the following formulas (X-1) to (X-4).
- R 11 to R 18 are each independently an alkyl group having 1 to 4 carbon atoms.
- P 11 to p 13 are each independently an integer of 0 to 2, preferably 0.
- p 14 , P 15 , p 16 and p 18 are each independently an integer of 0 to 3, preferably 0.
- p 17 is an integer of 0 to 4, preferably 0.
- Each 13 is independently a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.
- X 1 is a tetravalent group having 6 to 22 carbon atoms including at least one aromatic ring
- R 12 , R 13 , p 12 and p 13 in the formula (X-2) are represented by the formula (X—
- the tetravalent group represented by 2) is selected so that the number of carbon atoms falls within the range of 6-22.
- L 11 , R 14 , R 15 , p 14 and p 15 in formula (X-3) are such that the carbon number of the tetravalent group represented by formula (X-3) is in the range of 6-22.
- L 12 , L 13 , R 16 , R 17 , R 18 , p 16 , p 17 and p 18 in formula (X-4) are tetravalent represented by formula (X-4) Is selected so that the number of carbons in the group falls within the range of 6-22.
- X 1 is particularly preferably a tetravalent group represented by the following formula (X-5) or (X-6).
- R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms, preferably 5 to 14 carbon atoms, more preferably 5 to 12 carbon atoms.
- the chain aliphatic group means a group derived from a chain aliphatic compound, and the chain aliphatic compound may be saturated or unsaturated, Or may be branched, and may contain a heteroatom such as an oxygen atom.
- R 2 is preferably an alkylene group having 5 to 16 carbon atoms, more preferably an alkylene group having 5 to 14 carbon atoms, still more preferably an alkylene group having 5 to 12 carbon atoms, and particularly preferably an alkylene group having 6 to 12 carbon atoms.
- An alkylene group more preferably an alkylene group having 6 to 10 carbon atoms.
- the alkylene group may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group.
- R 2 is particularly preferably at least one selected from a hexamethylene group, an octamethylene group, and a decamethylene group.
- R 2 is a C 5-16 divalent chain aliphatic group containing an ether group.
- the carbon number is preferably 5 to 14 carbon atoms, more preferably 5 to 12 carbon atoms.
- a divalent group represented by the following formula (R2-1) or (R2-2) is preferable.
- M 21 and m 22 are each independently an integer of 1 to 15, preferably 1 to 13, more preferably 1 to 11, and still more preferably 2 to 6.
- m 23 to m 25 are respectively Independently, it is an integer of 1 to 14, preferably 1 to 12, more preferably 1 to 10, and still more preferably 2 to 4.
- R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms (preferably 5 to 14 carbon atoms, more preferably 5 to 12 carbon atoms), and therefore m 21 in the formula (R2-1).
- m 22 so that the carbon number of the divalent group represented by the formula (R2-1) falls within the range of 5 to 16 (preferably 5 to 14 carbon atoms, more preferably 5 to 12 carbon atoms). Selected.
- m 21 + m 22 is 5 to 16 (preferably 5 to 14, more preferably 5 to 12).
- the divalent group represented by the formula (R2-2) has 5 to 16 carbon atoms (preferably 5 to 14 carbon atoms, more preferably It is selected to fall within the range of 5 to 12 carbon atoms. That is, m 23 + m 24 + m 25 is 5 to 16 (preferably 5 to 14, more preferably 5 to 12).
- X 2 is defined in the same manner as X 1 in formula (1), and the preferred embodiment is also the same.
- the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is 20 to 70 mol%.
- the content ratio of the repeating structural unit of the formula (1) is within the above range, the polyimide resin can be sufficiently crystallized even in a general injection molding cycle.
- the content ratio is less than 20 mol%, the molding processability is lowered, and when it exceeds 70 mol%, the crystallinity is lowered, so that the heat resistance is lowered.
- the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is preferably 25 mol% or more from the viewpoint of moldability.
- the total content of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) with respect to all the repeating units constituting the polyimide resin of the present invention is preferably 50 to 100 mol%, more preferably 75 to It is 100 mol%, more preferably 80 to 100 mol%, still more preferably 85 to 100 mol%.
- the polyimide resin of the present invention may further contain a repeating structural unit of the following formula (3).
- the content ratio of the repeating structural unit of the formula (3) to the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is preferably 25 mol% or less.
- the lower limit is not particularly limited as long as it exceeds 0 mol%.
- the content ratio is preferably 5 mol% or more, more preferably 10 mol% or more, while from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less. Preferably it is 15 mol% or less.
- R 3 is a C 6-22 divalent group containing at least one aromatic ring.
- X 3 is a C 6-22 tetravalent group containing at least one aromatic ring.
- R 3 is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
- the aromatic ring may be a single ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
- R 3 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
- R 3 contains at least one aromatic ring, preferably 1 to 3 aromatic rings.
- a monovalent or divalent electron withdrawing group may be bonded to the aromatic ring.
- the monovalent electron withdrawing group include nitro group, cyano group, p-toluenesulfonyl group, halogen, halogenated alkyl group, phenyl group, acyl group and the like.
- the divalent electron withdrawing group include a fluorinated alkylene group (for example, —C (CF 3 ) 2 —, — (CF 2 ) p — (wherein p is an integer of 1 to 10)).
- a fluorinated alkylene group for example, —C (CF 3 ) 2 —, — (CF 2 ) p — (wherein p is an integer of 1 to 10).
- p is an integer of 1 to 10.
- halogenated alkylene group —CO—, —SO 2 —, —SO—, —CONH—, —COO— and the like can be mentioned.
- R 3 is preferably a divalent group represented by the following formula (R3-1) or (R3-2).
- M 31 and m 32 are each independently an integer of 0 to 2, preferably 0 or 1.
- m 33 and m 34 are each independently an integer of 0 to 2, preferably 0.
- R 21 , R 22 , and R 23 are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms.
- p 21 , p 22 and p 23 are integers of 0 to 4, preferably 0.
- L 21 is a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.) Note that since R 3 is a C 6-22 divalent group containing at least one aromatic ring, m 31 , m 32 , R 21 and p 21 in the formula (R3-1) are represented by the formula (R3- The divalent group represented by 1) is selected so that the number of carbon atoms is in the range of 6-22. Similarly, L 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 in the formula (R3-2) are represented by the number of carbon atoms of the divalent group represented by the formula (R3-2) It is selected to fall within the range of 12-22.
- X 3 is defined in the same manner as X 1 in formula (1), and the preferred embodiment is also the same.
- the content ratio of the repeating structural unit of the formula (3) with respect to all repeating structural units constituting the polyimide resin of the present invention is preferably 25 mol% or less.
- the lower limit is not particularly limited as long as it exceeds 0 mol%.
- the content ratio is preferably 5 mol% or more, more preferably 7 mol% or more, while from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less. Preferably it is 15 mol% or less.
- the polyimide resin of the present invention may further contain a repeating structural unit represented by the following formula (4).
- R 4 is a divalent group containing —SO 2 — or —Si (R x ) (R y ) O—, and R x and R y are each independently a chain aliphatic group having 1 to 3 carbon atoms.
- X 4 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. X 4 is defined in the same manner as X 1 in formula (1), and the preferred embodiment is also the same.
- the polyimide resin of the present invention is further characterized by having a chain aliphatic group having 5 to 14 carbon atoms at the terminal.
- the chain aliphatic group may be saturated or unsaturated, and may be linear or branched. Since the polyimide resin of this invention has the said specific group at the terminal, it is excellent in heat aging resistance. Specifically, even when a film containing the polyimide resin is stored for several days in a high temperature environment of 200 ° C. or higher, the decrease in molecular weight retention is small, and the mechanical strength (toughness) of the film is maintained.
- the polyimide resin has a benzyl group or a phenyl group at the terminal
- the polyimide resin is stored in a high temperature environment of 200 ° C. or higher
- the molecular weight retention rate is lowered and the mechanical strength is also lowered.
- the terminal chain aliphatic group has 4 or less carbon atoms
- a compound having a chain aliphatic group having 4 or less carbon atoms is used to introduce the group into the terminal of the polyimide resin. Is not preferable because it easily volatilizes during the production of the polyimide resin.
- Examples of the saturated chain aliphatic group having 5 to 14 carbon atoms include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, Lauryl group, n-tridecyl group, n-tetradecyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 2-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, isooctyl group, 2-ethylhexyl group 3-ethylhexyl group, isononyl group, 2-ethyloctyl group, isodecyl group, isododecyl group, isotridecyl group, isotetradecyl group and the like.
- Examples of the unsaturated chain aliphatic group having 5 to 14 carbon atoms include 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, 1-pentenyl group, Examples include octenyl group, 2-octenyl group, nonenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group and the like.
- the chain aliphatic group is preferably a saturated chain aliphatic group, and more preferably a saturated linear aliphatic group.
- the chain aliphatic group is preferably 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms. Preferably it is 10 or less carbon atoms, More preferably, it is 9 or less carbon atoms.
- the chain aliphatic group may be one type or two or more types.
- the chain aliphatic group is particularly preferably at least one selected from n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group.
- the polyimide resin of the present invention preferably has only a chain aliphatic group having 5 to 14 carbon atoms at the terminal in addition to the terminal amino group and the terminal carboxyl group.
- the content thereof is preferably 10 mol% or less, more preferably 5 mol% or less, based on a chain aliphatic group having 5 to 14 carbon atoms.
- the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin is preferably based on 100 mol% in total of all repeating structural units in the polyimide resin from the viewpoint of expressing excellent heat aging resistance. It is 0.01 mol% or more, More preferably, it is 0.1 mol% or more, More preferably, it is 0.2 mol% or more. In order to secure a sufficient molecular weight and obtain good mechanical properties, the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin is 100 in total of all repeating structural units in the polyimide resin.
- the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin can be obtained by depolymerizing the polyimide resin.
- the polyimide resin of the present invention preferably has a melting point of 360 ° C. or lower and a glass transition temperature of 150 ° C. or higher.
- the melting point of the polyimide resin is more preferably 280 ° C. or higher, more preferably 290 ° C. or higher, from the viewpoint of heat resistance, and preferably 345 ° C. or lower, more preferably 340 ° C., from the viewpoint of developing high moldability.
- it is more preferably 335 ° C. or lower.
- the glass transition temperature of the polyimide resin is more preferably 160 ° C. or higher, more preferably 170 ° C. or higher from the viewpoint of heat resistance, and preferably 250 ° C. or lower from the viewpoint of developing high moldability.
- the polyimide resin of the present invention is cooled at a cooling rate of 20 ° C./min after melting the polyimide resin by differential scanning calorimeter measurement from the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance.
- the amount of heat of the crystallization exothermic peak observed in this case is preferably 5.0 mJ / mg or more, more preferably 10.0 mJ / mg or more.
- the crystallization heat generation amount is not particularly limited, but is usually 45.0 mJ / mg or less.
- the melting point, glass transition temperature, and crystallization calorific value of the polyimide resin can be measured by the methods described in Examples.
- the logarithmic viscosity at 30 ° C. of a 5 mass% concentrated sulfuric acid solution of the polyimide resin of the present invention is preferably in the range of 0.2 to 2.0 dL / g, more preferably 0.3 to 1.8 dL / g.
- the logarithmic viscosity ⁇ is obtained from the following equation by measuring the flow time of concentrated sulfuric acid and the polyimide resin solution at 30 ° C. using a Canon Fenske viscometer.
- ⁇ ln (ts / t 0 ) / C t 0 : Time when concentrated sulfuric acid flows ts: Time when polyimide resin solution flows C: 0.5 (g / dL)
- the weight average molecular weight (Mw) of the polyimide resin of the present invention can be appropriately adjusted according to the use, but is preferably 10,000 to 100,000, more preferably 12,000 to 80,000, still more preferably. 13,000-60,000. If Mw is 10,000 or more, the mechanical strength is good, and if it is 100,000 or less, the moldability is good.
- the number average molecular weight (Mn) of the polyamide resin is preferably 3,000 to 80,000, more preferably 4,000 to 50,000, and still more preferably 5,000 to 30,000.
- the molecular weight (Mw, Mn) of the polyimide resin can be measured by gel filtration chromatography (GPC).
- the polyimide resin of the present invention is formed into a film having a thickness of 100 ⁇ m, and the Mw retention after heating at 200 ° C. for 72 hours is preferably 95% or more, more preferably 98% or more.
- the rate is preferably 83% or more, more preferably 85% or more. If the retention of Mw and Mn is in the above range, the heat aging resistance is good.
- the Mw retention rate may exceed 100%, and a preferred upper limit is 120%. When the Mw retention rate exceeds 100%, it is considered that crosslinking has occurred in the molecule.
- a preferable upper limit of the Mn retention rate is 100%.
- the Mw and Mn retention rates can be calculated from the following equations. ⁇ Molecular weight after heating at 200 ° C. for 72 hours / Molecular weight before heating ⁇ ⁇ 100 (%)
- the form of the polyimide resin of the present invention is not particularly limited, but is preferably in the form of powder from the viewpoint of handleability.
- the ratio of passing through a sieve having a nominal opening of 500 ⁇ m for JIS testing is preferably 90% by mass or more, more preferably 250 ⁇ m.
- the ratio of passing through the sieve is 90% by mass or more. Since the polyimide resin powder has such a particle size, processing unevenness at the time of molding is difficult to occur, it is easy to convey, the dispersibility when used as a filler is high, and the drying time can be shortened. Many advantages are obtained.
- the polyimide resin powder having the above particle size has high impregnation property to the fiber material when used as a continuous fiber composite material in polyimide resin-fiber composite materials, particularly carbon fiber reinforced plastic (CFRP) applications described later. Therefore, it is preferable.
- CFRP carbon fiber reinforced plastic
- the polyimide resin powder preferably has a D10 of 8 to 100 ⁇ m, a D50 of 10 to 250 ⁇ m, and a D90 of 20 to 500 ⁇ m, as determined by particle size measurement using a laser diffraction light scattering particle size distribution analyzer. Preferably there is. By setting it as the particle size of such a range, in addition to the above-mentioned advantage, filterability is favorable and the advantage that particle
- the polyimide resin powder having the above particle size and particle size includes, for example, a step of reacting a tetracarboxylic acid component and a diamine component in the presence of a solvent containing an alkylene glycol solvent represented by the formula (I) described later. It is obtained by using a manufacturing method. Moreover, the screening test of a polyimide resin powder and the particle size measurement by a particle size laser diffraction light scattering type particle size distribution measuring device can be specifically performed by the methods described in Examples.
- the method for producing a polyimide resin of the present invention preferably includes a step of mixing a tetracarboxylic acid component and a diamine component and then mixing and reacting a compound having a chain aliphatic group having 5 to 14 carbon atoms.
- the tetracarboxylic acid component contains a tetracarboxylic acid containing at least one aromatic ring and / or a derivative thereof
- the diamine component contains a diamine containing a alicyclic hydrocarbon structure and a chain aliphatic diamine.
- a compound having a chain aliphatic group having 5 to 14 carbon atoms seals the reactive terminal of a polyimide resin obtained by reacting a tetracarboxylic acid component and a diamine component. Any monoamine may be used as long as it can introduce the chain aliphatic group having 5 to 14 carbon atoms into the polyimide resin.
- the tetracarboxylic acid containing at least one aromatic ring is preferably a compound in which four carboxyl groups are directly bonded to the aromatic ring, and may contain an alkyl group in the structure.
- the tetracarboxylic acid preferably has 6 to 26 carbon atoms.
- Examples of the tetracarboxylic acid include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, and 3,3 ′, 4,4′-biphenyl. Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like are preferable. Among these, pyromellitic acid is more preferable.
- Examples of the derivative of tetracarboxylic acid containing at least one aromatic ring include an anhydride or an alkyl ester of tetracarboxylic acid containing at least one aromatic ring.
- the tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms.
- tetracarboxylic acid anhydrides include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl Sulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5, And 8-naphthalenetetracarboxylic dianhydride.
- alkyl ester of tetracarboxylic acid examples include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylic acid, 3,3 ′, 4 Dimethyl 4,4'-diphenylsulfonetetracarboxylate, dimethyl 3,3 ', 4,4'-benzophenone tetracarboxylate, dimethyl 3,3', 4,4'-biphenyltetracarboxylate, 1,4,5,8 -Dimethyl naphthalene tetracarboxylate and the like.
- the alkyl group preferably has 1 to 3 carbon atoms.
- At least one compound selected from the above may be used alone, or two or more compounds may be used in combination.
- the diamine containing at least one alicyclic hydrocarbon structure preferably has 6 to 22 carbon atoms, such as 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4- Bis (aminomethyl) cyclohexane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis (2-methylcyclohexylamine) , Carboxylic diamine, limonene diamine, isophorone diamine, norbornane diamine, bis (aminomethyl) tricyclo [5.2.1.0 2,6 ] decane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylpropane and the like
- the chain aliphatic diamine may be linear or branched, and has preferably 5 to 16, preferably 5 to 14, more preferably 5 to 12 carbon atoms. Further, when the chain portion has 5 to 16 carbon atoms, an ether bond may be included therebetween.
- chain aliphatic diamines examples include 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine 1,16-hexadecamethylenediamine, 2,2 ′-(ethylenedioxy) bis (ethyleneamine) and the like are preferable.
- a chain aliphatic diamine may be used alone or in combination as long as it is within the scope of the present invention.
- chain aliphatic diamines having 6 to 12 carbon atoms are preferable, and chain aliphatic diamines having 6 to 10 carbon atoms can be preferably used.
- 1,6-hexamethylenediamine, 1 , 8-octamethylenediamine and 1,10-decamethylenediamine can be preferably used.
- the molar amount of the diamine containing at least one alicyclic hydrocarbon structure relative to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine.
- the ratio is preferably 20 to 70 mol%.
- the molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, further preferably 32 mol% or more from the viewpoint of moldability, and from the viewpoint of developing high crystallinity, preferably 65 mol%. % Or less, more preferably 60 mol% or less, still more preferably 57 mol% or less.
- the diamine component may contain a diamine containing at least one aromatic ring.
- the number of carbon atoms of the diamine containing at least one aromatic ring is preferably 6 to 22, for example, orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-diethynylbenzenediamine, 1,3-diethynyl.
- the molar ratio of the charged amount of the diamine containing at least one aromatic ring to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is 25 mol% or less.
- the lower limit is not particularly limited as long as it exceeds 0 mol%.
- the molar ratio is preferably 5 mol% or more, more preferably 10 mol% or more from the viewpoint of improving heat resistance, and preferably 20 mol% or less from the viewpoint of maintaining crystallinity. Preferably it is 15 mol% or less.
- the molar ratio is preferably 12 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, and still more preferably 0 mol% from the viewpoint of reducing the coloration of the polyimide resin. .
- the charge ratio of the tetracarboxylic acid component and the diamine component is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component.
- the compound having a chain aliphatic group having 5 to 14 carbon atoms is preferably at least one selected from monoamines and dicarboxylic acids having a chain aliphatic group having 5 to 14 carbon atoms.
- Monoamines are more preferable.
- the monoamines monoamines having a saturated chain aliphatic group are preferable, and monoamines having a saturated linear aliphatic group are more preferable.
- the chain aliphatic group is preferably 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms.
- the chain aliphatic group contained in the terminal group introduction compound has 4 or less carbon atoms because the compound easily volatilizes during the production of the polyimide resin.
- the solubility of the end group introduction compound in the solvent decreases and the reactivity decreases.
- the monoamines include n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, laurylamine, n-tridecyl.
- the monoamines are particularly preferably at least one selected from n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine, and more preferably At least one selected from n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably selected from n-octylamine, isooctylamine, and 2-ethylhexylamine. At least one kind.
- the amount of the compound having a chain aliphatic group having 5 to 14 carbon atoms may be any amount that can introduce the desired amount of the chain aliphatic group having 5 to 14 carbon atoms described above into the polyimide resin,
- the amount is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, and still more preferably 0.002 to 0.035 mol with respect to 1 mol of the tetracarboxylic acid and / or derivative thereof.
- a polyimide resin having excellent heat aging resistance can be obtained.
- a known polymerization method for producing a polyimide resin can be applied, and is not particularly limited, and examples thereof include solution polymerization, melt polymerization, solid phase polymerization, suspension polymerization method and the like. It is done. Among these, suspension polymerization under high temperature conditions using an organic solvent is particularly preferable. When suspension polymerization is performed under high temperature conditions, the polymerization is preferably performed at 150 ° C. or higher, and more preferably at 180 to 250 ° C. The polymerization time is appropriately changed depending on the monomer used, but is preferably about 0.1 to 6 hours.
- the method for producing the polyimide resin preferably includes a step of reacting the tetracarboxylic acid component and the diamine component in the presence of a solvent containing an alkylene glycol solvent represented by the following formula (I). Thereby, a powdery polyimide resin can be obtained.
- a polyimide resin powder having a ratio of passing through a sieve having a nominal aperture of 500 ⁇ m for JIS testing of 90% by mass or more, and laser diffraction light scattering This is preferable in that a polyimide resin powder having a D10 of 8 to 100 ⁇ m, a D50 of 12 to 250 ⁇ m, and a D90 of 20 to 500 ⁇ m can be easily obtained by particle size measurement using a formula particle size distribution analyzer.
- the solvent containing the alkylene glycol solvent represented by the above formula (I) generally satisfies these two characteristics.
- the alkylene glycol solvent preferably has a boiling point of 140 ° C. or higher, more preferably 160 ° C. or higher, and still more preferably 180 ° C. or higher, from the viewpoint of enabling a polymerization reaction under normal pressure and high temperature conditions.
- Ra 1 in the formula (I) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
- Ra 2 in the formula (I) is a linear alkylene group having 2 to 6 carbon atoms, preferably a linear alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group.
- N in the formula (I) is an integer of 1 to 3, preferably 2 or 3.
- alkylene glycol solvent examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether (also known as 2- (2-methoxyethoxy) ethanol), triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether (also known as 2- (2-ethoxyethoxy) ethanol), ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl Ether, diethylene glycol mono Seo ether, ethylene glycol monoisobutyl ether, ethylene glycol, 1,3-propane diol.
- solvents may be used alone, or two or more solvents selected from these may be used in combination.
- 2- (2-methoxyethoxy) ethanol, triethylene glycol monomethyl ether, 2- (2-ethoxyethoxy) ethanol and 1,3-propanediol are preferable, and 2- (2- Methoxyethoxy) ethanol and 2- (2-ethoxyethoxy) ethanol.
- the content of the alkylene glycol solvent in the solvent is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 75% by mass or more, and particularly preferably 95% by mass or more.
- the solvent may consist only of the alkylene glycol solvent.
- the solvent includes the alkylene glycol solvent and other solvents
- specific examples of the “other solvents” include water, benzene, toluene, xylene, acetone, hexane, heptane, chlorobenzene, methanol, ethanol, n -Propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethyl Formamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, o-cresol, m-cresol, p-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxy Toluene
- a solution (a) containing a tetracarboxylic acid component in a solvent containing the above-mentioned alkylene glycol solvent, and a diamine component in the solvent containing the alkylene glycol solvent are used.
- the solution (b) is added to the solution (a) or the solution (a) is added to the solution (b) to contain the polyamic acid.
- the reaction between the tetracarboxylic acid component and the diamine component can be carried out under normal pressure or under pressure, but it is preferably carried out under normal pressure in that a pressure-resistant container is not required under normal pressure.
- the end group introduction compound is prepared by mixing the solution (a) and the solution (b), mixing the end group introduction compound in the mixed solution to prepare a solution (c) containing polyamic acid,
- the solution (c) is preferably heated, and after the addition of the solution (b) to the solution (a), the end group-introducing compound is added to prepare a solution (c) containing polyamic acid. Then, it is more preferable to heat the solution (c).
- the method for producing the polyimide resin includes: a tetracarboxylic acid component containing a tetracarboxylic dianhydride; and the tetracarboxylic acid component and the diamine component.
- the polyamic acid is added by adding the solution (b) containing the diamine component and the alkylene glycol solvent to the solution (a) containing the tetracarboxylic acid component and the alkylene glycol solvent.
- the addition amount of the diamine component per unit time with respect to 1 mol of the tetracarboxylic acid component is 0.1 mol / min or less. Sea urchin, adding the solution (b) to the solution (a), it is preferable.
- the polyimide resin of the present invention includes a matting agent, a crystal nucleating agent, a plasticizer, an antistatic agent, an anti-coloring agent, an anti-gelling agent, a resin modifier, and the like as long as the characteristics are not hindered Optional ingredients can be blended as needed.
- the polyimide resin of the present invention has a filler, a flame retardant, a colorant, a slidability improver, an antioxidant, and a conductive material from the viewpoint of imparting desired performance while utilizing the inherent properties of the polyimide resin. It is good also as a resin composition which mix
- an inorganic filler is preferable from the viewpoint of heat resistance and mechanical strength.
- the shape of the filler is not particularly limited, and any of granular, plate-like, and fibrous fillers can be used.
- granular or plate-like inorganic fillers include silica, alumina, kaolinite, wollastonite, mica, talc, clay, sericite, magnesium carbonate, magnesium sulfate, calcium oxide, silicon carbide, and trisulfide.
- examples include antimony, tin sulfide, copper sulfide, iron sulfide, bismuth sulfide, zinc sulfide, metal powder, glass powder, glass flake, and glass beads.
- fibrous inorganic filler examples include glass fiber, carbon fiber, metal fiber, graphite fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, Examples thereof include aluminum borate whiskers, magnesium-based whiskers, and silicon-based whiskers.
- the carbon fiber examples include polyacrylonitrile-based carbon fiber and pitch-based carbon fiber.
- flame retardants examples include halogen flame retardants, phosphorus flame retardants, metal oxide flame retardants, metal hydroxide flame retardants, metal salt flame retardants, nitrogen flame retardants, silicone flame retardants, and boron.
- Compound flame retardants and the like can be mentioned.
- the colorant, pigments, dyes, and the like can be appropriately selected according to the use and the purpose of coloring. You may use together a pigment and dye.
- the slidability improver include solid lubricants such as molybdenum disulfide and metal soap; liquid lubricants such as mineral oil, synthetic oil, and wax; and lubricating polymers such as fluororesin, polyolefin, and spherical phenol.
- antioxidant examples include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, copper-based antioxidants, and amine-based antioxidants.
- conductive agent examples include a carbon-based conductive agent, a metal-based conductive agent, a metal oxide-based conductive agent, and a surfactant. These additives can be used alone or in combination of two or more.
- the blending amount of the additive in the polyimide resin composition is not particularly limited, but preferably 0.0001 to 80% by mass from the viewpoint of expressing the effect of the additive while maintaining the physical properties of the polyimide resin.
- the amount is preferably 0.001 to 70% by mass, more preferably 0.01 to 65% by mass.
- the polyimide resin composition may also contain a resin other than the polyimide resin of the present invention.
- a resin other than the polyimide resin of the present invention By using the polyimide resin of the present invention in combination with another resin and using it as a polymer alloy, it is possible to impart functions according to various uses.
- the other resin is preferably a high heat resistance thermoplastic resin, for example, polyamide resin, polyester resin, polyimide resin other than the present invention, polycarbonate resin, polyetherimide resin, polyamideimide resin, polyphenylene etherimide resin, polyphenylene. Examples thereof include sulfide resins, polysulfone resins, polyether sulfone resins, polyarylate resins, liquid crystal polymers, polyether ether ketone resins, polybenzimidazole resins, and the like.
- polyetherimide resins polyphenylene sulfide resins, and polyether ether ketone resins are preferable, and polyether ether ketone resins are more preferable. preferable.
- the mixing ratio is not particularly limited, but from the viewpoint of developing the characteristics of the polyimide resin of the present invention, the polyimide resin of the present invention and the other resin
- the mixing ratio is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, and still more preferably 10/90 to 90/10.
- the polyimide resin acts like a nucleating agent to increase the crystallization heat generation amount of the obtained resin composition. There are effects such as letting.
- the polyimide resin of the present invention and the polyimide resin composition can be used for the production of a molded article and a polyimide resin-fiber composite described later.
- the above-mentioned polyimide resin powder has a sharp particle size distribution, the heat-resistant modifying filler, the sliding modifying filler, the resin paste, the fiber-impregnating resin material, the fabric-impregnating resin material, and the 3D printer. It can be used for resin materials, resin materials for compression molding, and the like.
- the molded product of the present invention contains the polyimide resin of the present invention. Since the polyimide resin of the present invention is excellent in molding processability, a molded body can be easily produced by thermoforming the polyimide resin and a polyimide resin composition containing the polyimide resin. Examples of thermoforming methods include injection molding, extrusion molding, blow molding, hot press molding, vacuum molding, pressure forming, laser molding, welding, welding, etc. Any molding method can be used as long as it is a thermal melting process. Is possible.
- the method for producing the molded article of the present invention preferably includes a step of thermoforming the polyimide resin of the present invention at 290 to 400 ° C.
- the procedure include the following methods. First, various optional components are added to the polyimide resin as necessary, dry blended, and then introduced into an extruder, preferably melt kneaded and extruded at 290 to 400 ° C. to produce pellets. Alternatively, a polyimide resin is introduced into an extruder, preferably melted at 290 to 400 ° C., and various optional components are introduced therein, melted and kneaded with the polyimide resin in the extruder, and extruded to produce the aforementioned pellets. May be.
- the pellets are introduced into various molding machines, and are preferably thermoformed at 290 to 400 ° C. to produce a molded body having a desired shape. Since the polyimide resin of the present invention and the polyimide resin composition containing the same can be subjected to thermoforming such as extrusion at a relatively low temperature of 290 to 400 ° C., it has excellent moldability and has a desired shape. A molded product can be manufactured easily.
- the temperature during thermoforming is preferably 300 to 380 ° C., more preferably 310 to 370 ° C.
- seat, a strand, a pellet, a fiber, a round bar, a square bar, a spherical shape, a pipe, a tube, a seamless belt, etc. are mentioned. Since the polyimide resin of the present invention and the polyimide resin composition containing the polyimide resin are particularly excellent in molding processability, they are suitably used for producing a molded article having a thin part having a thickness of 1000 ⁇ m or less at least in part.
- a film and a sheet having a uniform thickness of 1000 ⁇ m or less, an injection molded body having a thin portion having a thickness of 1000 ⁇ m or less in part, and the like can be given.
- the thickness is preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less.
- the use of the molded product of the present invention is not particularly limited, and representative examples include films, fibers, heat-resistant adhesives, color filters, solar cell substrates, wafer carriers, IC trays, seal rings, automobile bearings, Bearings for copiers, and fixing belts, intermediate transfer belts or transfer rolls for various electrophotographic image forming apparatuses such as copiers, printers, facsimiles and composite devices thereof, printed wiring boards, copper-clad laminates, insulating films , A heat-resistant protective film, a reflective material for lighting, a laminate material for a partition material for a vehicle or an aircraft, a separator for a fuel cell, a TAB spacer, a heat-resistant sheet, a flameproof sheet, and various switches.
- examples of applications requiring heat aging resistance include members such as gears, tubes, and pipes used in automobiles, sliding members used in copying machines, industrial piping, electronic members, electric wires, and electronic devices. Examples thereof include covering materials used for members, sensor members, piping, electric wires, and the like.
- the film which is the molded body of the present invention may be either an unstretched film or a stretched film, but a stretched film is preferable from the viewpoint of improving the mechanical strength and heat resistance of the film.
- a known film production method can be applied to produce the film.
- a method for producing an unstretched film for example, after drying the polyimide resin pellets produced by the above-described method, the pellets are introduced into an extruder and melted, and a normal T-die method or a cylindrical die method (inflation) Method) or the like, and a method of discharging the polyimide resin into a film shape and then cooling and solidifying with a cooling roll or the like to obtain a film.
- a single screw or twin screw extruder or the like can be used as the extruder.
- a method for producing an unstretched film a polyimide resin solution containing the polyimide resin of the present invention and an organic solvent, or a polyimide resin composition containing the polyimide resin and various additives described above are applied in a film form.
- a method of removing the organic solvent after molding may be used.
- Examples of the method for producing a stretched film include a method of stretching the unstretched film as a raw film.
- the thickness of the raw film is not particularly limited and can be appropriately selected according to the draw ratio, the drawing temperature, the theoretical thickness of the produced drawn film, and the like, but is usually in the range of 50 to 2000 ⁇ m.
- the stretching may be uniaxial stretching or biaxial stretching, and can be appropriately selected depending on the use of the film and the required physical properties.
- the biaxial stretching method a simultaneous biaxial stretching method or a sequential biaxial stretching method can be used. From the viewpoint of reducing anisotropy in the MD direction and TD direction of the film, biaxial stretching is preferred.
- the preheating temperature is preferably Tg + 5 ° C. or higher of the polyimide resin, more preferably Tg + 10 ° C. or higher of the polyimide resin in order to obtain a sufficient stretching ratio without causing breakage or defects, and an improvement in physical properties due to stretching is exhibited. Therefore, it is preferably in the range of Tg + 70 ° C. or less of the polyimide resin, more preferably Tg + 50 ° C. or less of the polyimide resin.
- the preheating time is preferably 10 seconds or more, more preferably 20 seconds or more, still more preferably 30 seconds or more from the viewpoint of uniformly heating the raw film to the set temperature, and from the viewpoint of productivity, preferably 90 seconds. Below, more preferably 60 seconds or less.
- the stretching ratio is preferably 1.1 times or more, more preferably 1.2 times or more, preferably 4.0 times or less, more preferably 3.5 times or less in either the MD direction or the TD direction.
- the draw ratio is 1.1 times or more, the stretch orientation is sufficient, and the effect of improving physical properties such as mechanical strength and heat resistance is easily exhibited. Moreover, if the draw ratio is 4.0 times or less, it is possible to prevent the film from being broken or defective due to stretching and the occurrence of uneven orientation, and a film having excellent appearance can be obtained.
- the product of the draw ratio in the MD direction and the TD direction of the stretched film varies depending on the thickness of the raw film used, but from the viewpoint of physical properties and appearance of the obtained film, it is preferably 1.5 to 16 times, More preferably 1.5 to 12.25 times, still more preferably 1.5 to 9.0 times, and still more preferably 1.5 to 6.25 times (in the case of uniaxial stretching, the magnification in the direction in which no stretching is performed) 1).
- stretching at different stretching ratios in the MD direction and the TD direction may be performed to reduce anisotropy. Is possible.
- the stretching temperature is preferably Tg + 10 ° C. or higher of the polyimide resin, more preferably Tg + 20 ° C. or higher of the polyimide resin, preferably Tg + 70 ° C. or lower of the polyimide resin, more preferably Tg + 60 ° C. or lower of the polyimide resin, more preferably of the polyimide resin. Tg + 50 ° C. or lower.
- Tg + 10 ° C. or higher of the polyimide resin it is possible to reduce stretching defects such as tears and defects, and it is possible to reduce the haze of the stretched film.
- stretching can fully express that extending
- the stretching speed is preferably 10% / min or more, more preferably 50% / min or more, from the viewpoint of sufficiently improving the physical properties of the resulting film.
- the upper limit of the stretching speed is not particularly limited as long as defects such as tearing do not occur, but it is usually 10,000% / min or less.
- a known uniaxial or biaxial stretching apparatus can be used for stretching.
- the heat setting is a process of heating and cooling the stretched film under tension or limited shrinkage.
- the heating temperature at the time of heat setting may be a temperature not lower than Tg of the polyimide resin and not higher than the melting point, but from the viewpoint of suppressing dimensional change of the film at the time of reheating, preferably Tg of the polyimide resin + 10 ° C or higher, more preferably It is Tg + 20 degreeC or more of a polyimide resin.
- the melting point of the polyimide resin is preferably ⁇ 30 ° C. or lower, more preferably the melting point of the polyimide resin ⁇ 50 ° C. or lower.
- the heating time is preferably 0.5 to 1000 minutes, more preferably 1 to 500 minutes, from the viewpoint of suppressing dimensional change of the film during reheating.
- the stretched film after the heat setting has little dimensional change during reheating.
- the coefficient of thermal expansion (CTE) measured in the temperature range of 100 to 150 ° C. is preferably 50 ppm or less, more preferably 40 ppm or less, and even more preferably 30 ppm or less.
- the lower limit of the coefficient of thermal linear expansion is preferably low, but it is measured in the temperature range of 100 to 150 ° C from the viewpoint of the properties of the polyimide resin film and from the viewpoint of avoiding a decrease in productivity due to prolonged heat setting.
- the linear thermal expansion coefficient is preferably 0 ppm or more. Specifically, the thermal expansion coefficient can be measured by the method described in the examples.
- the polyimide resin of the present invention can be impregnated into a fiber material to form a polyimide resin-fiber composite (hereinafter also simply referred to as “composite material”).
- Fiber materials used for the composite material include glass fibers, carbon fibers, alumina fibers, boron fibers, ceramic fibers, inorganic fibers such as metal fibers (steel fibers, etc.); aramid fibers, polyoxymethylene fibers, aromatic polyamide fibers, poly And synthetic fibers such as paraphenylene benzobisoxazole fibers, ultrahigh molecular weight polyethylene fibers, and aromatic polyimide fibers.
- carbon fibers are preferably used because they have excellent characteristics of high strength and high elastic modulus while being lightweight.
- the carbon fiber polyacrylonitrile-based carbon fiber and pitch-based carbon fiber can be preferably used.
- the fiber material may be in various forms such as a monofilament or multifilament simply arranged in one direction or alternately intersecting, a fabric such as a knitted fabric, a nonwoven fabric or a mat. Of these, the form of monofilament, fabric, nonwoven fabric or mat is preferable. Furthermore, a prepreg in which these are mounted or laminated and impregnated with a binder or the like is also preferably used.
- the average fiber diameter of the fiber material is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, still more preferably 4 to 20 ⁇ m, and particularly preferably 5 to 10 ⁇ m. When the average fiber diameter is within this range, processing is easy, and the resulting molded article has excellent elasticity and strength.
- the average fiber diameter can be measured by observation with a scanning electron microscope (SEM) or the like. More than 50 fibers can be selected at random, the length can be measured, and the average fiber diameter of the number average can be calculated.
- the fineness of the fiber material is preferably 20 to 3,000 tex, more preferably 50 to 2,000 tex. When the fineness is within this range, processing is easy, and the resulting molded article has excellent elastic modulus and strength.
- the fineness can be obtained by obtaining the weight of a long fiber having an arbitrary length and converting it to a weight per 1,000 m. Usually, a fiber material having a filament number of about 500 to 30,000 can be preferably used.
- the fiber length of the fiber material present in the composite material is an average fiber length, preferably 1 cm or more, more preferably 1.5 cm or more, still more preferably 2 cm or more, and particularly preferably 3 cm or more.
- the upper limit of the average fiber length varies depending on the use, but is preferably 500 cm or less, more preferably 300 cm or less, and still more preferably 100 cm or less.
- the method for measuring the average fiber length in the composite material is not particularly limited. For example, the fiber remaining after the composite material is placed in hexafluoroisopropanol (HFIP) or concentrated sulfuric acid to dissolve the polyimide resin. Can be measured by visual observation or, in some cases, observation with an optical microscope, a scanning electron microscope (SEM), or the like. One hundred fibers can be selected at random and the length can be measured to calculate a number average average fiber length.
- HFIP hexafluoroisopropanol
- SEM scanning electron microscope
- the average fiber length of the raw material before use of the fiber material to be used is not particularly limited, but is preferably in the range of 1 to 10,000 m, more preferably 100 to 10,000 m from the viewpoint of improving moldability. It is about 7,000 m, more preferably about 1,000 to 5,000 m.
- this composite material does not exclude using together the short fiber (D) of a fiber material.
- the average fiber diameter of a short fiber (D) is shorter than the average fiber diameter of a fiber material.
- those having a functional group having affinity or reactivity with the polyimide resin on the surface of the fiber material are preferable.
- a surface treatment with a surface treatment agent or a sizing agent is preferably mentioned.
- Examples of the surface treatment agent include those composed of a functional compound such as an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, and a titanate compound, such as a silane coupling agent and a titanate cup.
- Examples of the ring agent include silane coupling agents.
- Silane coupling agents include trialkoxy or triallyloxysilane compounds such as aminopropyltriethoxysilane, phenylaminopropyltrimethoxysilane, glycidylpropyltriethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and ureido Examples include silane, sulfide silane, vinyl silane, and imidazole silane.
- an epoxy resin such as a bisphenol A type epoxy resin, an epoxy acrylate resin having an acrylic group or a methacryl group in one molecule, a bisphenol A type vinyl ester resin, a novolac type vinyl ester resin, Preferred examples include vinyl ester resins such as brominated vinyl ester resins. Further, it may be a urethane-modified resin such as epoxy resin or vinyl ester resin.
- the polyimide resin is overlapped with the fiber material, and then heated or pressurized to melt the whole amount or at least a part of the polyimide resin and impregnate the fiber material layer, and the impregnated body is heated and pressurized. As a result, it becomes consolidated (dense) and becomes a composite material.
- the polyimide resin can be combined with the fiber material in any form such as film, fiber, powder, and pellet, but from the viewpoint of moldability, impregnation, etc. Or in powder form.
- the polyimide resin into a film or fiber
- a known method can be adopted.
- it is produced by a method in which fibers are produced from polyimide resin pellets by melt spinning, a resin is extruded from an extruder to continuously form a film, or a film is formed by a hot press.
- the step of impregnating the fiber material with the polyimide resin is preferably performed by continuously pressing with a plurality of rolls in a heated atmosphere when the polyimide resin is a film or a fiber.
- the air contained between the fiber materials can be pushed out to the outside of the composite material or the molded product obtained by molding this, and in the composite material or the molded product obtained by molding this Voids can be reduced.
- the roll which coated the roll surface with the fluororesin can be used preferably.
- the polyimide resin is in powder form, the polyimide resin powder can be dispersed on the surface of the fiber material, and then melted and impregnated by pressurization with a roll in a heated atmosphere or laser irradiation.
- the heating and pressurization may be performed by superimposing a plurality of laminated or laminated fiber materials on a polyimide resin film or fiber.
- heating is performed on a superposition of at least two sheets of a polyimide resin film / fiber material laminate, preferably five or more sheets so that both outer sides thereof become polyimide resin layers. It is desirable to apply pressure.
- the temperature for the polyimide resin impregnation into the fiber material layer and their integration needs to be equal to or higher than the temperature at which the polyimide resin is softened and melted, and differs depending on the type and molecular weight of the polyimide resin. It is preferably 300 to 400 ° C, more preferably 300 to 380 ° C.
- the press pressure during pressurization is preferably 0.1 MPa or more.
- the heating and pressurization is preferably performed under reduced pressure, particularly under vacuum. When performed under such conditions, it is preferable that air bubbles hardly remain in the obtained composite material.
- the composite material produced in this way may be solid, semi-solid or viscous, and the form is not particularly limited, but is usually solid or semi-solid.
- the composite material can be wound around a roll and stored.
- the polyimide resin is thermoplastic, the composite material can be further processed by heating to form a molded body by various molding methods.
- the composite material preferably has an area ratio of 20/80 to 80/20 in cross section of the polyimide resin / fiber material.
- the area ratio in the cross section is more preferably 30/70 to 70/30, and further 40/60 to 60/40.
- a cross section here means a cross section orthogonal to the longitudinal direction of a fiber material, when the fiber material is orientating in one direction.
- one direction is arbitrarily selected from the plurality of orientation directions, and a plane perpendicular to the longitudinal direction of the oriented fiber material is taken as a cross section.
- any one direction of the composite material is taken as a cross section.
- the area ratio of the polyimide resin / fiber material can be determined by observing the cross section with a scanning electron microscope (SEM).
- the composite material obtained by the above-described method has a structure in which both surfaces thereof are preferably formed of a polyimide resin layer containing the polyimide resin of the present invention. Since the composite material is made of a thermoplastic resin material, the composite material is used as it is, or cut into a desired shape and size, and used as a molding material, preferably heated, and then preferably heated. It is possible to obtain various molded products by putting them in a mold for molding and removing them from the mold. Moreover, said shaping
- the molded body obtained by molding the composite material may be further subjected to heat treatment.
- the heat treatment temperature is preferably 150 to 250 ° C.
- the melting point Tm, the glass transition temperature Tg, the crystallization temperature Tc, and the crystallization heat generation amount of the polyimide resin were measured using a differential scanning calorimeter (“DSC-6220” manufactured by SII Nanotechnology Co., Ltd.). Under a nitrogen atmosphere, a thermal history under the following conditions was imposed on the polyimide resin. The conditions for the thermal history are the first temperature increase (temperature increase rate 10 ° C./min), then cooling (temperature decrease rate 20 ° C./min), and then the second temperature increase (temperature increase rate 10 ° C./min).
- the melting point was determined by reading the peak top value of the endothermic peak observed at the second temperature increase.
- the glass transition temperature was determined by reading the value observed at the second temperature increase.
- the crystallization temperature was determined by reading the peak top value of the exothermic peak observed during cooling.
- the crystallization exotherm (mJ / mg) was calculated from the area of the crystallization exotherm peak observed during the cooling.
- ⁇ Semi-crystallization time> The half crystallization time of the polyimide resin was measured using a differential scanning calorimeter (“DSC-6220” manufactured by SII Nanotechnology Co., Ltd.). The measurement conditions for the polyimide resin with a semi-crystallization time of 20 seconds or less were maintained at a melting point + 20 ° C. for 10 minutes in a nitrogen atmosphere, and after the polyimide resin was completely melted, a rapid cooling operation was performed at a temperature drop rate of 70 ° C./min. The time taken to reach the peak top from the appearance of the observed crystallization exothermic peak was calculated and determined. In the examples and comparative examples in Table 2, those having a half crystallization time of less than 20 seconds are indicated as “20>”.
- IR measurement of the polyimide resin was performed using “JIR-WINSPEC50” manufactured by JEOL Ltd.
- ⁇ Laser diffraction particle size distribution measurement> For laser diffraction particle size distribution measurement of the polyimide resin powder, a laser diffraction particle size distribution analyzer “LMS-2000e” manufactured by Malvern Co., Ltd. was used. The measurement was carried out using water as a dispersion medium under conditions where the polyimide resin powder was sufficiently dispersed under ultrasonic conditions. The measurement range was 0.02 to 2000 ⁇ m.
- a polyimide resin was prepared into a film having a thickness of 100 ⁇ m, and then introduced into a ventilation constant temperature incubator “DN610” manufactured by Yamato Scientific Co., Ltd. and allowed to stand at 200 ° C. for 72 hours.
- the obtained film was subjected to GPC measurement, and the molecular weight (Mw, Mn) retention rate was determined from the change in molecular weight before and after heating.
- Mw, Mn molecular weight retention rate
- the polyimide resin of this invention can confirm the monomer composition ratio and the amount of terminal group introduction
- the monomer ratio was separated by a column (HP-5) manufactured by Agilent Technologies using gas chromatography (“HP6890” manufactured by HEWLETT PACKARD) (temperature rising condition was maintained at 50 ° C. for 10 minutes, then maintained at 10 ° C./min for 300 ° C.)
- the monomer composition ratio and the terminal group introduction amount are determined by calculating the area ratio of each monomer.
- the tetracarboxylic acid component is observed as a methyl ester form.
- a test film of 100 mm ⁇ 10 mm was cut out from the films obtained in Examples 2a to 2d and used for measurement.
- a tensile tester (“Strograph VG1E” manufactured by Toyo Seiki Seisakusho Co., Ltd.)
- JIS K7127 a tensile test was performed at a temperature of 23 ° C. and a test speed of 50 mm / min to determine the tensile modulus and tensile strength. It was measured.
- the films of Examples 2a to 2d were subjected to a tensile test in the MD direction.
- CTE Heat expansion coefficient
- Example 1 Manufacture of polyimide resin 1 2- (2-methoxyethoxy) ethanol (manufactured by Nippon Emulsifier Co., Ltd.) in a 2 L separable flask equipped with a Dean-Stark apparatus, Liebig condenser, thermocouple, four paddle blades ) 650 g and pyromellitic dianhydride (Mitsubishi Gas Chemical Co., Ltd.) 218.1 g (1.00 mol) were introduced, and after nitrogen flow, the mixture was stirred at 150 rpm so as to obtain a uniform suspension.
- Example 2 Manufacture of polyimide resin 2 2- (2-methoxyethoxy) ethanol (manufactured by Nippon Emulsifier Co., Ltd.) in a 2 L separable flask equipped with a Dean-Stark apparatus, Liebig condenser, thermocouple, and four paddle blades. ) 600 g and pyromellitic dianhydride (Mitsubishi Gas Chemical Co., Ltd.) 218.58 g (1.00 mol) were introduced, and after nitrogen flow, the mixture was stirred at 150 rpm so as to obtain a uniform suspension.
- Comparative Example 1 Production of Comparative Polyimide Resin 1 2- (2-methoxyethoxy) ethanol (Nippon Emulsifier Co., Ltd.) in a 2 L separable flask equipped with a Dean-Stark apparatus, Liebig condenser, thermocouple, and four paddle blades. 650 g and pyromellitic dianhydride (Mitsubishi Gas Chemical Co., Ltd.) 218.1 g (1.00 mol) were introduced, and after nitrogen flow, the mixture was stirred at 150 rpm to obtain a uniform suspension.
- 650 g and pyromellitic dianhydride Mitsubishi Gas Chemical Co., Ltd.
- Comparative Example 2 Production of comparative polyimide resin 2 2- (2-methoxyethoxy) ethanol (Nippon Emulsifier Co., Ltd.) in a 2 L separable flask equipped with a Dean-Stark apparatus, Liebig condenser, thermocouple, and four paddle blades. 650 g and pyromellitic dianhydride (Mitsubishi Gas Chemical Co., Ltd.) 218.1 g (1.00 mol) were introduced, and after nitrogen flow, the mixture was stirred at 150 rpm to obtain a uniform suspension.
- 650 g and pyromellitic dianhydride Mitsubishi Gas Chemical Co., Ltd.
- the polyimide resin of the present invention having a predetermined end group is excellent in heat resistance and heat aging resistance.
- Example 2a Production of unstretched film (raw film)
- the polyimide resin 2 obtained in Example 2 was melted at 330 ° C. from a twin-screw extruder (“Lab plast mill” manufactured by Toyo Seiki Seisakusho Co., Ltd.).
- An unstretched film having a thickness of 90 ⁇ m was produced by extrusion using a T-die-cooling roll method.
- T-die-cooling roll method was about the obtained film.
- various evaluation was performed by the said method. The results are shown in Table 3.
- Example 2b to 2d Production of stretched film
- the unstretched film produced in Example 2a was cut into a size of 100 mm x 100 mm and used as a raw film.
- the raw film was preheated by heating at 200 ° C. for 60 seconds, and then simultaneously biaxially stretched using a biaxial stretching apparatus (“EX10-S5” manufactured by Toyo Seiki Seisakusho Co., Ltd.).
- the stretching ratio, stretching temperature and stretching speed are as shown in Table 3.
- the stretched film was heat-set at 230 ° C. for 10 minutes under tension, and then air-cooled to obtain stretched films of Examples 2b to 2d.
- various evaluation was performed by the said method. The results are shown in Table 3.
- the films of Examples 2a to 2d made of the polyimide resin of the present invention have a low haze value and a low YI value, and a high total light transmittance.
- the stretched films of Examples 2b to 2d have higher mechanical strength than the unstretched film of Example 2a, a low coefficient of thermal expansion, and excellent heat resistance.
- the polyimide resin of the present invention is excellent in moldability, heat resistance and heat aging resistance. For example, even when a film containing the polyimide resin is stored for several days in a high temperature environment of 200 ° C. or higher, the decrease in molecular weight retention is small and the mechanical strength (toughness) of the film is maintained.
- the polyimide resin is used in applications requiring heat aging resistance, such as gears, tubes and pipes used in automobiles, sliding members used in copiers, industrial piping, electronic members, coating materials, etc. Preferably used.
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Abstract
Description
本発明の課題は、成形加工性及び耐熱性に優れ、特に耐熱老化性に優れる新規なポリイミド樹脂を提供することにある。
すなわち本発明は、下記式(1)で示される繰り返し構成単位及び下記式(2)で示される繰り返し構成単位を含み、該式(1)の繰り返し構成単位と該式(2)の繰り返し構成単位の合計に対する該式(1)の繰り返し構成単位の含有比が20~70モル%であり、かつ、炭素数5~14の鎖状脂肪族基を末端に有するポリイミド樹脂を提供する。
本発明のポリイミド樹脂は、下記式(1)で示される繰り返し構成単位及び下記式(2)で示される繰り返し構成単位を含み、該式(1)の繰り返し構成単位と該式(2)の繰り返し構成単位の合計に対する該式(1)の繰り返し構成単位の含有比が20~70モル%であり、かつ、炭素数5~14の鎖状脂肪族基を末端に有することを特徴とする。
R1は少なくとも1つの脂環式炭化水素構造を含む炭素数6~22の2価の基である。ここで、脂環式炭化水素構造とは、脂環式炭化水素化合物から誘導される環を意味し、該脂環式炭化水素化合物は、飽和であっても不飽和であってもよく、単環であっても多環であってもよい。
脂環式炭化水素構造としては、シクロヘキサン環等のシクロアルカン環、シクロヘキセン等のシクロアルケン環、ノルボルナン環等のビシクロアルカン環、及びノルボルネン等のビシクロアルケン環が例示されるが、これらに限定されるわけではない。これらの中でも、好ましくはシクロアルカン環、より好ましくは炭素数4~7のシクロアルカン環、さらに好ましくはシクロヘキサン環である。
R1の炭素数は6~22であり、好ましくは8~17である。
R1は脂環式炭化水素構造を少なくとも1つ含み、好ましくは1~3個含む。
X1の炭素数は6~22であり、好ましくは6~18である。
X1は芳香環を少なくとも1つ含み、好ましくは1~3個含む。
なお、X1は少なくとも1つの芳香環を含む炭素数6~22の4価の基であるので、式(X-2)におけるR12、R13、p12及びp13は、式(X-2)で表される4価の基の炭素数が6~22の範囲に入るように選択される。
同様に、式(X-3)におけるL11、R14、R15、p14及びp15は、式(X-3)で表される4価の基の炭素数が6~22の範囲に入るように選択され、式(X-4)におけるL12、L13、R16、R17、R18、p16、p17及びp18は、式(X-4)で表される4価の基の炭素数が6~22の範囲に入るように選択される。
R2は炭素数5~16の2価の鎖状脂肪族基であり、好ましくは炭素数5~14、より好ましくは炭素数5~12である。ここで、鎖状脂肪族基とは、鎖状脂肪族化合物から誘導される基を意味し、該鎖状脂肪族化合物は、飽和であっても不飽和であってもよく、直鎖状であっても分岐状であってもよく、酸素原子等のヘテロ原子を含んでいてもよい。
R2は、好ましくは炭素数5~16のアルキレン基であり、より好ましくは炭素数5~14、更に好ましくは炭素数5~12のアルキレン基であり、なかでも好ましくは炭素数6~12のアルキレン基、より好ましくは炭素数6~10のアルキレン基である。前記アルキレン基は、直鎖アルキレン基であっても分岐アルキレン基であってもよいが、好ましくは直鎖アルキレン基である。
R2は、特に好ましくはヘキサメチレン基、オクタメチレン基及びデカメチレン基から選ばれる少なくとも1種である。
なお、R2は炭素数5~16(好ましくは炭素数5~14、より好ましくは炭素数5~12)の2価の鎖状脂肪族基であるので、式(R2-1)におけるm21及びm22は、式(R2-1)で表される2価の基の炭素数が5~16(好ましくは炭素数5~14、より好ましくは炭素数5~12)の範囲に入るように選択される。すなわち、m21+m22は5~16(好ましくは5~14、より好ましくは5~12)である。
同様に、式(R2-2)におけるm23~m25は、式(R2-2)で表される2価の基の炭素数が5~16(好ましくは炭素数5~14、より好ましくは炭素数5~12)の範囲に入るように選択される。すなわち、m23+m24+m25は5~16(好ましくは5~14、より好ましくは5~12)である。
式(1)の繰り返し構成単位と式(2)の繰り返し構成単位の合計に対する、式(1)の繰り返し構成単位の含有比は、成形加工性の観点から、好ましくは25モル%以上、より好ましくは30モル%以上、更に好ましくは32モル%以上であり、高い結晶性を発現する観点から、好ましくは65モル%以下、より好ましくは60モル%以下、更に好ましくは57モル%以下である。
前記含有比は、耐熱性の向上という観点からは、好ましくは5モル%以上、より好ましくは10モル%以上であり、一方で結晶性を維持する観点からは、好ましくは20モル%以下、より好ましくは15モル%以下である。
R3の炭素数は6~22であり、好ましくは6~18である。
R3は芳香環を少なくとも1つ含み、好ましくは1~3個含む。
また、前記芳香環には1価もしくは2価の電子求引性基が結合していてもよい。1価の電子求引性基としてはニトロ基、シアノ基、p-トルエンスルホニル基、ハロゲン、ハロゲン化アルキル基、フェニル基、アシル基などが挙げられる。2価の電子求引性基としては、フッ化アルキレン基(例えば-C(CF3)2-、-(CF2)p-(ここで、pは1~10の整数である))のようなハロゲン化アルキレン基のほかに、-CO-、-SO2-、-SO-、-CONH-、-COO-などが挙げられる。
なお、R3は少なくとも1つの芳香環を含む炭素数6~22の2価の基であるので、式(R3-1)におけるm31、m32、R21及びp21は、式(R3-1)で表される2価の基の炭素数が6~22の範囲に入るように選択される。
同様に、式(R3-2)におけるL21、m33、m34、R22、R23、p22及びp23は、式(R3-2)で表される2価の基の炭素数が12~22の範囲に入るように選択される。
前記含有比は、耐熱性の向上という観点からは、好ましくは5モル%以上、より好ましくは7モル%以上であり、一方で結晶性を維持する観点からは、好ましくは20モル%以下、より好ましくは15モル%以下である。
X4は、式(1)におけるX1と同様に定義され、好ましい様態も同様である。
該鎖状脂肪族基は、飽和であっても不飽和であってもよく、直鎖状であっても分岐状であってもよい。本発明のポリイミド樹脂は上記特定の基を末端に有するため、耐熱老化性に優れる。具体的には、該ポリイミド樹脂を含むフィルムを200℃以上の高温環境下で数日保存しても分子量保持率の低下が少なく、該フィルムの機械的強度(靭性)が保持される。
これに対し、例えばポリイミド樹脂がベンジル基やフェニル基を末端に有する場合、該ポリイミド樹脂を200℃以上の高温環境下で保存すると分子量保持率が低下し、機械的強度も低下する。また末端の鎖状脂肪族基の炭素数が4以下である場合、ポリイミド樹脂の末端に該基を導入するために炭素数4以下の鎖状脂肪族基を有する化合物が用いられるが、該化合物はポリイミド樹脂の製造時に揮発しやすいため好ましくない。
炭素数5~14の不飽和鎖状脂肪族基としては、1-ペンテニル基、2-ペンテニル基、1-へキセニル基、2-へキセニル基、1-ヘプテニル基、2-ヘプテニル基、1-オクテニル基、2-オクテニル基、ノネニル基、デセニル基、ドデセニル基、トリデセニル基、テトラデセニル基等が挙げられる。
中でも、上記鎖状脂肪族基は飽和鎖状脂肪族基であることが好ましく、飽和直鎖状脂肪族基であることがより好ましい。また本発明の効果を得る観点から、上記鎖状脂肪族基は好ましくは炭素数6以上、より好ましくは炭素数7以上、更に好ましくは炭素数8以上であり、好ましくは炭素数12以下、より好ましくは炭素数10以下、更に好ましくは炭素数9以下である。上記鎖状脂肪族基は1種のみでもよく、2種以上でもよい。
上記鎖状脂肪族基は、特に好ましくはn-オクチル基、イソオクチル基、2-エチルヘキシル基、n-ノニル基、イソノニル基、n-デシル基、及びイソデシル基から選ばれる少なくとも1種であり、更に好ましくはn-オクチルアミン、イソオクチルアミン、2-エチルヘキシルアミン、n-ノニルアミン、及びイソノニルアミンから選ばれる少なくとも1種であり、最も好ましくはn-オクチル基、イソオクチル基、及び2-エチルヘキシル基から選ばれる少なくとも1種である。
また本発明のポリイミド樹脂は、耐熱老化性の観点から、末端アミノ基及び末端カルボキシル基以外に、炭素数5~14の鎖状脂肪族基のみを末端に有することが好ましい。上記以外の基を末端に有する含む場合、その含有量は、好ましくは炭素数5~14の鎖状脂肪族基に対し10モル%以下、より好ましくは5モル%以下である。
ポリイミド樹脂中の上記炭素数5~14の鎖状脂肪族基の含有量は、ポリイミド樹脂を解重合することにより求めることができる。
ポリイミド樹脂の融点、ガラス転移温度は、いずれも示差走査型熱量計により測定することができる。
また本発明のポリイミド樹脂は、結晶性、耐熱性、機械的強度、耐薬品性を向上させる観点から、示差走査型熱量計測定により、該ポリイミド樹脂を溶融後、降温速度20℃/分で冷却した際に観測される結晶化発熱ピークの熱量(以下、単に「結晶化発熱量」ともいう)が、5.0mJ/mg以上であることが好ましく、10.0mJ/mg以上であることがより好ましく、17.0mJ/mg以上であることが更に好ましい。結晶化発熱量の上限値は特に限定されないが、通常、45.0mJ/mg以下である。
ポリイミド樹脂の融点、ガラス転移温度、結晶化発熱量は、具体的には実施例に記載の方法で測定できる。
μ=ln(ts/t0)/C
t0:濃硫酸の流れる時間
ts:ポリイミド樹脂溶液の流れる時間
C:0.5(g/dL)
さらに本発明のポリイミド樹脂は、厚さ100μmのフィルム状に成形し、200℃で72時間加熱した後のMwの保持率が好ましくは95%以上、より好ましくは98%以上であり、Mnの保持率が好ましくは83%以上、より好ましくは85%以上である。Mw及びMnの保持率が上記範囲であれば、耐熱老化性が良好である。
なお、上記Mwの保持率は100%を超えてもよく、好ましい上限値は120%である。Mwの保持率が100%を超えている場合は、分子内で架橋が生じているものと考えられる。上記Mnの保持率の好ましい上限値は100%である。
上記Mw及びMnの保持率は、下記式から算出できる。
{200℃72時間加熱後の分子量/加熱前の分子量}×100(%)
上記粒径及び粒度を有するポリイミド樹脂粉末は、例えば、テトラカルボン酸成分とジアミン成分とを、後述する式(I)で表されるアルキレングリコール系溶媒を含む溶媒の存在下で反応させる工程を含む製造方法を用いることにより得られる。またポリイミド樹脂粉末のふるい分け試験、及び粒度レーザー回折光散乱式粒度分布測定器による粒度測定は、具体的には実施例に記載の方法で行うことができる。
本発明のポリイミド樹脂の製造方法は、テトラカルボン酸成分及びジアミン成分を混合し、次いで炭素数5~14の鎖状脂肪族基を有する化合物を混合して反応させる工程を有することが好ましい。該テトラカルボン酸成分は少なくとも1つの芳香環を含むテトラカルボン酸及び/又はその誘導体を含有し、該ジアミン成分は少なくとも1つの脂環式炭化水素構造を含むジアミン及び鎖状脂肪族ジアミンを含有する。炭素数5~14の鎖状脂肪族基を有する化合物(以下「末端基導入用化合物」ともいう)は、テトラカルボン酸成分とジアミン成分とを反応させて得られるポリイミド樹脂の反応末端を封止し、ポリイミド樹脂に前記炭素数5~14の鎖状脂肪族基を導入できるものであればよく、後述するモノアミン類が好ましい。
鎖状脂肪族ジアミンは本発明の範囲内であれば1種類あるいは複数を混合して使用してもよい。これらのうち、好ましくは炭素数が6~12の鎖状脂肪族ジアミン、より好ましくは炭素数が6~10の鎖状脂肪族ジアミンが好適に使用でき、特に1,6-ヘキサメチレンジアミン、1,8-オクタメチレンジアミン及び1,10-デカメチレンジアミンから選ばれる少なくとも1種が好適に使用できる。
前記モル比は、耐熱性の向上という観点からは、好ましくは5モル%以上、より好ましくは10モル%以上であり、一方で結晶性を維持する観点からは、好ましくは20モル%以下、より好ましくは15モル%以下である。
また、前記モル比は、ポリイミド樹脂の着色を少なくする観点からは、好ましくは12モル%以下、より好ましくは10モル%以下、更に好ましくは5モル%以下、より更に好ましくは0モル%である。
また本発明の効果を得る観点から、上記鎖状脂肪族基は好ましくは炭素数6以上、より好ましくは炭素数7以上、更に好ましくは炭素数8以上であり、好ましくは炭素数12以下、より好ましくは炭素数10以下、更に好ましくは炭素数9以下である。末端基導入用化合物が有する鎖状脂肪族基の炭素数が4以下であると、ポリイミド樹脂の製造時に当該化合物が揮発しやすいため好ましくない。一方、末端基導入用化合物が有する鎖状脂肪族基の炭素数が14を超えると、該末端基導入用化合物の溶媒溶解性が低くなり反応性が低下する。
当該モノアミン類の具体例としては、n-ペンチルアミン、n-ヘキシルアミン、n-ヘプチルアミン、n-オクチルアミン、n-ノニルアミン、n-デシルアミン、n-ウンデシルアミン、ラウリルアミン、n-トリデシルアミン、n-テトラデシルアミン、イソペンチルアミン、ネオペンチルアミン、2-メチルペンチルアミン、2-メチルヘキシルアミン、2-エチルペンチルアミン、3-エチルペンチルアミン、イソオクチルアミン、2-エチルヘキシルアミン、3-エチルヘキシルアミン、イソノニルアミン、2-エチルオクチルアミン、イソデシルアミン、イソドデシルアミン、イソトリデシルアミン、イソテトラデシルアミン等が挙げられる。これらは1種のみを用いてもよく、2種以上を用いてもよい。
当該モノアミン類は、特に好ましくはn-オクチルアミン、イソオクチルアミン、2-エチルヘキシルアミン、n-ノニルアミン、イソノニルアミン、n-デシルアミン、及びイソデシルアミンから選ばれる少なくとも1種であり、更に好ましくはn-オクチルアミン、イソオクチルアミン、2-エチルヘキシルアミン、n-ノニルアミン、及びイソノニルアミンから選ばれる少なくとも1種であり、最も好ましくはn-オクチルアミン、イソオクチルアミン、及び2-エチルヘキシルアミンから選ばれる少なくとも1種である。
均一な粉末状のポリイミド樹脂を得るには、ワンポットの反応において(1)ポリアミド酸を均一に溶解させる、あるいはナイロン塩を均一に分散させる、(2)ポリイミド樹脂を全く溶解、膨潤させない、の二つの特性が溶媒に備わっていることが望ましいと考えられる。上記式(I)で表されるアルキレングリコール系溶媒を含む溶媒はこの2つの特性を概ね満たしている。
前記アルキレングリコール系溶媒は、常圧において高温条件で重合反応を可能にする観点から、好ましくは140℃以上、より好ましくは160℃以上、さらに好ましくは180℃以上の沸点を有する。
式(I)中のRa2は炭素数2~6の直鎖のアルキレン基であり、好ましくは炭素数2~3の直鎖のアルキレン基であり、より好ましくはエチレン基である。
式(I)中のnは1~3の整数であり、好ましくは2又は3である。
前記アルキレングリコール系溶媒の具体例としては、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル(別名:2-(2-メトキシエトキシ)エタノール)、トリエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル(別名:2-(2-エトキシエトキシ)エタノール)、エチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノイソプロピルエーテル、トリエチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、エチレングリコールモノイソブチルエーテル、ジエチレングリコールモノイソブチルエーテル、エチレングリコールモノイソブチルエーテル、エチレングリコール、1,3-プロパンジオール等が挙げられる。これら溶媒を単独で用いてもよく、これらから選ばれる2つ以上の溶媒を組み合わせて用いてもよい。これら溶媒のうち、好ましくは2-(2-メトキシエトキシ)エタノール、トリエチレングリコールモノメチルエーテル、2-(2-エトキシエトキシ)エタノール及び1,3-プロパンジオールであり、より好ましくは2-(2-メトキシエトキシ)エタノール及び2-(2-エトキシエトキシ)エタノールである。
溶媒が、前記アルキレングリコール系溶媒とそれ以外の溶媒を含む場合、当該「それ以外の溶媒」の具体例としては水、ベンゼン、トルエン、キシレン、アセトン、ヘキサン、ヘプタン、クロロベンゼン、メタノール、エタノール、n-プロパノール、イソプロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジエチルアセトアミド、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N-メチルカプロラクタム、ヘキサメチルホスホルアミド、テトラメチレンスルホン、ジメチルスルホキシド、o-クレゾール、m-クレゾール、p-クレゾール、フェノール、p-クロルフェノール、2-クロル-4-ヒドロキシトルエン、ジグライム、トリグライム、テトラグライム、ジオキサン、γ-ブチロラクトン、ジオキソラン、シクロヘキサノン、シクロペンタノン、ジクロロメタン、クロロホルム、1,2-ジクロロエタン、1,1,2-トリクロロエタン、ジブロモメタン、トリブロモメタン、1,2-ジブロモエタン、1,1,2-トリブロモエタン等が挙げられる。これら溶媒を単独で用いてもよく、これらから選ばれる2つ以上の溶媒を組み合わせて用いてもよい。
テトラカルボン酸成分とジアミン成分との反応は、常圧下又は加圧下のいずれで行うこともできるが、常圧下であれば耐圧性容器を必要としない点で、常圧下で行われることが好ましい。
末端基導入用化合物は、溶液(a)と溶液(b)を混合し、この混合液中に該末端基導入用化合物を混合して、ポリアミド酸を含有する溶液(c)を調製し、次いで、前記溶液(c)を加熱することが好ましく、溶液(a)に溶液(b)を添加し終わった後に該末端基導入用化合物を添加して、ポリアミド酸を含有する溶液(c)を調製し、次いで、前記溶液(c)を加熱することがより好ましい。
さらに本発明のポリイミド樹脂は、該ポリイミド樹脂が本来有する物性を利用しつつ、所望の性能を付与する観点から、充填剤、難燃剤、着色剤、摺動性改良剤、酸化防止剤、及び導電剤から選ばれる少なくとも1種の添加剤を配合した樹脂組成物としてもよい。
充填剤としては、耐熱性及び機械的強度の観点からは無機充填剤が好ましい。充填剤の形状は特に限定されるものではなく、粒状、板状、及び繊維状の充填剤のいずれも用いることができる。無機充填剤のうち粒状又は板状の無機充填剤としては、シリカ、アルミナ、カオリナイト、ワラストナイト、マイカ、タルク、クレー、セリサイト、炭酸マグネシウム、硫酸マグネシウム、酸化カルシウム、炭化ケイ素、三硫化アンチモン、硫化錫、硫化銅、硫化鉄、硫化ビスマス、硫化亜鉛、金属粉末、ガラスパウダー、ガラスフレーク、ガラスビーズ等が挙げられる。繊維状無機充填剤としては、ガラス繊維、炭素繊維、金属繊維、グラファイト繊維、シリカ繊維、シリカ・アルミナ繊維、アルミナ繊維、ジルコニア繊維、窒化ホウ素繊維、窒化珪素繊維、ホウ素繊維、チタン酸カリウムウィスカー、ホウ酸アルミニウムウィスカー、マグネシウム系ウィスカー、珪素系ウィスカー等が挙げられる。炭素繊維としてはポリアクリロニトリル系炭素繊維、ピッチ系炭素繊維等が挙げられる。これらの無機充填剤は、表面処理を施したものでもよい。
難燃剤としては、例えば、ハロゲン系難燃剤、リン系難燃剤、金属酸化物系難燃剤、金属水酸化物系難燃剤、金属塩系難燃剤、窒素系難燃剤、シリコーン系難燃剤、及びホウ素化合物系難燃剤等が挙げられる。
着色剤としては顔料及び染料等を、用途及び着色目的に応じて適宜選択することができる。顔料と染料とは併用してもよい。
摺動性改良剤としては、二硫化モリブデン、金属石鹸等の固体潤滑剤;鉱油、合成油、ワックス等の液体潤滑剤;フッ素系樹脂、ポリオレフィン、及び球状フェノール等の潤滑性ポリマーが挙げられる。
酸化防止剤としては、フェノール系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤、銅系酸化防止剤、及びアミン系酸化防止剤等が挙げられる。また、導電剤としては、炭素系導電剤、金属系導電剤、金属酸化物系導電剤、及び界面活性剤等が挙げられる。
これらの添加剤は、1種又は2種以上を組み合わせて用いることができる。
本発明の成形体は、本発明のポリイミド樹脂を含む。本発明のポリイミド樹脂は成形加工性に優れるため、該ポリイミド樹脂及びこれを含むポリイミド樹脂組成物を熱成形することにより容易に成形体を製造できる。熱成形方法としては射出成形、押出成形、ブロー成形、熱プレス成形、真空成形、圧空成形、レーザー成形、溶接、溶着等が挙げられ、熱溶融工程を経る成形方法であればいずれの方法でも成形が可能である。
まず、ポリイミド樹脂に必要に応じて各種任意成分を添加してドライブレンドした後、これを押出機内に導入して、好ましくは290~400℃で溶融混練及び押出し、ペレットを作製する。あるいは、ポリイミド樹脂を押出機内に導入して、好ましくは290~400℃で溶融し、ここに各種任意成分を導入して押出機内でポリイミド樹脂と溶融混練し、押出すことで前述のペレットを作製してもよい。
上記ペレットを乾燥させた後、各種成形機に導入して好ましくは290~400℃で熱成形し、所望の形状を有する成形体を製造することができる。
本発明のポリイミド樹脂及びこれを含むポリイミド樹脂組成物は290~400℃という比較的低い温度で押出成形等の熱成形を行うことが可能であるため、成形加工性に優れ、所望の形状を有する成形品を容易に製造することができる。熱成形時の温度は、好ましくは300~380℃、より好ましくは310~370℃である。
本発明のポリイミド樹脂及びこれを含むポリイミド樹脂組成物は特に成形加工性に優れることから、少なくとも一部に厚み1000μm以下の薄肉部を有する成形体の作製に好適に用いられる。例えば、1000μm以下の均一な厚みを有するフィルム及びシートや、厚み1000μm以下の薄肉部を一部に有する射出成形体等が挙げられる。該厚みは、好ましくは1000μm以下、より好ましくは800μm以下である。
本発明の成形体がフィルムである場合、該フィルムの製造には公知のフィルムの製造方法を適用できる。無延伸フィルムの製造方法としては、例えば、前述の方法で作製したポリイミド樹脂のペレットを乾燥させた後、該ペレットを押出機内に導入して溶融させ、通常のTダイ法や円筒ダイ法(インフレーション法)等を使用してポリイミド樹脂をフィルム状に吐出し、次いで冷却ロール等により冷却、固化してフィルムを得る方法が挙げられる。押出機としては、単軸又は二軸のスクリュー押出機等を用いることができる。
その他、無延伸フィルムの製造方法としては、本発明のポリイミド樹脂と有機溶剤とを含有するポリイミド樹脂溶液、又はポリイミド樹脂と既述の種々の添加剤とを含むポリイミド樹脂組成物をフィルム状に塗布又は成形した後、該有機溶剤を除去する方法等が挙げられる。
延伸フィルムの製造において、延伸は一軸延伸でも二軸延伸でもよく、フィルムの用途や要求される物性により適宜選択することができる。二軸延伸方法としては、同時二軸延伸法あるいは逐次二軸延伸法を用いることができる。フィルムのMD方向とTD方向での異方性を低減する観点からは、二軸延伸が好ましい。
上記予熱を行い、原反フィルムが設定温度まで均一に加熱された状態で、一軸延伸の場合はMD方向又はTD方向に、二軸延伸の場合はMD方向及びTD方向に延伸する。延伸倍率は、MD方向又はTD方向のいずれにおいても、好ましくは1.1倍以上、より好ましくは1.2倍以上であり、好ましくは4.0倍以下、より好ましくは3.5倍以下、さらに好ましくは3.0倍以下、よりさらに好ましくは2.5倍以下である。延伸倍率が1.1倍以上であれば、延伸配向が十分であり、機械的強度や耐熱性等の物性向上効果を発現しやすい。また延伸倍率が4.0倍以下であれば、延伸によるフィルムの破断や欠陥、配向ムラの発生を防止することができ、外観性に優れるフィルムを得ることができる。
また延伸フィルムのMD方向とTD方向との延伸倍率の積は、使用する原反フィルムの厚みによっても異なるが、得られるフィルムの物性及び外観性の観点から、好ましくは1.5~16倍、より好ましくは1.5~12.25倍、さらに好ましくは1.5~9.0倍、よりさらに好ましくは1.5~6.25倍である(一軸延伸の場合は、延伸しない方向の倍率を1倍とする)。また、MD方向とTD方向に、同延伸倍率の延伸を行った際に異方性が見られる場合は、MD方向とTD方向で異なる延伸倍率の延伸を行い、異方性を低減させることも可能である。
延伸速度は、得られるフィルムの物性を十分に向上させる観点から、好ましくは10%/分以上、より好ましくは50%/分以上である。延伸速度の上限に関しては、破れなどの欠陥が発生しない限り特に制限はないが、通常10000%/分以下である。
延伸には、公知の一軸又は二軸延伸装置を用いることができる。
熱固定時の加熱温度は、ポリイミド樹脂のTg以上、融点以下の温度であればよいが、再加熱時のフィルムの寸法変化を抑制する観点から、好ましくはポリイミド樹脂のTg+10℃以上、より好ましくはポリイミド樹脂のTg+20℃以上である。また、フィルムの延伸配向を維持する観点からは、好ましくはポリイミド樹脂の融点-30℃以下、より好ましくはポリイミド樹脂の融点-50℃以下である。加熱時間は、再加熱時のフィルムの寸法変化を抑制する観点から、好ましくは0.5~1000分、より好ましくは1~500分である。
本発明のポリイミド樹脂は、繊維材料に含浸させてポリイミド樹脂-繊維複合材(以下、単に「複合材」ともいう)とすることもできる。
複合材に用いる繊維材料としては、ガラス繊維、炭素繊維、アルミナ繊維、ボロン繊維、セラミック繊維、金属繊維(スチール繊維等)等の無機繊維;アラミド繊維、ポリオキシメチレン繊維、芳香族ポリアミド繊維、ポリパラフェニレンベンゾビスオキサゾール繊維、超高分子量ポリエチレン繊維、芳香族ポリイミド繊維等の合成繊維;などが挙げられる。なかでも、軽量でありながら、高強度、高弾性率であるという優れた特徴を有するため、炭素繊維が好ましく用いられる。炭素繊維はポリアクリロニトリル系炭素繊維、ピッチ系炭素繊維を好ましく用いることができる。
なお、複合材中における平均繊維長の測定方法は、特に限定されるものではないが、たとえば複合材をヘキサフルオロイソプロパノール(HFIP)あるいは濃硫酸中に入れて、ポリイミド樹脂を溶解させた後に残る繊維の長さを測ればよく、目視、場合によっては光学顕微鏡や走査型電子顕微鏡(SEM)などによる観察によって測定することが可能である。100本の繊維を無作為に選んで長さを測定し、個数平均の平均繊維長を算出することができる。
ポリイミド樹脂と親和性や反応性を有する官能基を有する例として、表面処理剤または収束剤等で表面処理したものが好ましく挙げられる。
シラン系カップリング剤としては、アミノプロピルトリエトキシシラン、フェニルアミノプロピルトリメトキシシラン、グリシジルプロピルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン、ビニルトリエトキシシラン等のトリアルコキシまたはトリアリロキシシラン化合物、ウレイドシラン、スルフィドシラン、ビニルシラン、イミダゾールシラン等が挙げられる。
ポリイミド樹脂はフィルム状、繊維状、粉末状、およびペレット状などの如何なる形態であっても繊維材料と複合することが可能であるが、成形性、含浸性などの観点からはフィルム状、繊維状、又は粉末状であることが好ましい。
なお、ロールの材質に特に制限はないが、加熱加圧時にポリイミド樹脂のロールへの粘着を防ぐために、ロール表面をフッ素樹脂でコーティングしたロールを好ましく用いることができる。
ポリイミド樹脂が粉末状である場合は、繊維材料の表面にポリイミド樹脂粉末を分散させたのち、加熱雰囲気下でのロールによる加圧、あるいはレーザー照射によって溶融、含浸させることができる。
上記複合材は、熱可塑性樹脂材料からなるので、これをそのまま、あるいは所望の形状・サイズに切断して、これを成形用材料として使用し、好ましくはこれを加熱し、次いで、好ましくは加熱された成形用の型に入れて成形し、型から取り外して各種の成形体を得ることが可能である。また、上記の成形は、成形用の型を用いる方法に限らず、例えば、ロールを用いて行うこともできる。複合材を好ましくは加熱し、次いで、好ましくは加熱されたロールにより加圧し、成形することも可能である。
上記複合材を成形体とする方法には特に制限はなく、公知の技術が適用でき、圧縮成形法、真空成形法、真空圧縮成形法、加圧成形法等を利用できる。
また、複合材を成形して得られた成形体は、さらに熱処理を行ってもよい。成形体を熱処理することによって、反りが少なくなり、寸法安定性をより向上させることができる。熱処理温度は150~250℃が好ましい。
ポリイミド樹脂の対数粘度μは、得られたポリイミド樹脂を190~200℃で2時間乾燥した後、ポリイミド樹脂0.100gを濃硫酸(96%、関東化学(株)製)20mLに溶解し、キャノンフェンスケ粘度計を使用して30℃において測定を行った。対数粘度μは下記式により求めた。
μ=ln(ts/t0)/C
t0:濃硫酸の流れる時間
ts:ポリイミド樹脂溶液の流れる時間
C:0.5g/dL
ポリイミド樹脂の融点Tm、ガラス転移温度Tg、結晶化温度Tc、及び結晶化発熱量は、示差走査熱量計装置(エスアイアイ・ナノテクノロジー(株)製「DSC-6220」)を用いて測定した。窒素雰囲気下、ポリイミド樹脂に下記条件の熱履歴を課した。熱履歴の条件は、昇温1度目(昇温速度10℃/分)、その後冷却(降温速度20℃/分)、その後昇温2度目(昇温速度10℃/分)である。
融点は昇温2度目で観測された吸熱ピークのピークトップ値を読み取り決定した。ガラス転移温度は昇温2度目で観測された値を読み取り決定した。また、結晶化温度は冷却時に観測された発熱ピークのピークトップ値を読み取り決定した。
結晶化発熱量(mJ/mg)は、上記冷却時に観測された結晶化発熱ピークの面積から算出した。
ポリイミド樹脂の半結晶化時間は、示差走査熱量計装置(エスアイアイ・ナノテクノロジー(株)製「DSC-6220」)を用いて測定した。
半結晶化時間が20秒以下のポリイミド樹脂の測定条件は窒素雰囲気下、融点+20℃で10分保持し、ポリイミド樹脂を完全に溶融させたのち、降温速度70℃/分の急冷操作を行った際に、観測される結晶化発熱ピークの出現時からピークトップに達するまでにかかった時間を計算し、決定した。
なお表2の実施例、比較例において、半結晶化時間が20秒未満のものは「20>」と表示した。
ポリイミド樹脂のIR測定は日本電子(株)製「JIR-WINSPEC50」を用いて行った。
JIS K0069の方法により、公称目開き500μm及び公称目開き250μmのJIS試験用ふるいを用いてポリイミド樹脂粉末のふるい分け試験を行い粒径を確認した。
ポリイミド樹脂粉末のレーザー回折式粒度分布測定には、マルバーン社製のレーザー回折式粒度分布測定器「LMS-2000e」を使用した。測定は分散媒として水を使用し、超音波条件下によりポリイミド樹脂粉末が十分に分散する条件で行った。測定範囲は0.02~2000μmとした。
ポリイミド樹脂の分子量(Mw、Mn)測定については、昭和電工(株)製のゲルろ過クロマトグラフィー(GPC)測定装置「Shodex GPC-101」を用いて測定した。測定時条件は次に示す通りである:
カラム:Shodex HFIP-806M
移動相溶媒:トリフルオロ酢酸ナトリウム2mM含有ヘキサフルオロイソプロパノール(HFIP)
カラム温度:40℃
移動相流速:1.0mL/min
試料濃度:約0.1質量%
検出器:IR検出器
注入量:100μm
検量線:標準PMMA
ポリイミド樹脂を厚さ100μmのフィルム状に調製した後、ヤマト科学(株)製送風定温恒温器「DN610」に導入し、200℃、72時間静置した。得られたフィルムのGPC測定を行い、加熱前後の分子量の変化から分子量(Mw,Mn)保持率を求めた。また、加熱後のフィルムの靭性について、フィルムを2つ折りにした際に、いずれの箇所でも破断が見られない場合はA、破断が見られる箇所と破断が見られない箇所がある場合はB、いずれの箇所でも破断が見られる場合はCとして評価を行った。
水酸化ナトリウム4.0g、水50mL、メタノール50mLを混合して得られる1M-水酸化ナトリウム溶液から5mLを量りとり、そこに得られたポリイミド固体100mgを加えたのち、耐圧容器中で240℃、1時間加熱することで解重合が行われる。
得られた溶液に対して、クロロホルムと水による抽出操作を行い、解重合されたモノマーの溶液を分離する。モノマー比は、ガスクロマトグラフィー(HEWLETT PACKARD製「HP6890」)を用い、アジレントテクノロジー製のカラム(HP-5)により分離し(昇温条件は50℃で10min保持後、10℃/分で300℃まで昇温)、各モノマーの面積比を算出することでモノマー組成比及び末端基導入量を決定している。なお、テトラカルボン酸成分に関してはメチルエステル体として観測される。
上記方法により、本願実施例、比較例のポリイミド樹脂のモノマー組成比及び末端基導入量は、モノマー及び末端基導入用化合物の仕込みモル比と相違ないことを確認した。
実施例2a~2dで得られたフィルムについては、マイクロメーターを用いて異なる箇所の厚みを計10点測定し、その平均値をフィルムの実測厚みとした。
実施例2a~2dで得られたフィルムから100mm×10mmの試験フィルムを切り出し、測定に使用した。引張試験機((株)東洋精機製作所製「ストログラフVG1E」)を用いて、JIS K7127に準拠して、温度23℃、試験速度50mm/分で引張試験を行い、引張弾性率及び引張強度を測定した。なお実施例2a~2dのフィルムはMD方向について引張試験を行った。
エスアイアイ・ナノテクノロジー(株)製の熱機械的分析装置(TMA/SS6100)を用いて、昇温速度10℃/分の条件で、実施例2a~2dで得られたポリイミド樹脂フィルムのTMA測定を行い、100~150℃のCTEを求めた。実施例2a~2dのフィルムはMD方向について測定を行った。
分光ヘイズメーター(日本電色工業(株)製、型式:SH-7000)を使用して透過法によりフィルムのヘイズ値、YI値、及び全光線透過率を測定した。
ディーンスターク装置、リービッヒ冷却管、熱電対、4枚パドル翼を設置した2Lセパラブルフラスコ中に2-(2-メトキシエトキシ)エタノール(日本乳化剤(株)製)650gとピロメリット酸二無水物(三菱ガス化学(株)製)218.1g(1.00mol)を導入し、窒素フローした後、均一な懸濁溶液になるように150rpmで撹拌した。一方で、500mLビーカーを用いて、1,3-ビス(アミノメチル)シクロヘキサン(三菱ガス化学(株)製)70.60g(0.496mol)、1,6-ヘキサメチレンジアミン(和光純薬工業(株)製)46.13g(0.397mol)、4,4’-ジアミノジフェニルエーテル(和歌山精化工業(株)製)19.88g(0.0993mol)を2-(2-メトキシエトキシ)エタノール250gに溶解させ、混合ジアミン溶液を調製した。この混合ジアミン溶液を、プランジャーポンプを使用して徐々に加えた。混合ジアミン溶液の滴下中はすべて窒素フロー状態とし、撹拌翼回転数は250rpmとした。滴下が終わったのちに、2-(2-メトキシエトキシ)エタノール65gと、末端基導入用化合物であるn-オクチルアミン(関東化学(株)製)1.92g(0.0149mol)を加えさらに撹拌した。この段階で、黄色のポリアミド酸溶液が得られた。次に、撹拌速度を200rpmとした後に、2Lセパラブルフラスコ中のポリアミド酸溶液を190℃まで昇温した。昇温を行っていく過程において、液温度が130~140℃の間にポリイミド樹脂粉末の析出と、イミド化に伴う脱水が確認された。190℃で30分保持した後、室温まで放冷を行い、濾過を行った。得られたポリイミド樹脂粉末は2-(2-メトキシエトキシ)エタノール500gとメタノール500gにより洗浄、濾過を行った後、乾燥機で190℃、10時間乾燥を行い、311gのポリイミド樹脂1の粉末を得た。
得られたポリイミド樹脂1を用いて、前記測定及び評価を行った。結果を表2に示す。ポリイミド樹脂1のIRスペクトルを測定したところ、ν(C=O)1771、1699(cm-1)にイミド環の特性吸収が認められた。また、ポリイミド樹脂1の粉末をJIS K0069の方法により、目開き500μmのふるいに通したところ99質量%以上が通過し、目開き250μmのふるいに通したところ99質量%以上が通過した。
ディーンスターク装置、リービッヒ冷却管、熱電対、4枚パドル翼を設置した2Lセパラブルフラスコ中に2-(2-メトキシエトキシ)エタノール(日本乳化剤(株)製)600gとピロメリット酸二無水物(三菱ガス化学(株)製)218.58g(1.00mol)を導入し、窒素フローした後、均一な懸濁溶液になるように150rpmで撹拌した。一方で、500mLビーカーを用いて、1,3-ビス(アミノメチル)シクロヘキサン(三菱ガス化学(株)製)49.42g(0.347mol)、1,8-オクタメチレンジアミン(関東化学(株)製)93.16g(0.645mol)を2-(2-メトキシエトキシ)エタノール250gに溶解させ、混合ジアミン溶液を調製した。この混合ジアミン溶液を、プランジャーポンプを使用して徐々に加えた。混合ジアミン溶液の滴下中はすべて窒素フロー状態とし、撹拌翼回転数は250rpmとした。滴下が終わったのちに、2-(2-メトキシエトキシ)エタノール130gと、末端基導入用化合物であるn-オクチルアミン(関東化学(株)製)1.934g(0.0149mol)を加えさらに撹拌した。この段階で、淡黄色のポリアミド酸溶液が得られた。次に、撹拌速度を200rpmとした後に、2Lセパラブルフラスコ中のポリアミド酸溶液を190℃まで昇温した。昇温を行っていく過程において、液温度が120~140℃の間にポリイミド樹脂粉末の析出と、イミド化に伴う脱水が確認された。190℃で30分保持した後、室温まで放冷を行い、濾過を行った。得られたポリイミド樹脂粉末は2-(2-メトキシエトキシ)エタノール300gとメタノール300gにより洗浄、濾過を行った後、乾燥機で180℃、10時間乾燥を行い、316gのポリイミド樹脂2の粉末を得た。
得られたポリイミド樹脂2を用いて、前記測定及び評価を行った。結果を表2に示す。ポリイミド樹脂2のIRスペクトルを測定したところ、ν(C=O)1768、1697(cm-1)にイミド環の特性吸収が認められた。また、ポリイミド樹脂2の粉末をJIS K0069の方法により、目開き500μmのふるいに通したところ99質量%以上が通過し、目開き250μmのふるいに通したところ99質量%以上が通過した。また、前述の方法でレーザー回折光散乱式粒度分布測定器により粒度を測定したところ、D10が9.3μm、D50が14.5μm、D90が22.7μmの単峰性となり、粒度分布が狭いことが確認された。
ディーンスターク装置、リービッヒ冷却管、熱電対、4枚パドル翼を設置した2Lセパラブルフラスコ中に2-(2-メトキシエトキシ)エタノール(日本乳化剤(株)製)650gとピロメリット酸二無水物(三菱ガス化学(株)製)218.1g(1.00mol)を導入し、窒素フローした後、均一な懸濁溶液になるように150rpmで撹拌した。一方で、500mLビーカーを用いて、1,3-ビス(アミノメチル)シクロヘキサン(三菱ガス化学(株)製)70.60g(0.496mol)、1,6-ヘキサメチレンジアミン(和光純薬工業(株)製)46.13g(0.397mol)、4,4’-ジアミノジフェニルエーテル(和歌山精化工業(株)製)19.88g(0.0993mol)を2-(2-メトキシエトキシ)エタノール250gに溶解させ、混合ジアミン溶液を調製した。この混合ジアミン溶液を、プランジャーポンプを使用して徐々に加えた。混合ジアミン溶液の滴下中はすべて窒素フロー状態とし、撹拌翼回転数は250rpmとした。滴下が終わったのちに、2-(2-メトキシエトキシ)エタノール65gと、末端基導入用化合物であるベンジルアミン(関東化学(株)製)1.60g(0.0149mol)を加えさらに撹拌した。この段階で、黄色のポリアミド酸溶液が得られた。次に、撹拌速度を200rpmとした後に、2Lセパラブルフラスコ中のポリアミド酸溶液を190℃まで昇温した。昇温を行っていく過程において、液温度が130~140℃の間にポリイミド樹脂粉末の析出と、イミド化に伴う脱水が確認された。190℃で30分保持した後、室温まで放冷を行い、濾過を行った。得られたポリイミド樹脂粉末は2-(2-メトキシエトキシ)エタノール500gとメタノール500gにより洗浄、濾過を行った後、乾燥機で190℃、10時間乾燥を行い、310gの比較ポリイミド樹脂1の粉末を得た。
得られた比較ポリイミド樹脂1を用いて、前記測定及び評価を行った。結果を表2に示す。比較ポリイミド樹脂1のIRスペクトルを測定したところ、ν(C=O)1771、1699(cm-1)にイミド環の特性吸収が認められた。
ディーンスターク装置、リービッヒ冷却管、熱電対、4枚パドル翼を設置した2Lセパラブルフラスコ中に2-(2-メトキシエトキシ)エタノール(日本乳化剤(株)製)650gとピロメリット酸二無水物(三菱ガス化学(株)製)218.1g(1.00mol)を導入し、窒素フローした後、均一な懸濁溶液になるように150rpmで撹拌した。一方で、500mLビーカーを用いて、1,3-ビス(アミノメチル)シクロヘキサン(三菱ガス化学(株)製)70.24g(0.494mol)、1,6-ヘキサメチレンジアミン(和光純薬工業(株)製)45.90g(0.395mol)、4,4’-ジアミノジフェニルエーテル(和歌山精化工業(株)製)19.77g(0.0987mol)を2-(2-メトキシエトキシ)エタノール250gに溶解させ、混合ジアミン溶液を調製した。この混合ジアミン溶液を、プランジャーポンプを使用して徐々に加えた。混合ジアミン溶液の滴下中はすべて窒素フロー状態とし、撹拌翼回転数は250rpmとした。滴下が終わったのちに、2-(2-メトキシエトキシ)エタノール65gと、末端基導入用化合物であるアニリン(関東化学(株)製)2.30g(0.0247mol)を加えさらに撹拌した。この段階で、黄色のポリアミド酸溶液が得られた。次に、撹拌速度を200rpmとした後に、2Lセパラブルフラスコ中のポリアミド酸溶液を190℃まで昇温した。昇温を行っていく過程において、液温度が130~140℃の間にポリイミド樹脂粉末の析出と、イミド化に伴う脱水が確認された。190℃で30分保持した後、室温まで放冷を行い、濾過を行った。得られたポリイミド樹脂粉末は2-(2-メトキシエトキシ)エタノール500gとメタノール500gにより洗浄、濾過を行った後、乾燥機で190℃、10時間乾燥を行い、308gの比較ポリイミド樹脂2の粉末を得た。
得られた比較ポリイミド樹脂2を用いて、前記測定及び評価を行った。結果を表2に示す。比較ポリイミド樹脂2のIRスペクトルを測定したところ、ν(C=O)1771、1699(cm-1)にイミド環の特性吸収が認められた。
・PMDA;ピロメリット酸二無水物
・1,3-BAC;1,3-ビス(アミノメチル)シクロヘキサン
・HMDA;1,6-ヘキサメチレンジアミン
・OMDA;1,8-オクタメチレンジアミン
・ODA;4,4’-ジアミノジフェニルエーテル
[実施例2a]無延伸フィルム(原反フィルム)の製造
実施例2で得られたポリイミド樹脂2を二軸スクリュー押出機((株)東洋精機製作所製「ラボプラストミル」)から330℃で溶融押出して、Tダイ-冷却ロール法により、厚み90μmの無延伸フィルムを作製した。得られたフィルムについて、前記方法により各種評価を行った。結果を表3に示す。
実施例2aで作製した無延伸フィルムを100mm×100mmの大きさに切り取り、原反フィルムとして用いた。該原反フィルムを200℃で60秒加熱して予熱を行った後、二軸延伸装置((株)東洋精機製作所製「EX10-S5」)を用いて同時二軸延伸を行った。延伸倍率、延伸温度及び延伸速度は表3に示す通りである。次いで、上記延伸後のフィルムを230℃で10分、緊張下にて熱固定し、その後空冷することで、実施例2b~2dの延伸フィルムを得た。得られたフィルムについて、前記方法により各種評価を行った。結果を表3に示す。
Claims (11)
- R2が炭素数5~12のアルキレン基である、請求項1~3のいずれかに記載のポリイミド樹脂。
- 前記炭素数5~14の鎖状脂肪族基の含有量が、ポリイミド樹脂中の全繰り返し構成単位の合計100モル%に対し0.01モル%以上、10モル%以下である、請求項1~6のいずれかに記載のポリイミド樹脂。
- テトラカルボン酸成分及びジアミン成分を混合し、次いで炭素数5~14の鎖状脂肪族基を有する化合物を混合して反応させる工程を有する、請求項1~7のいずれかに記載のポリイミド樹脂の製造方法。
- 前記炭素数5~14の鎖状脂肪族基を有する化合物がモノアミン類である、請求項8に記載のポリイミド樹脂の製造方法。
- 請求項1~7のいずれかに記載のポリイミド樹脂を含む成形体。
- 少なくとも一部に厚み1000μm以下の薄肉部を有する、請求項10に記載の成形体。
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Also Published As
Publication number | Publication date |
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CN106715534A (zh) | 2017-05-24 |
US20170275425A1 (en) | 2017-09-28 |
US10174167B2 (en) | 2019-01-08 |
EP3272786A4 (en) | 2018-11-14 |
EP3272786A1 (en) | 2018-01-24 |
EP3272786B1 (en) | 2019-12-18 |
JP6037088B1 (ja) | 2016-11-30 |
KR20170027859A (ko) | 2017-03-10 |
JPWO2016147997A1 (ja) | 2017-04-27 |
KR101841977B1 (ko) | 2018-03-26 |
CN106715534B (zh) | 2018-10-19 |
TWI591099B (zh) | 2017-07-11 |
TW201641539A (zh) | 2016-12-01 |
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