JPH02208324A - Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet - Google Patents
Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheetInfo
- Publication number
- JPH02208324A JPH02208324A JP2949389A JP2949389A JPH02208324A JP H02208324 A JPH02208324 A JP H02208324A JP 2949389 A JP2949389 A JP 2949389A JP 2949389 A JP2949389 A JP 2949389A JP H02208324 A JPH02208324 A JP H02208324A
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- low dielectric
- sheet
- bis
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 claims abstract description 43
- 239000004642 Polyimide Substances 0.000 claims abstract description 38
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 32
- 239000011737 fluorine Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 5
- 239000002253 acid Substances 0.000 abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 12
- 150000004985 diamines Chemical class 0.000 abstract description 11
- -1 3,4-dicarboxyphenyl Chemical group 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 10
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000002798 polar solvent Substances 0.000 abstract description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 abstract 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000011800 void material Substances 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 239000011521 glass Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- 229920005575 poly(amic acid) Polymers 0.000 description 11
- 239000004744 fabric Substances 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- NZEXBCLLEJJKOM-UHFFFAOYSA-N 1,1,1,5,5,5-hexafluoropentane Chemical compound FC(F)(F)CCCC(F)(F)F NZEXBCLLEJJKOM-UHFFFAOYSA-N 0.000 description 1
- 125000004825 2,2-dimethylpropylene group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[*:1])C([H])([H])[*:2] 0.000 description 1
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- JCQRXXHEOZLSNO-UHFFFAOYSA-N 4-(4-amino-3-methylphenyl)-2-methylaniline;4-(4-aminophenyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1.C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 JCQRXXHEOZLSNO-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- BMNKWSYVOVYDDU-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)-difluoromethyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(F)(F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 BMNKWSYVOVYDDU-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- HJSYPLCSZPEDCQ-UHFFFAOYSA-N 5-[2-(3-amino-4-methylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C)C(N)=C1 HJSYPLCSZPEDCQ-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- GMOPCYUSBVOOBQ-UHFFFAOYSA-N FC(CC(F)(F)F)(F)F.OC1=CC=C(C=C1)O Chemical compound FC(CC(F)(F)F)(F)F.OC1=CC=C(C=C1)O GMOPCYUSBVOOBQ-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- AIJZIRPGCQPZSL-UHFFFAOYSA-N ethylenetetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)=C(C(O)=O)C(O)=O AIJZIRPGCQPZSL-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- YIYJIOTZXXQSHE-UHFFFAOYSA-N heptane-1,7-diamine;octane-1,8-diamine Chemical compound NCCCCCCCN.NCCCCCCCCN YIYJIOTZXXQSHE-UHFFFAOYSA-N 0.000 description 1
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 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
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NWRSLSNMQXMRHQ-UHFFFAOYSA-N octadecane-7,7-diamine Chemical compound CCCCCCCCCCCC(N)(N)CCCCCC NWRSLSNMQXMRHQ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- SHALVKVVWYJLCA-UHFFFAOYSA-N propane-1,1,1,2-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)(C(O)=O)C(O)=O SHALVKVVWYJLCA-UHFFFAOYSA-N 0.000 description 1
- 230000008054 signal transmission Effects 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
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業土の利用分野〉
本発明は低誘電率シート、該ン〜トを用いＣ々る績ノー
板および多層回路基板に関する。DETAILED DESCRIPTION OF THE INVENTION <Field of industrial application> The present invention relates to a low dielectric constant sheet, a circuit board and a multilayer circuit board using the sheet.
〈従来の技術〉
従来から電気・亀子機器、特にコンピュータに用イら几
るプリント配線基板としては、エポキシｍ脂ｖ−ｙエノ
ール樹脂を用いたガラスエポキシ積層板２紙フェノール
樹脂積層板などが汎用さ几でいたが、耐熱性ヤ高温時に
おける誘電特注の低下に問題があった。<Conventional technology> Traditionally, glass epoxy laminates and two-paper phenolic resin laminates using epoxy m-fat vy enol resin have been widely used as printed wiring boards for electrical equipment, especially computers. However, there was a problem with the deterioration of the heat resistance of the dielectric at high temperatures.
特に、近年の大型コンピュータの発達ＶＣよって。Especially with the recent development of large-scale computers, VC.
コンピュータの信号伝達速度の高速化には次式からも明
らかなように基板の低誘Ｉｊｔ率化が不可欠な課題とな
っている。In order to increase the signal transmission speed of computers, it is essential to reduce the dielectric constant of the substrate, as is clear from the following equation.
このような情況下において耐熱性、電気特性に優れるポ
リイミド圏刀旨ヤフッ素樹刀旨が注目され。Under these circumstances, polyimide fibers made of polyimide and fluorine resin have attracted attention due to their excellent heat resistance and electrical properties.
ガラス繊維とポリイミド樹脂との複合基材や、ガラス繊
維とフッ素樹力旨との複合基材からなるプリント配線基
板などが提案さｎている。Printed wiring boards made of composite base materials of glass fiber and polyimide resin, and composite base materials of glass fiber and fluorine resin have been proposed.
〈発明が解決しようとする課題〉
基板では誘電率が２．５程度であり満足ゆく特性値を有
するものの、加工性や寸法安定性、特に多１−回路基板
作製時の多層化工程における高温条件下では極めて寸法
安定性に劣るという欠点があった。<Problems to be solved by the invention> Although the substrate has a dielectric constant of about 2.5 and has satisfactory characteristic values, there are problems with workability and dimensional stability, especially the high temperature conditions in the multilayer process during the production of multi-circuit boards. However, the disadvantage was that the dimensional stability was extremely poor.
−万、最近多孔質フッ素樹脂基材にポリイミド樹脂を含
浸させた基材がプリント配線基板として提案されている
。これはポリイミド樹脂による加工性と寸法安定性の改
善、およびフッ素樹脂による低誘電率化を図ったもので
ある。しかし、ポリイミド樹脂の誘電率が本来、３．Ｕ
〜４．５であるために、低ｎｔ率化にも自ずと限界を有
するものである。-Recently, a porous fluororesin base material impregnated with polyimide resin has been proposed as a printed wiring board. This is intended to improve workability and dimensional stability using polyimide resin, and to lower the dielectric constant using fluororesin. However, the dielectric constant of polyimide resin is originally 3. U
˜4.5, there is naturally a limit to lowering the nt rate.
従って１本発明の目的は、従来のガラス繊維とフッ素樹
脂との複合基材からなるプリント配線基板が有する誘電
率に匹敵する低訪電特性を有し。Therefore, one object of the present invention is to have a low current visit characteristic comparable to the dielectric constant of a conventional printed wiring board made of a composite base material of glass fiber and fluororesin.
かつ刀ｎ工性や寸法安定性にも優れるシートを提供する
ことにある。The object of the present invention is to provide a sheet that is also excellent in machinability and dimensional stability.
また本発明の他の目的は５上記低誘電率シートを用いて
なるＩｊｔＪａ板ヤ多層回路基板を提供することにある
。Another object of the present invention is to provide an IjtJa multilayer circuit board using the above-mentioned low dielectric constant sheet.
本発明者らＶよ上記目的を達成すべく鋭意研死を璽２２
ｆ？：、結果１分子内にフッ素原子を有する特定構造の
ポリイミド樹脂を用いることにより、低誘電率シートを
得ることができ、ま之、積１−板ｆ多Ｉ−回路基板を作
製する際に力ロエ性ヤ寸法安定性にも優れることを見い
出し１本発明を完成するに至った。The inventors of the present invention, in order to achieve the above purpose, are committed to diligent research.22
f? :, As a result, by using a polyimide resin with a specific structure that has fluorine atoms in one molecule, it is possible to obtain a low dielectric constant sheet. The present invention was completed based on the discovery that it has excellent Loe resistance and dimensional stability.
即ち１本発明は、−形式（Ｉ）。That is, one aspect of the present invention is -Form (I).
ｊｌ 八
〇
〔但し、 Ａｒｔは四価の脂肪族基又は芳香族基、 Ａ
ｒ２は二価の芳香族基を示し、 ＡｒｔおよびＡｒｚの
少なくとも一万の基にパーフルオロアルキレン基を含む
〕で表わされる繰り返し単位を有する含フッ素ポリイミ
ド全用いてなる低誘電率シート、２よび該シートを用い
てなる！＊層体お工び多層回路基板を提！＃するもので
ある。jl 80 [However, Art is a tetravalent aliphatic group or aromatic group, A
r2 represents a divalent aromatic group, and at least 10,000 groups of Art and Arz contain a perfluoroalkylene group. Use a sheet! *We offer layered multilayer circuit boards! ＃It is something to do.
で、Ｒｆｔがパーフルオロアルキレン基、Ａｒ２トｌ−
ででばＡｒｌおよびＡｒ２の少なくともいずれか一方の
基にパーフルオロアルキレン基が導入されている。, Rft is a perfluoroalkylene group, Ar2 is a perfluoroalkylene group,
Preferably, a perfluoroalkylene group is introduced into at least one of Arl and Ar2.
で表わさ几、Ｒｔ’２がパーフルオロアルキレン基、Ｘ
およびＹが同一もしくは異なるアルキル基、フッ化アル
キル基から選ばれる少なくとも一種、ｎが０またはｌ、
ｍが０〜４の整数、ｅが０〜４の整数である基の少なく
ともいずれか一方の基を分子内［ｉする含フッ素ポリイ
ミド金用いてなるものが好適である。Represented by 几, Rt'2 is a perfluoroalkylene group,
and Y is at least one selected from the same or different alkyl groups and fluorinated alkyl groups, n is 0 or l,
It is preferable to use a fluorine-containing polyimide gold in which at least one of the groups m is an integer of 0 to 4 and e is an integer of 0 to 4 is contained in the molecule.
本発明に用いられる含フツ素ポリイミドは、ド記一般式
（１）Ｉｃで表わされる繰り返し単位を有するものであ
る。The fluorine-containing polyimide used in the present invention has a repeating unit represented by general formula (1) Ic.
ｋ、記−形式（１）においてＡｒ１は四価の脂肪族基ま
たは芳香族基、 Ａｒ２は二価の芳香族基全示し１本発
明の骨格ヲ有し、Ｒｆがパーフルオロアルキレン基であ
る四価の芳香族基が好ましく、さらにＲｆｔが。k, In the format (1), Ar1 is a tetravalent aliphatic group or an aromatic group, Ar2 is a divalent aromatic group, and has the skeleton of the present invention, and Rf is a perfluoroalkylene group. A valent aromatic group is preferred, and further Rft.
から選ばルる一種とすることが好ましい。It is preferable to use one selected from the following.
−万、上記−形式（１）中のＡｒｚは。- 10,000, above - Arz in form (1) is.
で表ワサれ、Ｒｆ２がパーフルオロアルキレン基、Ｘお
よびＹが同一もしくは異なるアルキル基、フッ化アルキ
ル基から選ばれる少なくとも一種、ｎが０または１１ｍ
がＯ〜４の整数、７！がＯ〜４の整数である二価の芳香
族基が低誘電率化℃電気絶縁性などの点から好−ましい
。Rf2 is a perfluoroalkylene group, X and Y are the same or different alkyl groups, at least one selected from fluorinated alkyl groups, and n is 0 or 11m
is an integer between O and 4, 7! A divalent aromatic group in which is an integer of 0 to 4 is preferred from the viewpoint of low dielectric constant and electrical insulation properties.
上記含フツ素ポリイミドは分子中にフッ素原子を有する
ポリイミドであり１本発明に分いては約１５〜６０重量
％、好ましくｒｌ：２０〜５０重量％の範囲のフン累含
量とすることによって、ポリイミド樹脂本来の特性を阻
害せずに低誘電特性を向上できるものである。The above-mentioned fluorine-containing polyimide is a polyimide having a fluorine atom in the molecule, and according to the present invention, the polyimide can be The low dielectric properties can be improved without impeding the original properties of the resin.
本発明において、を１含フッ素ポリイミドは２通常５重
合用モノマーとしてテトラカルボン酸またはその誘導体
からなる酸成分と、シアεン成分との略等モル反応によ
って得ることができる。但し、少なくともいずれかの成
分にフッ素原子を有する必要がある。In the present invention, the fluorine-containing polyimide (1) can be obtained by a substantially equimolar reaction of an acid component consisting of a tetracarboxylic acid or a derivative thereof as a monomer for polymerization, and a cyanine component (2) as a monomer for polymerization. However, at least one of the components must contain a fluorine atom.
上記テトラカルボン酸またはその誘導体のうち。Among the above tetracarboxylic acids or derivatives thereof.
フッ素を有しないものとしては１例えばブタンテトラカ
ルボン酸、エチレンテトラカルボン酸、プロパンテトラ
カルボン酸、シクロブタンテトラカルボン酸、ンクロベ
ンタンテトラカルボ７酸、 シクロヘキサンテトラカル
ボン酸、５−（２，５−ジオキソテトラヒドロフリル）
−３−メチル−３−フクロヘキセン−１，２−ジカルボ
ン酸などの脂肪族テトラカルボン酸。ピロメリット酸、
ベンゾフェノンテトラカルボン酸、 ２． ３．６．７
−ナフタレンテトラカルボン酸、 （ ２． ４． ５
−ナフタレンテトラカルボン酸、 （４．５．８−ナフ
タレンテトラカルボン酸、 ３．３．４．４−ジフェニ
ルテトラカルボン酸、 （ ３． ５． ６−ナフタレ
ンテトラカルボン酸、２． ２． ３．３−ジフェニル
テトラカルボン酸、３，４，９，１０−バーピレンテト
ラカルボン酸、ビス（３，４−ジカルボキ／フェニル〕
エーテル、テカハイドロナフタレン−１゜４、 ５．８
−テトラカルボン酸、４，８−ジメチル−１，２，３，
５，６，７−ヘキサハイドロナフタレン−１，２，５，
６−テトラカルボン酸、２，６−シクロロナフタレンー
（ ４． ５． ８−テトラカルボン酸、２．７−）ク
ロロナフタレン−１，４゜５．８−テトラカルボン酸、
２． ３．６． ７− テトラクロコナフタレン−１，
４，５，８−テトラカルボン酸、フェナンスノン−１，
８，９，１０−テトラカルボンｆｉ、 ２． ３．
４． ５−ピロリジンテトラカルボン酸、２．３． ｓ
、 ６−ピラジンテトラカルボン酸、チオフェンテト
ラカルボン酸、 ２． ２−ビス（３，４−ジカルボ
キシフェニル）プロパン２，２−ビス（２，３−ジカル
ボキシフェニル）プロパン、１，１−ビス（２，３−ジ
カルボキシフェニル）エタン、ｌ、１−ビス（３，４−
ジカルボキシフェニル）エタン ビス（２，３−ジカル
ボキシフェニル）メタン、ビス（３，４−）カルボキン
フェニル）メタン、ビス（３，４−ジカルボキシフェニ
ル）スルホンなどの芳香族テトラカルボン酸が挙げられ
、これらの酸二無水物、酸／・ロゲン化物、モノエステ
ル化物、ジエステル化物が誘導体として用いられる。Examples of those without fluorine include butanetetracarboxylic acid, ethylenetetracarboxylic acid, propanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclobentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, 5-(2,5-dioxo tetrahydrofuryl)
Aliphatic tetracarboxylic acids such as -3-methyl-3-fuclohexene-1,2-dicarboxylic acid. pyromellitic acid,
Benzophenone tetracarboxylic acid, 2. 3.6.7
-naphthalenetetracarboxylic acid, (2.4.5
-naphthalenetetracarboxylic acid, (4.5.8-naphthalenetetracarboxylic acid, 3.3.4.4-diphenyltetracarboxylic acid, (3. 5. 6-naphthalenetetracarboxylic acid, 2. 2. 3.3 -diphenyltetracarboxylic acid, 3,4,9,10-verpylenetetracarboxylic acid, bis(3,4-dicarboxy/phenyl)
Ether, thecahydronaphthalene-1°4, 5.8
-tetracarboxylic acid, 4,8-dimethyl-1,2,3,
5,6,7-hexahydronaphthalene-1,2,5,
6-tetracarboxylic acid, 2,6-cyclonaphthalene-(4.5.8-tetracarboxylic acid, 2.7-)chloronaphthalene-1,4°5.8-tetracarboxylic acid,
2. 3.6. 7- Tetracroconaphthalene-1,
4,5,8-tetracarboxylic acid, phenanthone-1,
8,9,10-tetracarvone fi, 2. 3.
4. 5-pyrrolidinetetracarboxylic acid, 2.3. s
, 6-pyrazinetetracarboxylic acid, thiophenetetracarboxylic acid, 2. 2-bis(3,4-dicarboxyphenyl)propane 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)ethane, l,1-bis (3,4-
Aromatic tetracarboxylic acids such as dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-)carboxyphenyl)methane, and bis(3,4-dicarboxyphenyl)sulfone are listed. and their acid dianhydrides, acid/logenides, monoesters, and diesters are used as derivatives.
また、含フッ累テトラカルボン酸または誘導体としては
、上記テトラカルボン酸のうち、アルキレン基を有する
テトラカルボン酸のアルキレン鎖中の水素原子を全てフ
ッ素原子ｖｃＨ換せしめたものが用いら几る。例えば、
ビス（３，４−ジカルボキシフェニル）ジフルオロメタ
ン、ｌ、：（−ビス（３，４−ジカルボキシフェニル）
へキサフルオロプロパン ２，２′−ビス（：３．４−
ジカルボキシフェニル）へキサフルオロプロパン、（４
−ビス（３，４−ジカルボキシフェニル）オクタフルオ
ロブタン、ｌ、５−ビス（３，４−ジカルボキシフェニ
ル）デカフルオロペンタン ｌ、 ６−ビス（３，４
−ジカルボキシフェニル）ドデカフルオロヘキサン ２
，２−ビス（３，４−ジカルボキシフェニル）へキサフ
ルオロプロパン、２゜２−ビス（４−（３，４−ジカル
ボキシフェノキン）フェニル〕ヘキサフルオロプロパン
、２．２’−ビス（３−（３，４〜ジカルボキンフエノ
キシ）フェニル〕へキサフルオロプロパンなどの含フツ
素芳香族テトラカルボン酸およびその誘導体が挙げら几
、低ｍ電率化の点から、２，２−ビス（３゜４−ジカル
ボキシフェニル）へキサフルオロプロパン、２，２−ビ
ス（４−（３，４−ジカルボキシフェノキン）フェニル
〕へキ丈フルオロプロノくン、２．２’−ビス（３−（
３，４−）カルボキシフェノキ／）フェニル〕へキサフ
ルオロプロパンおよびこれらの酸二無水物、酸ノ・ロゲ
ン化物、モノエステル化物、ジエステル化物などが好適
である。Further, as the fluorine-containing tetracarboxylic acid or derivative, a tetracarboxylic acid having an alkylene group, in which all hydrogen atoms in the alkylene chain are replaced with fluorine atoms vcH, is used. for example,
Bis(3,4-dicarboxyphenyl)difluoromethane, l, :(-bis(3,4-dicarboxyphenyl)
Hexafluoropropane 2,2'-bis(:3.4-
dicarboxyphenyl) hexafluoropropane, (4
-bis(3,4-dicarboxyphenyl)octafluorobutane, l,5-bis(3,4-dicarboxyphenyl)decafluoropentane l,6-bis(3,4
-dicarboxyphenyl)dodecafluorohexane 2
, 2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2゜2-bis(4-(3,4-dicarboxyphenoquine)phenyl)hexafluoropropane, 2.2'-bis(3 Fluorine-containing aromatic tetracarboxylic acids and their derivatives such as -(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane are mentioned, and 2,2-bis (3゜4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(4-(3,4-dicarboxyphenoquine)phenyl)hexafluoropronopropane, 2,2'-bis(3 −(
3,4-)carboxyphenoxy/)phenyl]hexafluoropropane and their acid dianhydrides, acid nologides, monoesters, diesters, and the like are preferred.
一万、上記酸成分と反応せしめるジアミン成分とし−Ｃ
，フッ素を有しないものとしては１例えば２．２−ジメ
チルプロピレンジアミン、２．５−ジメチルへキサメチ
レンジアミン ２，５〜ジメチルへブタメチレンジアミ
ン ４．４−７メチルへブタメチレンジアミン、３−メ
チルへブタメチレンジアミン ５−メチルノナメチレン
ジアミン２．１７−ニイコサデンレンジアミン、１，４
−ジアミノンクロヘキサン、（１０−ジアミノ−１゜１
０−ジメチルデカン ２，１１−ジアミノドデカン、
ｌ、 １２−ジアミノオクタデカン、ジアミノゾロ
ビルナトラメチレンジアミン、１，２−ビス（３−アミ
ノゾロボキシ〕エタン ３−メトキシへキサメチレンジ
アミン、ヘキサメチレンジアミン、ヘプタメチレンジア
ミン オクタメチレンジアミン、ノナメチレンジアミン
、デカメチレンジアミンなどの脂肪族ジアミン、ｐ−７
二二レンジアミン、ｍ−フ二二しンジアミン、４，４−
ジアミノジフェニルプロパン、４，４−ジアミノジフェ
ニルメタン、ベンジジン ３，３′−ジメチルベンジジ
ン、３，３−ジメトキシベンジジン ４゜４−ジアミノ
ジフェニルスルフィ）”、４．４−ジアミノジフェニル
スルホン、３，３−ジアミノジフェニル ３．３−ジア
ミノジフェニルスルホン４．４′−ジアミノジフェニル
クトン、４．４’−ジアミノジフェニルエ チル （
４−ジアミノナフタレン １，５−ジアミノナフタレン
、２，４−ビス（β−アミノ−ｔｅｒｔ−ブチル）トル
エンビス（ｐ−β−アミノ−ｔｅｒｔ−ブチルフェニル
）エーテル、ビス（ｐ−β−メチル−△−アミノーフェ
ニル〕ベンゼン、ビス（ｐ−１，１−ジメチル−ｔｅｒ
ｔ−アミノペンチル）ベンゼン １−１ノグロビル−２
，４−ｍ−フェニレンシアばン、ｍ−キシレンジアミン
、ビス（４−アミノフェニル）ｄ、ｄ’−ｐ−キジレン
ジアミンなどが挙げられ１本発明ではこれらのジアミン
をジイソシアネートに変性したものを用いてもよい。10,000, as a diamine component to be reacted with the above acid component -C
, Examples of those without fluorine include 1, such as 2,2-dimethylpropylene diamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 4,4-7methylhbutamethylenediamine, 3-methyl Hebutamethylenediamine 5-methylnonamethylenediamine 2.17-nicosadenediamine, 1,4
-diaminonechlorohexane, (10-diamino-1゜1
0-dimethyldecane 2,11-diaminododecane,
l, 12-diaminooctadecane, diaminozolobylnatramethylenediamine, 1,2-bis(3-aminozoloboxy]ethane 3-methoxyhexamethylenediamine, hexamethylenediamine, heptamethylenediamine octamethylenediamine, nonamethylenediamine, decamethylene Aliphatic diamines such as diamines, p-7
22enediamine, m-22enediamine, 4,4-
Diaminodiphenylpropane, 4,4-diaminodiphenylmethane, benzidine 3,3'-dimethylbenzidine, 3,3-dimethoxybenzidine 4゜4-diaminodiphenylsulfone), 4,4-diaminodiphenylsulfone, 3,3-diamino Diphenyl 3.3-Diaminodiphenylsulfone 4.4'-Diaminodiphenylctone, 4.4'-Diaminodiphenylethyl (
4-diaminonaphthalene 1,5-diaminonaphthalene, 2,4-bis(β-amino-tert-butyl)toluenebis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-△ -aminophenyl]benzene, bis(p-1,1-dimethyl-ter
t-aminopentyl)benzene 1-1 nogrovir-2
, 4-m-phenylenecyabane, m-xylene diamine, bis(4-aminophenyl) d, d'-p-xylene diamine, etc. In the present invention, these diamines modified into diisocyanates are used. May be used.
また、含フツ素ジアミン成分としては、上記ジアミン成
分のうち、アルキレン基を有するジアミンのアルキレン
鎖中の水素原子を全てフッ素原子に置換せしめたものが
用いられる。例えば、１゜３−ビス（アニリノ）へキサ
フルオロプロパン（４−ビス（アニリノ〕オクタフルオ
ロブタン（５−ビス（アニリノ）デカフルオロベンタン
（７−ビス（アニリノ）テトラデカフルオロへブタン、
２，２−ビス（４−アミノフェニル）へキサフルオロプ
ロパン、２，２−ビス（３−７ミノフエニル）へキサフ
ルオロプロパン、２．２−ビス（３−アミノ−４−メチ
ルフェニル）へキサフルオロプロパン ２，２−ビス（
４−アミノ−３−メチルフェニル）へキサフルオロプロ
パンなどの２核体の含フツ素芳香族ジアミンや、２，２
−ビス（４−（４−アミノフェノキン）フェニル〕へキ
サフルオロプロパン ２，２−ビス〔４−（３−アミノ
フェノキシ）フェニル〕へキサフルオロプロパン、２，
２−ビス（４−（２−アミノフェノキノ）フェニル〕へ
キサフルオロプロパン。Further, as the fluorine-containing diamine component, among the above-mentioned diamine components, a diamine having an alkylene group in which all hydrogen atoms in the alkylene chain are replaced with fluorine atoms is used. For example, 1° 3-bis(anilino)hexafluoropropane (4-bis(anilino)octafluorobutane (5-bis(anilino)decafluorobentane (7-bis(anilino)tetradecafluorohbutane),
2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-7minophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoro Propane 2,2-bis(
Dinuclear fluorine-containing aromatic diamines such as 4-amino-3-methylphenyl) hexafluoropropane, 2,2
-bis(4-(4-aminophenoquine)phenyl]hexafluoropropane 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,
2-bis(4-(2-aminophenoquino)phenyl)hexafluoropropane.
２．２−ビス（４−（２−アミノフェノキン〕−３，５
−ジメチルフェニル〕ヘキサフルオロプロパン、２，２
−ビス（４−（４−アミノ−２−トリフルオロメチルフ
ェノキシ）フェニル〕ヘキｔフルオロプロパン、２，２
−ビス（３−（３−アミノフェノキシ〕フェニル〕へキ
サフルオロプロパン２１，３−ビス（４−（４−アミノ
フェノキシ）フェニル〕へキサフルオロプロパン １，
３−ビス（４−（３−アミノフェノキシ）フェニル〕ヘ
キ？フルオロゾロパン １，４−ビス〔４−（４−アミ
ノフェノキン〕フェニル〕オクタフルオロブタン、１，
５−ビス（４−（４−アミノフェノキン）フェニル〕デ
カフルオロペンタン １゜５−ビス（４−（４−アミノ
−２−トリフルオロメチルフェノキシ）フェニル〕ヘキ
サフルオロペンタンなどの４核体の含フツ素芳香族ジア
ミンが挙げられる。これらの含フツ素芳香族ジアミンの
うち、低酵電率化の点から、２，２−ビス（４−アミノ
−２−アルキルフェニル）へキサフルオロプロパン、２
，２−ビス（４−アミノ−２−クロロフェニル）へキサ
フルオロプロパン ２．２−ビスＣ４−（４−アミノ−
２−アルキル−フェノキ／）フェニル〕へキサフルオロ
ブロノくン ２゜２−ビス（４−（４−アミノ−２−ク
ロロフェノキシ）フェニル〕へキサフルオロプロパン＋
２゜２−ビス（３−（４−アミノ−２−アルキルフェ
ノキン）フェニル〕へキサフルオロプロパン ２゜２−
ビス（３−（４−アミノ−２−クロロフェノキシ）フェ
ニル〕へキサフルオロプロパンヲ用いることが好ましい
。上記ジアミン成分はジインシアネートにｔさ換えて用
いてもよく、また二種以上を併用してもよい。2.2-bis(4-(2-aminophenoquine)-3,5
-dimethylphenyl]hexafluoropropane, 2,2
-bis(4-(4-amino-2-trifluoromethylphenoxy)phenyl)hextfluoropropane, 2,2
-bis(3-(3-aminophenoxy)phenyl]hexafluoropropane 21,3-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane 1,
3-bis(4-(3-aminophenoxy)phenyl]hex?fluorozolopane 1,4-bis[4-(4-aminophenoquine]phenyl)octafluorobutane, 1,
5-bis(4-(4-aminophenoquine)phenyl]decafluoropentane 1° 5-bis(4-(4-amino-2-trifluoromethylphenoxy)phenyl)hexafluoropentane and other tetranuclear compounds Among these fluorine-containing aromatic diamines, 2,2-bis(4-amino-2-alkylphenyl)hexafluoropropane, 2,2-bis(4-amino-2-alkylphenyl)hexafluoropropane,
,2-bis(4-amino-2-chlorophenyl)hexafluoropropane 2.2-bisC4-(4-amino-
2-alkyl-phenoxy/)phenyl hexafluorobrono 2゜2-bis(4-(4-amino-2-chlorophenoxy)phenyl)hexafluoropropane+
2゜2-bis(3-(4-amino-2-alkylphenoquine)phenyl]hexafluoropropane 2゜2-
It is preferable to use bis(3-(4-amino-2-chlorophenoxy)phenyl)hexafluoropropane.The above diamine component may be used in place of diincyanate, or two or more types may be used in combination. Good too.
本発明にて用いる含フッ累ポリイミドは、上記酸成分お
よびジアミノ成分のうち、少なくとも一万に含フッ累成
分を有するものを用い、Ｎ、Ｎ−ジメチルアセトアミド
やＮ−メチル−２−ピロリドンの如きＭ機極性溶媒中で
１通゛帛０〜９０℃にて１〜２４時間反応させて、ポリ
アミド酸とする。The fluorinated cumulative polyimide used in the present invention is one having a fluorinated cumulative component in at least 10,000 of the above acid components and diamino components, such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. The mixture is reacted once in a polar solvent at 0 to 90°C for 1 to 24 hours to obtain a polyamic acid.
本発明ではこの状態でキャスティングしたのち。In the present invention, after casting in this state.
加熱してイミド化してシート化したり、又、ポリアミド
酸浴液をさらに高温加熱したり、イミド化剤添加によっ
てイばド化を竹なって得られるポリイミド浴液をキャス
ティング、乾燥してシート化することができる。いずれ
の場合も、ポリアミド酸状態での固有粘度（Ｎ−メチル
−２−ピロリドン中０．５５／／ｄ６１１１！度、３１
１℃）を０．２〜７．０ 、好゛ましくは０，５・〜４
．０の範囲に調整することが、塗布作業性−？得られる
ポリイミドの機械的強度の点で望ましい。The polyimide bath solution is heated to imidize and form a sheet, or the polyamic acid bath solution is further heated to a high temperature, and the resulting polyimide bath solution is made into an imidizer by adding an imidizing agent, and the obtained polyimide bath solution is then dried to form a sheet. be able to. In both cases, the intrinsic viscosity in the polyamic acid state (0.55//d6111! degree in N-methyl-2-pyrrolidone, 31
1℃) from 0.2 to 7.0, preferably from 0.5 to 4.
．． Adjusting to a range of 0 improves coating workability. This is desirable in terms of the mechanical strength of the resulting polyimide.
上記のようＶこして得ろノ′しる宮フッ素ポリイミドは
誘電率が低く、絶縁性や機械的強度に優れるものである
が、屯合時の酸成分およびジアミノ成分の選択によって
は耐溶剤性に劣る場合がある。このような場合は５色合
性不飽和炭素結合を有するアミンクジアミン、ジカルボ
ン酸、トリカルボン酸、テトラカルボン酸、マレイン酸
、ナジック酸。As mentioned above, the fluorine polyimide obtained by V straining has a low dielectric constant and is excellent in insulation and mechanical strength, but depending on the selection of the acid component and diamino component at the time of combination, it may have poor solvent resistance. It may be inferior. In such cases, aminucdiamine, dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, maleic acid, and nadic acid having a pentachromic unsaturated carbon bond.
３〜エチル７タル酸、これらの無水物、エチニルアニリ
ノ、ンアノアニリンなどを添加して１合成分を変性、架
橋したり、フェノール注水酸基全カルボン酸を府する芳
香族ジアミン、例えばジアミノフェノール ３，３′−
ジヒドロキンベンジジン２．２−ビス（：３−アミノ−
４−ヒドロキシフェール）へキサフルオロプロパン、ン
アミノ安ａ、 否酸、カルボキシベンジンンなどで含フ
ツ素ポリイミドを変性、架橋して、耐浴剤性を向上させ
ることができる。Aromatic diamines containing all carboxylic acid groups, such as diaminophenol 3, 3'-
Dihydroquine benzidine 2,2-bis(:3-amino-
The bath agent resistance can be improved by modifying and crosslinking the fluorine-containing polyimide with 4-hydroxyphenol hexafluoropropane, amino acid, carboxybenzine, etc.
本発明の低誘電率シートは、上記含フツ素ポリイミドを
公知の方法にてシート化することによって得ることがで
さ、このシートはＩＭＨｚの周波数における誘電率が３
以丁であり、従来のものと比して極めて低く、プリント
配線基板の絶縁＃−？接看膚として用いることができる
。The low dielectric constant sheet of the present invention can be obtained by forming the above-mentioned fluorine-containing polyimide into a sheet by a known method, and this sheet has a dielectric constant of 3 at a frequency of IMHz.
The insulation of the printed wiring board is extremely low compared to conventional ones. It can be used for skin contact.
また２機械的強度の向上ヤ取り扱い性、経済性などの点
から、上記含フツ素ポリイミドを、多孔質基材１例えば
ガラスクロス ガラスペーパーガラスマットの如きガラ
ス繊維や、芳香族ポリアミド繊維、炭素繊維、炭化ケイ
素繊維、不織布の如き繊維、多孔質プラスチック基材な
どＶこ含浸させて低誘電率シートとすることもできる。In addition, from the viewpoints of improving mechanical strength, ease of handling, and economic efficiency, the above-mentioned fluorine-containing polyimide is used as a porous substrate 1, such as glass fiber such as glass cloth, glass paper, glass mat, aromatic polyamide fiber, carbon fiber, etc. , silicon carbide fibers, fibers such as nonwoven fabrics, porous plastic substrates, etc. can be impregnated with V to form a low dielectric constant sheet.
絶縁性ｆ低誘電率化の点から、基材をフッ素樹脂製とす
ることが好筐しぐ１例えば多孔質フッ素樹脂シートを基
材に用いることが好適である。From the viewpoint of insulation f and low dielectric constant, it is preferable to use a fluororesin as the base material. For example, it is preferable to use a porous fluororesin sheet as the base material.
このような多孔質基材は、孔径０．１〜５μｍで、空孔
率５０〜８５％程度のものを採用すると、含フツ素ポリ
イミドの含浸性ヤ誘電特性の向上から好ましい。It is preferable to employ such a porous base material having a pore diameter of 0.1 to 5 μm and a porosity of about 50 to 85%, since this improves the impregnability and dielectric properties of the fluorine-containing polyimide.
さらに２本発明の低誘電率シートを基材の片面もしくは
両面に設けて積１−板とし、該積層板を多）−回路基板
の内ノー基材間ｆ内Ｉ−基材と外層基材との接看用グリ
グレグとして用いることもできる。Further, two low dielectric constant sheets of the present invention are provided on one or both sides of the base material to form a laminated board, and the laminated board is formed between the inner base material of the circuit board and the inner base material and the outer layer base material. It can also be used as a grip for viewing.
Ｌ記基材としては目的に応じて任意のものが選択され１
例えば前記多孔質基材のほか７金属箔ヤ金属板、プラス
チックシートなどが用いられる。Any material may be selected as the base material L depending on the purpose.
For example, in addition to the porous substrate described above, metal foils, metal plates, plastic sheets, etc. can be used.
低誘電率化のためには、基材に言フッ累樹脂を用いるこ
とが好ましく、特にポリ四フッ化エチレンをガラス繊維
に言授させた複合基材を用いると。In order to lower the dielectric constant, it is preferable to use a fluorocarbon resin as the base material, especially a composite base material in which polytetrafluoroethylene is bonded to glass fiber.
例えば多層回路基板の製造Ｖこおける多ｌ１ｊｉ化工程
（，７１１］熱成形工程）での寸法安定性に優れ、内層
基材同士を接看する接４ｆ層として好適なものとなる。For example, it has excellent dimensional stability in the multilayer process (, 711) thermoforming process in the production of multilayer circuit boards, and is suitable as a contact layer that contacts inner layer base materials.
な２１本発明における低誘電率７−トの厚みは５〜５０
０μ恒、好ましくは１０〜３００μ慣とし、積層板とし
ての厚みは１０〜５，０００μへ、好ましくは５０〜３
，０００μｍとすることがよい。上記厚み範囲よジ小さ
いと耐電圧の点で好葦しくなく、また厚みが大＠すぎる
と、多ノー化する上で実用的でない。21 The thickness of the low dielectric constant 7-t in the present invention is 5 to 50
0 μ constant, preferably 10 to 300 μ, and the thickness of the laminate is 10 to 5,000 μ, preferably 50 to 3
,000 μm. If the thickness is smaller than the above range, it is unfavorable in terms of withstand voltage, and if the thickness is too large, it is not practical in terms of increasing the number of nodes.
〈実施例〉
以ＦＶＣ本発明の実施例を示し、さらに具体的に説明す
るう
実施例１
フラスコ内ＶＣ２，２−ビス（４−（４−１ミノフエノ
キシ〕フエニルＪヘキサフルオログロパン４４．０．９
（０，０８５モル）と、Ｎ−メチル−２−ピロリドン
３２７ｇを入れて撹拌【−、ジアミン成分を溶解した。<Example> Hereinafter, Examples of the FVC present invention will be shown and explained in more detail. Example 1 VC in flask 2,2-bis(4-(4-1 minophenoxy)phenyl J hexafluoroglopane 44.0. 9
(0,085 mol) and 327 g of N-methyl-2-pyrrolidone were added and stirred to dissolve the diamine component.
次いで、２，２−ビス（３，４−ジカルボキシフェニル
）へキサフルオロプロパンニ無水物３７．８、ｌｉ’
（０，０８５％ ル）を徐々ＶｃＲＤえ、その後、３０
℃以下の温度にて３時間撹＃を行ない、固形分調度２０
．０重量％のポリアミド酸Ｍ液を得た。なお、固有粘度
（Ｎ−メチル−２−ピロリドン中、０．５ｇ／ａｇ ｍ
ｉ 、 ３０−Ｃ） ｆ′１０．９４ テ２） ツｆｒ
ニー。Then, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropanihydride 37.8, li'
(0,085% le) gradually to VcRD, then 30
Stirring was carried out for 3 hours at a temperature below ℃, and the solid content was adjusted to 20.
．． A 0% by weight polyamic acid M solution was obtained. In addition, the intrinsic viscosity (in N-methyl-2-pyrrolidone, 0.5 g/ag m
i, 30-C) f'10.94 Te2) TSfr
knee.
得られたポリアミド酸浴液２０４ｇを１６ （Ｊ ℃に
加熱しながら２４時間撹拌し、脱水閉環、イミド化を行
なった。固有粘度（上記と同条件）は０．６０であつ之
、
得らｎたポリイミド浴液を水中に排出し、メタノール洗
浄後、 １２０℃で２４時間減圧乾燥して含フツ素ポリ
イミド粉末１９．８．９を得た。204 g of the obtained polyamic acid bath solution was stirred for 24 hours while heating to 16 J °C to perform dehydration, ring closure, and imidization.The intrinsic viscosity (under the same conditions as above) was 0.60. The polyimide bath solution was discharged into water, washed with methanol, and then dried under reduced pressure at 120° C. for 24 hours to obtain fluorine-containing polyimide powder 19.8.9.
上記にて得たポリイミド粉末を金型に入れ、３００℃、
７０に９／ｃＡで３０分間、 ７１１２熱、７７１１
１圧ｆｆ形り、厚す０．３朗の低誘電率シートを得た。The polyimide powder obtained above was put into a mold, heated to 300°C,
70 to 9/cA for 30 minutes, 7112 fever, 7711
A low dielectric constant sheet of 1 pressure FF shape and a thickness of 0.3 mm was obtained.
このシートの誘電率、誘電正接１休積抵抗率をＪＩＳ
Ｃ６４８１に従って測定したところ、２．７（ＩＭＨｚ
） 、 Ｏ，ＵＯ２（ＩＭＨｚ ） 、 ｌＸｌ０”
Ω−４であり、極めて低い誘電率を有するものであった
。The permittivity and dielectric loss tangent of this sheet are JIS
When measured according to C6481, it was 2.7 (IMHz
), O, UO2(IMHz), lXl0”
It had an extremely low dielectric constant of Ω-4.
次に、上記低誘電率シートに厚み３５μ煤の銅箔を載置
し、２８０℃、７０に９／ｃ４で１５分間加熱カｎ圧成
形し、銅張積層板を得た。Next, a copper foil having a thickness of 35 μm was placed on the low dielectric constant sheet, and heated and pressed at 280° C. and 70° C. for 15 minutes to obtain a copper-clad laminate.
この積層板の鋼蒲引き剥し強さをＪＩＳ Ｃ６４８１に
従って測定したところ、常温で２．９々／ｃｌｒ、２６
０℃のハンダ浴に１２０秒間浸漬後で２．７ｋｇ１−と
強接着状態でめった。When the steel peel strength of this laminate was measured according to JIS C6481, it was 2.9/clr, 26
After being immersed in a solder bath at 0° C. for 120 seconds, it was soldered with a strong bond of 2.7 kg.
実施例２
実施例ＩＶｒＣて得たポリアミド酸溶液をアプリケータ
にてガラス板上に流延塗布し、ｉｏｏ℃、 ２００′Ｃ
１３００℃にて−ｆ：ｆＬそれ１時間ずつ段階加熱し。Example 2 The polyamic acid solution obtained in Example IVrC was cast onto a glass plate using an applicator, and heated at 200'C.
Heating was carried out stepwise at 1300° C. using -f:fL for 1 hour each.
含フツ素ポリイミドからなる厚み４０〜５０μｍの低誘
電率シートを得た。A low dielectric constant sheet made of fluorine-containing polyimide and having a thickness of 40 to 50 μm was obtained.
このシートの誘電率および誘電正接は２．７ （ＩＭＨ
ｚ ） ０．００２ （ＩＭＨｚ ）であった。The dielectric constant and dielectric loss tangent of this sheet are 2.7 (IMH
z) 0.002 (IMHz).
次に、上記低誘電率シートとメタ系アラミドクロス（デ
ュポン社製、厚み６０〜７０μｑｒＬ）を−ｆ：ｎぞＡ
５枚ずつ交互にＮね、最上層に厚み３５μｍの銅箔を滅
ばし、３００℃、７０ Ｋｆｌ／ｃＡで３０分１川刀口
熱刀日圧成形し、３５０μ情厚の銅張檀ノー板を得た。Next, the above-mentioned low dielectric constant sheet and meta-aramid cloth (manufactured by DuPont, thickness 60-70 μqrL) were placed in -f:nzoA.
Alternately lay out 5 sheets at a time, destroy a 35μm thick copper foil on the top layer, heat and press mold for 30 minutes at 300℃ and 70Kfl/cA, and make a 350μ thick copper clad wood board. I got it.
この積層板の誘電率２よび誘電正接は、３．０（１皿１
および０．０１ （ＩＭＨｚ ）であった。また銅箔引
さ剥し強さを実施例１と同様の方法にて測定したところ
、常温で２．２ Ｋｌｉ’／ｃｔｌ 、ノ・ンダ浴浸漬
後で２．０ゆ／ｃＡであった。The dielectric constant 2 and dielectric loss tangent of this laminate are 3.0 (1 plate 1
and 0.01 (IMHz). Further, the peel strength of the copper foil was measured in the same manner as in Example 1, and it was found to be 2.2 Kli'/ctl at room temperature and 2.0 Yu/cA after immersion in a non-da bath.
実施例３
実施例Ｉ ＶＣで得たポリイミド溶液を厚さ１００μｍ
のガラスクロス（日東紡社製）に含浸させ、 １００
′Ｃおよび２（）０℃にてそ几ぞれ６０分間ずつ乾燥し
て。Example 3 Example I A polyimide solution obtained by VC was made to a thickness of 100 μm.
Impregnated with glass cloth (manufactured by Nittobo),
Dry for 60 minutes at 20°C and 20°C.
含フッ素ポリイミド含有分７５型童％のプリプレグシー
トを得た。A prepreg sheet having a fluorine-containing polyimide content of 75% was obtained.
このプリプレグシートを１０枚重ね、最上層に３５ｐｍ
厚の銅箔を載置し、３００℃、７０ｋｇ／ｃ４で１５分
間加熱加圧成形し、９００μ情厚の銅張積層板を得た。Stack 10 of these prepreg sheets and add 35pm to the top layer.
A thick copper foil was placed thereon and heated and pressed at 300° C. and 70 kg/c4 for 15 minutes to obtain a copper-clad laminate with a thickness of 900 μm.
この積ｊ−板の誘電率および誘電正接はそれぞれ３．１
（ＩＭｆ（ｚ ） 、 （Ｊ、００２ （ＩＭＨｚ
）であり、銅箔引き剥し強さは常温で２．４ ｋｇ／ｄ
、ハンダ浴Ｖ漬後で２．４ｋｇ／ｄでめった。The dielectric constant and dielectric loss tangent of this product J-plate are each 3.1
(IMf(z), (J, 002 (IMHz)
), and the copper foil peel strength is 2.4 kg/d at room temperature.
, it was soldered at 2.4 kg/d after being immersed in a solder bath.
実施例４
フラスコ内に実施例１にて用いたテトラカルボン酸二無
水物およびジアミンをＯ，ｔ）８５モルずつ。Example 4 85 moles each of the tetracarboxylic dianhydride and diamine used in Example 1 were placed in a flask.
およびＮ、Ｎ−ジメチルアセトアミド３００ ｇ、
トルエン４０ｇを人ｎ、窒素ガス雰囲気丁、室温にて一
夜撹拌を続け゛Ｃポリアミド酸溶液を得た。and 300 g of N,N-dimethylacetamide,
40 g of toluene was stirred overnight at room temperature under a nitrogen gas atmosphere to obtain a polyamic acid solution.
さらに温度を１６０℃まで昇温して８時間反応させ、脱
水閉環、イミド化を行ない、室温まで放冷して含フツ素
ポリイミド溶液を得た。The temperature was further raised to 160° C. and reacted for 8 hours to perform dehydration ring closure and imidization, and the mixture was allowed to cool to room temperature to obtain a fluorine-containing polyimide solution.
得らｆ″Ｌ７’（ポリイミド浴液を実施例１と同様にし
て粉末化し、この粉末を１０匝菫％濃度となるようにメ
チルエチルケトン９０１１に再浴解した。The obtained polyimide bath liquid was powdered in the same manner as in Example 1, and the powder was re-dissolved in methyl ethyl ketone 9011 to a concentration of 10% violet.
次に、この溶液に平均孔径３μｍ、空孔率８０％。Next, this solution had an average pore diameter of 3 μm and a porosity of 80%.
厚さ１００μ想の多孔質四フフ化エチレンシートを浸漬
、含浸させて、 １００℃で１０分間乾燥した。A porous polytetrafluoroethylene sheet with a thickness of approximately 100 μm was dipped and impregnated, and dried at 100° C. for 10 minutes.
上記と同様の浸漬、含浸操作を３回繰り返し。Repeat the same dipping and impregnating operations as above three times.
含フッ素ポリイミド含■率５０屯量％の低誘電率シート
を得た。このシートの誘電率は２．４ （ＩＭＨｚ ）
。A low dielectric constant sheet having a fluorine-containing polyimide content of 50% by weight was obtained. The dielectric constant of this sheet is 2.4 (IMHz)
.
誘電正接は０．００１ （ＩＭＨｚ ）であった。The dielectric loss tangent was 0.001 (IMHz).
次に、ガラスクロスに上記にて得た含フツ素ポリイミド
ｍ液を７５重量％となるように含浸してシート（内ノー
基材）とし、その両面に上記低誘電率シートおよび１８
μｍＳ−の銅箔を載置し、３２０℃。Next, glass cloth was impregnated with 75% by weight of the fluorine-containing polyimide m liquid obtained above to form a sheet (inner base material), and the low dielectric constant sheet and 18
A μmS- copper foil was placed at 320°C.
５０ ＫＩＩ／ｃ４で２０分間力ロ熱刀Ｉ圧することに
よって。By applying pressure at 50 KII/c4 for 20 minutes.
一体化された両面鋼張の積層板（厚み４００μｍ）を得
た（第１図参照）。この積＋ｍ板の誘電率および誘電正
接はｌ ＩｖｌＨｚで、それぞれ２．８および０．００
１６であった。An integrated double-sided steel-clad laminate (thickness: 400 μm) was obtained (see FIG. 1). The dielectric constant and dielectric loss tangent of this product + m plate are 2.8 and 0.00, respectively, at l IvlHz.
It was 16.
実施例５
テトラカルボン酸としてピロメリット酸二無水物を用い
た以外は、実施例４と同様にしてポリアミド酸浴液を得
た。Example 5 A polyamic acid bath solution was obtained in the same manner as in Example 4 except that pyromellitic dianhydride was used as the tetracarboxylic acid.
次に、この溶液ｌｏｇ ｉｃメメチエチルケトン３０ｇ
を加えて平均孔径１μ塩、空孔率７２％、４牟８０μｍ
の多孔質四フッ化エチレンシートに含浸させ。Next, this solution log ic memethiethyl ketone 30g
with an average pore diameter of 1 μm, porosity of 72%, and 4 μm of 80 μm.
impregnated into a porous tetrafluoroethylene sheet.
１００℃で１５分間、２５０’Ｃで６０分間、３００℃
で６０分間段階的に加熱乾燥を行ない、含フツ素ポリイ
ミド含有率が４１ Ｍ量％の低誘電率シート（厚み８０
μ想）を得た。このシートの誘電率および誘電正接はｌ
＋Ｖｆ（ｚで、それぞれ２．８および０．００１５であ
った。100'C for 15 minutes, 250'C for 60 minutes, 300'C
A low dielectric constant sheet with a fluorine-containing polyimide content of 41 M% (thickness 80
I got the μ idea). The dielectric constant and dielectric loss tangent of this sheet are l
+Vf(z) were 2.8 and 0.0015, respectively.
一万、ガラスクロスに四フッ化エチレンヲ７５重量％と
なるように含浸して誘電体シート（厚み１００μｍ）に
したものを２枚重ね、その両面に１８μ惰厚の銅箔を配
設して、３８０℃、５０に９／ｃ４で３０分間ＺＪＯ熱
加圧することによって、一体化された両面銅張の積Ｉ―
板（厚み１３５μ惰）とし、さらにエツチングＶこでパ
ターン加工を施こして内層基材とした。10,000, two dielectric sheets (thickness 100 μm) were made by impregnating 75% by weight of tetrafluoroethylene into glass cloth, and copper foil with a thickness of 18 μm was placed on both sides. The integrated double-sided copper-clad product I-
A plate (thickness: 135 μm) was prepared, and a pattern was processed using V-etching to obtain an inner layer base material.
次に、第２図に示すように、内メー基材、低誘電率シー
ト、誘電体１所、＠箔（厚み１８μｍ）を積層し、３２
０℃、５０＃／ｃ４で２０分間カロ熱訓圧を行ない。Next, as shown in FIG.
Calorie heat conditioning was performed at 0°C and 50 #/c4 for 20 minutes.
−本化された多層回路基板を作製した。- A full-sized multilayer circuit board was produced.
比較例１
実施例４に２いて、ポリイミドをピロメリット酸二無水
物と、４．４’−ジアミノフェニルエーテルから得た以
外は、同様の操作を行ない、ポリイミドが５０重′ｆ＃
、％含浸した多孔質四フフ化エチレンシートを作製した
。このシートの誘電率および誘電正接は、 ＩＭＨｚ
ＶＣおいてそれぞれ２．８および０．００３であった。Comparative Example 1 The same procedure as in Example 4 was carried out except that the polyimide was obtained from pyromellitic dianhydride and 4,4'-diaminophenyl ether.
A porous tetrafluoroethylene sheet impregnated with . The dielectric constant and dielectric loss tangent of this sheet are IMHz
VC was 2.8 and 0.003, respectively.
また、上記シートを用いて実施１１＋’Ｕ ４と同様の
操作を行ない両面鋼張の積層板を作製したが、誘電率お
よび誘電正接は、 ＩＭＨｚにおいて４．０およびｏ、
ｏ ｏ ｓであった。In addition, a double-sided steel-clad laminate was prepared using the above sheet in the same manner as in Example 11+'U4, but the dielectric constant and dielectric loss tangent were 4.0 and o at IMHz.
It was oos.
実施例６ 実施例４Ｖこて得た含フッ累ポリイミド溶液を。Example 6 Example 4 A fluorine-containing polyimide solution obtained using a V trowel.
キャスティング法にて５０μ恒厚の低誘電率シートを得
た。A low dielectric constant sheet with a constant thickness of 50 μm was obtained by a casting method.
一万、上記含フッ素ポリイミド浴液を１００μ恒厚のガ
ラスクロスＫ ５５ ｆ（−ｌ１％となるように含浸。10,000, impregnated glass cloth K 55 f (-l1%) with a constant thickness of 100μ with the above fluorine-containing polyimide bath solution.
乾燥させて内１−基材とし、その両面Ｖこ上記低誘電率
シートおよび１８μ惧厚の銅箔を順次配設し。After drying, a low dielectric constant sheet and an 18 μm thick copper foil were successively arranged on both sides of the base material.
３３０℃、６０に９／ｃ４で２０分間加熱加圧して、積
Ｊ−板（第１図参照）を得た。この積層板の誘電率およ
び誘電正接は、 ＩＭＨｚ ＶＣ寂いてそれぞれ３．１
および０．００２であった。The product was heated and pressed at 330 DEG C. and 60° C.9/c4 for 20 minutes to obtain a J-shaped plate (see FIG. 1). The dielectric constant and dielectric loss tangent of this laminate are 3.1 and 3.1, respectively.
and 0.002.
実施例７
実施例５にて得られたポリアミド酸溶液を１１３０μ恒
厚のガラスクロスに會浸率５８１蓋％となるようにして
含浸させた以外は、同様にして低誘電率シートＡを作製
した。このシートの誘電率および誘電正接ば、 ＩＭＨ
ｚに２いて−を几それ３．７および０．００４であった
。Example 7 Low dielectric constant sheet A was produced in the same manner as in Example 5, except that a glass cloth with a constant thickness of 1130 μm was impregnated with the polyamic acid solution obtained in Example 5 at a coverage rate of 581%. . If the dielectric constant and dielectric loss tangent of this sheet are, IMH
z was 3.7 and 0.004.
上記にて得た低誘電率シートＡを内Ｉ−基材として七の
両面に、実施例６にて得た低誘電率シートおよび１８μ
恒厚の銅箔を順次配設し、３；３０℃、６０に９／ｃＡ
で２０分間加熱加圧して積ｊ−板とした。誘電４２よび
誘電正接は、 ＩＭＨｚにおいてそれぞれ３．３および
０．Ｏ１２でめった。The low dielectric constant sheet A obtained in Example 6 and the 18μ
Copper foil of constant thickness was placed in sequence, 3:30℃, 9/cA at 60
This was heated and pressurized for 20 minutes to form a stacked J-board. The dielectric 42 and dissipation tangent are 3.3 and 0.3 at IMHz, respectively. I missed O12.
な２．多層回路基板の接着用グリプレグとして上記積層
板の銅箔層をエツチングしたものを用いることができる
口
実施例８
実施例４においてジアミン成分を４，４−ジアミノジフ
ェニルエーテルを用いた以外は、実施例４と同様にして
ポリアミド酸溶液を得た。2. Example 8 The etched copper foil layer of the above laminate can be used as a grippreg for adhesion of multilayer circuit boards. Example 4 Example 4 except that 4,4-diaminodiphenyl ether was used as the diamine component in Example 4. A polyamic acid solution was obtained in the same manner as above.
得られたポリアミド酸ｍ液を実施例７と同様にしてガラ
スクロスに含浸させ、含浸４５０ルｔ％の低誘電率シー
トＢを作製した。このシートの誘電率および誘電正接は
、 ＩＭＨｚにおいてそれぞれ３．８および０．００４
でめった。A glass cloth was impregnated with the obtained polyamic acid m solution in the same manner as in Example 7 to produce a low dielectric constant sheet B with an impregnation of 450 t%. The dielectric constant and dielectric loss tangent of this sheet are 3.8 and 0.004, respectively, at IMHz.
I failed.
と記にて得た低誘電率シー）Ｂを内層基材とした以外は
実施例７と同様にして積層板を作製〔７た。A laminate was produced in the same manner as in Example 7, except that the low dielectric constant sheet) B obtained in Example 7 was used as the inner layer base material.
誘電率および誘電正接ば、 ＩＭＨｚにおいて−ｆ：ｎ
ぞれ３．３および０．００３であった。If permittivity and dielectric loss tangent, -f:n at IMHz
They were 3.3 and 0.003, respectively.
実施例９
実施例６における低誘電率シートの厚みを２０（）μ惰
とし７た以外は同様にして低誘電率シート（誘電率２．
７）を作製した。一方、四フッ化エチレン含浸ガラスク
ロスを誘電体層とする３００μ恒厚の両面鋼張基板（エ
ツチングパターン加工したもの）を内層材（誘電率２．
５）とじ−Ｃ１その両面に上記低誘電率シートを接着層
として介在させて１８μｍ厚の電解鋼箔を配設し、３１
０℃、ｓｏＱ／ｃ４で２０分間加熱加圧することによっ
て多ノー回路基板を作製した。Example 9 A low dielectric constant sheet (dielectric constant 2.0 μm) was prepared in the same manner as in Example 6 except that the thickness of the low dielectric constant sheet was changed to 20 μm.
7) was produced. On the other hand, a double-sided steel-clad substrate (with an etching pattern) having a constant thickness of 300 μm and a dielectric layer made of tetrafluoroethylene-impregnated glass cloth was used as an inner layer material (dielectric constant 2.
5) Binding-C1 Electrolytic steel foil with a thickness of 18 μm is placed on both sides of the sheet with the above-mentioned low dielectric constant sheet interposed as an adhesive layer, and 31
A multi-no circuit board was prepared by heating and pressurizing at 0° C. and soQ/c4 for 20 minutes.
実施例１０
実施例９Ｖこおいて、含フツ素ポリイミドをＩｔ）０μ
恒厚のガラス繊維ｖｃ６０＠童％含浸させた基材の両面
に％１００μ毒厚の會フッ素ポリイミドシート（実施例
６参照）を接着ｊ−として配設した以外は。Example 10 In Example 9V, the fluorine-containing polyimide was
Except that a fluoropolyimide sheet (see Example 6) with a thickness of 100 μm was disposed as an adhesive on both sides of the base material impregnated with glass fiber VC60 of constant thickness.
同様にして多層回路基板を作製した。A multilayer circuit board was produced in the same manner.
〈発明の効果〉
本発明の低誘電率シート、積層板および多層回路基板は
、以上のように特定の含フツ素ポリイミドを用いている
ので、従来品と比べて誘電率が小さく、信号伝播の高速
化が可能となるものである。<Effects of the Invention> The low dielectric constant sheets, laminates, and multilayer circuit boards of the present invention use the specific fluorine-containing polyimide as described above, so they have a lower dielectric constant than conventional products, and have improved signal propagation. This makes it possible to increase the speed.
また、ガラス繊維とふっ素樹脂の複合基板を内層材とし
て多Ｉ−基板を作製する場合、従来はふっ素樹脂を接着
層として用いていたが１本発明の低誘＋を率シートを接
斬ｌ緬とすｒしば、比較的低温−ドでの積７ｆｌｉｌが
可能であるために、、ｖＯ工１ｇ、ｆ寸法安定性にも優
れるものである。In addition, when producing a multi-I substrate using a composite substrate of glass fiber and fluororesin as an inner layer material, fluororesin was conventionally used as an adhesive layer, but the low dielectric strength sheet of the present invention is used as an adhesive layer. Moreover, since it is possible to achieve a product of 7flI at a relatively low temperature, it also has excellent VO process 1g and f dimensional stability.
第１図は両面に銅箔を張着した不発明の＆ｊ−板の分解
断面図、第２図は本発明の多層回路基板の分解断面図を
示す。
１・・・内層基材、 ２・・・低誘゛邂率シート、
３・・・＠箔、 ４・・・エツチングパターン、
５・・・２Ｅ１体シートFIG. 1 is an exploded cross-sectional view of an uninvented &j-board with copper foil pasted on both sides, and FIG. 2 is an exploded cross-sectional view of a multilayer circuit board of the present invention. 1... Inner layer base material, 2... Low dielectric constant sheet,
3... @ foil, 4... etching pattern,
5...2E1 body sheet
Claims (12)
＿２の少なくとも一方の基にパーフルオロアルキレン基
を含む〕 で表わされる繰り返し単位を有する含フッ素ポリイミド
を用いてなる低誘電率シート。(1) General formula (I), ▲Mathematical formulas, chemical formulas, tables, etc.▼...(I) [However, Ar_1 is a tetravalent aliphatic group or aromatic group. Ar_2 represents a divalent aromatic group, and Ar_1 and Ar
At least one group of _2 contains a perfluoroalkylene group] A low dielectric constant sheet made of a fluorine-containing polyimide having a repeating unit represented by the following.
等があります▼であり、Ｒｆ＿１がパーフルオロアルキ
レン基である請求項（１）記載の低誘電率シート。(2) The low dielectric constant sheet according to claim (1), wherein Ar_1 in general formula (I) is ▲a numerical formula, chemical formula, table, etc.▼, and Rf_1 is a perfluoroalkylene group.
ある 請求項（２）記載の低誘電率シート。(3) The low dielectric constant sheet according to claim (2), wherein Rf_1 is a type selected from ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼.
およびＹが同一もしくは異なるアルキル基、フッ化アル
キル基から選ばれる少なくとも一種、ｎが０または１、
ｍが０〜４の整数、ｌが０〜４の整数である請求項（１
）記載の低誘電率シート。(4) Ar_2 in general formula (I) is represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Rf_2 is a perfluoroalkylene group,
and Y is the same or different alkyl group, at least one selected from fluorinated alkyl group, n is 0 or 1,
Claim (1) wherein m is an integer of 0 to 4, and l is an integer of 0 to 4.
) low dielectric constant sheet.
含フッ素ポリイミドを多孔質基材に含浸してなる低誘電
率シート。(5) A low dielectric constant sheet obtained by impregnating a porous base material with a fluorine-containing polyimide having a repeating unit represented by the general formula (I).
項（５）記載の低誘電率シート。(6) The low dielectric constant sheet according to claim (5), wherein the porous base material is a porous fluororesin sheet.
を、基材の片面もしくは両面に設けてなる積層板。(7) A laminate comprising the low dielectric constant sheet according to claim (1) or (5) provided on one or both sides of a base material.
なる多層回路基板。(8) A multilayer circuit board using the laminate according to claim (7) as an adhesive layer.
ート側に、金属箔層を設けてなる積層板。(9) The laminate according to claim (7), wherein a metal foil layer is provided on the low dielectric constant sheet side.
トを、一般式（Ｉ）で表わされる繰り返し単位を有する
含フッ素ポリイミドが含浸された多孔質基材の片面もし
くは両面に設けてなる積層板。(10) The low dielectric constant sheet according to claim (1) or (5) is provided on one or both sides of a porous base material impregnated with a fluorine-containing polyimide having a repeating unit represented by general formula (I). Laminated board.
いてなる多層回路基板。(11) A multilayer circuit board using the laminate according to claim (10) as an adhesive layer.
率シート側に金属箔層を設けてなる積層板。(12) The laminate according to claim 10, wherein a metal foil layer is provided on the low dielectric constant sheet side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2949389A JPH02208324A (en) | 1989-02-08 | 1989-02-08 | Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2949389A JPH02208324A (en) | 1989-02-08 | 1989-02-08 | Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02208324A true JPH02208324A (en) | 1990-08-17 |
Family
ID=12277595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2949389A Pending JPH02208324A (en) | 1989-02-08 | 1989-02-08 | Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02208324A (en) |
Cited By (9)
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|---|---|---|---|---|
| JPH04352387A (en) * | 1991-05-29 | 1992-12-07 | Kyocera Corp | Multilayer circuit board and manufacture thereof |
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| JP2001151929A (en) * | 1999-11-29 | 2001-06-05 | Ube Ind Ltd | Method for manufacturing porous polyimide film and film |
| JP2001217554A (en) * | 1999-11-26 | 2001-08-10 | Toppan Printing Co Ltd | Multilayer wiring board |
| WO2006022207A1 (en) * | 2004-08-23 | 2006-03-02 | Mitsubishi Gas Chemical Company, Inc. | Metal-clad white laminate |
| JP2006110999A (en) * | 2004-08-23 | 2006-04-27 | Mitsubishi Gas Chem Co Inc | Metal clad white laminated body |
| WO2016002775A1 (en) * | 2014-07-03 | 2016-01-07 | ダイキン工業株式会社 | Metal-clad laminated plate |
| JP2021178956A (en) * | 2020-05-11 | 2021-11-18 | ダイキン工業株式会社 | Fluorinated amide compound, fluorinated nitrogen-containing heterocyclic compound, and fluorinated compound |
| WO2023219085A1 (en) * | 2022-05-09 | 2023-11-16 | ダイキン工業株式会社 | Fluorinated polyamide compound, fluorinated polyimide compound, low dielectric material, and high-frequency electronic component |
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| JPS63500185A (en) * | 1985-11-25 | 1988-01-21 | ヒユ−ズ・エアクラフト・カンパニ− | Manufacturing method, products and uses of high molecular weight polyimide |
| JPS62127827A (en) * | 1985-11-29 | 1987-06-10 | Hitachi Chem Co Ltd | Composition for oriented film for liquid crystal |
| JPS6369637A (en) * | 1986-09-11 | 1988-03-29 | 松下電工株式会社 | Printed wiring substrate |
| JPH02151630A (en) * | 1988-09-30 | 1990-06-11 | Hoechst Celanese Corp | Polymer obtained from 2-(3-aminophenyl)- 2-(4-aminophenyl)hexafluoropropane |
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| JPH04352387A (en) * | 1991-05-29 | 1992-12-07 | Kyocera Corp | Multilayer circuit board and manufacture thereof |
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| JPH07233325A (en) * | 1991-10-25 | 1995-09-05 | Internatl Business Mach Corp <Ibm> | Radiation-reactive composition |
| US5780199A (en) * | 1991-10-25 | 1998-07-14 | International Business Machines Corporation | Polyamic acid and polyimide from fluorinated reactant |
| JP2001217554A (en) * | 1999-11-26 | 2001-08-10 | Toppan Printing Co Ltd | Multilayer wiring board |
| JP2001151929A (en) * | 1999-11-29 | 2001-06-05 | Ube Ind Ltd | Method for manufacturing porous polyimide film and film |
| WO2006022207A1 (en) * | 2004-08-23 | 2006-03-02 | Mitsubishi Gas Chemical Company, Inc. | Metal-clad white laminate |
| JP2006110999A (en) * | 2004-08-23 | 2006-04-27 | Mitsubishi Gas Chem Co Inc | Metal clad white laminated body |
| US8642181B2 (en) | 2004-08-23 | 2014-02-04 | Mitsubishi Gas Chemical Company, Inc. | Metal-clad white laminate |
| WO2016002775A1 (en) * | 2014-07-03 | 2016-01-07 | ダイキン工業株式会社 | Metal-clad laminated plate |
| JP2016026926A (en) * | 2014-07-03 | 2016-02-18 | ダイキン工業株式会社 | Metal-clad laminated plate |
| JP2021178956A (en) * | 2020-05-11 | 2021-11-18 | ダイキン工業株式会社 | Fluorinated amide compound, fluorinated nitrogen-containing heterocyclic compound, and fluorinated compound |
| WO2023219085A1 (en) * | 2022-05-09 | 2023-11-16 | ダイキン工業株式会社 | Fluorinated polyamide compound, fluorinated polyimide compound, low dielectric material, and high-frequency electronic component |
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