JP2016032098A - Resin substrate for circuit board, resin composition for circuit board, and circuit board - Google Patents
Resin substrate for circuit board, resin composition for circuit board, and circuit board Download PDFInfo
- Publication number
- JP2016032098A JP2016032098A JP2015106299A JP2015106299A JP2016032098A JP 2016032098 A JP2016032098 A JP 2016032098A JP 2015106299 A JP2015106299 A JP 2015106299A JP 2015106299 A JP2015106299 A JP 2015106299A JP 2016032098 A JP2016032098 A JP 2016032098A
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- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- circuit board
- polymer
- resin substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title claims abstract description 71
- 239000011347 resin Substances 0.000 title claims abstract description 71
- 239000011342 resin composition Substances 0.000 title claims description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 68
- 125000004432 carbon atom Chemical group C* 0.000 claims description 62
- 239000003960 organic solvent Substances 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000000732 arylene group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000002635 aromatic organic solvent Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- -1 bis (trifluoromethyl) phenyl group Chemical group 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000012783 reinforcing fiber Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 4
- 229940087189 2,2,2-trifluoroacetophenone Drugs 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002954 polymerization reaction product Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- VEAFKIYNHVBNIP-UHFFFAOYSA-N 1,3-Diphenylpropane Chemical compound C=1C=CC=CC=1CCCC1=CC=CC=C1 VEAFKIYNHVBNIP-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- FBGHCYZBCMDEOX-UHFFFAOYSA-N 1-(2,3,4,5,6-pentafluorophenyl)ethanone Chemical compound CC(=O)C1=C(F)C(F)=C(F)C(F)=C1F FBGHCYZBCMDEOX-UHFFFAOYSA-N 0.000 description 1
- FCWITTYOAQFQCE-UHFFFAOYSA-N 1-(2,3,4,5,6-pentafluorophenyl)propan-1-one Chemical compound CCC(=O)C1=C(F)C(F)=C(F)C(F)=C1F FCWITTYOAQFQCE-UHFFFAOYSA-N 0.000 description 1
- OIKFIOGYFGWPAB-UHFFFAOYSA-N 1-(3-methoxypropyl)pyrrolidin-2-one Chemical compound COCCCN1CCCC1=O OIKFIOGYFGWPAB-UHFFFAOYSA-N 0.000 description 1
- NNFAFRAQHBRBCQ-UHFFFAOYSA-N 1-pentylpyrrolidin-2-one Chemical compound CCCCCN1CCCC1=O NNFAFRAQHBRBCQ-UHFFFAOYSA-N 0.000 description 1
- LUVQSCCABURXJL-UHFFFAOYSA-N 1-tert-butylpyrrolidin-2-one Chemical compound CC(C)(C)N1CCCC1=O LUVQSCCABURXJL-UHFFFAOYSA-N 0.000 description 1
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IKMBXKGUMLSBOT-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(F)C(F)=C(F)C(F)=C1F IKMBXKGUMLSBOT-UHFFFAOYSA-N 0.000 description 1
- LGCODSNZJOVMHV-UHFFFAOYSA-N 2-(2,3,4,5,6-pentafluorophenyl)acetic acid Chemical compound OC(=O)CC1=C(F)C(F)=C(F)C(F)=C1F LGCODSNZJOVMHV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PLMFIWDPKYXMGE-UHFFFAOYSA-N 2-chloro-9,10-diphenylanthracene Chemical compound C=12C=CC=CC2=C(C=2C=CC=CC=2)C2=CC(Cl)=CC=C2C=1C1=CC=CC=C1 PLMFIWDPKYXMGE-UHFFFAOYSA-N 0.000 description 1
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical compound CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 description 1
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- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 1
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- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 description 1
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- 229910052582 BN Inorganic materials 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 239000004952 Polyamide Substances 0.000 description 1
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- 239000004642 Polyimide Substances 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
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- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 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
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- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
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- 239000003017 thermal stabilizer Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
本発明は、回路基板に好適な樹脂基板、回路基板用樹脂組成物および前記樹脂基板を有する回路基板に関する。 The present invention relates to a resin substrate suitable for a circuit board, a resin composition for a circuit board, and a circuit board having the resin substrate.
携帯電話に代表される移動体通信機器では、処理速度の高速化のために、高周波の電気信号が用いられている。また、電気信号の伝播速度を高速化するために、半導体素子の小型化や、実装基板の高密度化などにより、配線の長さを短縮する方法もあるが、基板自体の比誘電率（εr）を低くすることによっても、伝播速度を高速化することができる。ところで、電気信号は高周波になればなるほど減衰しやすく、伝送損失が大きくなる傾向にある。このため基板には誘電正接（ｔａｎδ）の低い材料が求められている。さらに、移動体通信機器の使用態様が多様化するため、基板材料には、周波数や温度によって、εrやｔａｎδの変化が小さいことが求められている。このような材料としては、液晶ポリマー（ＬＣＰ）を用いた基板が知られている（特許文献１〜２）。 In mobile communication devices typified by mobile phones, high-frequency electrical signals are used to increase the processing speed. In order to increase the propagation speed of electric signals, there is a method of reducing the length of the wiring by reducing the size of the semiconductor element or increasing the density of the mounting substrate, but the relative dielectric constant (ε The propagation speed can also be increased by reducing r ). By the way, the electric signal tends to attenuate as the frequency becomes higher, and the transmission loss tends to increase. For this reason, a material having a low dielectric loss tangent (tan δ) is required for the substrate. Furthermore, since usage modes of mobile communication devices are diversified, the substrate material is required to have small changes in ε r and tan δ depending on the frequency and temperature. As such a material, a substrate using a liquid crystal polymer (LCP) is known (Patent Documents 1 and 2).
本発明は、比誘電率（εr）および誘電正接（ｔａｎδ）の値が小さく、さらに、比誘電率（εr）および誘電正接（ｔａｎδ）の周波数および温度に対する依存性の少ない回路基板用樹脂基板、それを用いた回路基板ならびに回路基板用樹脂組成物を提供することを課題としている。 The present invention has a specific dielectric constant (epsilon r) and the value of the dielectric loss tangent (tan [delta) is small, furthermore, the dielectric constant (epsilon r) and dielectric loss tangent (tan [delta) less dependent on the circuit resin substrate with respect to the frequency and temperature It is an object of the present invention to provide a substrate, a circuit substrate using the substrate, and a resin composition for a circuit substrate.
本発明は、次の〔１〕〜〔６〕に関する。
〔１〕下記式（１）で表される構造単位を有する重合体（Ａ）を少なくとも含有することを特徴とする回路基板用樹脂基板。
The present invention relates to the following [1] to [6].
[1] A circuit board resin substrate comprising at least a polymer (A) having a structural unit represented by the following formula (1).
〔２〕前記重合体（Ａ）が、前記式（１）で表される構造単位を５０質量％以上含有する、前記〔１〕に記載の回路基板用樹脂基板。
〔３〕前記式（１）中のＲ1とＥＷＧとの、ハメット（Hammett）置換基定数の差が、０．１〜２の範囲である、前記〔１〕または〔２〕のいずれかに記載の回路基板用樹脂基板。
〔４〕下記式（１）で表される構造単位を有する重合体（Ａ）と、有機溶剤（Ｂ）とを少なくとも含有することを特徴とする回路基板用樹脂組成物。
[2] The resin substrate for circuit boards according to [1], wherein the polymer (A) contains 50% by mass or more of the structural unit represented by the formula (1).
[3] The difference in Hammett substituent constant between R 1 and EWG in the formula (1) is in the range of 0.1 to 2, in either [1] or [2] The resin substrate for circuit boards as described.
[4] A resin composition for circuit boards, comprising at least a polymer (A) having a structural unit represented by the following formula (1) and an organic solvent (B).
〔５〕前記有機溶剤（Ｂ）が、芳香族系有機溶剤、ケトン系有機溶剤およびアミド系有機溶剤よりなる群から選ばれる少なくとも１種である、前記〔４〕に記載の回路基板用樹脂組成物。
〔６〕前記〔１〕〜〔３〕のいずれかに記載の回路基板用樹脂基板を有する回路基板。
[5] The resin composition for a circuit board according to [4], wherein the organic solvent (B) is at least one selected from the group consisting of an aromatic organic solvent, a ketone organic solvent, and an amide organic solvent. object.
[6] A circuit board having the resin substrate for circuit boards according to any one of [1] to [3].
本発明の回路基板用樹脂基板は、比誘電率（εr）の値が小さく、誘電正接（ｔａｎδ）の値が小さく、しかも比誘電率（εr）および誘電正接（ｔａｎδ）の周波数および温度への依存性がいずれも少ない。 The resin substrate for a circuit board of the present invention has a small value of relative dielectric constant (ε r ), a small value of dielectric loss tangent (tan δ), and a frequency and temperature of relative dielectric constant (ε r ) and dielectric loss tangent (tan δ). There is little dependence on.
本発明の回路基板用樹脂組成物は、本発明の回路基板用樹脂基板の製造に好適に用いることができる。本発明の回路基板は、本発明の回路基板用樹脂基板を有することから、精密機器用の回路基板として有用である。 The resin composition for circuit boards of this invention can be used suitably for manufacture of the resin board for circuit boards of this invention. Since the circuit board of the present invention has the resin substrate for circuit boards of the present invention, it is useful as a circuit board for precision instruments.
以下、本発明について具体的に説明する。
＜回路基板用樹脂組成物＞
本発明の回路基板用樹脂組成物は、重合体（Ａ）と、有機溶剤（Ｂ）とを含有するものであり、回路基板用樹脂基板の製造に適した樹脂組成物である。
Hereinafter, the present invention will be specifically described.
<Resin composition for circuit board>
The resin composition for circuit boards of this invention contains a polymer (A) and an organic solvent (B), and is a resin composition suitable for manufacture of the resin board for circuit boards.
重合体（Ａ）
重合体（Ａ）は、下記式（１）で表される構造単位を有する。
Polymer (A)
The polymer (A) has a structural unit represented by the following formula (1).
Ａr1およびＡｒ2は、それぞれ独立に、炭素数６〜３０のアリーレン基、または炭素数６〜３０のアリーレン基が有する少なくとも１つの水素原子を水酸基、ハロゲン原子又は１価の有機基に置き換えてなる基である。アリーレン基の炭素数は、好ましくは６〜１８、より好ましくは６〜１２である。 A r1 and Ar 2 each independently replaced arylene group having 6 to 30 carbon atoms, or at least one hydrogen atom has an arylene group having 6 to 30 carbon atoms hydroxyl, a halogen atom or a monovalent organic group Is a group. Carbon number of an arylene group becomes like this. Preferably it is 6-18, More preferably, it is 6-12.
Ａｒ1およびＡｒ2のアリーレン基は、単環でも多環でもよく、また縮合環であってもよい。前記炭素数６〜３０のアリーレン基としては、例えば、フェニレン基、ナフチレン基、およびアントリレン基が挙げられる。 The arylene group of Ar 1 and Ar 2 may be monocyclic or polycyclic, or may be a condensed ring. Examples of the arylene group having 6 to 30 carbon atoms include a phenylene group, a naphthylene group, and an anthrylene group.
前記ハロゲン原子としては、例えば、塩素原子、臭素原子、およびフッ素原子等のハロゲン原子が挙げられる。前記１価の有機基としては、例えば、メチル基、エチル基、プロピル基、およびノニル基等の炭素数１〜１２のアルキル基；シクロプロピル基、シクロヘキシル基、およびイソボルニル基等の炭素数３〜２０のシクロアルキル基；メトキシ基、エトキシ基、およびブトキシ基等の炭素数１〜１２のアルコキシ基；フェニル基、１−ナフチル基、および２−ナフチル基等の炭素数６〜１８のアリール基；並びにフェノキシ基等の炭素数６〜１８のアリーロキシ基が挙げられる。なお、上記アリーレン基が有してもよい、水酸基、ハロゲン原子及び１価の有機基から選ばれる置換基は、１種でもよく、２種以上でもよい。 As said halogen atom, halogen atoms, such as a chlorine atom, a bromine atom, and a fluorine atom, are mentioned, for example. Examples of the monovalent organic group include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a nonyl group; and 3 to 3 carbon atoms such as a cyclopropyl group, a cyclohexyl group, and an isobornyl group. An cycloalkyl group having 20 carbon atoms; an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; an aryl group having 6 to 18 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group; Moreover, C6-C18 aryloxy groups, such as a phenoxy group, are mentioned. The arylene group may have one or more substituents selected from a hydroxyl group, a halogen atom and a monovalent organic group.
Ｒ1は、炭素数１〜２０のアルキル基、または炭素数６〜３０のアリール基である。Ｒ1において、アルキル基の炭素数は、好ましくは１〜１２、より好ましくは１〜４であり、アリール基の炭素数は、好ましくは６〜１８、より好ましくは６〜１２である。前記炭素数１〜２０のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、およびデシル基が挙げられる。前記炭素数６〜３０のアリール基としては、例えば、フェニル基、１−ナフチル基、２−ナフチル基、および１−アントリル基が挙げられる。 R 1 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms. In R 1 , the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, and the aryl group preferably has 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group and decyl group are mentioned. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 1-anthryl group.
Ｒ2は、直接結合、炭素数１〜２０のアルカンジイル基、−Ｏ−、−Ｓ−、または、−（Ｒ3 2ＳｉＯ）a−である。ただしＲ3は、それぞれ独立に、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、または炭素数１〜１２のアルコキシ基であり、ａは１以上の整数である。Ｒ2がアルカンジイル基である場合、その炭素数は好ましくは１〜１８、より好ましくは１〜６である。前記炭素数１〜２０のアルカンジイル基としては、例えば、メチレン基、エタン−１，２−ジイル基、プロパン−１，３−ジイル基、ブタン−１，４−ジイル基、オクタン−１，８−ジイル基が挙げられる。Ｒ3における炭素数１〜２０のアルキル基および炭素数６〜３０のアリール基としては、前記Ｒ1で示した炭素数１〜２０のアルキル基および炭素数６〜３０のアリール基と同様の基が挙げられ、Ｒ3における炭素数１〜１２のアルコキシ基としては、前記１価の有機基で示した炭素数１〜１２のアルコキシ基と同様の基が挙げられる。 R 2 is a direct bond, an alkanediyl group having 1 to 20 carbon atoms, —O—, —S—, or — (R 3 2 SiO) a —. However R 3 are independently an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkoxy group having 1 to 12 carbon atoms, 6 to 30 carbon atoms, a is an integer of 1 or more. When R 2 is alkanediyl group, the number of carbon atoms is preferably 1 to 18, more preferably 1-6. Examples of the alkanediyl group having 1 to 20 carbon atoms include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and an octane-1,8. -A diyl group is mentioned. Examples of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 30 carbon atoms in R 3 are the same groups as the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 30 carbon atoms represented by R 1. Examples of the alkoxy group having 1 to 12 carbon atoms in R 3 include the same groups as the alkoxy group having 1 to 12 carbon atoms represented by the monovalent organic group.
ＥＷＧは、電子求引性基（electron withdrawing group）を示す。式（１）中におけるＥＷＧは、Ｒ1およびＥＷＧが結合する炭素の電子をＲ1よりも求引するもの、すなわちＲ1よりも電子求引性の高い基であればよい。上記式（１）において、Ｒ1とＥＷＧとのハメット（Hammett）置換基定数の差が、好ましくは０．１〜２、より好ましくは０．２〜１．５の範囲である。 EWG represents an electron withdrawing group. The EWG in the formula (1) may be any group that draws electrons of the carbon to which R 1 and EWG are bonded rather than R 1 , that is, a group having higher electron withdrawing properties than R 1 . In the above formula (1), the difference in Hammett substituent constant between R 1 and EWG is preferably in the range of 0.1 to 2, more preferably 0.2 to 1.5.
ＥＷＧとしては、例えば、炭素数１〜４のパーハロアルキル基、パーハロアリール基、パーハロアルキル基置換アリール基、ハロゲン原子、シアノ基、ニトロ基が挙げられる。パーハロアルキル基としては、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ノナフルオロブチル基等のパーフルオロアルキル基、パークロロアルキル基、パーブロモアルキル基が挙げられる。パーハロアリール基およびパーハロアルキル基置換アリール基としては、例えば、ペンタフルオロフェニル基、ビス（トリフルオロメチル）フェニル基が挙げられる。ハロゲン原子としては、例えば、フッ素、塩素、臭素およびヨウ素が挙げられる。 Examples of EWG include a perhaloalkyl group having 1 to 4 carbon atoms, a perhaloaryl group, a perhaloalkyl group-substituted aryl group, a halogen atom, a cyano group, and a nitro group. Examples of the perhaloalkyl group include a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group, a perchloroalkyl group, and a perbromoalkyl group. Examples of the perhaloaryl group and perhaloalkyl group-substituted aryl group include a pentafluorophenyl group and a bis (trifluoromethyl) phenyl group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
これらのＥＷＧの中でも、熱安定性の観点から、パーフルオロアルキル基、パーハロアリール基およびパーハロアルキル基置換アリール基が好ましく、トリフルオロメチル基、ペンタフルオロフェニル基およびビス（トリフルオロメチル）フェニル基がより好ましい。 Among these EWGs, from the viewpoint of thermal stability, a perfluoroalkyl group, a perhaloaryl group, and a perhaloalkyl group-substituted aryl group are preferable, and a trifluoromethyl group, a pentafluorophenyl group, and a bis (trifluoromethyl) phenyl group. Is more preferable.
ｎは０以上の整数であり、好ましくは０〜５の整数である。
本発明に係る重合体（Ａ）は、前記式（１）で表される構造単位を１種のみ含有してもよく、２種以上含有していてもよい。
n is an integer greater than or equal to 0, Preferably it is an integer of 0-5.
The polymer (A) according to the present invention may contain only one type of structural unit represented by the formula (1), or may contain two or more types.
本発明に係る重合体（Ａ）は、前記式（１）で表される構造単位を、好ましくは５０質量％以上、より好ましくは７０質量％以上、さらに好ましくは９９質量％以上含有する。構造単位の含有割合は、1Ｈ−ＮＭＲで測定した値である。
重合体（Ａ）は、１種単独で用いてもよく、２種以上を併用してもよい。
The polymer (A) according to the present invention preferably contains 50% by mass or more, more preferably 70% by mass or more, and further preferably 99% by mass or more of the structural unit represented by the formula (1). The content ratio of the structural unit is a value measured by 1 H-NMR.
A polymer (A) may be used individually by 1 type, and may use 2 or more types together.
重合体（Ａ）の製造方法
本発明の重合体（Ａ）は、例えば、下記式（ａ）で表される化合物（以下、化合物（ａ）ともいう）と、下記式（ｂ）で表される化合物（以下、化合物（ｂ）ともいう）とを、強酸の存在下で重縮合反応させることで得ることができる。
Production Method of Polymer (A) The polymer (A) of the present invention is represented by, for example, a compound represented by the following formula (a) (hereinafter also referred to as compound (a)) and the following formula (b). The compound (hereinafter also referred to as compound (b)) can be obtained by polycondensation reaction in the presence of a strong acid.
上記方法の反応条件および反応機構の詳細については、Macromolecules 2004, 37, 6227-6235、Macromolecules 2008, 41, 8504-8512、Chem. Commun., 2004, 1030-1031などの記載を参照することができる。 For details of the reaction conditions and reaction mechanism of the above method, the description of Macromolecules 2004, 37, 6227-6235, Macromolecules 2008, 41, 8504-8512, Chem. Commun., 2004, 1030-1031, etc. can be referred to. .
・化合物（ａ）
化合物（ａ）は、下記式（ａ）で表される。
Compound (a)
The compound (a) is represented by the following formula (a).
化合物（ａ）としては、例えば、ペンタフルオロフェニルメチルケトン、ペンタフルオロフェニルエチルケトン、トリフルオロメチルメチルケトン、および２，２，２−トリフルオロアセトフェノンが挙げられる。
化合物（ａ）は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the compound (a) include pentafluorophenyl methyl ketone, pentafluorophenyl ethyl ketone, trifluoromethyl methyl ketone, and 2,2,2-trifluoroacetophenone.
A compound (a) may be used individually by 1 type, and may use 2 or more types together.
・化合物（ｂ）
化合物（ｂ）は、下記式（ｂ）で表される。
Compound (b)
The compound (b) is represented by the following formula (b).
化合物（ｂ）としては、例えば、ベンゼン、ナフタレン、アントラセン、パラターフェニル、パラクオターフェニル、９，１０−ジフェニルアントラセン等の芳香族炭化水素；１，２−ジフェニルエタン、１，３−ジフェニルプロパン、１，４−ジフェニルブタン、１，８−ジフェニルオクタン等のジフェニルアルカン；ジフェニルエーテル等のジアリールエーテル；ジフェニルスルフィド等のジアリールチオエーテル；２−クロロ−９，１０−ジフェニルアントラセン等のハロゲン化物；が挙げられる。
化合物（ｂ）は、１種単独で用いてもよく、２種以上を併用してもよい。
化合物（ａ）と化合物（ｂ）との重縮合では、式（ｂ）中の水素原子に結合する芳香環炭素が、式（ａ）中の活性カルボニル炭素と結合して、重合体が形成される。
Examples of the compound (b) include aromatic hydrocarbons such as benzene, naphthalene, anthracene, paraterphenyl, paraquaterphenyl, and 9,10-diphenylanthracene; 1,2-diphenylethane, 1,3-diphenylpropane, Diphenylalkanes such as 1,4-diphenylbutane and 1,8-diphenyloctane; diaryl ethers such as diphenyl ether; diaryl thioethers such as diphenyl sulfide; halides such as 2-chloro-9,10-diphenylanthracene;
A compound (b) may be used individually by 1 type, and may use 2 or more types together.
In the polycondensation of the compound (a) and the compound (b), the aromatic ring carbon bonded to the hydrogen atom in the formula (b) is bonded to the active carbonyl carbon in the formula (a) to form a polymer. The
・強酸
重合体（Ａ）の製造において、強酸は、上述の化合物（ａ）および化合物（ｂ）の重縮合反応の触媒として用いる。
-Strong acid In manufacture of a polymer (A), a strong acid is used as a catalyst of the polycondensation reaction of the above-mentioned compound (a) and a compound (b).
強酸としては、例えば、トリフルオロ酢酸、ペンタフルオロフェニル酢酸、フルオロスルホン酸、クロロスルホン酸、メタンスルホン酸、トリフルオロメタンスルホン酸、炭素数２以上のパーフルオロアルカンスルホン酸（例えば、Ｃ2Ｆ5ＳＯ3Ｈ、Ｃ4Ｆ9ＳＯ3Ｈ、Ｃ5Ｆ11ＳＯ3Ｈ、Ｃ6Ｆ13ＳＯ3Ｈ、およびＣ8Ｆ17ＳＯ3Ｈ）、ペンタフルオロフェニルスルホン酸、ペンタフルオロプロピオン酸が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いることもできる。 Examples of the strong acid include trifluoroacetic acid, pentafluorophenylacetic acid, fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, perfluoroalkanesulfonic acid having 2 or more carbon atoms (for example, C 2 F 5 SO 3 H, C 4 F 9 SO 3 H, C 5 F 11 SO 3 H, C 6 F 13 SO 3 H, and C 8 F 17 SO 3 H) , pentafluorophenyl sulfonic acid, pentafluoropropionic acid . These may be used alone or in combination of two or more.
触媒の好適例としては、トリフルオロメタンスルホン酸を単独で使用する例、トリフルオロメタンスルホン酸と、メタンスルホン酸およびトリフルオロ酢酸から選ばれる少なくとも１種とを組み合わせて使用する例が挙げられる。
強酸は、１種以上の化合物（ａ）の合計１モルに対して、通常０．０１〜１００モル、好ましくは０．１〜５０モルの量で用いることができる。
Preferable examples of the catalyst include an example in which trifluoromethanesulfonic acid is used alone, and an example in which trifluoromethanesulfonic acid is used in combination with at least one selected from methanesulfonic acid and trifluoroacetic acid.
The strong acid can be used in an amount of usually 0.01 to 100 mol, preferably 0.1 to 50 mol, per 1 mol of the total of one or more compounds (a).
・重合溶剤
重合体（Ａ）の製造においては、上記強酸または上記重縮合反応に対して不活性な重合溶剤を用いることができる。前記不活性な重合溶剤としては、例えば、塩化メチレン、ヘキサクロロベンゼン、およびパーフルオロヘキサン等のハロゲン化炭化水素（上記重縮合反応で反応する化合物を除く）；炭素数４〜１２のｎ−アルカン；酢酸メチル、酢酸エチル、酢酸ｎ−ブチル等の酢酸アルキルエステル；並びにパーフルオロポリエーテル等のフルオロアルキルエーテル；が挙げられる。
-Polymerization solvent In manufacture of a polymer (A), the polymerization solvent inactive with respect to the said strong acid or the said polycondensation reaction can be used. Examples of the inert polymerization solvent include halogenated hydrocarbons such as methylene chloride, hexachlorobenzene, and perfluorohexane (excluding compounds that react in the polycondensation reaction); n-alkanes having 4 to 12 carbon atoms; Examples include acetic acid alkyl esters such as methyl acetate, ethyl acetate, and n-butyl acetate; and fluoroalkyl ethers such as perfluoropolyether.
・重縮合反応
化合物（ｂ）の合計の使用量は、化合物（ａ）の合計１モルに対して、通常０．５〜１．５モル、好ましくは０．９〜１．１モル、より好ましくは０．９５〜１．０５モルである。例えば、１種の化合物（ａ）と２種の化合物（ｂ）とを用いて重縮合反応を行う場合、化合物（ａ）の使用量と、２種の化合物（ｂ）の合計の使用量とは、等モル程度が好ましい。
Polycondensation reaction The total amount of compound (b) used is usually 0.5 to 1.5 mol, preferably 0.9 to 1.1 mol, more preferably 1 mol of compound (a) in total. Is 0.95 to 1.05 mol. For example, when the polycondensation reaction is performed using one kind of compound (a) and two kinds of compound (b), the use amount of compound (a) and the total use amount of two kinds of compound (b) Is preferably about equimolar.
反応時の反応液温度は、好ましくは−５０〜１５０℃、より好ましくは−３０〜５０℃、である。反応時間は、好ましくは０．１〜８時間、より好ましくは０．５〜４時間である。 The reaction solution temperature during the reaction is preferably −50 to 150 ° C., more preferably −30 to 50 ° C. The reaction time is preferably 0.1 to 8 hours, more preferably 0.5 to 4 hours.
反応終了後は、得られた重合体（Ａ）は、公知の方法で精製することができる。
上述のようにして得られた重合体（Ａ）を含む重合反応物は、強酸を触媒として用いるため、一般の重合触媒を用いた場合に反応物中に不純物として通常含まれる塩化銅、塩化カリウム、炭酸カリウム等の無機塩類を含まない状態で得られる。このため不純物として残存する無機塩類による劣化の恐れがなく、重合反応物から煩雑な工程で不純物除去を行う必要がないという利点がある。
After completion of the reaction, the obtained polymer (A) can be purified by a known method.
Since the polymerization reaction product containing the polymer (A) obtained as described above uses a strong acid as a catalyst, copper chloride and potassium chloride usually contained as impurities in the reaction product when a general polymerization catalyst is used. And obtained without containing inorganic salts such as potassium carbonate. Therefore, there is an advantage that there is no risk of deterioration due to inorganic salts remaining as impurities, and there is no need to remove impurities from the polymerization reaction product in a complicated process.
重合体（Ａ）の特性
本発明に係る重合体（Ａ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法で測定した、ポリスチレン換算の重量平均分子量（Ｍｗ）が、好ましくは１０，０００〜１，０００，０００、さらに好ましくは３０，０００〜２００，０００である。また、分子量分布（Ｍｗ／Ｍｎ）は、好ましくは１．０〜４．０、より好ましくは１．０〜３．０である。分子量は、例えば強酸の使用量により調節することができる。
Characteristics of Polymer (A) The polymer (A) according to the present invention has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC), preferably 10,000 to 1, 000,000, more preferably 30,000 to 200,000. Moreover, molecular weight distribution (Mw / Mn) becomes like this. Preferably it is 1.0-4.0, More preferably, it is 1.0-3.0. The molecular weight can be adjusted, for example, by the amount of strong acid used.
本発明に係る重合体（Ａ）の示差走査熱量法（ＤＳＣ）で測定したガラス転移温度（Ｔｇ）は、好ましくは１７０〜３５０℃、より好ましくは２００〜３００℃である。
本発明に係る重合体（Ａ）は、熱重量分析法（ＴＧＡ）で測定した熱分解温度（５％重量減少温度）が、好ましくは３５０℃以上、より好ましくは３８０℃以上である。上限値は特に限定されないが、例えば５５０℃である。
The glass transition temperature (Tg) measured by the differential scanning calorimetry (DSC) of the polymer (A) according to the present invention is preferably 170 to 350 ° C, more preferably 200 to 300 ° C.
The polymer (A) according to the present invention has a thermal decomposition temperature (5% weight loss temperature) measured by thermogravimetric analysis (TGA) of preferably 350 ° C. or higher, more preferably 380 ° C. or higher. Although an upper limit is not specifically limited, For example, it is 550 degreeC.
本発明に係る重合体（Ａ）は、上記式（１）で表される構造単位を有することから、フィルム状、シート状などに成形した場合には、比誘電率（εr）の値が小さく、誘電正接（ｔａｎδ）の値が小さく、しかも比誘電率（εr）および誘電正接（ｔａｎδ）がいずれも周波数および温度への依存性が少ない。これは、重合体（Ａ）の短軸方向（重合体の主鎖と垂直方向）は分極が小さく、且つ、分極が生じる箇所が４級炭素構造であることから、分子の回転がおきにくいためであると推定される。このため、本発明に係る重合体（Ａ）は、回路基板用の樹脂基板の製造に特に有用である。 Since the polymer (A) according to the present invention has the structural unit represented by the above formula (1), when it is formed into a film shape, a sheet shape or the like, the value of relative dielectric constant (ε r ) is The dielectric loss tangent (tan δ) is small, and the relative permittivity (ε r ) and the dielectric loss tangent (tan δ) are both less dependent on frequency and temperature. This is because the minor axis direction of the polymer (A) (perpendicular to the main chain of the polymer) is small in polarization, and the portion where the polarization occurs is a quaternary carbon structure, so that it is difficult for the molecule to rotate. It is estimated that. For this reason, the polymer (A) according to the present invention is particularly useful for the production of a resin substrate for a circuit board.
有機溶剤（Ｂ）
有機溶剤（Ｂ）は、重合体（Ａ）を溶解する溶剤であって、回路基板用樹脂組成物を取り扱いやすいものとするために用いるものである。このような有機溶剤（Ｂ）としては、芳香族系有機溶剤、ケトン系有機溶剤およびアミド系有機溶剤よりなる群から選ばれる少なくとも１種であることが、回路基板用樹脂組成物から形成される回路基板用樹脂基板のεrおよびｔａｎδの値が小さく、さらに、その周波数や温度に対する依存性の少ない回路基板用樹脂基板を形成することができることから好ましい。有機溶剤（Ｂ）は、１種単独で用いてもよく、２種以上を併用してもよい。
Organic solvent (B)
The organic solvent (B) is a solvent that dissolves the polymer (A) and is used to make the circuit board resin composition easy to handle. Such an organic solvent (B) is formed from the resin composition for circuit boards to be at least one selected from the group consisting of an aromatic organic solvent, a ketone organic solvent and an amide organic solvent. The circuit board resin substrate is preferable because the values of ε r and tan δ of the circuit board resin substrate are small, and further, the resin substrate for circuit board can be formed with less dependency on the frequency and temperature. An organic solvent (B) may be used individually by 1 type, and may use 2 or more types together.
前記芳香族系有機溶剤としては、アニソール、トルエン、メシチレン、およびキシレン等が挙げられる。前記ケトン系有機溶剤としては、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、およびシクロヘキサノン等が挙げられる。前記アミド系有機溶剤としては、３−メトキシ−Ｎ，Ｎ−ジメチルプロパンアミド、３−ブトキシ−Ｎ，Ｎ−ジメチルプロパンアミド、３−ヘキシルオキシ−Ｎ，Ｎ−ジメチルプロパンアミド、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，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドン、Ｎ−ペンチル−２−ピロリドン、Ｎ−（メトキシプロピル）−２−ピロリドン、Ｎ−（ｔ−ブチル）−２−ピロリドン、およびＮ−シクロヘキシル−２−ピロリドン等が挙げられる。 Examples of the aromatic organic solvent include anisole, toluene, mesitylene, and xylene. Examples of the ketone organic solvent include 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone. Examples of the amide organic solvent include 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, N, N-dimethyl. Formamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-pentyl-2-pyrrolidone, N- (methoxypropyl) -2-pyrrolidone , N- (t-butyl) -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone and the like.
これらの中では、塗工性、経済性の観点から、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、トルエンおよびメシチレンがより好ましく用いられる。
本発明の回路基板用樹脂組成物中の重合体（Ａ）の含有割合は、通常、１〜４０質量％、好ましくは５〜２５質量％である。組成物中の重合体（Ａ）の含有割合が前記範囲にあると、塗膜を形成する場合に厚膜化が可能で、ピンホールが生じにくく、表面平滑性に優れる回路基板用樹脂基板を形成することができる。
Among these, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, toluene and mesitylene are more preferably used from the viewpoints of coatability and economy.
The content rate of the polymer (A) in the resin composition for circuit boards of this invention is 1-40 mass% normally, Preferably it is 5-25 mass%. When the content ratio of the polymer (A) in the composition is in the above range, it is possible to increase the thickness when forming a coating film, to prevent a pinhole, and to provide a resin substrate for a circuit board excellent in surface smoothness. Can be formed.
その他の成分
本発明の回路基板用樹脂組成物は、重合体（Ａ）および有機溶剤（Ｂ）に加えて、本発明の目的を損なわない範囲でその他の成分を含有してもよい。本発明の回路基板用樹脂組成物に含まれていてもよいその他の成分としては、例えば、無機粒子、重合体（Ａ）以外の樹脂成分、難燃剤、老化防止剤、熱安定剤、酸化防止剤、ＵＶ吸収剤、界面活性剤、滑剤、および充填剤が挙げられる。
Other Components In addition to the polymer (A) and the organic solvent (B), the resin composition for circuit boards of the present invention may contain other components as long as the object of the present invention is not impaired. Examples of other components that may be contained in the circuit board resin composition of the present invention include inorganic particles, resin components other than the polymer (A), flame retardants, anti-aging agents, thermal stabilizers, and antioxidants. Agents, UV absorbers, surfactants, lubricants, and fillers.
前記無機粒子は、回路基板用樹脂組成物から形成される回路基板用樹脂基板に低熱膨張性を付与するために用いられるものである。
無機粒子の材質としては、例えば、シリカ、水酸化アルミニウム、アルミナ、Ｅガラス、Ｓガラス、Ｄガラス、Ｈガラス、窒化ホウ素、窒化アルミニウム、カオリン、タルク、マイカ、クレー、水酸化マグネシウム、酸化モリブデン、酸化チタン、酸化亜鉛、チタン酸バリウムが挙げられる。無機粒子の粒子径は、通常、０．１〜１００μｍである。
The said inorganic particle is used in order to provide low thermal expansibility to the resin substrate for circuit boards formed from the resin composition for circuit boards.
Examples of the material of the inorganic particles include silica, aluminum hydroxide, alumina, E glass, S glass, D glass, H glass, boron nitride, aluminum nitride, kaolin, talc, mica, clay, magnesium hydroxide, molybdenum oxide, Examples thereof include titanium oxide, zinc oxide, and barium titanate. The particle diameter of the inorganic particles is usually 0.1 to 100 μm.
前記無機粒子は、回路基板用樹脂組成物に均一に分散できるように、また、回路基板用樹脂組成物から形成される回路基板用樹脂基板の耐熱性を向上させるために、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等のシランカップリング剤で表面処理されたものを用いることができる。 In order to uniformly disperse the inorganic particles in the circuit board resin composition and to improve the heat resistance of the circuit board resin substrate formed from the circuit board resin composition, γ-glycidoxy is used. What was surface-treated with a silane coupling agent such as propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-methacryloxypropyltrimethoxysilane can be used.
前記重合体（Ａ）以外の樹脂成分は、前記重合体（Ａ）に由来する機能以外の機能を付与するために用いられるものである。前記重合体（Ａ）以外の樹脂成分としては、エチレン、プロピレン、ブタジエン、イソプレン、スチレン、ジビニルベンゼン、メタクリル酸、アクリル酸、メタクリル酸エステル、アクリル酸エステル、塩化ビニル、アクリロニトリル、無水マレイン酸、酢酸ビニル、四フッ化エチレン等のビニル化合物の単独重合体及び２種以上のビニル化合物の共重合体、ポリアミド、ポリイミド、ポリカーボネート、ポリエステル、ポリアセタール、ポリフェニレンスルフィド、およびポリエチレングリコール等の熱可塑性樹脂；並びにフェノール樹脂、エポキシ樹脂、及びシアネートエステル系樹脂；を挙げることができる。 The resin component other than the polymer (A) is used for imparting a function other than the function derived from the polymer (A). Resin components other than the polymer (A) include ethylene, propylene, butadiene, isoprene, styrene, divinylbenzene, methacrylic acid, acrylic acid, methacrylic ester, acrylic ester, vinyl chloride, acrylonitrile, maleic anhydride, acetic acid. Homopolymers of vinyl compounds such as vinyl and tetrafluoroethylene and copolymers of two or more vinyl compounds, thermoplastic resins such as polyamide, polyimide, polycarbonate, polyester, polyacetal, polyphenylene sulfide, and polyethylene glycol; and phenol And resins, epoxy resins, and cyanate ester resins.
前記難燃剤は、回路基板用樹脂組成物から形成される回路基板用樹脂基板の難燃性を付与するものであり、例えば、三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、及びほう酸亜鉛等の無機難燃剤；ヘキサブロモベンゼン、デカブロモジェフェニルエタン、４，４−ジブロモフェニル、及びエチレンビステトラブロモフタルイミド等の芳香族臭素化合物；が挙げられる。 The flame retardant imparts flame retardancy of a circuit board resin substrate formed from a circuit board resin composition, such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, and zinc borate. Inorganic flame retardants; aromatic bromine compounds such as hexabromobenzene, decabromojephenylethane, 4,4-dibromophenyl, and ethylenebistetrabromophthalimide;
前記老化防止剤は、回路基板用樹脂組成物から形成される回路基板用樹脂基板の耐久性をより向上させるために用いるものであり、例えば、ヒンダードフェノール系化合物が挙げられる。 The anti-aging agent is used to further improve the durability of the circuit board resin substrate formed from the circuit board resin composition, and includes, for example, a hindered phenol compound.
回路基板用樹脂組成物の製造方法
本発明の回路基板用樹脂組成物は、各成分を均一に混合することにより製造できる。また、ゴミを取り除くために、各成分を均一に混合した後、得られた混合物をフィルター等で濾過してもよい。
Manufacturing method of resin composition for circuit boards The resin composition for circuit boards of this invention can be manufactured by mixing each component uniformly. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.
本発明の回路基板用樹脂組成物の粘度は、通常、５０〜１００，０００ｍＰａ・ｓ、好ましくは５００〜５０，０００ｍＰａ・ｓ、より好ましくは１，０００〜２０，０００ｍＰａ・ｓである。粘度は、ＪＩＳ Ｋ７１１７に従い回転粘度計により測定される値である。回路基板用樹脂組成物の粘度が前記範囲にあると、塗膜を形成する際などの成膜中において組成物の滞留性に優れ、厚みの調整が容易であるため、所望の回路基板用樹脂基板を容易に成形することができる。 The viscosity of the resin composition for circuit boards of the present invention is usually 50 to 100,000 mPa · s, preferably 500 to 50,000 mPa · s, and more preferably 1,000 to 20,000 mPa · s. The viscosity is a value measured by a rotational viscometer according to JIS K7117. When the viscosity of the resin composition for circuit boards is in the above range, the composition has excellent retention during film formation such as when a coating film is formed, and the thickness can be easily adjusted. The substrate can be easily formed.
＜回路基板用樹脂基板＞
本発明の回路基板用樹脂基板は、上述した重合体（Ａ）を含有する。
本発明の回路基板用樹脂基板は、重合体（Ａ）を含有することから、比誘電率（εr）および誘電正接（ｔａｎδ）の値が小さく、さらに、これらの周波数および温度に対する依存性の少ない回路基板用樹脂基板となる。
<Resin board for circuit boards>
The resin substrate for circuit boards of the present invention contains the polymer (A) described above.
Since the resin substrate for a circuit board of the present invention contains the polymer (A), the values of the relative dielectric constant (ε r ) and the dielectric loss tangent (tan δ) are small, and the dependence on the frequency and temperature is also low. There are few resin substrates for circuit boards.
本発明の回路基板用樹脂基板は、重合体（Ａ）を含有していればどのような方法で製造してもよいが、本発明の回路基板用樹脂組成物から製造する方法が好ましい。
本発明の回路基板用樹脂組成物から回路基板用樹脂基板を製造する方法は、回路基板用樹脂組成物から揮発成分を除去することにより、回路基板用樹脂基板を製造することができ、例えば、回路基板用樹脂組成物を、支持体上に塗布して塗膜を形成した後、または強化繊維基材に含浸させた後、前記有機溶剤（Ｂ）等の揮発成分を除去することで、回路基板用樹脂基板を製造することができる。
The resin substrate for circuit boards of the present invention may be manufactured by any method as long as it contains the polymer (A), but the method of manufacturing from the resin composition for circuit boards of the present invention is preferable.
The method for producing a circuit board resin substrate from the circuit board resin composition of the present invention can produce a circuit board resin substrate by removing volatile components from the circuit board resin composition. After the resin composition for a circuit board is applied on a support to form a coating film or impregnated in a reinforcing fiber base material, a volatile component such as the organic solvent (B) is removed to remove the circuit. A resin substrate for a substrate can be manufactured.
前記塗布方法としては、ロールコート法、グラビアコート法、スピンコート法、スリットコート法およびドクターブレードを用いる方法等が挙げられる。前記支持体としては、ポリエチレンテレフタレート（ＰＥＴ）フィルムおよびＳＵＳ板などが挙げられる。前記塗膜の厚さは、最終的に得られる回路基板用樹脂基板の膜厚により適宜決めればよく、通常、１〜１０００μｍである。 Examples of the coating method include a roll coating method, a gravure coating method, a spin coating method, a slit coating method, and a method using a doctor blade. Examples of the support include a polyethylene terephthalate (PET) film and a SUS plate. The thickness of the coating film may be appropriately determined depending on the film thickness of the finally obtained resin substrate for circuit boards, and is usually 1-1000 μm.
回路基板用樹脂組成物を強化繊維基材に含浸させる場合、強化繊維基材としては、例えば、ロービングクロス、クロス、チョップドマット、サーフェシングマット等の各種ガラス布；アスベスト布、金属繊維布、及びその他合成もしくは天然の無機繊維布；全芳香族ポリアミド繊維、全芳香族ポリエステル繊維、ポリベンゾオキサゾール繊維等の液晶繊維から得られる織布又は不織布；綿布、麻布、フェルト等の天然繊維布；カーボン繊維布、クラフト紙、コットン紙、紙−ガラス混繊糸から得られる布等の天然セルロース系基材；ポリテトラフルオロエチレン多孔質フィルム；が挙げられる。強化繊維基材は１種を単独で、または２種以上組合せて用いることができる。 When the reinforcing fiber base material is impregnated with the resin composition for circuit boards, examples of the reinforcing fiber base material include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; asbestos cloth, metal fiber cloth, and Other synthetic or natural inorganic fiber cloths; Woven or non-woven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton, linen, and felt; carbon fibers And natural cellulose-based substrates such as cloth, kraft paper, cotton paper, cloth obtained from paper-glass mixed yarn; and polytetrafluoroethylene porous film. The reinforcing fiber base can be used alone or in combination of two or more.
前記有機溶剤（Ｂ）等の揮発成分を除去する方法としては、例えば、加熱する方法が挙げられる。前記加熱の条件は、通常、３０℃〜３００℃の温度で、１０分〜５時間である。なお、加熱は二段階以上で行ってもよい。具体的には、３０〜８０℃の温度で１０分〜２時間乾燥後、１００℃〜２５０℃でさらに１０分〜３時間加熱するなどである。また、必要に応じて、窒素雰囲気下もしくは減圧下にて乾燥を行ってもよい。 Examples of the method for removing volatile components such as the organic solvent (B) include a heating method. The heating conditions are usually 30 ° C. to 300 ° C. and 10 minutes to 5 hours. Note that heating may be performed in two or more stages. Specifically, after drying at a temperature of 30 to 80 ° C. for 10 minutes to 2 hours, heating is further performed at 100 to 250 ° C. for 10 minutes to 3 hours. Moreover, you may dry in nitrogen atmosphere or pressure reduction as needed.
支持体上に塗布して塗膜を形成する場合、得られた樹脂基板は、支持体から剥離して回路基板用樹脂基板として用いてもよく、または支持体から剥離せずにそのまま回路基板用樹脂基板として用いてもよい。 When a coating film is formed by coating on a support, the obtained resin substrate may be peeled off from the support and used as a circuit board resin substrate, or may be used as it is without being peeled off from the support. It may be used as a resin substrate.
また、回路基板用樹脂組成物を強化繊維基材に含浸させる場合、得られる回路基板用樹脂基板中に含まれる重合体（Ａ）の含有割合は、３０質量％以上、好ましくは３０〜８０質量％、より好ましくは４０〜７０質量％である。 When the reinforcing fiber base material is impregnated with the circuit board resin composition, the content ratio of the polymer (A) contained in the obtained circuit board resin substrate is 30% by mass or more, preferably 30 to 80% by mass. %, More preferably 40 to 70% by mass.
本発明の回路基板用樹脂基板の厚みは、所望の用途に応じて適宜選択でき、通常、１〜２５０μｍ、好ましくは２〜１５０μｍ、より好ましくは５〜１２５μｍである。
樹脂基板中の残存溶剤量は、回路基板用樹脂基板１００重量％に対し、通常、０〜１．２重量％、好ましくは０〜１重量％である。残存溶剤量がこの範囲にあることで、比誘電率（εr）および誘電正接（ｔａｎδ）の値が小さく、さらに、その周波数および温度に対する依存性の少ない回路基板用樹脂基板を得ることができる。
The thickness of the resin substrate for circuit boards of the present invention can be appropriately selected according to the desired application, and is usually 1 to 250 μm, preferably 2 to 150 μm, more preferably 5 to 125 μm.
The amount of residual solvent in the resin substrate is usually 0 to 1.2% by weight, preferably 0 to 1% by weight, based on 100% by weight of the resin substrate for circuit boards. When the amount of the residual solvent is within this range, it is possible to obtain a resin substrate for a circuit board that has small values of relative dielectric constant (ε r ) and dielectric loss tangent (tan δ) and is less dependent on frequency and temperature. .
本発明の回路基板用樹脂基板の引張強度は、通常、５０〜４００ＭＰａであり、破断伸びは、通常、５〜１００％であり、引張弾性率は、通常、２．５〜４．０ＧＰａであり、線膨張係数は、通常、８０ｐｐｍ／Ｋ以下であり、湿度膨張係数は、通常、１５ｐｐｍ／％ＲＨ以下である。 The tensile strength of the resin substrate for circuit boards of the present invention is usually 50 to 400 MPa, the elongation at break is usually 5 to 100%, and the tensile elastic modulus is usually 2.5 to 4.0 GPa. The linear expansion coefficient is usually 80 ppm / K or less, and the humidity expansion coefficient is usually 15 ppm /% RH or less.
引張強度および引張弾性率はＪＩＳ Ｋ ７１６１、破断伸びはＪＩＳ Ｚ ２２４１：２０１１、線膨張係数はＪＩＳ Ｚ ２２８５：２００３に準じ、湿度膨張係数は、相対湿度の変更率（％）当たりのサイズ変更率（％）で算出した値である。 Tensile strength and tensile modulus are in accordance with JIS K 7161, elongation at break is in accordance with JIS Z 2241: 2011, linear expansion coefficient is in accordance with JIS Z 2285: 2003, and the humidity expansion coefficient is the size change rate per% change in relative humidity. It is a value calculated in (%).
＜回路基板＞
本発明の回路基板は、本発明の回路基板用樹脂基板を有するものであり、回路基板用樹脂基板の片面または両面に配線部を設けることで得られる。このような回路基板は、比誘電率（εr）の値が小さく、誘電正接（ｔａｎδ）の値が小さく、しかも比誘電率（εr）および誘電正接（ｔａｎδ）の周波数および温度に対する依存性の少ない本発明の回路基板用樹脂基板を有するため、伝送速度が大きく、伝送損失が小さいため、高周波領域で好適に用いることができる。
<Circuit board>
The circuit board of the present invention has the resin substrate for circuit boards of the present invention, and can be obtained by providing a wiring part on one side or both sides of the circuit board resin substrate. Such a circuit board has a small value of relative dielectric constant (ε r ), a small value of dielectric loss tangent (tan δ), and dependency of relative dielectric constant (ε r ) and dielectric loss tangent (tan δ) on frequency and temperature. Since the circuit board resin substrate of the present invention with a small amount is provided, the transmission speed is high and the transmission loss is small, so that it can be suitably used in a high frequency region.
前記配線部を形成する方法としては、例えば、ラミネート法、メタライジング法、スパッタリング法、蒸着法、塗布法および印刷法等により、前記回路基板用樹脂基板上に、銅、インジウムスズ酸化物（ＩＴＯ）、ポリチオフェン、ポリアニリンおよびポリピロール等の導電性材料からなる導電層を形成し、前記導電層をパターニングすることで配線部を形成することができる。また、導電層を形成する前に、回路基板用樹脂基板と導電層との接着力を向上させるために、プラズマ処理などにより回路基板用樹脂基板の表面を改質してもよく、接着剤を回路基板用樹脂基板上に塗布しておいてもよい。 Examples of the method for forming the wiring portion include copper, indium tin oxide (ITO) on the circuit board resin substrate by, for example, a laminating method, a metalizing method, a sputtering method, a vapor deposition method, a coating method, and a printing method. ), Forming a conductive layer made of a conductive material such as polythiophene, polyaniline, and polypyrrole, and patterning the conductive layer, thereby forming a wiring portion. Before forming the conductive layer, the surface of the resin substrate for circuit boards may be modified by plasma treatment or the like in order to improve the adhesion between the resin substrate for circuit boards and the conductive layer. You may apply | coat on the resin substrate for circuit boards.
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。以下の実施例等の記載において、特に言及しない限り、「部」は「質量部」の意味で用いる。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.
＜測定・評価方法＞
樹脂の重量平均分子量（Ｍｗ）、および分子量分布（Ｍｗ／Ｍｎ）
下記条件下でゲルパーミエーションクロマトグラフィー法にて重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、および分子量分布を測定した。
・カラム：東ソー社製カラムの「ＴＳＫｇｅｌ αＭ」および「ＴＳＫｇｅｌ α２５００」を直列に接続
・溶媒：臭化リチウムおよびリン酸を添加したＮ−メチル−２−ピロリドン
・温度：４０℃
・検出方法：屈折率法
・標準物質：ポリスチレン
・ＧＰＣ装置：東ソー製、装置名「ＨＬＣ-８０２０-ＧＰＣ」
<Measurement and evaluation method>
Weight average molecular weight (Mw) of resin and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution were measured by gel permeation chromatography under the following conditions.
Column: Tosoh column “TSKgel αM” and “TSKgel α2500” connected in series Solvent: N-methyl-2-pyrrolidone to which lithium bromide and phosphoric acid were added Temperature: 40 ° C.
・ Detection method: Refractive index method ・ Standard material: Polystyrene ・ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8020-GPC”
構造解析
構造解析は、下記条件で、1Ｈ−ＮＭＲにより行った。
・装置：ＪＥＯＬ社製、装置名「ＥＣＰ−４００Ｐ」
・重溶媒：重クロロホルム、重メタノールおよび重水から選ばれる重溶媒の内、もっとも溶解性の高い重溶媒を選択した。
Structural analysis Structural analysis was performed by 1 H-NMR under the following conditions.
・ Device: JEOL, device name “ECP-400P”
-Heavy solvent: Among the heavy solvents selected from deuterated chloroform, deuterated methanol and deuterated water, the desolvent having the highest solubility was selected.
ガラス転移温度（Ｔｇ）、熱分解温度
重合体のガラス転移温度（Ｔｇ）は、Ｒｉｇａｋｕ社製８２３０型ＤＳＣ測定装置を用いて、昇温速度２０℃／分にて測定した。また、重合体の５％重量減少温度を、熱重量分析法（ＴＧＡ）で、窒素雰囲気下、昇温速度１０℃／分にて測定し、これを重合体の熱分解温度とした。
Glass transition temperature (Tg) and pyrolysis temperature The glass transition temperature (Tg) of the polymer was measured using a Rigaku 8230 type DSC measuring apparatus at a heating rate of 20 ° C./min. The 5% weight loss temperature of the polymer was measured by thermogravimetric analysis (TGA) in a nitrogen atmosphere at a heating rate of 10 ° C./min, and this was defined as the thermal decomposition temperature of the polymer.
誘電特性（比誘電率（ε r ）および誘電正接（ｔａｎδ））
各温度条件（２３℃、４０℃、８５℃、および１００℃）、周波数条件（１ＧＨｚ、１０ＧＨｚ、および１００ＧＨｚ）、並びに相対湿度（４５ＲＨ、５０ＲＨ、および８５ＲＨ）における比誘電率（εr）および誘電正接（ｔａｎδ）を、評価用フィルムを用い、ＫＥＹＣＯＭ社製、装置名「ＦＰＲ−１１０」を用いて摂動方式共振法により測定した。
Dielectric properties (relative permittivity (ε r ) and dielectric loss tangent (tan δ))
Specific permittivity (ε r ) and dielectric at each temperature condition (23 ° C., 40 ° C., 85 ° C., and 100 ° C.), frequency condition (1 GHz, 10 GHz, and 100 GHz), and relative humidity (45 RH, 50 RH, and 85 RH) Tangent (tan δ) was measured by a perturbation resonance method using an evaluation film and using a device name “FPR-110” manufactured by KEYCOM.
［実施例１］
・重合体（Ａ−１）の製造
撹拌機および窒素導入管付き三方コックを取り付けた３００ｍＬの３つ口フラスコを用い、内部を窒素置換して、２，２，２−トリフルオロアセトフェノンを１０．２８ｇ、ジフェニルエーテルを１０．０４ｇ、および塩化メチレンを５０ｍＬ添加した。
[Example 1]
Production of polymer (A-1) Using a 300 mL three-necked flask equipped with a stirrer and a three-way cock with a nitrogen inlet tube, the inside was purged with nitrogen, and 2,2,2-trifluoroacetophenone was changed to 10. 28 g, 10.04 g of diphenyl ether, and 50 mL of methylene chloride were added.
続いてトリフルオロメタンスルホン酸２７．１４ｇを加え、撹拌を開始し、−２０℃で３時間反応させた。反応終了後に反応液をメタノールに投じて反応物を沈殿させ、濾物を単離した。得られた濾物を６０℃で一晩真空乾燥し、白色粉末の重合体（Ａ−１）を得た。収量は１８．３０ｇであり、収率は９５％であった。 Subsequently, 27.14 g of trifluoromethanesulfonic acid was added, stirring was started, and reaction was performed at −20 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into methanol to precipitate the reaction product, and the filtrate was isolated. The obtained residue was vacuum dried at 60 ° C. overnight to obtain a white powder polymer (A-1). The yield was 18.30 g, and the yield was 95%.
得られた重合体（Ａ−１）のＭｗは８６，０００、Ｍｗ／Ｍｎは２．７であり、Ｔｇは２２０℃、熱分解温度は５１０℃であった。得られた重合体（Ａ−１）の1Ｈ−ＮＭＲスペクトル（図１）より、得られた重合体が、下記式の構造単位を有することを確認した。 Mw of the obtained polymer (A-1) was 86,000, Mw / Mn was 2.7, Tg was 220 ° C., and the thermal decomposition temperature was 510 ° C. From the 1 H-NMR spectrum (FIG. 1) of the obtained polymer (A-1), it was confirmed that the obtained polymer had a structural unit of the following formula.
・樹脂基板の製造
上記で得た重合体（Ａ−１）を、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）に溶解し、重合体濃度２０質量％の樹脂組成物を得た。この樹脂組成物を、ポリエチレンテレフタレート（ＰＥＴ）からなる支持体上にドクターブレードを用いて塗布し、７０℃で３０分乾燥させ、ついで１００℃で３０分乾燥してフィルムとした後、支持体より剥離した。その後、フィルムを金枠に固定し、さらに１８０℃で２時間乾燥して、膜厚３０μｍのフィルム状の樹脂基板を得た。得られたフィルム状の樹脂基板を評価用サンプルとして用い、誘電特性を評価した。評価結果を表１に示す。
-Production of Resin Substrate The polymer (A-1) obtained above was dissolved in N, N-dimethylacetamide (DMAc) to obtain a resin composition having a polymer concentration of 20% by mass. The resin composition was applied onto a support made of polyethylene terephthalate (PET) using a doctor blade, dried at 70 ° C. for 30 minutes, and then dried at 100 ° C. for 30 minutes to form a film. It peeled. Thereafter, the film was fixed to a metal frame and further dried at 180 ° C. for 2 hours to obtain a film-like resin substrate having a film thickness of 30 μm. The obtained film-like resin substrate was used as an evaluation sample to evaluate dielectric properties. The evaluation results are shown in Table 1.
［実施例２］
・重合体（Ａ−２）の製造
撹拌機および窒素導入管付き三方コックを取り付けた３００ｍＬの３つ口フラスコを用い、内部を窒素置換して、２，２，２−トリフルオロアセトフェノンを５．４９ｇ、ジフェニルエーテルを２．５５ｇ、パラターフェニルを３．４５ｇ、および塩化メチレンを５０ｍＬ添加した。
[Example 2]
-Production of polymer (A-2) Using a 300 mL three-necked flask equipped with a stirrer and a three-way cock with a nitrogen inlet tube, the inside was purged with nitrogen, and 2,2,2-trifluoroacetophenone was changed to 5. 49 g, 2.55 g diphenyl ether, 3.45 g paraterphenyl, and 50 mL methylene chloride were added.
続いてトリフルオロメタンスルホン酸１６．９６ｇを加え、撹拌を開始し、−２０℃で５時間反応させた。反応終了後に反応液をメタノールに投じて反応物を沈殿させ、濾物を単離した。得られた濾物を６０℃で一晩真空乾燥し、白色粉末の重合体（Ａ−２）を得た。収量は１０．５６ｇであり、収率は９６％であった。 Subsequently, 16.96 g of trifluoromethanesulfonic acid was added, stirring was started, and reaction was performed at −20 ° C. for 5 hours. After completion of the reaction, the reaction solution was poured into methanol to precipitate the reaction product, and the filtrate was isolated. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder polymer (A-2). The yield was 10.56 g and the yield was 96%.
得られた重合体（Ａ−２）のＭｗは１０２，０００、Ｍｗ／Ｍｎは２．８であり、Ｔｇは２９０℃、熱分解温度は５１２℃であった。得られた重合体（Ａ−２）の1Ｈ−ＮＭＲスペクトル（図２）より、得られた重合体が、下記式の構造単位を有することを確認した。 Mw of the obtained polymer (A-2) was 102,000, Mw / Mn was 2.8, Tg was 290 ° C, and the thermal decomposition temperature was 512 ° C. From the 1 H-NMR spectrum (FIG. 2) of the obtained polymer (A-2), it was confirmed that the obtained polymer had a structural unit of the following formula.
・樹脂基板の製造
重合体（Ａ−１）に代えて、上記で得た重合体（Ａ−２）を用いたことの他は、実施例１と同様にして樹脂基板の製造を行い、膜厚３０μｍのフィルム状の樹脂基板を得た。得られたフィルム状の樹脂基板を評価用サンプルとして用い、誘電特性を評価した。評価結果を表１に示す。
-Production of resin substrate A resin substrate was produced in the same manner as in Example 1 except that the polymer (A-2) obtained above was used instead of the polymer (A-1). A film-like resin substrate having a thickness of 30 μm was obtained. The obtained film-like resin substrate was used as an evaluation sample to evaluate dielectric properties. The evaluation results are shown in Table 1.
［実施例３］
・重合体（Ａ−３）の製造
撹拌機および窒素導入管付き三方コックを取り付けた３００ｍＬの３つ口フラスコを用い、内部を窒素置換して、２，２，２−トリフルオロアセトフェノンを３．５３ｇ、ジフェニルエーテルを０．５１ｇ、パラターフェニルを６．２２ｇ、および塩化メチレンを５０ｍＬ添加した。
[Example 3]
-Production of polymer (A-3) Using a 300 mL three-necked flask equipped with a stirrer and a three-way cock with a nitrogen introduction tube, the inside was purged with nitrogen, and 2,2,2-trifluoroacetophenone was added in 3. 53 g, 0.51 g of diphenyl ether, 6.22 g of paraterphenyl, and 50 mL of methylene chloride were added.
続いてトリフルオロメタンスルホン酸１６．９６ｇを加え、撹拌を開始し、−２０℃で５時間反応させた。反応終了後に反応液をメタノールに投じて反応物を沈殿させ、濾物を単離した。得られた濾物を６０℃で一晩真空乾燥し、白色粉末の重合体（Ａ−３）を得た。収量は１０．５６ｇであり、収率は９６％であった。 Subsequently, 16.96 g of trifluoromethanesulfonic acid was added, stirring was started, and reaction was performed at −20 ° C. for 5 hours. After completion of the reaction, the reaction solution was poured into methanol to precipitate the reaction product, and the filtrate was isolated. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder polymer (A-3). The yield was 10.56 g and the yield was 96%.
得られた重合体（Ａ−３）のＭｗは７６，０００、Ｍｗ／Ｍｎは２．６であり、Ｔｇは３３０℃、熱分解温度は５０５℃であった。得られた重合体（Ａ−３）の1Ｈ−ＮＭＲスペクトルより、得られた重合体（Ａ−３）が、下記式の構造単位を有することを確認した。 Mw of the obtained polymer (A-3) was 76,000, Mw / Mn was 2.6, Tg was 330 ° C., and the thermal decomposition temperature was 505 ° C. From the 1 H-NMR spectrum of the obtained polymer (A-3), it was confirmed that the obtained polymer (A-3) had a structural unit represented by the following formula.
・樹脂基板の製造
重合体（Ａ−１）に代えて、上記で得た重合体（Ａ−３）を用いたことの他は、実施例１と同様にして樹脂基板の製造を行い、膜厚３０μｍのフィルム状の樹脂基板を得た。得られたフィルム状の樹脂基板を評価用サンプルとして用い、誘電特性を評価した。評価結果を表１に示す。
-Production of resin substrate A resin substrate was produced in the same manner as in Example 1 except that the polymer (A-3) obtained above was used instead of the polymer (A-1), and the membrane was obtained. A film-like resin substrate having a thickness of 30 μm was obtained. The obtained film-like resin substrate was used as an evaluation sample to evaluate dielectric properties. The evaluation results are shown in Table 1.
［比較例１］
ポリイミドフィルム（商品名「カプトン１００Ｈ／Ｖ」、東レ・デュポン社製、膜厚２５μｍ）を評価用サンプルとして用い、誘電特性を評価した。評価結果を表１に示す。
[Comparative Example 1]
Dielectric properties were evaluated using a polyimide film (trade name “Kapton 100H / V”, manufactured by Toray DuPont, film thickness 25 μm) as an evaluation sample. The evaluation results are shown in Table 1.
［比較例２］
液晶ポリマーフィルム（商品名「ベクスター ＣＴ−Ｚ」、クラレ（株）製、膜厚２５μｍ）を評価用サンプルとして用い、誘電特性を評価した。評価結果を表１に示す。
[Comparative Example 2]
Dielectric properties were evaluated using a liquid crystal polymer film (trade name “BEXTER CT-Z”, manufactured by Kuraray Co., Ltd., film thickness 25 μm) as an evaluation sample. The evaluation results are shown in Table 1.
本発明の回路基板用樹脂基板は、各種回路基板の製造に好適に用いることができる。また本発明の回路基板用樹脂組成物は、回路基板用樹脂基板の製造に好適に用いることができる。本発明の回路基板は、精密機械用の回路基板として有用である。 The resin substrate for circuit boards of the present invention can be suitably used for manufacturing various circuit boards. Moreover, the resin composition for circuit boards of this invention can be used suitably for manufacture of the resin board for circuit boards. The circuit board of the present invention is useful as a circuit board for precision machinery.
Claims (6)
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| JP6206445B2 (en) | 2017-10-04 |
| TWI644968B (en) | 2018-12-21 |
| TW201604232A (en) | 2016-02-01 |
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