JP5285949B2 - Composite molded body - Google Patents
Composite molded body Download PDFInfo
- Publication number
- JP5285949B2 JP5285949B2 JP2008106858A JP2008106858A JP5285949B2 JP 5285949 B2 JP5285949 B2 JP 5285949B2 JP 2008106858 A JP2008106858 A JP 2008106858A JP 2008106858 A JP2008106858 A JP 2008106858A JP 5285949 B2 JP5285949 B2 JP 5285949B2
- Authority
- JP
- Japan
- Prior art keywords
- norbornene
- group
- atom
- molded body
- composite molded
- 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.)
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- 239000002131 composite material Substances 0.000 title claims description 87
- 239000000178 monomer Substances 0.000 claims description 72
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 68
- 229920000642 polymer Polymers 0.000 claims description 45
- 239000007769 metal material Substances 0.000 claims description 36
- 239000007822 coupling agent Substances 0.000 claims description 22
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 20
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 238000012662 bulk polymerization Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 26
- 239000000945 filler Substances 0.000 description 22
- -1 tricyclopentadiene Chemical compound 0.000 description 22
- 229910052742 iron Inorganic materials 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 18
- 238000007142 ring opening reaction Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002685 polymerization catalyst Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 125000005842 heteroatom Chemical group 0.000 description 10
- 238000005649 metathesis reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012765 fibrous filler Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 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 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000012327 Ruthenium complex Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- QYCGBAJADAGLLK-UHFFFAOYSA-N 1-(cyclohepten-1-yl)cycloheptene Chemical group C1CCCCC=C1C1=CCCCCC1 QYCGBAJADAGLLK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- LURVUWBWEGPODG-UHFFFAOYSA-L dichlororuthenium;tricyclohexylphosphane Chemical compound [Cl-].[Cl-].[Ru+2].C1CCCCC1P(C1CCCCC1)C1CCCCC1 LURVUWBWEGPODG-UHFFFAOYSA-L 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000004611 light stabiliser Substances 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000010107 reaction injection moulding Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- LAGGTOBQMQHXON-GGWOSOGESA-N (2e,6e)-octa-2,6-diene Chemical compound C\C=C\CC\C=C\C LAGGTOBQMQHXON-GGWOSOGESA-N 0.000 description 1
- LAGGTOBQMQHXON-CIIODKQPSA-N (2z,6e)-octa-2,6-diene Chemical compound C\C=C\CC\C=C/C LAGGTOBQMQHXON-CIIODKQPSA-N 0.000 description 1
- LAGGTOBQMQHXON-GLIMQPGKSA-N (2z,6z)-octa-2,6-diene Chemical compound C\C=C/CC\C=C/C LAGGTOBQMQHXON-GLIMQPGKSA-N 0.000 description 1
- ZVFFWOKVVPSTAL-WAYWQWQTSA-N (3z)-2,5-dimethylhexa-1,3,5-triene Chemical compound CC(=C)\C=C/C(C)=C ZVFFWOKVVPSTAL-WAYWQWQTSA-N 0.000 description 1
- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical compound C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-N 0.000 description 1
- AFVDZBIIBXWASR-WAYWQWQTSA-N (Z)-1,3,5-hexatriene Chemical compound C=C\C=C/C=C AFVDZBIIBXWASR-WAYWQWQTSA-N 0.000 description 1
- GCYUJISWSVALJD-UHFFFAOYSA-N 1,1-diethylcyclohexane Chemical compound CCC1(CC)CCCCC1 GCYUJISWSVALJD-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical compound CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 0.000 description 1
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 1
- JGLIHSMBVDZMSA-UHFFFAOYSA-N 5-(cyclohexen-1-yl)bicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CCCCC1 JGLIHSMBVDZMSA-UHFFFAOYSA-N 0.000 description 1
- HHKDWDAAEFGBAC-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl(triethoxy)silane Chemical compound C1C2C([Si](OCC)(OCC)OCC)CC1C=C2 HHKDWDAAEFGBAC-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MSJGKOBBXLEODT-UHFFFAOYSA-N [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-(3-methylbut-2-enylidene)ruthenium tricyclohexylphosphane Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1.CC(C)=CC=[Ru]=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C MSJGKOBBXLEODT-UHFFFAOYSA-N 0.000 description 1
- PQXNSNRSYLCYSB-UHFFFAOYSA-L [Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(C(CC1)P(C1CCCC1)C1CCCC1)=CC=C(C)C)C Chemical compound [Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(C(CC1)P(C1CCCC1)C1CCCC1)=CC=C(C)C)C PQXNSNRSYLCYSB-UHFFFAOYSA-L 0.000 description 1
- INZGOCCQOQZMKS-UHFFFAOYSA-L [Ru](Cl)Cl.CC(=CC(P(C1CCCC1)(C1CCCC1)C1CCCC1)P(C1CCCC1)(C1CCCC1)C1CCCC1)C Chemical compound [Ru](Cl)Cl.CC(=CC(P(C1CCCC1)(C1CCCC1)C1CCCC1)P(C1CCCC1)(C1CCCC1)C1CCCC1)C INZGOCCQOQZMKS-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
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- 230000000994 depressogenic effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- LQOASDRTPMAQCZ-UHFFFAOYSA-L dichlororuthenium;tricyclohexyl-[phenyl-(tricyclohexyl-$l^{5}-phosphanyl)methyl]-$l^{5}-phosphane Chemical compound Cl[Ru]Cl.C1CCCCC1P(C1CCCCC1)(C1CCCCC1)C(P(C1CCCCC1)(C1CCCCC1)C1CCCCC1)C1=CC=CC=C1 LQOASDRTPMAQCZ-UHFFFAOYSA-L 0.000 description 1
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- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical group O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
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- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- JFKBLKGQCUHUHJ-UHFFFAOYSA-N tricyclo[6.2.1.02,7]undec-9-ene Chemical compound C12CCCCC2C2CC1C=C2 JFKBLKGQCUHUHJ-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Description
本発明は、ノルボルネン系モノマーを塊状開環重合させることにより得られる重合体と、金属材料からなる複合化用部材とを一体成形してなる複合成形体に関する。 The present invention relates to a composite molded body obtained by integrally molding a polymer obtained by bulk ring-opening polymerization of a norbornene-based monomer and a composite member made of a metal material.
ノルボルネン系モノマーなどのシクロオレフィンモノマーを含む重合性単量体を、メタセシス重合触媒存在下で重合させて得られるシクロオレフィン重合体は、電気特性、機械的特性、耐衝撃特性、耐熱性、耐候性などに優れるため、幅広い分野の成形体について実用化が進められている。 A cycloolefin polymer obtained by polymerizing a polymerizable monomer containing a cycloolefin monomer such as a norbornene-based monomer in the presence of a metathesis polymerization catalyst has electrical characteristics, mechanical characteristics, impact resistance characteristics, heat resistance, and weather resistance characteristics. As such, it is being put to practical use for compacts in a wide range of fields.
このようなシクロオレフィン重合体は、剛性を向上させるために、ガラス補強材などを添加して用いられる場合があるが、シクロオレフィン重合体は極性が極めて低く、そのため、ガラス補強材などの無機材料との密着性が悪いという問題がある。これに対し、たとえば、特許文献１では、シクロオレフィン重合体に特定のシランカップリング剤を添加して、シクロオレフィン重合体とガラス補強材との密着性の改善が図られている。 In order to improve the rigidity, such a cycloolefin polymer may be used by adding a glass reinforcing material or the like, but the cycloolefin polymer has a very low polarity, and therefore, an inorganic material such as a glass reinforcing material. There is a problem of poor adhesion. In contrast, for example, in Patent Document 1, a specific silane coupling agent is added to the cycloolefin polymer to improve the adhesion between the cycloolefin polymer and the glass reinforcing material.
一方で、シクロオレフィン重合体は、その優れた電気特性や耐熱性から、たとえば、プリント配線板や電子部品の端子電極などの電気絶縁材料として好適に用いられている。特に、このようなプリント配線板の配線層をはんだなどを利用して形成する場合には、これを絶縁する電気絶縁材料や、このようなプリント配線板に実装される電子部品の端子電極を封止するために用いられる電気絶縁材料には、電気特性に加えて、はんだ耐熱性が必要とされるため、このような電気絶縁材料として、シクロオレフィン重合体が好適に用いられている。 On the other hand, the cycloolefin polymer is suitably used as an electrical insulating material such as a printed wiring board or a terminal electrode of an electronic component because of its excellent electrical properties and heat resistance. In particular, when the wiring layer of such a printed wiring board is formed using solder or the like, an electrical insulating material that insulates the wiring layer or a terminal electrode of an electronic component mounted on such a printed wiring board is sealed. Since the electrical insulating material used for stopping requires solder heat resistance in addition to electrical characteristics, a cycloolefin polymer is suitably used as such an electrical insulating material.
しかしながら、このようなシクロオレフィン重合体は極性が極めて低いため、上述のガラス材料の場合と同様に、金属材料との密着性も低く、そのため、プリント配線板などの電気絶縁材料として用いた場合において、プリント配線板や電子部品の端子電極を構成する金属との間の密着性が低く、信頼性が不十分となるという問題があった。 However, since such a cycloolefin polymer has a very low polarity, as in the case of the glass material described above, the adhesion to the metal material is also low, and therefore when used as an electrical insulating material such as a printed wiring board. There is a problem that the adhesion between the printed wiring board and the metal constituting the terminal electrode of the electronic component is low and the reliability is insufficient.
本発明は、このような実状に鑑みてなされ、ノルボルネン系モノマーを塊状開環重合させることにより得られるノルボルネン系重合体と、金属材料からなる複合化用部材とを一体成形してなる複合成形体において、ノルボルネン系モノマーの塊状開環重合体と複合化用部材との間の密着力が向上された複合成形体を提供することを目的とする。 The present invention has been made in view of such circumstances, and is a composite molded body obtained by integrally molding a norbornene-based polymer obtained by bulk ring-opening polymerization of a norbornene-based monomer and a composite member made of a metal material. An object of the present invention is to provide a composite molded article having improved adhesion between the bulk ring-opening polymer of a norbornene-based monomer and the composite member.
本発明者は、上記課題を解決すべく鋭意研究した結果、ノルボルネン系モノマーを塊状開環重合させて得られる重合体と、金属材料からなる複合化用部材とを一体成形してなる複合成形体において、金属材料からなる複合化用部材の、ノルボルネン系モノマーの塊状開環重合体との接触界面のうちの少なくとも一部を、所定のカップリング剤で処理することにより、上記目的を達成できることを見出し、本発明を完成させるに至った。 As a result of diligent research to solve the above-mentioned problems, the present inventor has integrally formed a polymer obtained by bulk ring-opening polymerization of a norbornene-based monomer and a composite member made of a metal material. The above-mentioned object can be achieved by treating at least part of the contact interface between the metal ring composite member and the norbornene monomer bulk ring-opening polymer with a predetermined coupling agent. The headline and the present invention have been completed.
すなわち、本発明によれば、ノルボルネン系モノマーを型内で塊状開環重合させて得られる重合体と、金属材料からなる複合化用部材と、を一体成形してなる複合成形体であって、前記複合化用部材は、前記重合体との接触界面のうちの少なくとも一部が下記式（１）で表されるカップリング剤で処理されていることを特徴とする複合成形体が提供される。
好ましくは、前記Ｒ１が下記式（２）で表される置換基である。
好ましくは、前記複合成形体は、前記複合化用部材を配置した型内に、前記ノルボルネン系モノマーを含有する反応液を注入して塊状重合させることによって得られるものである。
また、前記複合成形体が、ノルボルネン系モノマーを塊状開環重合させて得られる重合体と金属材料との積層体であることが好ましい。
Preferably, the composite molded body is obtained by injecting a reaction solution containing the norbornene-based monomer into a mold in which the composite member is arranged and performing bulk polymerization.
Moreover, it is preferable that the said composite molded object is a laminated body of the polymer and metal material which are obtained by carrying out bulk ring-opening polymerization of a norbornene-type monomer.
本発明によれば、複合成形体を構成する重合体を、ノルボルネン系モノマーを塊状開環重合させることにより得られる重合体としているため、電気特性、機械的特性、耐衝撃特性、耐熱性および耐候性に優れた複合成形体を提供することができる。しかも、本発明においては、金属材料からなる複合化用部材の、ノルボルネン系モノマーの塊状開環重合体との接触界面のうちの少なくとも一部を、上記所定のカップリング剤で処理しているため、重合前のノルボルネン系モノマーを含有する重合性組成物と、金属材料からなる複合化用部材との間のぬれ性を向上させることができ、これにより、ノルボルネン系モノマーの塊状開環重合体と、金属材料からなる複合化用部材との間の反応点を増やすことができる。そして、結果として、得られる複合成形体における、ノルボルネン系モノマーの塊状開環重合体と、金属材料からなる複合化用部材との間の密着性を向上させることができ、これにより信頼性の高い複合成形体、特に積層体を提供することができる。 According to the present invention, since the polymer constituting the composite molded body is a polymer obtained by bulk ring-opening polymerization of a norbornene-based monomer, electrical characteristics, mechanical characteristics, impact resistance characteristics, heat resistance, and weather resistance A composite molded body having excellent properties can be provided. In addition, in the present invention, at least a part of the contact interface of the composite member made of the metal material with the norbornene monomer bulk ring-opening polymer is treated with the predetermined coupling agent. , The wettability between the polymerizable composition containing the norbornene-based monomer before polymerization and the composite member made of a metal material can be improved, and thereby the bulk-opening polymer of the norbornene-based monomer and The reaction points between the composite member made of a metal material can be increased. As a result, it is possible to improve the adhesion between the bulk ring-opening polymer of norbornene-based monomer and the compositing member made of a metal material in the obtained composite molded body, and thereby high reliability. A composite molded body, particularly a laminate can be provided.
本発明の複合成形体は、ノルボルネン系モノマーを塊状開環重合させて得られる重合体と、金属材料からなる複合化用部材とを一体成形してなる複合成形体であって、金属材料からなる複合化用部材の、ノルボルネン系モノマーの塊状開環重合体との接触界面のうちの少なくとも一部が、後述する所定のカップリング剤で処理されていることを特徴とする。 The composite molded body of the present invention is a composite molded body formed by integrally molding a polymer obtained by bulk ring-opening polymerization of a norbornene-based monomer and a composite member made of a metal material, and made of a metal material. At least a part of the contact interface between the complexing member and the norbornene monomer bulk ring-opening polymer is treated with a predetermined coupling agent to be described later.
重合性組成物
本発明に係るノルボルネン系モノマーを塊状開環重合させることにより得られる重合体は、ノルボルネン系モノマーと、重合触媒と、を含有する重合性組成物を用いて、これを塊状開環重合させることにより得られる重合体である。
まず、ノルボルネン系モノマーの塊状開環重合体を形成するために用いられる重合性組成物に含有される各成分について説明する。
Polymerizable composition The polymer obtained by subjecting the norbornene-based monomer according to the present invention to bulk ring-opening polymerization uses a polymerizable composition containing a norbornene-based monomer and a polymerization catalyst. It is a polymer obtained by polymerizing.
First, each component contained in the polymerizable composition used for forming a bulk ring-opening polymer of a norbornene-based monomer will be described.
ノルボルネン系モノマーとしては、ノルボルネン環構造を有する化合物であれば良く、特に限定はされないが、ノルボルネン、ノルボルナジエン等の二環体；ジシクロペンタジエン（シクロペンタジエン二量体）、ジヒドロジシクロペンタジエン等の三環体；テトラシクロドデセン等の四環体；シクロペンタジエン三量体等の五環体；シクロペンタジエン四量体等の七環体；等を挙げることができる。
これらのノルボルネン系モノマーは、メチル基、エチル基、プロピル基、ブチル基等のアルキル基；ビニル基等のアルケニル基；エチリデン基等のアルキリデン基；フェニル基、トリル基、ナフチル基等のアリール等の置換基を有していてもよく、さらに、これらのノルボルネン系モノマーは、エステル基、エーテル基、シアノ基、ハロゲン原子等の極性基を有していてもよい。
The norbornene-based monomer is not particularly limited as long as it is a compound having a norbornene ring structure, but it is not limited to bicyclic compounds such as norbornene and norbornadiene; tricyclopentadiene (cyclopentadiene dimer), dihydrodicyclopentadiene and the like A ring; a tetracycle such as tetracyclododecene; a pentacycle such as cyclopentadiene trimer; a heptacycle such as cyclopentadiene tetramer; and the like.
These norbornene monomers include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups such as vinyl group; alkylidene groups such as ethylidene group; aryl such as phenyl group, tolyl group and naphthyl group; These norbornene monomers may have a polar group such as an ester group, an ether group, a cyano group, or a halogen atom.
このようなノルボルネン系モノマーの具体例としては、ジシクロペンタジエン、トリシクロペンタジエン、シクロペンタジエン−メチルシクロペンタジエン共二量体、５−エチリデンノルボルネン、ノルボルネン、ノルボルナジエン、５−シクロヘキセニルノルボルネン、１，４，５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、１，４−メタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−エチリデン−１，４，５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、６−エチリデン−１，４−メタノ−１，４，４ａ，５，６，７，８，８ａ−オクタヒドロナフタレン、１，４，５，８−ジメタノ−１，４，４ａ，５，６，７，８，８ａ−ヘキサヒドロナフタレン、エチレンビス（５−ノルボルネン）等が挙げられる。
ノルボルネン系モノマーは、１種を単独で使用してもよく、２種以上を組み合わせて用いてもよい。
Specific examples of such norbornene-based monomers include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene codimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4, 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydro Naphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4-methano-1,4 4a, 5,6,7,8,8a-octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-hex Tetrahydronaphthalene, ethylenebis (5-norbornene), and the like.
Norbornene monomers may be used alone or in combination of two or more.
上記ノルボルネン系モノマーのうちでは、入手が容易であり、反応性に優れ、得られる複合成形体を耐熱性に優れたものとすることができる点から、三環体、四環体または五環体のノルボルネン系モノマーが好ましい。 Among the norbornene-based monomers, tricyclic, tetracyclic or pentacyclic are easy to obtain, have excellent reactivity, and can make the resulting composite molded article excellent in heat resistance. Norbornene monomers are preferred.
また、塊状重合により生成する開環重合体が熱硬化型となることが好ましく、そのためには、上記ノルボルネン系モノマーの中でも、対称性のシクロペンタジエン三量体等の、反応性の二重結合を二個以上有する架橋性モノマーを少なくとも含むものを用いることが好ましい。このような架橋性モノマーの割合は、全ノルボルネン系モノマー中に、２〜３０重量％であることが好ましい。 Further, the ring-opening polymer produced by bulk polymerization is preferably a thermosetting type. For this purpose, among the norbornene monomers, a reactive double bond such as a symmetric cyclopentadiene trimer is used. It is preferable to use one containing at least two crosslinkable monomers. The ratio of such a crosslinkable monomer is preferably 2 to 30% by weight in the total norbornene-based monomer.
なお、本発明の目的を損なわない範囲で、ノルボルネン系モノマーと開環共重合し得るシクロブテン、シクロペンテン、シクロペンタジエン、シクロオクテン、シクロドデセン等の単環シクロオレフィン等を、コモノマーとして用いてもよい。 In addition, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene, which can be ring-opening copolymerized with a norbornene-based monomer, may be used as a comonomer within a range that does not impair the object of the present invention.
重合性組成物に含有させる重合触媒としては、メタセシス重合触媒が好ましい。
メタセシス重合触媒は、遷移金属原子を中心原子として、複数のイオン、原子、多原子イオンおよび／または化合物が結合してなる錯体である。遷移金属原子としては、周期表（長周期型周期表、以下同じ）第５、６および８族の原子が使用される。このような遷移金属原子としては、特に限定されないが、第５族の原子としては、たとえばタンタルが挙げられ、第６族の原子としては、たとえばモリブデンやタングステンが挙げられ、第８族の原子としては、たとえばルテニウムやオスミウムが挙げられる。
A metathesis polymerization catalyst is preferable as the polymerization catalyst contained in the polymerizable composition.
The metathesis polymerization catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. As transition metal atoms, atoms of Groups 5, 6 and 8 of the periodic table (long-period periodic table, the same shall apply hereinafter) are used. Such a transition metal atom is not particularly limited. Examples of the Group 5 atom include tantalum. Examples of the Group 6 atom include molybdenum and tungsten. Examples of the Group 8 atom include Examples include ruthenium and osmium.
これらの中でも、第８族のルテニウムやオスミウムの錯体をメタセシス重合触媒として用いることが好ましく、ルテニウムカルベン錯体が特に好ましい。ルテニウムカルベン錯体は、触媒活性に優れるため重合性組成物の開環重合反応率を高くすることができ、生産性に優れるという利点を有する。また、得られる重合体における未反応の環状オレフィンに由来する臭気を低減することができる。さらに、酸素や空気中の水分に対して比較的安定であって、失活しにくいので、大気下でも生産が可能であるという利点も有する。 Among these, it is preferable to use a group 8 ruthenium or osmium complex as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. The ruthenium carbene complex has an advantage that the ring opening polymerization reaction rate of the polymerizable composition can be increased because the catalyst activity is excellent, and the productivity is excellent. Moreover, the odor derived from the unreacted cyclic olefin in the obtained polymer can be reduced. Furthermore, since it is relatively stable against oxygen and moisture in the air and is not easily deactivated, it has an advantage that it can be produced even in the atmosphere.
ルテニウムカルベン錯体としては、下記式（３）または（４）で表される錯体化合物が好ましい。
なお、ヘテロ原子とは、周期表第１５族および第１６族の原子を意味し、具体的には、Ｎ、Ｏ、Ｐ、Ｓ、Ａｓ、Ｓｅ原子などを挙げることができる。これらの中でも、安定なカルベン化合物が得られる観点から、Ｎ、Ｏ、Ｐ、Ｓ原子などが好ましく、Ｎ原子が特に好ましい。
The ruthenium carbene complex is preferably a complex compound represented by the following formula (3) or (4).
The hetero atom means an atom belonging to Group 15 and Group 16 of the periodic table, and specifically includes N, O, P, S, As, Se atoms, and the like. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.
ヘテロ原子含有カルベン化合物としては、カルベン炭素の両側にヘテロ原子が隣接して結合しているものが好ましく、さらにカルベン炭素原子とその両側のヘテロ原子とを含むヘテロ環が構成されているものがより好ましい。また、カルベン炭素に隣接するヘテロ原子には嵩高い置換基を有していることが好ましい。
このようなヘテロ原子含有カルベン化合物としては、下記式（５）または（６）で示される化合物が好ましい。
As such a hetero atom-containing carbene compound, a compound represented by the following formula (5) or (6) is preferable.
上記式（３）および（４）において、アニオン性配位子Ｘ２、Ｘ３は、中心金属から引き離されたときに負の電荷を持つ配位子であり、たとえば、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子；ジケトネート基、置換シクロペンタジエニル基、アルコキシ基、アリールオキシ基、カルボキシル基などを挙げることができる。これらの中でもハロゲン原子が好ましく、塩素原子がより好ましい。 In the above formulas (3) and (4), the anionic ligands X 2 and X 3 are ligands having a negative charge when separated from the central metal, for example, F, Cl, Br, A halogen atom such as I; a diketonate group, a substituted cyclopentadienyl group, an alkoxy group, an aryloxy group, a carboxyl group, and the like. Among these, a halogen atom is preferable and a chlorine atom is more preferable.
また、中性の電子供与性化合物は、中心金属から引き離されたときに中性の電荷を持つ配位子であればいかなるものでもよく、たとえば、カルボニル、アミン類、ピリジン類、エーテル類、ニトリル類、エステル類、ホスフィン類、チオエーテル類、芳香族化合物、オレフィン類、イソシアニド類、チオシアネート類などが挙げられる。これらの中でも、ホスフィン類、エーテル類およびピリジン類が好ましく、トリアルキルホスフィンがより好ましい。 Further, the neutral electron donating compound may be any ligand as long as it has a neutral charge when separated from the central metal, such as carbonyl, amines, pyridines, ethers, nitriles. , Esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates and the like. Among these, phosphines, ethers and pyridines are preferable, and trialkylphosphine is more preferable.
上記式（３）または（４）で表される錯体化合物の具体例としては、ベンジリデン（１，３−ジメシチルイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（１，３−ジメシチルイミダゾリジン−２−イリデン）（３−メチル−２−ブテン−１−イリデン）（トリシクロペンチルホスフィン）ルテニウムジクロリド、ベンジリデン（１，３−ジメシチル−２，３−ジヒドロベンズイミダゾール−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、トリシクロヘキシルホスフィン［１，３−ビス（２，４，６−トリメチルフェニル）−４，５−ジヒドロイミダゾル−２−イリデン］［ ３−メチル−２−ブテニリデン］ルテニウムジクロライド、などのＬ１、Ｌ２がそれぞれヘテロ原子含有カルベン化合物および中性の電子供与性化合物であるルテニウム錯体化合物；ベンジリデンビス（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（３−メチル−２−ブテン−１−イリデン）ビス（トリシクロペンチルホスフィン）ルテニウムジクロリドなどのＬ１、Ｌ２ともに中性電子供与性化合物であるルテニウム化合物；ベンジリデンビス（１，３−ジシクロヘキシルイミダゾリジン−２−イリデン）ルテニウムジクロリド、ベンジリデンビス（１，３−ジイソプロピル−４−イミダゾリン−２−イリデン）ルテニウムジクロリドなどのＬ１、Ｌ２ともヘテロ原子含有カルベン化合物であるルテニウム錯体化合物；などが挙げられるが、これらの中でも（Ｉ）Ｌ１、Ｌ２がそれぞれヘテロ原子含有カルベン化合物および中性の電子供与性化合物であるルテニウム錯体化合物、または、（ＩＩ）Ｌ１、Ｌ２ともヘテロ原子含有カルベン化合物であるルテニウム錯体化合物が好ましい。 Specific examples of the complex compound represented by the above formula (3) or (4) include benzylidene (1,3-dimesityrimimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3- Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) ) (Tricyclohexylphosphine) ruthenium dichloride, tricyclohexylphosphine [1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene] [3-methyl-2-butenylidene] L 1 and L 2 such as ruthenium dichloride Telo atom-containing carbene compound and neutral electron donating compound ruthenium complex compound; benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride A ruthenium compound which is a neutral electron donating compound such as L 1 and L 2 ; benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline- 2-ylidene) ruthenium dichloride L 1, L 2 both ruthenium complex compound is a hetero atom-containing carbene compounds, such as but like, among these (I) L 1, L 2 are hetero atom-containing carbene respectively Compound and ruthenium complex compounds which are neutral electron donating compounds, or, a ruthenium complex compound is preferably (II) L 1, L 2 both hetero atom-containing carbene compound.
また、上記式（５）および（６）で表される化合物の具体例としては、１，３−ジメシチルイミダゾリジン−２−イリデン、１，３−ジメシチル−４−イミダゾリン−２−イリデン、１，３−ジ（１−フェニルエチル）−４−イミダゾリン−２−イリデン、１，３−ジメシチル−２，３−ジヒドロベンズイミダゾール−２−イリデンなどが挙げられる。さらに、上記式（５）および（６）で表される化合物の他に、１，３，４−トリフェニル−２，３，４，５−テトラヒドロ−１Ｈ−１，２，４−トリアゾール−５−イリデン、１，３，４−トリフェニル−４，５−ジヒドロ−１Ｈ−１，２，４−トリアゾール−５−イリデンなどのヘテロ原子含有カルベン錯体化合物なども使用できる。 Specific examples of the compounds represented by the above formulas (5) and (6) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-dimesityl-4-imidazoline-2-ylidene, Examples include 1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene and 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene. Further, in addition to the compounds represented by the above formulas (5) and (6), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5 -Heteroatom-containing carbene complex compounds such as ylidene and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-ylidene can also be used.
なお、これらのルテニウム錯体化合物は、たとえば、Ｏｒｇ．Ｌｅｔｔ．，１９９９年，第１巻，９５３頁、Ｔｅｔｒａｈｅｄｒｏｎ．Ｌｅｔｔ．，１９９９年，第４０巻，２２４７頁などに記載された方法によって製造することができる。 These ruthenium complex compounds are described in, for example, Org. Lett. 1999, Vol. 1, p. 953, Tetrahedron. Lett. 1999, Vol. 40, page 2247, and the like.
メタセシス重合触媒の量は、触媒中の金属原子：ノルボルネン系モノマーのモル比で、通常１：２，０００〜１：２，０００，０００、好ましくは１：５，０００〜１：１，０００，０００、より好ましくは１：１０，０００〜１：５００，０００の範囲である。 The amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: 1,000, in the molar ratio of metal atom to norbornene monomer in the catalyst. 000, more preferably in the range of 1: 10,000 to 1: 500,000.
メタセシス重合触媒を使用する際には、必要に応じて、少量の不活性溶剤に溶解または懸濁して使用することができる。このような溶媒としては、特に限定されないが、たとえば、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、流動パラフィン、ミネラルスピリットなどの鎖状脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、トリシクロデカン、シクロオクタンなどの飽和脂環式炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素；ニトロメタン、ニトロベンゼン、アセトニトリルなどの含窒素炭化水素；ジエチルエーテル、テトラヒドロフランなどの含酸素炭化水素；などが挙げられる。これらの中では、工業的に汎用な芳香族炭化水素や脂肪族炭化水素、飽和脂環式炭化水素の使用が好ましい。また、メタセシス重合触媒としての活性を低下させないものであれば、液状の老化防止剤、液状の可塑剤、液状のエラストマーなど、得られる重合体の性能に寄与する機能性液状化合物を溶剤として用いてもよい。 When using a metathesis polymerization catalyst, it can be used by dissolving or suspending in a small amount of an inert solvent, if necessary. Examples of such a solvent include, but are not limited to, chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane , Saturated cycloaliphatic hydrocarbons such as trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, tricyclodecane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing compounds such as nitromethane, nitrobenzene and acetonitrile Hydrocarbons; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; and the like. Among these, it is preferable to use industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons, and saturated alicyclic hydrocarbons. Moreover, as long as the activity as a metathesis polymerization catalyst is not reduced, a functional liquid compound that contributes to the performance of the obtained polymer, such as a liquid anti-aging agent, a liquid plasticizer, or a liquid elastomer, is used as a solvent. Also good.
さらに、重合性組成物には、メタセシス重合触媒の重合活性を制御したり、重合反応率を向上させたりする目的で、重合活性剤（共触媒）や重合遅延剤を重合性組成物中に配合してもよい。重合活性剤としては、有機アルミニウム化合物、有機亜鉛化合物、または有機スズ化合物などが挙げられる。 Furthermore, in the polymerizable composition, a polymerization activator (co-catalyst) or a polymerization retarder is incorporated into the polymerizable composition for the purpose of controlling the polymerization activity of the metathesis polymerization catalyst or improving the polymerization reaction rate. May be. Examples of the polymerization activator include organoaluminum compounds, organozinc compounds, and organotin compounds.
重合活性剤の具体例としては、トリアルコキシアルミニウム、トリフェノキシアルミニウム、ジアルコキシアルキルアルミニウム、アルコキシジアルキルアルミニウム、トリアルキルアルミニウム、ジアルコキシアルミニウムクロリド、アルコキシアルキルアルミニウムクロリド、ジアルキルアルミニウムクロリド、トリアルコキシスカンジウム、テトラアルコキシチタン、テトラアルコキシスズ、テトラアルコキシジルコニウムなどが挙げられる。 Specific examples of the polymerization activator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxy. Examples thereof include titanium, tetraalkoxytin, and tetraalkoxyzirconium.
重合遅延剤としては、たとえば、１，５−ヘキサジエン、２，５−ジメチル−１，５−ヘキサジエン、（シス，シス）−２，６−オクタジエン、（シス，トランス）−２，６−オクタジエン、（トランス，トランス）−２，６−オクタジエンなどの鎖状ジエン化合物；（トランス）−１，３，５−ヘキサトリエン、（シス）−１，３，５−ヘキサトリエン、（トランス）−２，５−ジメチル−１，３，５−ヘキサトリエン、（シス）−２，５−ジメチル−１，３，５−ヘキサトリエンなどの鎖状トリエン化合物；トリフェニルホスフィン、トリ−ｎ−ブチルホスフィン、メチルジフェニルホスフィンなどのホスフィン類；アニリンなどのルイス塩基；などが挙げられる。 Examples of the polymerization retarder include 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, (cis, cis) -2,6-octadiene, (cis, trans) -2,6-octadiene, Chain diene compounds such as (trans, trans) -2,6-octadiene; (trans) -1,3,5-hexatriene, (cis) -1,3,5-hexatriene, (trans) -2, Linear triene compounds such as 5-dimethyl-1,3,5-hexatriene and (cis) -2,5-dimethyl-1,3,5-hexatriene; triphenylphosphine, tri-n-butylphosphine, methyl Phosphines such as diphenylphosphine; Lewis bases such as aniline; and the like.
重合活性剤や重合遅延剤の量は、使用する化合物や目的に応じて任意に設定されるが、「メタセシス重合触媒中の遷移金属原子：重合活性剤または重合遅延剤」のモル比で、通常１：０．０５〜１：１００、好ましくは１：０．２〜１：２０、より好ましくは１：０．５〜１：１０の範囲である。 The amount of the polymerization activator and the polymerization retarder is arbitrarily set according to the compound used and the purpose, but is usually a molar ratio of “transition metal atom in the metathesis polymerization catalyst: polymerization activator or polymerization retarder”. It is in the range of 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably 1: 0.5 to 1:10.
また、本発明で用いる重合性組成物には、任意成分として、充填材を配合してもよい。充填材としては、種々の充填材を用いることができ、特に限定されないが、アスペクト比が５〜１００の繊維状充填材やアスペクト比が１〜２の粒子状充填材からなる無機充填材を用いることが好ましい。充填材のアスペクト比とは、充填材の平均長軸径と５０％体積累積径との比をいう。ここで、平均長軸径は、光学顕微鏡写真で無作為に選んだ１００個の充填材の長軸径を測定し、その算術平均値として算出される個数平均長軸径である。 また、５０％体積累積径は、Ｘ線透過法で粒度分布を測定することにより求められる値である。 Moreover, you may mix | blend a filler as an arbitrary component with the polymeric composition used by this invention. Various fillers can be used as the filler, and although not particularly limited, an inorganic filler made of a fibrous filler having an aspect ratio of 5 to 100 or a particulate filler having an aspect ratio of 1 to 2 is used. It is preferable. The aspect ratio of the filler refers to the ratio between the average major axis diameter of the filler and the 50% volume cumulative diameter. Here, the average major axis diameter is a number average major axis diameter calculated as an arithmetic average value obtained by measuring the major axis diameters of 100 fillers randomly selected from an optical micrograph. The 50% volume cumulative diameter is a value obtained by measuring the particle size distribution by the X-ray transmission method.
繊維状充填材と粒子状充填材とはそれぞれ単独で用いることができるが、両者を混合して用いてもよい。繊維状充填材と粒子状充填材とを混合して用いる場合における、これらの含有重量比率（繊維状充填材／粒子状充填材）は、好ましくは９５／５〜５５／４５であり、より好ましくは８０／２０〜６０／４０である。これらの比率を上記範囲内とすることにより、得られる複合成形体における、ノルボルネン系モノマーの塊状開環重合体と、複合化用部材との間の密着性のさらなる向上を図ることができる。 Although the fibrous filler and the particulate filler can be used alone, they may be used in combination. When the fibrous filler and the particulate filler are mixed and used, their content weight ratio (fibrous filler / particulate filler) is preferably 95/5 to 55/45, more preferably. Is 80 / 20-60 / 40. By setting these ratios within the above range, it is possible to further improve the adhesion between the bulk-opening polymer of norbornene-based monomer and the composite member in the obtained composite molded body.
上記繊維状充填材としては、５〜１００のアスペクト比を有するものであることが好ましく、１０〜５０のアスペクト比を有するものであることがより好ましい。繊維状充填材の５０％体積累積径は、好ましくは０．１〜５０μｍ、より好ましくは１〜３０μｍである。５０％体積累積径が小さすぎても、また大きすぎても、密着性の向上効果が低くなる傾向にある。 The fibrous filler preferably has an aspect ratio of 5 to 100, and more preferably has an aspect ratio of 10 to 50. The 50% volume cumulative diameter of the fibrous filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. If the 50% volume cumulative diameter is too small or too large, the effect of improving the adhesion tends to be low.
このような繊維状充填材の具体例としては、ガラス繊維、ウォラストナイト、チタン酸カリウム、ゾノライト、塩基性硫酸マグネシウム、ホウ酸アルミニウム、テトラポッド型酸化亜鉛、石膏繊維、ホスフェート繊維、アルミナ繊維、ウィスカー状炭酸カルシウム、ウィスカー状ベーマイト等を挙げることができる。中でも、塊状重合を阻害せず、密着性の向上効果を少ない使用量で高めることができるウォラストナイトおよびウィスカー状炭酸カルシウムが好ましい。 Specific examples of such fibrous fillers include glass fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, Examples include whisker-like calcium carbonate and whisker-like boehmite. Among these, wollastonite and whisker-like calcium carbonate that can increase the adhesion improving effect with a small amount of use without inhibiting bulk polymerization are preferable.
また、上記粒子状充填材は、１〜２のアスペクト比を有するものであることが好ましく、１〜１．５のアスペクト比を有するものであることがより好ましい。粒子状充填材の５０％体積累積径は、好ましくは０．１〜５０μｍ、より好ましくは１〜３０μｍ、特に好ましくは１〜１０μｍである。５０％体積累積径が小さすぎても、また大きすぎても、密着性の向上効果が低くなる傾向にある。 Further, the particulate filler preferably has an aspect ratio of 1 to 2, and more preferably has an aspect ratio of 1 to 1.5. The 50% volume cumulative diameter of the particulate filler is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and particularly preferably 1 to 10 μm. If the 50% volume cumulative diameter is too small or too large, the effect of improving the adhesion tends to be low.
このような粒子状充填材の具体例としては、炭酸カルシウム、水酸化カルシウム、ケイ酸カルシウム、硫酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、酸化チタン、酸化亜鉛、チタン酸バリウム、シリカ、アルミナ、カーボンブラック、グラファイト、酸化アンチモン、赤燐、各種金属粉、クレー、各種フェライト、ハイドロタルサイト等を挙げることができる。中でも、塊状重合反応を阻害しないので、炭酸カルシウムおよび水酸化カルシウムが好ましい。 Specific examples of such particulate fillers include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, carbon Examples thereof include black, graphite, antimony oxide, red phosphorus, various metal powders, clay, various ferrites, and hydrotalcite. Of these, calcium carbonate and calcium hydroxide are preferred because they do not inhibit the bulk polymerization reaction.
上記充填材は、その表面を疎水化処理したものであることが好ましい。疎水化処理した充填材を用いることにより、重合性組成物中における充填材の凝集・沈降を防止でき、また、ノルボルネン系モノマーの塊状開環重合体中における充填材の分散を均一にすることができる。そして、結果として、得られる複合成形体における、ノルボルネン系モノマーの塊状開環重合体と、複合化用部材との間の密着性の向上効果のさらなる向上が可能となる。疎水化処理に用いられる処理剤としては、ビニルシラン等のシランカップリング剤、チタネートカップリング剤、アルミニウムカップリング剤、ステアリン酸等の脂肪酸、油脂、界面活性剤、ワックス等を挙げることができる。充填材の疎水化処理は、重合性組成物を調製する際に、疎水化処理剤を同時に混合することによっても可能であるが、予め疎水化処理を行なった充填材を用いて重合性組成物の調製を行なうことが好ましい。 It is preferable that the surface of the filler is hydrophobized. By using the hydrophobized filler, aggregation and sedimentation of the filler in the polymerizable composition can be prevented, and the dispersion of the filler in the bulk ring-opening polymer of the norbornene monomer can be made uniform. it can. As a result, it is possible to further improve the effect of improving the adhesion between the bulk ring-opening polymer of norbornene-based monomer and the composite member in the obtained composite molded body. Examples of the treating agent used for the hydrophobizing treatment include silane coupling agents such as vinyl silane, titanate coupling agents, aluminum coupling agents, fatty acids such as stearic acid, fats and oils, surfactants, and waxes. Hydrophobic treatment of the filler can be performed by mixing the hydrophobizing agent at the same time when preparing the polymerizable composition, but the polymerizable composition can be prepared using a filler that has been previously hydrophobized. It is preferable to carry out the preparation of
本発明において、充填材の量は、ノルボルネン系モノマーおよび触媒の合計量１００重量部に対して、５〜５５重量部であることが好ましく、１０〜４５重量部であることがより好ましい。充填材の量が多すぎると、密着性が低下してくる場合がある。一方、少なすぎると、充填材の添加効果が得難くなる。 In the present invention, the amount of the filler is preferably 5 to 55 parts by weight, and more preferably 10 to 45 parts by weight with respect to 100 parts by weight of the total amount of the norbornene monomer and the catalyst. If the amount of the filler is too large, the adhesion may decrease. On the other hand, if the amount is too small, it is difficult to obtain the effect of adding the filler.
また、重合性組成物には、上記以外の各種添加剤を含有させてもよい。このような添加剤としては、改質剤、酸化防止剤、着色剤、光安定剤、難燃剤などが例示される。 Moreover, you may make the polymeric composition contain various additives other than the above. Examples of such additives include modifiers, antioxidants, colorants, light stabilizers, flame retardants, and the like.
改質剤としては、たとえば、天然ゴム、ポリブタジエン、ポリイソプレン、スチレン−ブタジエン共重合体（ＳＢＲ）、スチレン−ブタジエン−スチレンブロック共重合体（ＳＢＳ）、スチレン−イソプレン−スチレン共重合体（ＳＩＳ）、エチレン−プロピレン−ジエンターポリマー（ＥＰＤＭ）、エチレン−酢酸ビニル共重合体（ＥＶＡ）及びこれらの水素化物などのエラストマーなどが挙げられる。酸化防止剤としては、例えば、ヒンダードフェノール系、リン系、アミン系などの各種のプラスチック・ゴム用酸化防止剤などが挙げられる。 Examples of the modifier include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), and styrene-isoprene-styrene copolymer (SIS). And elastomers such as ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and hydrides thereof. Examples of the antioxidant include various plastic and rubber antioxidants such as hindered phenol, phosphorus, and amine.
着色剤としては、染料、顔料などが用いられる。染料の種類は多様であり、公知のものを適宜選択して使用すればよい。また、顔料としては、たとえば、カーボンブラック、黒鉛、黄鉛、酸化鉄黄色、二酸化チタン、酸化亜鉛、四酸化三鉛、鉛丹、酸化クロム、紺青、チタンブラックなどが挙げられる。
光安定剤としては、たとえば、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、サリシレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、オギザニリド系紫外線吸収剤、ヒンダードアミン系紫外線吸収剤、ベンゾエート系紫外線吸収剤などが挙げられる。
難燃剤としては、リン系難燃剤、窒素系難燃剤、ハロゲン系難燃剤、水酸化アルミニウムまたは水酸化マグネシウムなどの金属水酸化物系難燃剤などが挙げられる。
As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used. Examples of the pigment include carbon black, graphite, yellow lead, iron oxide yellow, titanium dioxide, zinc oxide, trilead tetraoxide, red lead, chromium oxide, bitumen, and titanium black.
Examples of light stabilizers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. Agents and the like.
Examples of the flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a halogen flame retardant, and a metal hydroxide flame retardant such as aluminum hydroxide or magnesium hydroxide.
これらの添加剤の量は、用途に応じた量とすれば良いが、ノルボルネン系モノマー１００重量部に対して、それぞれ０．００１〜１０００重量部の範囲とすることが好ましい。 The amount of these additives may be set according to the use, but is preferably in the range of 0.001 to 1000 parts by weight with respect to 100 parts by weight of the norbornene monomer.
複合化用部材
本発明で用いる複合化用部材は、金属材料から構成され、上述の重合性組成物を塊状開環重合させることにより得られるノルボルネン系モノマーの塊状開環重合体と一体成形されるものである。
Composite member The composite member used in the present invention is composed of a metal material and is integrally formed with a norbornene monomer bulk ring-opening polymer obtained by bulk ring-opening polymerization of the polymerizable composition described above. Is.
複合化用部材を構成する金属材料としては、特に限定されないが、鉄、銅、ニッケル、金、銀、白金、パラジウム、コバルト、亜鉛、鉛、スズ、チタン、クロム、アルミニウム、マグネシウム、マンガンおよびこれらの合金などの各種金属材料を挙げることができる。 The metal material constituting the composite member is not particularly limited, but iron, copper, nickel, gold, silver, platinum, palladium, cobalt, zinc, lead, tin, titanium, chromium, aluminum, magnesium, manganese, and these And various metal materials such as alloys of
また、複合化用部材の形状も、特に限定されないが、ノルボルネン系モノマーの塊状開環重合体と積層体を形成することができることから、板状又は薄膜状のものが好ましい。板状又は薄膜状の場合、その厚みは、好ましくは０．００１〜１００ｍｍ、より好ましくは０．１〜５０ｍｍ、特に好ましくは０．５〜４０ｍｍである。
複合化用部材は、金属箔であっても良いし、さらには、プリント配線板の製造用基板等の基板や、各種電子部品の端子電極などでも良い。特に、複合化用部材を、各種電子部品の端子電極とし、これらとノルボルネン系モノマーの塊状開環重合体とを一体成形することにより、ノルボルネン系モノマーの塊状開環重合体を、封止材として用いることができる。
Further, the shape of the compositing member is not particularly limited, but a plate-like or thin-film-like one is preferable because it can form a laminated body with a bulk ring-opening polymer of norbornene-based monomer. In the case of a plate or thin film, the thickness is preferably 0.001 to 100 mm, more preferably 0.1 to 50 mm, and particularly preferably 0.5 to 40 mm.
The composite member may be a metal foil, or may be a substrate such as a printed wiring board manufacturing substrate or a terminal electrode of various electronic components. In particular, the composite member is used as a terminal electrode for various electronic components, and the bulk-opening polymer of the norbornene-based monomer is integrally formed with the bulk-opening polymer of the norbornene-based monomer as the sealing material. Can be used.
カップリング剤
本発明の複合成形体は、上述の重合性組成物を塊状開環重合させて得られるノルボルネン系モノマーの塊状開環重合体と、上述の金属材料からなる複合化用部材とを一体成形してなる複合成形体であり、金属材料からなる複合化用部材の、ノルボルネン系モノマーの塊状開環重合体との接触界面のうちの少なくとも一部が、以下に説明する所定のカップリング剤で処理されてなるものである。なお、接触界面のうちの５０％以上、好ましくは７０％以上、特に好ましくは９０％以上が所定のカップリング剤で処理されてなることが好ましい。
以下、本発明で用いられるカップリング剤について説明する。
Coupling Agent The composite molded body of the present invention is a combination of a norbornene monomer bulk ring-opening polymer obtained by bulk ring-opening polymerization of the polymerizable composition and a composite member made of the metal material described above. At least a part of the contact interface with the bulk-opening polymer of the norbornene-based monomer of the composite member made of a metal material is a predetermined coupling agent described below It is processed by. In addition, it is preferable that 50% or more, preferably 70% or more, particularly preferably 90% or more of the contact interface is treated with a predetermined coupling agent.
Hereinafter, the coupling agent used in the present invention will be described.
本発明で用いられるカップリング剤は、下記式（１）で示される化合物である。
上記式（１）において、Ｒ１は、ノルボルネン構造を有する置換基であれば良いが、本発明の効果がより一層顕著になることから、下記式（２）で表される置換基が好ましい。
上記式（２）において、酸素原子を含む官能基としては、たとえば、ヒドロキシル、アルコキシル、アリールオキシ、カルボニル、ヒドロキシカルボニル、アルコキシカルボニル、アリールオキシカルボニル、酸無水物等が挙げられる。窒素原子を含む官能基としては、たとえば、アミノ、アルキルアミノ、アリールアミノ、シアノ等が挙げられる。酸素原子および窒素原子を含む官能基としては、たとえば、アミノカルボニル、アルキルアミノカルボニル、アリールアミノカルボニル等が挙げられる。硫黄原子を含む官能基としては、たとえば、メルカプト、アルキルチオ、アリールチオ等が挙げられる。ケイ素原子を含む官能基としては、たとえば、シリル、アルキルシリル、アリールシリル等が挙げられる。酸素原子およびケイ素原子を含む官能基としては、たとえば、アルコキシシリル、アリールオキシシリル等が挙げられる。 In the above formula (2), examples of the functional group containing an oxygen atom include hydroxyl, alkoxyl, aryloxy, carbonyl, hydroxycarbonyl, alkoxycarbonyl, aryloxycarbonyl, acid anhydride and the like. Examples of the functional group containing a nitrogen atom include amino, alkylamino, arylamino, cyano and the like. Examples of the functional group containing an oxygen atom and a nitrogen atom include aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl and the like. Examples of the functional group containing a sulfur atom include mercapto, alkylthio, arylthio and the like. Examples of the functional group containing a silicon atom include silyl, alkylsilyl, arylsilyl and the like. Examples of the functional group containing an oxygen atom and a silicon atom include alkoxysilyl and aryloxysilyl.
このような上記式（２）で表される置換基の具体例としては、ビシクロヘプテニル基（ノルボルネニル基）、ジシクロペンタジエニル基、テトラシクロドデセニル基、トリシクロペンタジエニル基等の置換基が挙げられる。 Specific examples of the substituent represented by the above formula (2) include a bicycloheptenyl group (norbornenyl group), a dicyclopentadienyl group, a tetracyclododecenyl group, and a tricyclopentadienyl group. And the like.
上記式（１）中、Ｒ２、Ｒ３は、エーテル基またはエステル基を含有しても良い炭素数１〜３のアルキル基および／またはアシル基であり、Ｒ２、Ｒ３の具体例としては、メチル基、エチル基、アセトキシ基、プロピル基などが挙げられる。また、上記式（１）中、Ｘ１はハロゲン原子であり、Ｆ、Ｃｌ、Ｂｒ、Ｉなどが挙げられる。 In the above formula (1), R 2, R 3 is an alkyl and / or acyl group having 1 to 3 carbon atoms which may contain ether or ester groups, specific examples of R 2, R 3 Includes a methyl group, an ethyl group, an acetoxy group, a propyl group, and the like. In the above formula (1), X 1 is a halogen atom, and examples thereof include F, Cl, Br, and I.
上記式（１）中、ｋは２〜１０の整数であり、好ましくは２〜６の整数である。ｋの値が小さすぎると、すなわち、ノルボルネン構造を有する置換基とＳｉとの間の炭素数が少なすぎると、重合前のノルボルネン系モノマーを含有する重合性組成物と、上述の金属材料からなる複合化用部材とのぬれ性が低下し、結果として、複合成形体とした場合における、ノルボルネン系モノマーの塊状開環重合体と、上述の金属材料からなる複合化用部材との密着性が低下してしまう。一方、ｋの値が大きすぎると、すなわち、ノルボルネン構造を有する置換基とＳｉとの間の炭素数が多すぎると、螺旋構造となるため密着性が低下してしまう。また、ｍ、ｎは０〜３の整数（ただし、ｍ＋ｎ≦３）であれば良い。
上記式（１）で表される化合物の具体例としては、ビシクロヘプテニルエチルトリエトキシシラン、ビシクロヘプテニルプロピルトリエトキシシラン、ビシクロヘプテニルブチルトリエトキシシラン、ビシクロヘプテニルヘキシルトリエトキシシランなどのｍ＝３かつｎ＝０で表されるもの；ビシクロヘプテニルエチルトリエチルシラン、ビシクロヘプテニルプロピルトリメチルシラン、ビシクロヘプテニルブチルトリプロピルシラン、ビシクロヘプテニルヘキシルトリエチルシランなどのｍ＝０かつｎ＝０で表されるもの；ビシクロヘプテニルエチルトリクロロシラン、ビシクロヘプテニルプロピルトリブロモシランなどのｍ＝０かつｎ＝３で表されるもの；が挙げられるが、本発明の効果がより一層顕著になることから、ｍ＝３かつｎ＝０で表されるものが好ましい。
In said formula (1), k is an integer of 2-10, Preferably it is an integer of 2-6. When the value of k is too small, that is, when the number of carbon atoms between the substituent having the norbornene structure and Si is too small, the polymerizable composition containing the norbornene-based monomer before polymerization and the above-described metal material are used. As a result, the wettability with the composite member decreases, and as a result, the adhesiveness between the bulk-opening polymer of norbornene-based monomer and the composite member made of the above-described metal material in the case of a composite molded body decreases. Resulting in. On the other hand, if the value of k is too large, that is, if the number of carbon atoms between the substituent having the norbornene structure and Si is too large, the helical structure is formed and the adhesion is deteriorated. Moreover, m and n should just be an integer of 0-3 (however, m + n <= 3).
Specific examples of the compound represented by the above formula (1) include m, such as bicycloheptenylethyltriethoxysilane, bicycloheptenylpropyltriethoxysilane, bicycloheptenylbutyltriethoxysilane, and bicycloheptenylhexyltriethoxysilane. = 3 and n = 0; bicycloheptenylethyltriethylsilane, bicycloheptenylpropyltrimethylsilane, bicycloheptenylbutyltripropylsilane, bicycloheptenylhexyltriethylsilane, etc. where m = 0 and n = 0 Those represented by m = 0 and n = 3, such as bicycloheptenylethyltrichlorosilane, bicycloheptenylpropyltribromosilane, etc., but the effects of the present invention become more prominent. From m = 3 and n = In those represented by it is preferred.
このようなカップリング剤を用いて、金属材料からなる複合化用部材の表面を処理する方法としては、特に限定されないが、たとえば、以下に説明する浸漬処理法が挙げられる。 Although it does not specifically limit as a method of processing the surface of the compounding member which consists of metal materials using such a coupling agent, For example, the immersion treatment method demonstrated below is mentioned.
浸漬処理法は、カップリング剤を水または有機溶剤に溶解させた溶液を用い、金属材料からなる複合化用部材を、好ましくは０．１〜１２０分間、より好ましくは３〜３０分間浸漬することにより、金属材料からなる複合化用部材に対して表面処理を行う方法である。これにより、金属材料からなる複合化用部材の表面に、上述のカップリング剤を付着させることができる。浸漬処理法に用いる溶液中におけるカップリング剤の濃度は、特に限定されず、複合化用部材を構成する金属材料の種類や、浸漬処理時間などに応じて適宜調整すれば良いが、好ましくは０．５〜３００ｍｍｏｌ／Ｌ、より好ましくは５〜２００ｍｍｏｌ／Ｌ、特に好ましくは１０〜１００ｍｍｏｌ／Ｌである。また、浸漬処理を行う際における溶液の温度は、複合化用部材を構成する金属材料の種類や、溶液中のカップリング剤の濃度、さらには溶液を調製する際に用いる溶媒の種類に応じて適宜調整すれば良い。 In the dipping treatment method, a solution in which a coupling agent is dissolved in water or an organic solvent is used, and the composite member made of a metal material is preferably dipped for 0.1 to 120 minutes, more preferably for 3 to 30 minutes. Thus, the surface treatment is performed on the composite member made of the metal material. Thereby, the above-mentioned coupling agent can be made to adhere to the surface of the compounding member made of a metal material. The concentration of the coupling agent in the solution used for the immersion treatment method is not particularly limited, and may be appropriately adjusted according to the type of metal material constituting the composite member, the immersion treatment time, and the like, but preferably 0. 0.5 to 300 mmol / L, more preferably 5 to 200 mmol / L, and particularly preferably 10 to 100 mmol / L. In addition, the temperature of the solution when performing the immersion treatment depends on the type of metal material constituting the composite member, the concentration of the coupling agent in the solution, and the type of solvent used when preparing the solution. What is necessary is just to adjust suitably.
さらに、浸漬処理法により表面処理を行った後に、必要に応じて、金属材料からなる複合化用部材に対して、熱処理を行ってもよい。熱処理を行うことにより、金属材料からなる複合化用部材の表面に、上述のカップリング剤をより確実に固定させることができ、上述の重合性組成物と、上述の金属材料からなる複合化用部材とのぬれ性をより向上させることができ、これにより、ノルボルネン系モノマーの塊状開環重合体と、金属材料からなる複合化用部材との密着性の更なる向上を図ることができる。
上記熱処理温度は、５０℃以上が好ましく、７０℃以上がより好ましく、９０℃以上が特に好ましい。また、熱処理温度の上限は、２５０℃以下が好ましく、１５０℃以下が特に好ましい。
なお、熱処理時間は、好ましくは１０秒〜１００分、より好ましくは１〜５０分、特に好ましくは２〜２０分である。
Furthermore, after the surface treatment is performed by the immersion treatment method, the composite member made of a metal material may be heat-treated as necessary. By performing the heat treatment, the above-mentioned coupling agent can be more reliably fixed to the surface of the composite member made of the metal material, and the composite composition made of the above-described polymerizable composition and the above-mentioned metal material can be used. The wettability with the member can be further improved, whereby the adhesion between the bulk-opening polymer of norbornene-based monomer and the compositing member made of a metal material can be further improved.
The heat treatment temperature is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 90 ° C. or higher. The upper limit of the heat treatment temperature is preferably 250 ° C. or lower, and particularly preferably 150 ° C. or lower.
The heat treatment time is preferably 10 seconds to 100 minutes, more preferably 1 to 50 minutes, and particularly preferably 2 to 20 minutes.
複合成形体
本発明の複合成形体は、上述の重合性組成物を、上述の複合化用部材に塗布する方法などにより、重合性組成物と複合化用部材とを一体化させ、次いで、重合性組成物中に含有されるノルボルネン系モノマーを塊状開環重合させ、これらを一体成形することにより製造される。なお、この際において、複合化用部材の表面のうち、上述のカップリング剤で表面処理された面の少なくとも一部が、重合性組成物と接するような状態で、これらを一体化する。このような状態とすることにより、上述のシランカップリング剤を用いた効果を十分に発揮させることができ、結果として、ノルボルネン系モノマーの塊状開環重合体と複合化用部材との密着性の向上を図ることができる。
Composite molded body The composite molded body of the present invention is obtained by integrating the polymerizable composition and the composite member by a method such as applying the above-described polymerizable composition to the composite member described above, and then polymerizing. The norbornene-based monomer contained in the adhesive composition is produced by bulk ring-opening polymerization and integrally molding them. In this case, at least a part of the surface of the composite member that has been surface-treated with the above-described coupling agent is integrated with the polymerizable composition. By adopting such a state, the effect of using the above-mentioned silane coupling agent can be sufficiently exerted, and as a result, the adhesion between the bulk-opening polymer of the norbornene monomer and the composite member Improvements can be made.
重合性組成物と複合化用部材とを塗布法により一体化させる場合には、たとえば、スプレーコート法、ディップコート法、ロールコート法、カーテンコート法、ダイコート法、スリットコート法などの公知の塗布方法を採用することができる。 When the polymerizable composition and the composite member are integrated by a coating method, for example, a known coating method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, or a slit coating method. The method can be adopted.
また、重合性組成物を塊状開環重合させる方法としては、特に限定されないが、重合性組成物と複合化用部材とを一体化させた状態で、加熱し、これにより塊状開環重合させることが好ましい。塊状開環重合させるための加熱温度は、通常、３０〜２５０℃、好ましくは５０〜２１０℃である。また、重合時間は、適宜選択すればよいが、好ましくは、１０秒〜２０分である。 In addition, the method for bulk ring-opening polymerization of the polymerizable composition is not particularly limited, but heating is performed in a state where the polymerizable composition and the composite member are integrated, thereby performing bulk ring-opening polymerization. Is preferred. The heating temperature for bulk ring-opening polymerization is usually 30 to 250 ° C, preferably 50 to 210 ° C. Moreover, what is necessary is just to select superposition | polymerization time suitably, Preferably, it is 10 second-20 minutes.
重合性組成物を所定温度に加熱することにより重合反応が開始する。この重合反応は発熱反応であり、一旦反応が開始すると、組成物の温度が急激に上昇し、短時間（例えば、１０秒から５分程度）でピーク温度に到達する。 A polymerization reaction is started by heating the polymerizable composition to a predetermined temperature. This polymerization reaction is an exothermic reaction, and once the reaction starts, the temperature of the composition rises rapidly and reaches the peak temperature in a short time (for example, about 10 seconds to 5 minutes).
なお、本発明においては、上述した方法の他、重合性組成物を２以上の反応原液（たとえば、（１）ノルボルネン系モノマーと重合触媒とを含有する反応原液と、（２）ノルボルネン系モノマーと重合活性剤とを含有する反応原液と、の２つの反応原液）に分け、反応射出成形（ＲＩＭ）により、これらを、上述の複合化用部材を配置した型内に別々に注入し、型内で塊状重合させることにより製造しても良い。この場合において、反応射出成形（ＲＩＭ）装置として公知の衝突混合装置を用いることができる。 In the present invention, in addition to the above-described method, the polymerizable composition is mixed with two or more reaction stock solutions (for example, (1) a reaction stock solution containing a norbornene monomer and a polymerization catalyst, and (2) a norbornene monomer. Reaction stock solution containing a polymerization activator and two reaction stock solutions), and these are separately injected into the mold in which the above-mentioned composite member is arranged by reaction injection molding (RIM). It may be produced by bulk polymerization. In this case, a known collision mixing device can be used as a reaction injection molding (RIM) device.
以上のようにして本発明の複合成形体を製造することができる。このようにして製造される本発明の複合成形体は、ノルボルネン系モノマーを塊状開環重合させることにより得られる重合体を用いているため、電気特性、機械的特性、耐衝撃特性、耐熱性および耐候性に優れたものである。しかも、本発明の複合成形体は、複合化用部材の、ノルボルネン系モノマーの塊状開環重合体との接触界面のうちの少なくとも一部を、所定のカップリング剤で処理してなるものであるため、重合前のノルボルネン系モノマーを含有する重合性組成物と、上述の金属材料からなる複合化用部材とのぬれ性が高く、これにより、本発明の複合成形体は、ノルボルネン系モノマーの塊状開環重合体と、複合化用部材との間の密着性が高く、高い信頼性を有するものである。 The composite molded body of the present invention can be produced as described above. The composite molded body of the present invention produced in this way uses a polymer obtained by bulk ring-opening polymerization of a norbornene-based monomer, so that electrical characteristics, mechanical characteristics, impact resistance characteristics, heat resistance and Excellent weather resistance. Moreover, the composite molded body of the present invention is obtained by treating at least a part of the contact interface of the composite member with the bulk ring-opening polymer of the norbornene-based monomer with a predetermined coupling agent. Therefore, the wettability of the polymerizable composition containing the norbornene-based monomer before polymerization and the composite member made of the above-described metal material is high, whereby the composite molded body of the present invention is a lump of norbornene-based monomer. Adhesion between the ring-opening polymer and the composite member is high, and has high reliability.
特に、複合化用部材を、プリント配線板の製造用基板や各種電子部品の端子電極とし、これらとノルボルネン系モノマーの塊状開環重合体とを一体成形して得られる複合成形体、より具体的には、ノルボルネン系モノマーの塊状開環重合体を、プリント配線板の製造用基板や各種電子部品の端子電極と一体成形させて封止材として用いた場合においても、これらは高い密着性および耐熱性を有するため、融点が比較的高い鉛フリーはんだを用いても、剥離することはなく、十分な信頼性を確保することできる。 In particular, a composite molded body obtained by integrally molding a composite member as a printed wiring board manufacturing substrate or terminal electrode of various electronic components and a norbornene monomer bulk ring-opening polymer, more specifically In the case of using a ring-opening polymer of norbornene-based monomer as a sealing material by integrally forming with a printed wiring board manufacturing substrate or terminal electrodes of various electronic components, they have high adhesion and heat resistance. Therefore, even if a lead-free solder having a relatively high melting point is used, it does not peel off and sufficient reliability can be ensured.
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、実施例および比較例における部および％は、特に断りのない限り重量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.
実施例１
まず、（ａ）ノルボルネン系モノマーとしてのジシクロペンタジエン９０部およびトリシクロペンタジエン１０部を混合したモノマー５６部と、（ｂ）ジシクロペンタジエン９０部およびトリシクロペンタジエン１０部を混合したモノマー７６部に、ウォラストナイト７５部および炭酸カルシウム２５部を混合してなるＲＦ−０５０１Ｆ液（ＲＩＭＴＥＣ社製）４４部とを用意し、（ａ）と（ｂ）を混合することにより反応原液を得た（反応原液中の無機充填剤含有量は２５部）。次いで、メタセシス重合触媒としてのトリシクロヘキシルホスフィン［１，３−ビス(２，４，６−トリメチルフェニル)−４，５−ジヒドロイミダゾル−２−イリデン］［３−メチル−２−ブテニリデン］ルテニウム（ＩＶ）ジクロライド(アルドリッチ社製)７部をトルエン９３部に溶解させることにより、触媒液を得た。そして、メタセシス重合触媒とノルボルネン系モノマーとの比率がモル比で１：２０，０００となるように、得られた反応原液１００重量部に対して、触媒液を０．４３重量部添加し、撹拌・撹拌・混合することにより、重合性組成物を調製した。
Example 1
First, (a) a monomer obtained by mixing 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene as a norbornene-based monomer, and (b) 76 parts of a monomer obtained by mixing 90 parts of dicyclopentadiene and 10 parts of tricyclopentadiene. 44 parts of RF-0501F liquid (manufactured by RIMTEC) prepared by mixing 75 parts of wollastonite and 25 parts of calcium carbonate was prepared, and a reaction stock solution was obtained by mixing (a) and (b) ( The inorganic filler content in the reaction stock solution is 25 parts). Subsequently, tricyclohexylphosphine [1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene] [3-methyl-2-butenylidene] ruthenium ( IV) A catalyst solution was obtained by dissolving 7 parts of dichloride (manufactured by Aldrich) in 93 parts of toluene. Then, 0.43 parts by weight of the catalyst solution was added to 100 parts by weight of the obtained reaction stock solution so that the molar ratio of the metathesis polymerization catalyst to the norbornene monomer was 1: 20,000, and the mixture was stirred. -The polymerizable composition was prepared by stirring and mixing.
一方で、上記とは別に、長さ１５０ｍｍ×幅２５ｍｍ×厚さ１ｍｍの鉄板を２枚準備し、これらの鉄板をアルカリ洗浄し、次いで、これら２枚の鉄板について、下記式（７）で表されるビシクロヘプテニルエチルトリエトキシシランで表面処理を行った。なお、表面処理は、濃度１８ｍｍｏｌ／Ｌのビシクロヘプテニルエチルトリエトキシシランのエタノール溶液を調整し、この溶液に２枚の鉄板を１０分間浸漬した後取り出し、次いで、１１０℃、１０分の条件で加熱処理することにより行った。
そして、上記にて調製した重合性組成物を、表面処理を行った鉄板のうち１枚の鉄板の一方の面に塗布することにより重合性組成物層を形成し、次いで、重合性組成物層の表面に、もう１枚の鉄板を重ねることにより、鉄板／重合性組成物層／鉄板の三層からなる積層構造体を得た。なお、本実施例では、積層構造体は、鉄板と重合性組成物層とが重なり合う面積が１２．５ｍｍ×２５．０ｍｍとなるような構成とし、一対の鉄板は、長さ方向の一方の端部側で互いに重なるようにするとともに、長さ方向の他方の端部が反対側となるように配置した。また、重合性組成物層の厚みは、塊状開環重合後の厚みが１ｍｍとなるように調整した。 And the polymeric composition layer is formed by apply | coating the polymeric composition prepared above to one surface of one iron plate among the iron plates which performed surface treatment, and then polymerizable composition layer By laminating another iron plate on the surface, a laminated structure composed of three layers of iron plate / polymerizable composition layer / iron plate was obtained. In this example, the laminated structure has a configuration in which the area where the iron plate and the polymerizable composition layer overlap is 12.5 mm × 25.0 mm, and the pair of iron plates has one end in the length direction. They were arranged so that they overlap each other on the part side, and the other end in the length direction was on the opposite side. Further, the thickness of the polymerizable composition layer was adjusted so that the thickness after the bulk ring-opening polymerization was 1 mm.
次いで、積層構造体を、２００℃、１０分加熱することにより、塊状開環重合反応を行い、鉄板／ノルボルネン系モノマーの塊状重合体／鉄板の三層からなる複合成形体を得た。
そして、得られた複合成形体について、引張り剪断接着強度測定およびぬれ性の評価を行った。引張り剪断接着強度測定は、引張り試験機を用い、引張り速度５ｍｍ／ｍｉｎ．の条件とした。
また、ぬれ性の評価は、引張り試験後の、鉄板から剥離したノルボルネン系モノマーの塊状重合体表面を観察し、基材としての鉄板と密着せず、成形収縮により表面が窪んでいる部分を、重合性組成物層を形成した際におけるぬれていない部分と判断し、ノルボルネン系モノマーの塊状重合体と、基材としての鉄板との接触面積に対する、密着している部分の面積比を求め、これを「ぬれている部分の面積比」とした。なお、ぬれている部分の面積比が多いほど、反応前の重合性組成物と基材としての鉄板とのぬれ性は高いものと判断することができる。結果を表１に示す。
Next, the laminated structure was heated at 200 ° C. for 10 minutes to perform a bulk ring-opening polymerization reaction, thereby obtaining a composite molded body composed of three layers of a bulk polymer of iron plate / norbornene monomer / iron plate.
Then, the obtained composite molded body was subjected to tensile shear adhesive strength measurement and wettability evaluation. The tensile shear bond strength was measured using a tensile tester and a tensile speed of 5 mm / min. Conditions.
In addition, the wettability evaluation was performed by observing the bulk polymer surface of the norbornene-based monomer peeled off from the iron plate after the tensile test, without being in close contact with the iron plate as the base material, and the portion where the surface was depressed due to molding shrinkage, Judging the area where the polymeric composition layer is not wet when forming the polymeric composition layer, the area ratio of the intimate contact to the contact area between the bulk polymer of the norbornene monomer and the iron plate as the base material is obtained. Was defined as the “area ratio of the wetted part”. In addition, it can be judged that the wettability of the polymeric composition before reaction and the iron plate as a base material is so high that the area ratio of the wet part is large. The results are shown in Table 1.
実施例２，３
一対の鉄板の代わりに、それぞれ、一対のアルミ板（実施例２）、および一対のステンレス（ＳＵＳ３０４）板（実施例３）を使用した以外は、実施例１と同様にして、複合成形体を作製し、同様に評価を行った。結果を表１に示す。
Examples 2 and 3
A composite molded body was obtained in the same manner as in Example 1 except that a pair of aluminum plates (Example 2) and a pair of stainless steel (SUS304) plates (Example 3) were used instead of the pair of iron plates. It produced and evaluated similarly. The results are shown in Table 1.
実施例４
シランカップリング剤として、ビシクロヘプテニルエチルトリエトキシシランの代わりに、下記式（８）で表されるビシクロヘプテニルヘキシルトリエトキシシランを使用した以外は、実施例１と同様にして、複合成形体を作製し、同様に評価を行った。結果を表１に示す。
As the silane coupling agent, a composite molded article was obtained in the same manner as in Example 1, except that bicycloheptenylhexyltriethoxysilane represented by the following formula (8) was used instead of bicycloheptenylethyltriethoxysilane. Were prepared and evaluated in the same manner. The results are shown in Table 1.
実施例５，６
一対の鉄板の代わりに、それぞれ、一対のアルミ板（実施例５）、および一対のステンレス（ＳＵＳ３０４）板（実施例６）を使用した以外は、実施例４と同様にして、複合成形体を作製し、同様に評価を行った。結果を表１に示す。
Examples 5 and 6
A composite molded body was obtained in the same manner as in Example 4 except that a pair of aluminum plates (Example 5) and a pair of stainless steel (SUS304) plates (Example 6) were used instead of the pair of iron plates. It produced and evaluated similarly. The results are shown in Table 1.
比較例１
シランカップリング剤として、ビシクロヘプテニルエチルトリエトキシシランの代わりに、下記式（９）で表されるビシクロヘプテニルトリエトキシシランを使用した以外は、実施例１と同様にして、複合成形体を作製し、同様に評価を行った。結果を表１に示す。
In the same manner as in Example 1, except that bicycloheptenyltriethoxysilane represented by the following formula (9) was used as the silane coupling agent instead of bicycloheptenylethyltriethoxysilane, a composite molded body was obtained. It produced and evaluated similarly. The results are shown in Table 1.
比較例２，３
一対の鉄板の代わりに、それぞれ、一対のアルミ板（比較例２）、および一対のステンレス（ＳＵＳ３０４）板（比較例３）を使用した以外は、比較例１と同様にして、複合成形体を作製し、同様に評価を行った。結果を表１に示す。
Comparative Examples 2 and 3
A composite molded body was prepared in the same manner as in Comparative Example 1 except that a pair of aluminum plates (Comparative Example 2) and a pair of stainless steel (SUS304) plates (Comparative Example 3) were used instead of the pair of iron plates. It produced and evaluated similarly. The results are shown in Table 1.
表１に示すように、所定のシランカップリング剤を用いた場合には、重合前のノルボルネン系モノマーを含有する重合性組成物と金属材料からなる複合化用部材とのぬれ性（ぬれている部分の面積比）が高く、これにより、得られる複合成形体の、ノルボルネン系モノマーの塊状開環重合体と金属材料からなる複合化用部材との間の密着性が高くなる結果となった（実施例１〜６）。
一方、カップリング剤として、ビシクロヘプテニル基とＳｉとの間の炭素数が０（すなわち、上記式（１）において、ｋ＝０）であるカップリング剤を用いた場合には、重合前のノルボルネン系モノマーを含有する重合性組成物と金属材料からなる複合化用部材とのぬれ性（ぬれている部分の面積比）が悪く、得られる複合成形体の、ノルボルネン系モノマーの塊状開環重合体と金属材料からなる複合化用部材との間の密着性も低くなる結果となった（比較例１〜３）。
As shown in Table 1, when a predetermined silane coupling agent is used, the wettability (wetting) between the polymerizable composition containing the norbornene-based monomer before polymerization and the composite member made of a metal material The area ratio of the portion) is high, and as a result, the adhesion between the bulk ring-opening polymer of the norbornene-based monomer and the composite member made of the metal material of the resulting composite molded body is increased (( Examples 1-6).
On the other hand, when a coupling agent having 0 carbon atoms between the bicycloheptenyl group and Si (that is, k = 0 in the above formula (1)) is used as the coupling agent, The wetting property (area ratio of the wetted part) between the polymerizable composition containing the norbornene monomer and the composite member made of a metal material is poor, and the resulting ring-shaped weight of the norbornene monomer in the composite molded product As a result, the adhesion between the coalescing member and the composite member made of a metal material was also lowered (Comparative Examples 1 to 3).
Claims (3)
前記複合化用部材は、前記重合体との接触界面のうちの少なくとも一部が下記式（１）で表されるカップリング剤で処理されていることを特徴とする複合成形体。
The composite member is characterized in that at least a part of a contact interface with the polymer is treated with a coupling agent represented by the following formula (1).
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