JP2001279065A - Plastic molded product - Google Patents
Plastic molded productInfo
- Publication number
- JP2001279065A JP2001279065A JP2000097863A JP2000097863A JP2001279065A JP 2001279065 A JP2001279065 A JP 2001279065A JP 2000097863 A JP2000097863 A JP 2000097863A JP 2000097863 A JP2000097863 A JP 2000097863A JP 2001279065 A JP2001279065 A JP 2001279065A
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- group
- plastic molded
- molded article
- inorganic filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003023 plastic Polymers 0.000 title claims abstract description 33
- 239000004033 plastic Substances 0.000 title claims abstract description 33
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 26
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 25
- 239000011256 inorganic filler Substances 0.000 claims abstract description 24
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 24
- 239000003365 glass fiber Substances 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000002685 polymerization catalyst Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010137 moulding (plastic) Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 229910052762 osmium Chemical group 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical group [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- -1 tetracyclododecene Chemical class 0.000 description 25
- 239000011521 glass Substances 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 17
- 239000004744 fabric Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 7
- 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 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000002848 norbornenes Chemical class 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 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
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UCQHUEOREKHIBP-UHFFFAOYSA-N heptacyclo[9.6.1.14,7.113,16.02,10.03,8.012,17]icosa-5,14-diene Chemical group C1C(C23)C4C(C=C5)CC5C4C1C3CC1C2C2C=CC1C2 UCQHUEOREKHIBP-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- LSIXBBPOJBJQHN-UHFFFAOYSA-N 2,3-Dimethylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C(C)=C(C)C1C2 LSIXBBPOJBJQHN-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- JHDNFMVFXUETMC-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-4-methylphenol Chemical compound CC1=CC=C(O)C(C=2C=3N=NNC=3C=CC=2)=C1 JHDNFMVFXUETMC-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QSILYWCNPOLKPN-UHFFFAOYSA-N 3-chloro-3-methylbut-1-yne Chemical compound CC(C)(Cl)C#C QSILYWCNPOLKPN-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- VEEKCIOFMIAGSF-UHFFFAOYSA-N 4-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CCCC)C2 VEEKCIOFMIAGSF-UHFFFAOYSA-N 0.000 description 1
- WXOFQPMQHAHBKI-UHFFFAOYSA-N 4-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CC)C2 WXOFQPMQHAHBKI-UHFFFAOYSA-N 0.000 description 1
- TTYVECQWCUJXCS-UHFFFAOYSA-N 4-fluoropyridine Chemical compound FC1=CC=NC=C1 TTYVECQWCUJXCS-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 229920002544 Olefin fiber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- IQWSILHONYLIFD-KSBRXOFISA-L benzyl(trimethyl)azanium;(z)-but-2-enedioate Chemical compound [O-]C(=O)\C=C/C([O-])=O.C[N+](C)(C)CC1=CC=CC=C1.C[N+](C)(C)CC1=CC=CC=C1 IQWSILHONYLIFD-KSBRXOFISA-L 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- KWYLNOQTLCTWCF-UHFFFAOYSA-L copper oct-2-enoate Chemical compound [Cu+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O KWYLNOQTLCTWCF-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WFSOQEZHBFMIPW-UHFFFAOYSA-L cycloocta-1,3-diene;ruthenium(2+);dichloride Chemical compound [Cl-].[Cl-].[Ru+2].C1CCC=CC=CC1 WFSOQEZHBFMIPW-UHFFFAOYSA-L 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GUOAPVPPPVLIQQ-UHFFFAOYSA-N dimethyldicyclopentadiene Chemical compound C1=CC2CC1C1C2C(C)C(C)=C1 GUOAPVPPPVLIQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004767 olefin fiber Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- IKRMQEUTISXXQP-UHFFFAOYSA-N tetrasulfane Chemical compound SSSS IKRMQEUTISXXQP-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- FVRDYQYEVDDKCR-DBRKOABJSA-N tiazofurine Chemical compound NC(=O)C1=CSC([C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)=N1 FVRDYQYEVDDKCR-DBRKOABJSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プラスチック成形
品に関し、さらに詳しくは、チオ系カップリング剤と少
なくとも１種の無機充填材とノルボルネン型シクロオレ
フィンとメタセシス重合触媒からなる高強度、高剛性の
プラスチック成形体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic molded product, and more particularly, to a high-strength and high-rigidity plastic molding comprising a thio coupling agent, at least one inorganic filler, a norbornene-type cycloolefin, and a metathesis polymerization catalyst. The present invention relates to a plastic molding.
【０００２】[0002]
【従来の技術】ジシクロペンタジエンなどをメタセシス
重合して得られる架橋重合成形体は、機械物性が良好で
あり、耐薬品性や電気特性に優れていることから、種々
の製品への適用が期待されている。ジシクロペンタジエ
ン等のノルボルネン型シクロオレフィン類をメタセシス
触媒系を用いて塊状重合させて、架橋重合成形体を得る
方法は従来知られている。また、その際、充填材やガラ
ス繊維で補強することも従来から知られている。例え
ば、特開昭５８−１２９０１３号公報には、メタセシス
触媒系の触媒成分及びモノマーとの混合物から成る溶液
Ａと、メタセシス触媒系の活性化剤及びモノマーとの混
合物から成る溶液Ｂとを反応射出成形（ＲｌＭ）法によ
り架橋重合成形体を製造する方法が開示されており、ま
た、前記成形体に補強剤を含有することも開示されてい
る。この方法では、溶液Ａと溶液Ｂを混合すると、短い
誘導時間を経た後に急激に発熱反応し、架橋重合成形体
が得られる。また、特開平２−２７６８５２号公報や特
開平２−６５２５号公報には、式−ＣＨ＝ＣＨ−で表さ
れる鎖状オレフィン基を有するシランカップリング剤や
エポキシシランカップリング剤で処理したガラス繊維を
補強剤として用いることにより、ノルボルネン系モノマ
ーの開環重合を阻害することなく、曲げ弾性率や曲げ強
さなどの機械強度が向上するガラス繊維補強化ノルボル
ネン系ポリマーが得られることが開示されている。2. Description of the Related Art A crosslinked polymer molded product obtained by metathesis polymerization of dicyclopentadiene or the like is expected to be applied to various products because of its excellent mechanical properties, chemical resistance and electrical properties. Have been. 2. Description of the Related Art A method for obtaining a crosslinked polymer molded product by bulk polymerization of norbornene-type cycloolefins such as dicyclopentadiene using a metathesis catalyst system has been conventionally known. At that time, reinforcement with a filler or glass fiber has been conventionally known. For example, Japanese Patent Application Laid-Open No. 58-129003 discloses that a solution A consisting of a mixture of a metathesis catalyst-based catalyst component and a monomer and a solution B consisting of a mixture of a metathesis catalyst-based activator and a monomer are reacted and injected. A method for producing a crosslinked polymer molded article by a molding (RIM) method is disclosed, and it is also disclosed that the molded article contains a reinforcing agent. In this method, when the solution A and the solution B are mixed, an exothermic reaction occurs rapidly after a short induction time, and a crosslinked polymer molded article is obtained. JP-A-2-276852 and JP-A-2-6525 disclose glass treated with a silane coupling agent having a chain olefin group represented by the formula -CH = CH- or an epoxysilane coupling agent. It is disclosed that by using fiber as a reinforcing agent, a glass fiber reinforced norbornene-based polymer having improved mechanical strength such as bending elastic modulus and bending strength can be obtained without inhibiting ring-opening polymerization of the norbornene-based monomer. ing.
【０００３】[0003]
【発明が解決しようとする課題】上記の充填材やガラス
繊維で補強された架橋重合体は、曲げ強さ、曲げ弾性率
などの機械物性において比較的優れた値を示している
が、これらの機械物性では、その商品用途には制限があ
り、また、近年のエンジニアリングプラスチックに要求
される物性値に対して、充分で有るとはいいがたい。本
発明は、この問題に鑑みなされたもので、ノルボルネン
型シクロオレフィンの開環重合を阻害することなく、曲
げ強さ、曲げ弾性率などの機械物性に特に優れた高強
度、高剛性のプラスチック成形体を提供することを目的
とするものである。The above-mentioned crosslinked polymers reinforced with fillers and glass fibers show relatively excellent values in mechanical properties such as flexural strength and flexural modulus. In terms of mechanical properties, there are restrictions on the application of the product, and it is hard to say that it is sufficient for the physical properties required for engineering plastics in recent years. The present invention has been made in view of this problem, and has been disclosed as a high-strength, high-rigidity plastic molding that is particularly excellent in mechanical properties such as flexural strength and flexural modulus without inhibiting ring-opening polymerization of norbornene-type cycloolefin. It is intended to provide the body.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するため
に、本発明はチオ系カップリング剤で処理した少なくと
も１種の無機充填材とノルボルネン型シクロオレフィン
類のメタセシス重合体から成るプラスチック成形体であ
り、高強度、高剛性のプラスチック成形体を提供するも
のである。無機充填材がガラス繊維であると好ましい成
形体である。ガラス繊維をチオ系カップリング剤０．１
〜２．５重量％で処理すると好ましいプラスチック成形
体である。無機充填材が２００μｍ以下の粉粒体である
と好ましいプラスチック成形体である。無機充填材がフ
レーク形状であると好ましいプラスチック成形体であ
る。そして、無機充填材１〜９５重量％とノルボルネン
型シクロオレフィン類のメタセシス重合体９９〜５重量
％からなると好ましいプラスチック成形体である。ま
た、本発明は、ノルボルネン型シクロオレフィン類のメ
タセシス重合体が一般式（Ａ）または一般式（Ｂ）で表
されるメタセシス重合触媒を用いて重合したことを特徴
とする上記のいずれかに記載のプラスチック成形体であ
る。In order to achieve the above object, the present invention provides a plastic molded article comprising at least one inorganic filler treated with a thio coupling agent and a metathesis polymer of a norbornene-type cycloolefin. It is intended to provide a high-strength, high-rigidity plastic molded article. It is a preferred molded article that the inorganic filler is glass fiber. Glass fiber with thio coupling agent 0.1
It is a preferred plastic molded article to be treated at up to 2.5% by weight. It is a preferable plastic molded article when the inorganic filler is a powder having a particle size of 200 μm or less. It is a preferable plastic molded product when the inorganic filler is in a flake shape. A preferred plastic molded article is composed of 1 to 95% by weight of an inorganic filler and 99 to 5% by weight of a metathesis polymer of a norbornene-type cycloolefin. Further, in the present invention, the metathesis polymer of a norbornene-type cycloolefin is polymerized using a metathesis polymerization catalyst represented by the general formula (A) or (B). Plastic molded article.
【化３】 Embedded image
【化４】 （一般式（Ａ）、（Ｂ）で、Ｍはルテニウム又はオスミ
ウム；Ｒ及びＲ1は、それぞれ独立に水素、炭素数１〜
２０のアルキル基、炭素数２〜２０のアルケニル基、炭
素数２〜２０のアルキニル基、アリール基、炭素数１〜
２０のカルボキシレート基、炭素数１〜２０のアルコキ
シ基、炭素数２〜２０のアルケニルオキシ基、アリール
オキシ基、炭素数２〜２０のアルコキシカルボニル基、
炭素数１〜２０のアルキルチオ基、炭素数１〜２０のア
ルキルスルフォニル基又は炭素数１〜２０のアルキルス
ルフィニル基から選ばれ、それぞれは炭素数１〜５のア
ルキル基、ハロゲン、炭素数１〜５のアルコキシ基又は
フェニル類で置換されていても良く、前記フェニル類は
ハロゲン、炭素数１〜５のアルキル基、炭素数１〜５の
アルコキシ基で置換されていても良い；Ｘ及びＸ1はア
ニオン性配位子；Ｌ及びＬ1は中性の電子供与基を示
す。）Embedded image (In the general formulas (A) and (B), M is ruthenium or osmium; R and R 1 are each independently hydrogen and carbon number 1 to 1)
20 alkyl groups, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups,
A carboxylate group of 20; an alkoxy group having 1 to 20 carbon atoms; an alkenyloxy group having 2 to 20 carbon atoms; an aryloxy group; an alkoxycarbonyl group having 2 to 20 carbon atoms;
It is selected from an alkylthio group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms and an alkylsulfinyl group having 1 to 20 carbon atoms. X or X 1 may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; L and L 1 each represent a neutral electron donating group. )
【０００５】[0005]
【発明の実施の形態】本発明のプラスチック成形体に用
いられる、ノルボルネン型シクロオレフィン系モノマー
としては、置換又は非置換のノルボルネン、ジヒドロジ
シクロペンタジエン、メチルノルボルネン、ジメチルノ
ルボルネン、エチルノルボルネン、エチリデンノルボル
ネン、ブチルノルボルネンなどの二環ノルボルネン、ジ
シクロペンタジエン（シクロペンタジエンの二量体）、
ジヒドロジシクロペンタジエン、メチルジシクロペンタ
ジエン、ジメチルジシクロペンタジエンなどの三環ノル
ボルネン、テトラシクロドデセン、メチルテトラシクロ
ドデセン、ジメチルシクロテトラドデセンなどの四環ノ
ルボルネン、トリシクロペンタジエン（シクロペンタジ
エンの三量体）、テトラシクロペンタジエン（シクロペ
ンタジエンの四量体）などの五環以上のノルボルネン、
シクロブテン、シクロペンテン、シクロオクテン、シク
ロオクタジエン、シクロドデセン、シクロドデカトリエ
ン、テトラヒドロインデン、メチルテトラヒドロインデ
ンなどが挙げられる。また、２個以上のノルボルネン基
を有する化合物、例えばノルボルナジエン、テトラシク
ロドデカジエン、対称型トリシクロペンタジエン等を多
官能架橋剤として用いることもできる。さらに、ハイミ
ック酸、無水ハイミック酸などのノルボルネン誘導体も
用いることができる。これらの中でも、弾性率の高さ、
経済性などからジシクロペンタジエン、メチルテトラシ
クロドデセン、エチリデンノルボルネン、トリシクロペ
ンタジエン、テトラシクロペンタジエンなどの多環体の
シクロオレフィン化合物を単独、または複数のシクロオ
レフィン化合物と混合して用いることが好ましい。特
に、これらの多環体のシクロオレフィン化合物をメタセ
シス重合して得られるポリマは高弾性率であり、必要に
応じてこれらに、シクロオクテン、シクロオクタジエ
ン、シクロドデカトリエンなどの単環体のシクロオレフ
ィン化合物を組み合わせることにより、弾性率を任意に
制御することが可能である。BEST MODE FOR CARRYING OUT THE INVENTION The norbornene-type cycloolefin-based monomer used in the plastic molded article of the present invention includes substituted or unsubstituted norbornene, dihydrodicyclopentadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, Bicyclic norbornene such as butyl norbornene, dicyclopentadiene (a dimer of cyclopentadiene),
Tricyclic norbornenes such as dihydrodicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene; tetracyclic norbornenes such as tetracyclododecene, methyltetracyclododecene, and dimethylcyclotetradodecene; tricyclopentadiene (three-membered cyclopentadiene) Pentamer), norbornene having five or more rings such as tetracyclopentadiene (tetramer of cyclopentadiene),
Examples thereof include cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclododecene, cyclododecatriene, tetrahydroindene, and methyltetrahydroindene. Further, a compound having two or more norbornene groups, for example, norbornadiene, tetracyclododecadiene, symmetric tricyclopentadiene, or the like can be used as the polyfunctional crosslinking agent. Furthermore, norbornene derivatives such as hymic acid and hymic anhydride can be used. Among these, high elastic modulus,
It is preferable to use a polycyclic cycloolefin compound such as dicyclopentadiene, methyltetracyclododecene, ethylidene norbornene, tricyclopentadiene, and tetracyclopentadiene alone or in combination with a plurality of cycloolefin compounds from the viewpoint of economy and the like. . In particular, polymers obtained by subjecting these polycyclic cycloolefin compounds to metathesis polymerization have a high elastic modulus, and if necessary, these may be added to monocyclic cycloolefins such as cyclooctene, cyclooctadiene and cyclododecatriene. The elastic modulus can be arbitrarily controlled by combining olefin compounds.
【０００６】本発明では、従来知られているような金属
触媒成分とアルキルアルミニウム系活性化剤とを組み合
わせた２液系のメタセシス重合触媒系とは異なり、空気
中の酸素や水分によって容易に触媒活性を失わずにシク
ロオレフィン系化合物をメタセシス反応で開環重合させ
ることができる特定のメタセシス重合触媒を用いると好
ましい。そのようなメタセシス重合触媒として一般式
（Ａ）または（Ｂ）に挙げるようなＲｕカルベン触媒が
ある。In the present invention, unlike a conventionally known two-part metathesis polymerization catalyst system in which a metal catalyst component and an alkylaluminum-based activator are combined, the catalyst can be easily formed by oxygen or moisture in the air. It is preferable to use a specific metathesis polymerization catalyst capable of ring-opening polymerizing a cycloolefin compound by a metathesis reaction without losing the activity. As such a metathesis polymerization catalyst, there is a Ru carbene catalyst as shown in the general formula (A) or (B).
【化５】 Embedded image
【化６】 スミウム；Ｒ及びＲ1は、それぞれ独立に水素、炭素数
１〜２０のアルキル基、炭素数２〜２０のアルケニル
基、炭素数２〜２０のアルキニル基、アリール基、炭素
数１〜２０のカルボキシレート基、炭素数１〜２０のア
ルコキシ基、炭素数２〜２０のアルケニルオキシ基、ア
リールオキシ基、炭素数２〜２０のアルコキシカルボニ
ル基、炭素数１〜２０のアルキルチオ基、炭素数１〜２
０のアルキルスルフォ二ル基又は炭素数１〜２０のアル
キルスルフィニル基から選ばれ、それぞれは炭素数１〜
５のアルキル基、ハロゲン、炭素数１〜５のアルコキシ
基又はフェニル類で置換されていても良く、前記フェニ
ル類はハロゲン、炭素数１〜５のアルキル基、炭素数１
〜５のアルコキシ基で置換されていても良い；Ｘ及びＸ
1はアニオン性配位子であり、中心金属への配位を外し
たときに陰性電荷をもつ基のことであり、例えば、水
素、ハロゲン、ＣＦ3ＣＯ2、ＣＨ3ＣＯ2、ＣＦＨ2Ｃ
Ｏ2、（ＣＨ3）3ＣＯ、（ＣＦ3）2（ＣＨ3）ＣＯ、（Ｃ
Ｆ3）（ＣＨ3）2ＣＯ、炭素数１〜５のアルキル基、炭
素数１〜５のアルコキシ基、フェニル基、フェノキシ
基、トシル基、メシル基、トリフルオロメタンスルホネ
ート基等があり、特に好ましいものは両方共にハロゲン
（特に、塩素）である。ＬおよびＬ1はそれぞれ独立に
中性の電子供与基を示す。中性の電子供与基は、中心金
属への配位を外したときに中性電荷をもつ基のことであ
る。このような基としては、例えば、ＰＲ2Ｒ3Ｒ4（こ
こで、Ｒ2は２級のアルキル基またはシクロアルキル
基、Ｒ3およびＲ4はそれぞれ独立に、アリール基、炭素
数１〜１０の１級アルキル基もしくは２級アルキル基、
シクロアルキル基を示す。）で表されるホスフィン系電
子供与基や、1,3−ジ置換イミダゾール、ｐ−置換ピリ
ジン、ピリジン、ｐ-フルオロピリジン、イミダゾリリ
デン化合物等がある。特に好ましいものは、トリシクロ
ペンチルホスフィン、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)イミダゾ
ール−２−イリデン、１，３−−ジメシチル−４，５−
ジヒドロ−２−イミダゾールなどが好ましい。Embedded image R and R 1 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, and a carboxy group having 1 to 20 carbon atoms; Rate group, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and having 1 to 2 carbon atoms.
0 alkylsulfonyl groups or alkylsulfinyl groups having 1 to 20 carbon atoms, each of which has 1 to 1 carbon atoms.
5 alkyl groups, halogens, alkoxy groups having 1 to 5 carbon atoms or phenyls, wherein the phenyls are halogens, alkyl groups having 1 to 5 carbon atoms, 1 carbon atoms.
X and X may be substituted with
1 is an anionic ligand, which is a group having a negative charge when the coordination to the central metal is removed, for example, hydrogen, halogen, CF 3 CO 2 , CH 3 CO 2 , CFH 2 C
O 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 ) CO, (C
F 3 ) (CH 3 ) 2 CO, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a phenoxy group, a tosyl group, a mesyl group, a trifluoromethanesulfonate group and the like, and particularly preferred Both are halogens (especially chlorine). L and L 1 each independently represent a neutral electron donating group. A neutral electron donating group is a group that has a neutral charge when decoordinated to a central metal. Examples of such a group include, for example, PR 2 R 3 R 4 (where R 2 is a secondary alkyl group or a cycloalkyl group, R 3 and R 4 are each independently an aryl group, a group having 1 to 10 carbon atoms. A primary alkyl group or a secondary alkyl group of
Shows a cycloalkyl group. ), 1,3-disubstituted imidazole, p-substituted pyridine, pyridine, p-fluoropyridine, imidazolylidene compounds and the like. Particularly preferred are tricyclopentylphosphine, tricyclohexylphosphine,
1,3-bis (2,4,6-trimethylphenyl) imidazole-2-ylidene, 1,3-dimesityl-4,5-
Dihydro-2-imidazole is preferred.
【０００７】上記の金属カルベン化合物は、公知の合成
法により得ることができる。例えば、Organometallics
第16巻、18号、3867ページ（1997年）に示されているプ
ロパギルクロライドを使用する方法が挙げられる。以下
に触媒の合成例を示す。 合成例 ５００ｍｌのFisher−Porter bottleにシクロオクタジ
エンルテニウムジクロライド（２１ｍモル）、トリシク
ロヘキシルホスフィン（４２ｍモル）、水酸化ナトリウ
ム（７．２ｇ）、酸素を除去したsec−ブタノール２５
０ｍｌを入れ、水素２０３ｋＰａ（２気圧）下で９０℃
で加熱する。水素の吸収が終了するまで数回加圧を繰り
返し、一晩撹拌を続ける。水素の圧力をかけたままで室
温まで冷却し、淡黄色の沈殿物を得る。水３０ｍｌを加
え沈殿物を濾過し、水素気流中で乾燥して、Ｒｕ（Ｈ）
2（Ｈ2）2（Ｐｃｈ3）2を得る（収率約８０％、ｃｈは
シクロヘキシルを示す）。次に、このＲｕ（Ｈ）
2（Ｈ2）2（Ｐｃｈ3）2（１．５ｍモル）をジクロロエ
タン溶液３０ｍｌに溶解し、−３０℃に冷却する。３−
クロロ−３−メチル−１−ブチン（１．５ｍモル）を加
える。溶液は即座に赤紫に変わり、そのまま１５分反応
させる。冷却浴をはずし、脱ガスしたメタノール（２０
ｍｌ）を加えると紫色の結晶が沈殿する。メタノールで
洗浄し、乾燥させて前記式（Ａ）のＲｕカルベン触媒
（Ｃｌ）2（Ｐｃｈ3）2Ｒｕ＝ＣＨ−ＣＨ＝Ｃ（ＣＨ3）
2を得る（収率９５％）。（参考文献：Organometallics
第16巻、18号、3867ページ（1997年））The above metal carbene compound can be obtained by a known synthesis method. For example, Organometallics
Vol. 16, No. 18, p. 3867 (1997) using propargyl chloride. An example of the synthesis of the catalyst is shown below. Synthesis Example Cyclooctadiene ruthenium dichloride (21 mmol), tricyclohexylphosphine (42 mmol), sodium hydroxide (7.2 g), sec-butanol 25 from which oxygen was removed, in a 500 ml Fisher-Porter bottle.
0 ml and 90 ° C under 203 kPa (2 atm) of hydrogen
Heat with. Pressurization is repeated several times until the absorption of hydrogen is completed, and stirring is continued overnight. Cool to room temperature while applying hydrogen pressure to obtain a pale yellow precipitate. 30 ml of water was added, the precipitate was filtered, dried in a stream of hydrogen and Ru (H)
2 (H 2 ) 2 (Pch 3 ) 2 is obtained (yield about 80%, ch represents cyclohexyl). Next, this Ru (H)
2 (H 2 ) 2 (Pch 3 ) 2 (1.5 mmol) is dissolved in 30 ml of dichloroethane solution and cooled to -30 ° C. 3-
Chloro-3-methyl-1-butyne (1.5 mmol) is added. The solution immediately turns reddish purple and is allowed to react for 15 minutes. The cooling bath was removed and the degassed methanol (20
ml), purple crystals precipitate. Wash with methanol, dry and dry Ru carbene catalyst of formula (A) (Cl) 2 (Pch 3 ) 2 Ru = CH-CH = C (CH 3 )
2 is obtained (95% yield). (Reference: Organometallics
(Vol. 16, No. 18, p. 3867 (1997))
【０００８】これら触媒を使用することにより、プラス
チック成形体の製作が簡単になる。特に繊維補強したプ
ラスチック成形体をハンドレイアップ成形で作製する際
に好適である。これらの触媒は、単独に又は２種類以上
を組み合わせて使用できる。これらのメタセシス重合触
媒の添加量は、ノルボルネン型シクロオレフィンに対し
０．００１〜２０重量％であるが、経済性および硬化速
度の理由から好ましくは０．０１〜５重量％の範囲が好
ましい。The use of these catalysts simplifies the production of plastic moldings. It is particularly suitable for producing a fiber-reinforced plastic molded body by hand lay-up molding. These catalysts can be used alone or in combination of two or more. The addition amount of these metathesis polymerization catalysts is 0.001 to 20% by weight based on the norbornene-type cycloolefin, but is preferably in the range of 0.01 to 5% by weight for reasons of economy and curing rate.
【０００９】本発明で用いられる無機充填材とは、繊維
状、粉粒体、フレーク形状などいかなる形状のものも用
いることができる。繊維充填材としては、例えばガラス
繊維、炭素繊維、炭化珪素繊維、スチール繊維、アモル
ファス繊維などが挙げられ、繊維以外の無機充填材とし
ては、例えば、ガラスフレーク、ガラスビーズ、ガラス
バルーン、ミルドガラス、鱗片状ガラス粉、ケイ酸カル
シウム、シリカ粉末、ケイ藻土、酸化チタン、酸化マグ
ネシウム、軽石粉、軽石バルーン、水酸化アルミニウ
ム、水酸化マグネシウム、塩基性炭酸マグネシウム、炭
酸カルシウム、炭酸マグネシウム、硫酸カルシウム、硫
酸バリウム、亜硫酸カルシウム、タルク、クレー、マイ
カ、モンモリロイド、ベントナイト、グラファイト、シ
ラスバルーン、パーライト、フライアッシュ、Ｑセル、
石炭灰、カーボン粉、アルミナ粉、フッ化アルミ、鉄
粉、銅粉、硫化モリブデン、酸化アンチモン、赤燐、シ
リコンカーバイドなどが挙げられるが、無機充填材はこ
れらに限定されるものではなく、上記記載の無機充填材
以外の市販品も利用可能である。また、数種類の無機充
填材を併用することもでき、その使用量および粒径、形
状、品位などのグレードはプラスチック成形体の使用用
途により、適宜決めることができるが、無機充填材の使
用量は１〜９５重量％が好適である。The inorganic filler used in the present invention may be of any shape, such as fibrous, granular, flake, and the like. Examples of the fiber filler include glass fiber, carbon fiber, silicon carbide fiber, steel fiber, amorphous fiber, and the like.Examples of the inorganic filler other than the fiber include, for example, glass flake, glass beads, glass balloon, milled glass, Flaky glass powder, calcium silicate, silica powder, diatomaceous earth, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, calcium sulfate, Barium sulfate, calcium sulfite, talc, clay, mica, montmorilloid, bentonite, graphite, shirasu balloon, perlite, fly ash, Q cell,
Coal ash, carbon powder, alumina powder, aluminum fluoride, iron powder, copper powder, molybdenum sulfide, antimony oxide, red phosphorus, silicon carbide and the like, but the inorganic filler is not limited to these, Commercial products other than the described inorganic fillers are also available. Also, several types of inorganic fillers can be used in combination, and the amount and particle size, shape, grade, such as quality, can be appropriately determined according to the intended use of the plastic molded body. 1-95% by weight is preferred.
【００１０】また、上記記載のガラス繊維としては、そ
の形態について特に限定されるものではなく、ガラス織
布、チョップドストランド、チョップドストランドマッ
ト、ロ一ビング、ガラスクロス、ロ一ビングクロス、ミ
ルドファィバーなどが挙げられるが、これら以外の市販
品も利用可能である。また、形態に応じてフィラメント
径と収束本数を適宜決めることができるが、好ましくは
フィラメント径８〜２３μｍ、ストランド集束本数は５
０〜４０００フィラメントである。The above-mentioned glass fiber is not particularly limited in its form, and may be a glass woven fabric, chopped strand, chopped strand mat, lobing, glass cloth, lobing cloth, milled fiber, or the like. However, commercially available products other than these are also available. Further, the filament diameter and the number of converging filaments can be appropriately determined according to the form. Preferably, the filament diameter is 8 to 23 μm, and the number of strand bundles is 5
0 to 4000 filaments.
【００１１】本発明で用いるチオ系カップリング剤とし
ては、その骨格中にＳ元素を含むものであれば、特に制
限されるものでなく、代表的なものとして、メルカプト
シラン（ ＨＳ‐Ｃ3Ｈ6‐Ｓｉ-（ＯＣＨ3）3 ）、
テトラスルファンシラン（Ｃ2Ｈ5Ｏ）3-Ｓｉ-Ｃ3Ｈ6-Ｓ
-Ｓ-Ｓ-Ｓ−Ｃ3Ｈ6-Ｓｉ-（ＯＣ2Ｈ5）3等が挙げられ、
また、メルカプト基を有するシリコンオリゴマーなどの
非シラン系のカップリング剤なども挙げられる。ガラス
繊維への処理剤としては、ガラス繊維製品形態に大きく
依存するが、合成樹脂エマルジョン、カップリング剤、
界面活性剤、及び帯電防止剤からなる、またはそれら一
部を含む一般的なサイジング剤において使用可能であ
り、その付着量はガラス繊維重量に対し、０．１〜２．
５重量％が好適である。The thio coupling agent used in the present invention is not particularly limited as long as it contains an S element in its skeleton. As a typical example, mercaptosilane (HS-C 3 H) is used. 6 -Si- (OCH 3) 3) ,
Tetrasulfane silane (C 2 H 5 O) 3 -Si-C 3 H 6 -S
—S—S—S—C 3 H 6 —Si— (OC 2 H 5 ) 3 and the like,
Further, a non-silane coupling agent such as a silicon oligomer having a mercapto group may also be used. As a treatment agent for glass fiber, it greatly depends on the form of glass fiber product, but synthetic resin emulsion, coupling agent,
It can be used in a general sizing agent consisting of a surfactant and an antistatic agent or containing a part thereof, and the amount of the sizing agent is 0.1 to 2.
5% by weight is preferred.
【００１２】本発明のプラスチック成形体には、前記し
たノルボルネン型シクロオレフィンとメタセシス重合触
媒、無機充填材、チオ系カップリング剤が必須成分であ
るが、必要に応じ有機充填材、改質剤、重合速度調節
剤、着色剤、光安定剤などを任意に添加することができ
る。The above-mentioned norbornene-type cycloolefin, a metathesis polymerization catalyst, an inorganic filler, and a thio coupling agent are essential components in the plastic molded article of the present invention. If necessary, an organic filler, a modifier, A polymerization rate regulator, a colorant, a light stabilizer and the like can be optionally added.
【００１３】本発明で用いられる有機充填材とは、アラ
ミド繊維、ポリエステル繊維、ポリエチレンやポリプロ
ピレンなどのオレフィン系繊維、木粉、ポリエステルや
ポリスチレンビーズなどが挙げられる。これら有機充填
材の使用量は、併用する無機充填材の使用量にもよる
が、ノルボルネン型シクロオレフィン１００重量部に対
し、１０〜３００重量部が好適である。The organic filler used in the present invention includes aramid fibers, polyester fibers, olefin fibers such as polyethylene and polypropylene, wood flour, polyester and polystyrene beads. The amount of the organic filler to be used depends on the amount of the inorganic filler used in combination, but is preferably from 10 to 300 parts by weight based on 100 parts by weight of the norbornene-type cycloolefin.
【００１４】本発明で使用される改質剤としては例え
ば、エラストマー、天然ゴム、ブタジエン系ゴム、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−マレイン酸共重合体、エチレン−酢酸ビニル共重合
体、ポリメタクリル酸メチル、ポリ酢酸ビニル、ポリス
チレンなどの熱可塑性樹脂が挙げられる。また、これら
の熱可塑性樹脂はエステル化されていても良く、極性基
がグラフトされていてもよい。さらにエポキシ系、ウレ
タン系、ポリエステル系、シリコン系プレポリマを共重
合あるいは分散させることでポリマの物性を改良するこ
ともできる。共重合プレポリマとしては例えば、エポキ
シとノルボルネンモノカルボキシリックアシッドを反応
させて得られる化合物、イソシアネート化合物とノルボ
ルネン-オールを反応させて得られる化合物、ハイミッ
ク酸変性ポリエステルなどが挙げられる。分散による改
質を目的とするポリマとしてはエポキシ樹脂、エポキシ
アクリレートなどの誘導体、同様にウレタン樹脂および
ウレタンアクリレートなどの誘導体、飽和ポリエステル
樹脂、不飽和ポリエステル樹脂、フェノール樹脂、ポリ
アミド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、
ポリエ一テル樹脂など公知の熱硬化性樹脂が挙げられ
る。The modifier used in the present invention includes, for example, elastomer, natural rubber, butadiene rubber, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene- Thermoplastic resins such as maleic acid copolymer, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyvinyl acetate, and polystyrene are exemplified. Further, these thermoplastic resins may be esterified, and a polar group may be grafted. Further, the physical properties of the polymer can be improved by copolymerizing or dispersing an epoxy-based, urethane-based, polyester-based, or silicon-based prepolymer. Examples of the copolymerized prepolymer include a compound obtained by reacting an epoxy with norbornene monocarboxylic acid, a compound obtained by reacting an isocyanate compound with norbornene-ol, and a hymic acid-modified polyester. Polymers for the purpose of modification by dispersion include derivatives such as epoxy resins and epoxy acrylates, as well as derivatives such as urethane resins and urethane acrylates, saturated polyester resins, unsaturated polyester resins, phenolic resins, polyamide resins, polyimide resins, polyamides Imide resin,
A known thermosetting resin such as a polyester resin may be used.
【００１５】さらに石油樹脂も挙げられる。石油樹脂と
してはエチレンプラントから精製される公知のＣ５また
はＣ９留分を原料に製造されるものが挙げられる。例え
ば、日本ゼオン株式会社製商品名クイントンや同社製熱
可塑性ポリノルボルネン商品名ノルソレックスなどがあ
げられる。これら石油樹脂は、数平均分子量が２０００
以上であることが好ましく、樹脂骨格中に水酸基やエス
テル基などの官能基を有していることがより望ましい。
これら改質剤の使用量は目的とするポリマーの物性にも
よるが、通常ノルボルネン型シクロオレフィン１００重
量部に対し０．２〜９５重量部の範囲で用いることがで
きる。より好ましくは０．５〜６０重量部の範囲であ
る。Furthermore, petroleum resins can be used. Examples of the petroleum resin include those produced using a known C5 or C9 fraction purified from an ethylene plant as a raw material. Examples include Quinton (trade name) manufactured by Zeon Corporation and Norsolex (trade name) thermoplastic polynorbornene manufactured by Nippon Zeon Co., Ltd. These petroleum resins have a number average molecular weight of 2000
The above is preferable, and it is more preferable that the resin skeleton has a functional group such as a hydroxyl group or an ester group.
The amount of these modifiers used depends on the physical properties of the target polymer, but can be usually used in the range of 0.2 to 95 parts by weight per 100 parts by weight of the norbornene-type cycloolefin. More preferably, it is in the range of 0.5 to 60 parts by weight.
【００１６】本発明で使用される重合速度調節剤として
は、アクリル樹脂やポリエステル樹脂などのラジカル重
合性樹脂、メチルスチレンダイマーなどの連鎖移動を起
こさせるもの、オレフィン系樹脂、トリイソプロピルフ
ォスフィン、トリフェニルフォスフィン、トリシクロヘ
キシルフォスフィンなどのリン酸塩が挙げられ、これら
はノルボルネン型シクロオレフィン化合物１００重量部
に対し０．００５〜２０重量部用いることができる。こ
の使用量は可使時間を制御する目的であり、可使時間が
短くても良い時にはその使用量を少なくし、長くしたい
ときは多くする。Examples of the polymerization rate regulator used in the present invention include radical polymerizable resins such as acrylic resins and polyester resins, those capable of causing chain transfer such as methylstyrene dimer, olefin resins, triisopropylphosphine, and triisopropylphosphine. Phosphates such as phenylphosphine and tricyclohexylphosphine are exemplified, and these can be used in an amount of 0.005 to 20 parts by weight based on 100 parts by weight of the norbornene-type cycloolefin compound. This usage amount is for the purpose of controlling the pot life, and when the pot life is short, the usage quantity is reduced, and when it is desired to be long, the pot quantity is increased.
【００１７】着色剤としては、二酸化チタン、コバルト
ブルー、カドミウムエローなどの無機顔料、カーボンブ
ラック、アニリンブラック、β−ナフトール、フタロシ
アニン、キナクリドン、アゾ系、キノフタロン、インダ
ンスレンブルーなどの有機系顔料が挙げられ、所望する
色調に応じでそれぞれを配合する。これらは、２種以上
組み合わせて使用しても良い。通常、これら顔料の添加
量はノルボルネン型シクロオレフィン１００重量部に対
し、０．１〜５０重量部添加することができる。Examples of the coloring agent include inorganic pigments such as titanium dioxide, cobalt blue and cadmium yellow, and organic pigments such as carbon black, aniline black, β-naphthol, phthalocyanine, quinacridone, azo, quinophthalone and indanthrene blue. And each is blended according to the desired color tone. These may be used in combination of two or more. Usually, the addition amount of these pigments can be 0.1 to 50 parts by weight based on 100 parts by weight of the norbornene-type cycloolefin.
【００１８】本発明に用いられる安定化剤としては、紫
外線吸収剤、光安定化剤および酸化防止剤が挙げられ
る。紫外線吸収剤としては、例えばフェニルサリシレー
ト、パラ-ｔ-ブチルフェニルサリシレートなどのサリチ
ル酸系紫外線吸収剤、２，４-ジヒドロキシベンゾフェ
ノン、２-ヒドロキシ-４-メトキシベンゾフェノン、
２，２’-ジヒドロキシ-４，４’-ジメトキシベンゾフ
ェノンなどのベンゾフェノン系紫外線吸収剤、２-
（２’-ヒドロキシ-５’-メチルフェニル）ベンゾトリ
アゾ-ル、２-（２’-ヒドロキシ-３’，５’-ジ−ｔ−
ブチルフェニル）ベンゾトリアゾール、２-（２’-ヒド
ロキシ-３’，５’-ジ-ｔ-アミルフェニル）ベンゾトリ
アゾールなどのベンゾトリアゾール系紫外線吸収剤、２
-エチルヘキシル-２-シアノ-３，３’-ジフェニルアク
リレート、エチル-２-シアノ-３，３’-ジフェニルアク
リレートなどのシアノアクリレート系紫外線吸収剤が挙
げられる。これらは単独または２種類以上併用しても良
い。これら紫外線吸収剤の添加量は接着剤の使用環境、
要求特性により適宜決められるが、通常ノルボルネン型
シクロオレフィン１００重量部に対し、０．０５〜２０
重量部が好ましい。The stabilizer used in the present invention includes an ultraviolet absorber, a light stabilizer and an antioxidant. Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate and para-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
Benzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-
Benzotriazole-based ultraviolet absorbers such as butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole,
And cyanoacrylate-based ultraviolet absorbers such as -ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate. These may be used alone or in combination of two or more. The amount of these UV absorbers added depends on the usage environment of the adhesive,
Although it is appropriately determined according to required characteristics, usually 0.05 to 20 parts by weight per 100 parts by weight of norbornene-type cycloolefin is used.
Parts by weight are preferred.
【００１９】また光安定化剤としてはビス（２，２，
６，６-テトラメチル-４-ビベリジル）セバケート、ビ
ス（１，２，２，６，６-ペンタメチル-４-ピペリジニ
ル）セバケート、コハク酸ジメチル・１-（２-ヒドロキ
シエチル）-４-ヒドロキシ-２，２，６，６-テトラメチ
ルピペリジン重縮合物などのヒンダードアミン系光安定
剤が挙げられる。この光安定剤は通常ノルボルネン型シ
クロオレフィン１００重量部に対し０．０５〜２０重量
部添加できる。As a light stabilizer, bis (2,2,2)
6,6-tetramethyl-4-biberidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy- Hindered amine light stabilizers such as 2,2,6,6-tetramethylpiperidine polycondensate are exemplified. This light stabilizer can be usually added in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the norbornene-type cycloolefin.
【００２０】さらに本発明に用いられる酸化防止剤とし
ては、パラベンゾキノン、トルキノン、ナフトキノンな
どのキノン類、ハイドロキノン、パラ-ｔ-ブチルカテコ
ール、２，５-ジ-ｔ-ブチルハイドロキノンなどのハイ
ドロキノン類、ジ-ｔ-ブチル・パラクレゾール、ハイド
ロキノンモノメチルエーテル、ピロガロールなどのフェ
ノール類、ナフテン酸銅やオクテン酸銅などの銅塩、ト
リメチルベンジルアンモニウムクロライド、トリメチル
ベンジルアンモニウムマレエート、フェニルトリメチル
アンモニウムクロライドなどの第４級アンモニウム塩
類、キノンジオキシムやメチルエチルケトオキシムなど
のオキシム類、トリエチルアミン塩酸塩やジブチルアミ
ン塩酸塩などのアミン塩酸塩類が挙げられる。これら酸
化防止剤は充填材との相性や目的とする成形作業性およ
び樹脂保存安定性などの条件により種類、量を変えて添
加する。通常、添加量はノルボルネン型シクロオレフィ
ン１００重量部に対し１０〜２０，０００ｐｐｍであ
る。Examples of the antioxidant used in the present invention include quinones such as parabenzoquinone, tolquinone and naphthoquinone; hydroquinones such as hydroquinone, para-t-butylcatechol and 2,5-di-t-butylhydroquinone; Phenols such as di-t-butyl paracresol, hydroquinone monomethyl ether, pyrogallol, copper salts such as copper naphthenate and copper octenoate, and quaternary salts such as trimethylbenzylammonium chloride, trimethylbenzylammonium maleate and phenyltrimethylammonium chloride. Quaternary ammonium salts, oximes such as quinone dioxime and methyl ethyl ketoxime, and amine hydrochlorides such as triethylamine hydrochloride and dibutylamine hydrochloride. These antioxidants are added in different kinds and amounts depending on conditions such as compatibility with the filler, intended molding workability and resin storage stability. Usually, the addition amount is 10 to 20,000 ppm based on 100 parts by weight of the norbornene-type cycloolefin.
【００２１】この他にも、難燃材、消泡剤、湿潤剤、分
散剤などを本発明の目的を損なわない範囲で使用するこ
とができる。In addition, flame retardants, defoamers, wetting agents, dispersants, and the like can be used within a range that does not impair the object of the present invention.
【００２２】 本発明のプラスチック成形体とは、前記
ノルボルネン型シクロオレフィンとメタセシス触媒とチ
オ系シランカップリング剤と少なくとも１種の無機充填
材からなり、ノルボルネン型シクロオレフィンとメタセ
シス触媒のメタセシス重合反応により硬化した成形体で
ある。触媒をノルボルネン型シクロオレフィンに混合す
る際の温度は、通常は０〜８０℃、好ましくは室温〜５
０℃である。また、使用目的により前記した各種添加剤
を添加することができる。プラスチック成形体の機械物
性を十分に発現させるためには、硬化物の硬化度（１０
０％−［２５０℃における重量減少率％］）を９４％以
上にすることが好ましい。成形体の硬化度を９４％以上
にするために、通常は加熱操作を行う。加熱操作は、外
部から１段階、２段階、多段加熱で行うことができる。
１段階加熱とする場合は、その温度は、通常０〜２５０
℃、好ましくは２０〜２００℃である。２段階加熱とす
る場合は、１段階目の温度は、通常は０〜１５０℃、好
ましくは３０〜８０℃で、重合時間は触媒の量および重
合温度により適宜決めることができるが、通常１分〜５
０時間である。２段階目の温度は、通常は２０〜２００
℃、好ましくは１００〜１８０℃であり、重合時間は触
媒の量および重合温度により適宜決めることができる
が、通常１分〜５０時間である。多段加熱とする場合
は、２段階加熱の温度範囲から適宜温度を選択して加熱
することができる。また、前述のようにチオ系カップリ
ング剤の付着量は、無機充填材に対し、０．１重量％よ
り少ないとその効果が現れず、２．５重量％より多いと
ノルボルネン型シクロオレフィンの硬化阻害を起こすた
め、０．１〜２．５重量％が好適である。さらに、無機
充填材の使用量は１から９５重量％で、使用用途により
適宜決めることができる。The plastic molded article of the present invention comprises the norbornene-type cycloolefin, a metathesis catalyst, a thiosilane coupling agent and at least one inorganic filler, and is formed by a metathesis polymerization reaction of the norbornene-type cycloolefin and the metathesis catalyst. It is a cured molded body. The temperature at which the catalyst is mixed with the norbornene-type cycloolefin is usually from 0 to 80 ° C, preferably from room temperature to 5 ° C.
0 ° C. The various additives described above can be added depending on the purpose of use. In order to sufficiently exhibit the mechanical properties of the plastic molded product, the degree of cure of the cured product (10
0%-[% weight loss at 250 ° C]) is preferably 94% or more. In order to make the degree of curing of the molded body 94% or more, a heating operation is usually performed. The heating operation can be performed by one-stage, two-stage, or multi-stage heating from the outside.
In the case of one-stage heating, the temperature is usually 0 to 250.
° C, preferably 20-200 ° C. In the case of two-stage heating, the temperature of the first stage is usually from 0 to 150 ° C., preferably from 30 to 80 ° C., and the polymerization time can be appropriately determined depending on the amount of the catalyst and the polymerization temperature, but is usually 1 minute. ~ 5
0 hours. The temperature of the second stage is usually 20 to 200
° C, preferably 100 to 180 ° C, and the polymerization time can be appropriately determined depending on the amount of the catalyst and the polymerization temperature, and is usually 1 minute to 50 hours. In the case of multi-stage heating, heating can be performed by appropriately selecting a temperature from a temperature range of two-stage heating. As described above, if the amount of the thio-based coupling agent is less than 0.1% by weight with respect to the inorganic filler, the effect is not exhibited. If the amount is more than 2.5% by weight, the curing of the norbornene-type cycloolefin is performed. To cause inhibition, 0.1 to 2.5% by weight is preferred. Further, the amount of the inorganic filler used is 1 to 95% by weight, which can be appropriately determined depending on the intended use.
【００２３】[0023]
【実施例】以下、本発明を実施例により具体的に説明す
る。なお実施例中、部とあるのは特に限定しない限り重
量部を意味する。The present invention will be described below in more detail with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified.
【００２４】（実施例１）メルカプトシラン( ＨＳ−
Ｃ3Ｈ6−Ｓｉ−（ＯＣＨ3）3 )０．４重量％及び酢酸
０．２５重量％、蒸留水９９．３５重量％からなる処理
液を作製した。上記処理液中にガラスクロス（ＷＦ２３
０；富士ファイバーグラス株式会社製商品名、質量 ２
０３（ｇ／ｍ2）、織り密度タテ／ヨコ＝１９／１８
（本））を浸し、マングルにて加圧し、処理液ピックア
ップがガラスクロスに対して５０重量％になるように調
整し、ガラスクロスを乾燥機にて１２０℃、２０分間乾
燥する。乾燥したガラスクロスを約１５０ｍｍの正方形
に切断した後、さらに１２０℃の高温槽で約２時間乾燥
させ、その後水分を吸収しないように冷却する。次に、
市販の純度９９重量％のジシクロペンタジエン（以下Ｄ
ＣＰＤ）を約４０℃に加熱したのち、ＤＣＰＤ１００部
に対してトリフェニルホスフィン（以下ＴＰＰ）０．１
３部を加えて溶かし、次いで下記の構造式（Ｃ）のＲｕ
カルベン触媒０．１部を溶解させ配合液とした。Example 1 Mercaptosilane (HS-
C 3 H 6 -Si- (OCH 3 ) 3) 0.4 wt% and acetic acid 0.25 wt%, to prepare a treatment solution consisting of distilled water 99.35 wt%. Glass cloth (WF23)
0; trade name, mass 2 manufactured by Fuji Fiber Glass Co., Ltd.
03 (g / m 2 ), woven density length / width = 19/18
(Book)), pressurize it with a mangle, adjust the treatment liquid pickup to 50% by weight with respect to the glass cloth, and dry the glass cloth with a dryer at 120 ° C. for 20 minutes. After the dried glass cloth is cut into a square of about 150 mm, it is further dried in a high-temperature bath at 120 ° C. for about 2 hours, and then cooled so as not to absorb moisture. next,
Commercially available 99% by weight of dicyclopentadiene (hereinafter referred to as D
After heating CPD) to about 40 ° C., triphenylphosphine (hereinafter referred to as TPP) 0.1 was added to 100 parts of DCPD.
3 parts were added and dissolved, and then Ru of the following structural formula (C) was
0.1 part of the carbene catalyst was dissolved to prepare a mixed solution.
【００２５】[0025]
【化７】 Embedded image
【００２６】この配合液を上記の乾燥したガラスクロス
に滴下しロ一ラーで含浸、脱泡（ハンドレイアップ）さ
せ、中間体とした。その後、その中間体をガラス板で挟
み込み真空引きを行った。真空引き終了後、高温槽に入
れ４０℃、３時間、１２５℃、１時間の２段階加熱を行
った後、室温まで冷却し、ガラス繊維で補強されたプラ
スチック成形体を得た。This mixed solution was dropped onto the above dried glass cloth, impregnated with a roller, and defoamed (hand laid up) to obtain an intermediate. Thereafter, the intermediate was sandwiched between glass plates and evacuated. After the evacuation was completed, the mixture was placed in a high-temperature bath and heated at 40 ° C. for 3 hours at 125 ° C. for 1 hour, followed by cooling to room temperature to obtain a plastic molded body reinforced with glass fibers.
【００２７】（比較例１）実施例１のメルカプトシラン
処理ガラスクロスをアミノシラン処理ガラスクロスに置
換えた以外は、上記実施例１と同様にしてガラス繊維で
補強されたプラスチック成形体を得た。Comparative Example 1 A plastic molded article reinforced with glass fibers was obtained in the same manner as in Example 1 except that the glass cloth treated with mercaptosilane in Example 1 was replaced with a glass cloth treated with aminosilane.
【００２８】(比較例２)メルカプトシラン処理ガラスク
ロスをエポキシシラン処理ガラスクロスに置換えた以外
は、上記実施例１と同様にしてガラス繊維で補強された
プラスチック成形体を得た。Comparative Example 2 A plastic molded article reinforced with glass fibers was obtained in the same manner as in Example 1 except that the glass cloth treated with mercaptosilane was replaced with the glass cloth treated with epoxysilane.
【００２９】（比較例３）メルカプトシラン処理ガラス
クロスをウレイドシラン処理ガラスクロスに置換えた以
外は、上記実施例１と同様にしてガラス繊維で補強され
たプラスチック成形体を得た。Comparative Example 3 A plastic molded article reinforced with glass fibers was obtained in the same manner as in Example 1 except that the glass cloth treated with mercaptosilane was replaced with the glass cloth treated with ureidosilane.
【００３０】(比較例４)メルカプトシラン処理ガラスク
ロスを無処理ガラスクロスに置換えた以外は、上記実施
例１と同様にしてガラス繊維で補強されたプラスチック
成形体を得た。Comparative Example 4 A plastic molded article reinforced with glass fibers was obtained in the same manner as in Example 1 except that the glass cloth treated with mercaptosilane was replaced with an untreated glass cloth.
【００３１】上記成形にて得られたプラスチック成形体
から、ダイヤモンドカッター、打ち抜き型により、Ｊｌ
Ｓに準じた試験片を作製した。そして、これら試験片を
用い、曲げ試験、引張試験、ＩＺＯＤ衝撃の各種評価を
行った。その結果を表１に示した。From the plastic molded body obtained by the above molding, Jl was cut with a diamond cutter and a punching die.
A test piece according to S was prepared. Using these test pieces, a bending test, a tensile test, and various evaluations of IZOD impact were performed. The results are shown in Table 1.
【００３２】[0032]
【表１】 [Table 1]
【００３３】実施例１のメルカプトシランで処理したガ
ラスクロスを用いたプラスチック成形体が、その他のシ
ランカップリング剤及び無処理のガラスクロスを用いた
プラスチック成形体と比較し、より高い曲げ強さ、曲げ
弾性率を示しており、高強度、高剛性のプラスチック成
形体を得ることができる。The plastic molded article using the glass cloth treated with the mercaptosilane of Example 1 has a higher bending strength than the plastic molded article using the other silane coupling agent and the untreated glass cloth. It shows a flexural modulus, and a high-strength, high-rigidity plastic molded body can be obtained.
【００３４】[0034]
【発明の効果】本発明により、チオ系カップリング剤と
少なくとも１種の無機充填材とノルボルネン型シクロオ
レフィンとメタセシス重合触媒を含む高強度、高剛性の
プラスチック成形体を提供することができる。このプラ
スチック成形体は、ジシクロペンタジエンなどをメタセ
シス重合して得られる架橋重合成形体の、優れた諸物性
に加え、高強度、高剛性が得られたころから、高強度、
高剛性を要求する広い分野での利用が可能であり、例え
ば浄化槽、浴槽、キッチン天板、タンク、パイプユニッ
トバス、壁パネル、プレジャーボート、下水槽、防食ラ
イニング、波板、配線板、絶縁材などの成形品、電気部
品、電子部品などの用途に利用可能である。According to the present invention, a high-strength and high-rigidity plastic molded article containing a thio coupling agent, at least one inorganic filler, a norbornene-type cycloolefin, and a metathesis polymerization catalyst can be provided. This plastic molded product, in addition to excellent physical properties of the crosslinked polymer molded product obtained by metathesis polymerization of dicyclopentadiene, etc., from the time when high strength and high rigidity were obtained, high strength,
Can be used in a wide range of fields requiring high rigidity, such as septic tanks, bathtubs, kitchen tops, tanks, pipe unit baths, wall panels, pleasure boats, sewer tanks, anticorrosive linings, corrugated boards, wiring boards, insulating materials It can be used for applications such as molded articles, electric parts, and electronic parts.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｋ 7/00 Ｃ０８Ｋ 7/00 7/14 7/14 9/04 9/04 Ｃ０９Ｃ 3/10 Ｃ０９Ｃ 3/10 (72)発明者 木村 徹 茨城県つくば市和台48 日立化成工業株式 会社総合研究所内 (72)発明者 山崎 仁 茨城県つくば市和台48 日立化成工業株式 会社総合研究所内 Ｆターム(参考） 4F071 AA69 AB03 AB05 AB08 AB15 AB18 AB23 AB24 AB26 AB28 AB30 AD01 AD02 AD05 BA02 BB12 BC01 4F072 AA02 AA08 AB09 AB28 AC06 AD11 AE02 AE09 AE10 AK05 AK20 AL01 4J002 CE001 DA036 DA056 DA086 DD036 DE076 DE096 DE136 DE146 DE236 DG026 DG046 DG056 DJ006 DJ016 DJ036 DJ046 DJ056 DL006 FA046 FB156 FD016 FD030 FD040 FD050 FD070 FD090 4J032 CA68 CD02 CE06 CE16 CE22 CG07 4J037 AA01 AA04 AA08 AA09 AA17 AA18 AA22 AA27 AA30 CB21 CC12 DD05 DD10 EE02 FF17Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (Reference) C08K 7/00 C08K 7/00 7/14 7/14 9/04 9/04 C09C 3/10 C09C 3/10 (72 Inventor Toru Kimura 48 Wadai, Tsukuba, Ibaraki Prefecture, Hitachi Chemical Co., Ltd. (72) Inventor Hitoshi Yamazaki 48 Wadai, Tsukuba, Ibaraki Prefecture, Hitachi Chemical Co., Ltd.F-term (reference) 4F071 AA69 AB03 AB05 AB08 AB15 AB18 AB23 AB24 AB26 AB28 AB30 AD01 AD02 AD05 BA02 BB12 BC01 4F072 AA02 AA08 AB09 AB28 AC06 AD11 AE02 AE09 AE10 AK05 AK20 AL01 4J002 CE001 DA036 DA056 DA086 DD036 DE076 DE096 DJ036 DE076 DJ006 DG0 FD016 FD030 FD040 FD050 FD070 FD090 4J032 CA68 CD02 CE06 CE16 CE22 CG07 4J037 AA01 AA04 AA08 AA09 AA17 AA18 AA22 AA27 AA30 CB21 CC12 DD05 DD10 EE02 FF17
Claims (7)
とも１種の無機充填材とノルボルネン型シクロオレフィ
ン類のメタセシス重合体から成るプラスチック成形体。1. A plastic molding comprising at least one inorganic filler treated with a thio coupling agent and a metathesis polymer of a norbornene-type cycloolefin.
に記載のプラスチック成形体。2. The method according to claim 1, wherein the inorganic filler is glass fiber.
The plastic molded article according to the above.
１〜２．５重量％で処理した請求項２に記載のプラスチ
ック成形体。3. A glass fiber containing a thio coupling agent.
The plastic molded article according to claim 2, which is treated with 1 to 2.5% by weight.
ある請求項１に記載のプラスチック成形体。4. The plastic molded article according to claim 1, wherein the inorganic filler is a powder having a particle size of 200 μm or less.
１に記載のプラスチック成形体。5. The plastic molded article according to claim 1, wherein the inorganic filler has a flake shape.
ン型シクロオレフィン類のメタセシス重合体９９〜５重
量％からなる請求項１ないし請求項５のいずれかに記載
のプラスチック成形体。6. The plastic molded article according to claim 1, comprising 1 to 95% by weight of an inorganic filler and 99 to 5% by weight of a metathesis polymer of a norbornene-type cycloolefin.
タセシス重合体が一般式（Ａ）または一般式（Ｂ）で表
されるメタセシス重合触媒を用いて重合したことを特徴
とする請求項１ないし請求項６のいずれかに記載のプラ
スチック成形体。 【化１】 【化２】 （一般式（Ａ）、（Ｂ）で、Ｍはルテニウム又はオスミ
ウム；Ｒ及びＲ1は、それぞれ独立に水素、炭素数１〜
２０のアルキル基、炭素数２〜２０のアルケニル基、炭
素数２〜２０のアルキニル基、アリール基、炭素数１〜
２０のカルボキシレート基、炭素数１〜２０のアルコキ
シ基、炭素数２〜２０のアルケニルオキシ基、アリール
オキシ基、炭素数２〜２０のアルコキシカルボニル基、
炭素数１〜２０のアルキルチオ基、炭素数１〜２０のア
ルキルスルフォニル基又は炭素数１〜２０のアルキルス
ルフィニル基から選ばれ、それぞれは炭素数１〜５のア
ルキル基、ハロゲン、炭素数１〜５のアルコキシ基又は
フェニル類で置換されていても良く、前記フェニル類は
ハロゲン、炭素数１〜５のアルキル基、炭素数１〜５の
アルコキシ基で置換されていても良い；Ｘ及びＸ1はア
ニオン性配位子；Ｌ及びＬ1は中性の電子供与基を示
す。）7. The metathesis polymer of a norbornene-type cycloolefin is polymerized using a metathesis polymerization catalyst represented by the general formula (A) or (B). A plastic molded article according to any one of the above. Embedded image Embedded image (In the general formulas (A) and (B), M is ruthenium or osmium; R and R 1 are each independently hydrogen and carbon number 1 to 1)
20 alkyl groups, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups,
A carboxylate group of 20; an alkoxy group having 1 to 20 carbon atoms; an alkenyloxy group having 2 to 20 carbon atoms; an aryloxy group; an alkoxycarbonyl group having 2 to 20 carbon atoms;
It is selected from an alkylthio group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms and an alkylsulfinyl group having 1 to 20 carbon atoms. X or X 1 may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; L and L 1 each represent a neutral electron donating group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000097863A JP2001279065A (en) | 2000-03-30 | 2000-03-30 | Plastic molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000097863A JP2001279065A (en) | 2000-03-30 | 2000-03-30 | Plastic molded product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001279065A true JP2001279065A (en) | 2001-10-10 |
Family
ID=18612432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000097863A Pending JP2001279065A (en) | 2000-03-30 | 2000-03-30 | Plastic molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001279065A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1640153A1 (en) * | 2003-06-27 | 2006-03-29 | Zeon Corporation | Multilayer body and method for producing same |
| JP2006205591A (en) * | 2005-01-28 | 2006-08-10 | Nippon Zeon Co Ltd | Resin mold for curable resin and manufacturing method of curable resin molded body |
| WO2007058249A1 (en) * | 2005-11-18 | 2007-05-24 | Rimtec Corporation | Norbornene resin moldings and process for production thereof |
| JP2010111881A (en) * | 2003-01-31 | 2010-05-20 | Nippon Zeon Co Ltd | Method for producing cycloolefin-based resin film and method for producing cycloolefin-based polymer sheet or film |
-
2000
- 2000-03-30 JP JP2000097863A patent/JP2001279065A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111881A (en) * | 2003-01-31 | 2010-05-20 | Nippon Zeon Co Ltd | Method for producing cycloolefin-based resin film and method for producing cycloolefin-based polymer sheet or film |
| EP1640153A1 (en) * | 2003-06-27 | 2006-03-29 | Zeon Corporation | Multilayer body and method for producing same |
| EP1640153A4 (en) * | 2003-06-27 | 2009-09-23 | Zeon Corp | Multilayer body and method for producing same |
| JP2006205591A (en) * | 2005-01-28 | 2006-08-10 | Nippon Zeon Co Ltd | Resin mold for curable resin and manufacturing method of curable resin molded body |
| WO2007058249A1 (en) * | 2005-11-18 | 2007-05-24 | Rimtec Corporation | Norbornene resin moldings and process for production thereof |
| JP5357428B2 (en) * | 2005-11-18 | 2013-12-04 | Ｒｉｍｔｅｃ株式会社 | Norbornene-based resin molded body and method for producing the same |
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