JP2008274138A - Fiber reinforced cyclic olefin resin composition and molded product - Google Patents
Fiber reinforced cyclic olefin resin composition and molded product Download PDFInfo
- Publication number
- JP2008274138A JP2008274138A JP2007120159A JP2007120159A JP2008274138A JP 2008274138 A JP2008274138 A JP 2008274138A JP 2007120159 A JP2007120159 A JP 2007120159A JP 2007120159 A JP2007120159 A JP 2007120159A JP 2008274138 A JP2008274138 A JP 2008274138A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- fibers
- resin composition
- cyclic olefin
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 209
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 56
- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 43
- 239000008188 pellet Substances 0.000 claims abstract description 19
- 239000004760 aramid Substances 0.000 claims abstract description 12
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 9
- 229920001230 polyarylate Polymers 0.000 claims abstract description 6
- -1 cyclic olefin Chemical class 0.000 claims description 94
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 22
- 239000004952 Polyamide Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920002577 polybenzoxazole Polymers 0.000 claims description 5
- 229920002972 Acrylic fiber Polymers 0.000 claims description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 description 29
- 150000001336 alkenes Chemical class 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 23
- 238000000465 moulding Methods 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000005452 bending Methods 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 6
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229920006231 aramid fiber Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002848 norbornenes Chemical class 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920001494 Technora Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920006221 acetate fiber Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229920006127 amorphous resin Polymers 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006713 (C5-C10) cycloalkyl group Chemical group 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- FMZITCJWMYHQFG-UHFFFAOYSA-N 1,2,3,4,4a,5,8,8a-octahydro-2-methyl-1,4:5,8-dimethanonaphthalene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C FMZITCJWMYHQFG-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- VSSAADCISISCOY-UHFFFAOYSA-N 1-(4-furo[3,4-c]pyridin-1-ylphenyl)furo[3,4-c]pyridine Chemical compound C1=CN=CC2=COC(C=3C=CC(=CC=3)C3=C4C=CN=CC4=CO3)=C21 VSSAADCISISCOY-UHFFFAOYSA-N 0.000 description 1
- ZGNJHKOQQSEQRR-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(F)(F)F)C2C(F)(F)F ZGNJHKOQQSEQRR-UHFFFAOYSA-N 0.000 description 1
- IXYRIJMHJORGEM-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C2C(C(F)(F)F)=C(C(F)(F)F)C1C=C2 IXYRIJMHJORGEM-UHFFFAOYSA-N 0.000 description 1
- LAZHUUGOLCHESB-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(C)C(C)C1C=C2 LAZHUUGOLCHESB-UHFFFAOYSA-N 0.000 description 1
- BCIDSTPBNXYOCW-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C2C(C)=C(C)C1C=C2 BCIDSTPBNXYOCW-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 1
- OGJJVYFQXFXJKU-UHFFFAOYSA-N 3-methylbicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C2C(C)=CC1C=C2 OGJJVYFQXFXJKU-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- YAICWJNVEOOIEM-UHFFFAOYSA-N 3-phenylbicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C(C=2)C=CC1C=2C1=CC=CC=C1 YAICWJNVEOOIEM-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- VSQLAQKFRFTMNS-UHFFFAOYSA-N 5-methylhexa-1,4-diene Chemical compound CC(C)=CCC=C VSQLAQKFRFTMNS-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- AGKXEJXQWQZXOC-UHFFFAOYSA-N 9,10-dimethyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2C(C)C1C AGKXEJXQWQZXOC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
Description
本発明は、有機繊維で強化された環状オレフィン系樹脂組成物及びその製造方法、並びにこの繊維強化樹脂組成物を用いて得られる成形体に関する。 The present invention relates to a cyclic olefin-based resin composition reinforced with organic fibers, a method for producing the same, and a molded body obtained using the fiber-reinforced resin composition.
環状オレフィン系樹脂は、透明性、耐薬品性、防湿性などに優れるため、光学用途や、医薬又は医療機器用途などの材料として用いられている。例えば、射出成形やブロー成形、押出成形などの各種成形方法によって、レンズや光記録材料などの光学部品、コネクターやコンデンサなどの電気又は電子用部品、薬品用容器や注射器などの医薬又は医療機器用品、ビーカーや光学用セルなどの実験器具などが成形されている。しかし、環状オレフィン系樹脂は、脆くて剛性が低く、引張特性、曲げ特性、耐衝撃性などの機械的特性も充分ではない。そこで、これらの欠点を改良するために、環状オレフィン系樹脂を、無機繊維で強化することが提案されている。 Cyclic olefin-based resins are excellent in transparency, chemical resistance, moisture resistance, and the like, and are therefore used as materials for optical applications, pharmaceuticals, medical devices, and the like. For example, by various molding methods such as injection molding, blow molding, extrusion molding, etc., optical parts such as lenses and optical recording materials, electrical or electronic parts such as connectors and capacitors, pharmaceutical or medical equipment supplies such as chemical containers and syringes Laboratory tools such as beakers and optical cells are molded. However, cyclic olefin-based resins are brittle and have low rigidity, and mechanical properties such as tensile properties, bending properties, and impact resistance are not sufficient. In order to improve these drawbacks, it has been proposed to reinforce the cyclic olefin resin with inorganic fibers.
例えば、特開平６−２５６６０４号公報（特許文献１）には、シクロオレフィンポリマーとガラス繊維とを含み、両者の屈折率差を調整したガラス繊維強化シクロオレフィンポリマー材料が開示されている。 For example, Japanese Patent Laid-Open No. 6-256604 (Patent Document 1) discloses a glass fiber reinforced cycloolefin polymer material containing a cycloolefin polymer and glass fiber and adjusting the difference in refractive index between the two.
また、特開２００３−１３８０３１号公報（特許文献２）には、ポリオレフィン０．１〜９０重量％、アモルファスシクロオレフィンポリマー０．１〜５０重量％、強化用繊維５〜７５重量％及び他の添加剤１０重量％以下を含む３ｍｍ以上の長さの長繊維強化ポリオレフィン構造体が開示されている。この文献には、強化用繊維として、タルク、スチール繊維、珪灰石、ガラス繊維が記載されている。 JP-A-2003-138031 (Patent Document 2) includes 0.1 to 90% by weight of polyolefin, 0.1 to 50% by weight of amorphous cycloolefin polymer, 5 to 75% by weight of reinforcing fibers, and other additions. A long fiber reinforced polyolefin structure having a length of 3 mm or more containing 10% by weight or less of the agent is disclosed. This document describes talc, steel fiber, wollastonite, and glass fiber as reinforcing fibers.
さらに、特開２００６−３１２７０６号公報（特許文献３）には、環状ポリオレフィン系樹脂とガラスフィラーとを含有し、両者の屈折率及びアッベ数の差が小さく、ヘイズも２０％未満である環状ポリオレフィン系樹脂組成物が開示されている。この文献には、ガラスフィラーとして、ガラスパウダー、ガラスフレーク、ミルドファイバー、ガラスビーズが記載されている。 Furthermore, JP-A-2006-312706 (Patent Document 3) contains a cyclic polyolefin resin and a glass filler, the difference between the refractive index and the Abbe number is small, and the haze is less than 20%. -Based resin compositions are disclosed. This document describes glass powder, glass flakes, milled fibers, and glass beads as glass fillers.
しかし、これらのガラス繊維などの無機繊維で強化された環状オレフィン系樹脂組成物であっても、引張強さ、曲げ強さ及び弾性率、耐衝撃性などの機械的特性に加えて、耐熱性を高度に向上できない。さらに、無機繊維は、焼成温度が高く廃棄も困難である。
従って、本発明の目的は、引張特性、曲げ特性、耐衝撃性などの機械的特性に優れた繊維強化環状オレフィン系樹脂組成物及びその製造方法、並びに前記繊維強化樹脂組成物を用いて得られる成形体を提供することにある。 Therefore, the object of the present invention can be obtained by using a fiber-reinforced cyclic olefin resin composition excellent in mechanical properties such as tensile properties, bending properties, and impact resistance, a method for producing the same, and the fiber-reinforced resin composition. The object is to provide a molded body.
本発明の他の目的は、機械的特性を高度に向上でき、かつ耐熱性も高い繊維強化環状オレフィン系樹脂組成物を提供することにある。 Another object of the present invention is to provide a fiber-reinforced cyclic olefin resin composition that can improve mechanical properties to a high degree and has high heat resistance.
本発明のさらに他の目的は、機械的特性や耐熱性が高く、廃棄も容易な繊維強化環状オレフィン系樹脂組成物を提供することにある。 Still another object of the present invention is to provide a fiber-reinforced cyclic olefin-based resin composition that has high mechanical properties and high heat resistance and can be easily discarded.
本発明者は、前記課題を達成するため鋭意検討した結果、環状オレフィン系樹脂と有機繊維とを組み合わせると、環状オレフィン系樹脂で構成されていても、引張特性、曲げ特性、耐衝撃性などの機械的特性を高度に向上できることを見いだし、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned problems, the inventor has combined the cyclic olefin resin and the organic fiber, such as tensile characteristics, bending characteristics, impact resistance, etc. The present inventors have found that the mechanical characteristics can be improved to a high degree and completed the present invention.
すなわち、発明の繊維強化樹脂組成物は、環状オレフィン系樹脂及び有機繊維で構成されている。前記環状オレフィン系樹脂は、多環式オレフィンを重合成分としてもよい。この多環式オレフィンの割合は全単量体中２０〜８０モル％程度である。前記有機繊維は、ポリエステル系繊維、ポリアミド系繊維、アクリル系繊維、セルロース系繊維、ポリベンズオキサゾール系繊維（特に、全芳香族ポリアミド系繊維、ポリアリレート系繊維、ポリパラフェニレンベンズオキサゾール系繊維）などであってもよい。有機繊維の平均繊維径は５〜２０μｍ程度である。環状オレフィン系樹脂と有機繊維との割合（重量比）は、環状オレフィン系樹脂／有機繊維＝３０／７０〜９５／５程度である。本発明の繊維強化樹脂組成物は、さらに、環状オレフィン系樹脂１００重量部に対して０．０１〜２０重量部の割合で、酸変性オレフィン系樹脂を含んでいてもよい。さらに、本発明の繊維強化樹脂組成物は、平均繊維長が３〜５０ｍｍのストランド状ペレットであり、かつこのペレットの長さ方向に対して平行に配列した有機繊維を含有してもよい。 That is, the fiber reinforced resin composition of the invention is composed of a cyclic olefin resin and organic fibers. The cyclic olefin-based resin may use a polycyclic olefin as a polymerization component. The ratio of this polycyclic olefin is about 20 to 80 mol% in all monomers. Examples of the organic fibers include polyester fibers, polyamide fibers, acrylic fibers, cellulose fibers, polybenzoxazole fibers (particularly wholly aromatic polyamide fibers, polyarylate fibers, polyparaphenylene benzoxazole fibers), and the like. It may be. The average fiber diameter of the organic fibers is about 5 to 20 μm. The ratio (weight ratio) between the cyclic olefin-based resin and the organic fiber is about cyclic olefin-based resin / organic fiber = 30/70 to 95/5. The fiber reinforced resin composition of the present invention may further contain an acid-modified olefin resin at a ratio of 0.01 to 20 parts by weight with respect to 100 parts by weight of the cyclic olefin resin. Furthermore, the fiber reinforced resin composition of the present invention may be a strand-like pellet having an average fiber length of 3 to 50 mm, and may contain organic fibers arranged in parallel to the length direction of the pellet.
本発明には、有機繊維のロービングを引き抜き成形して前記繊維強化樹脂組成物を製造する方法も含まれる。さらに、本発明には、前記繊維強化樹脂成物で形成された成形体も含まれる。 The present invention also includes a method for producing the fiber-reinforced resin composition by drawing an organic fiber roving. Further, the present invention includes a molded body formed of the fiber reinforced resin composition.
本発明では、環状オレフィン系樹脂と有機繊維とを組み合わせているため、環状オレフィン系樹脂で構成されていても、引張特性、曲げ特性、耐衝撃性などの機械的特性を向上できる。また、機械的特性を高度に向上できるとともに、耐熱性も向上できる。さらに、有機繊維を用いるため、機械的特性や耐熱性が高いだけでなく、廃棄も容易である。 In the present invention, since the cyclic olefin-based resin and the organic fiber are combined, mechanical properties such as tensile properties, bending properties, and impact resistance can be improved even when the cyclic olefin-based resin is used. In addition, the mechanical properties can be improved to a high degree and the heat resistance can be improved. Furthermore, since organic fibers are used, not only are the mechanical properties and heat resistance high, but they are also easy to discard.
本発明の繊維強化樹脂組成物は、環状オレフィン系樹脂及び有機繊維で構成されている。本発明の繊維強化樹脂組成物は、さらに酸変性オレフィン系樹脂を含んでいてもよい。 The fiber reinforced resin composition of the present invention is composed of a cyclic olefin resin and organic fibers. The fiber reinforced resin composition of the present invention may further contain an acid-modified olefin resin.
（環状オレフィン系樹脂）
環状オレフィン系樹脂は、環内にエチレン性二重結合を有する重合性の環状オレフィンを少なくとも重合成分とする樹脂であればよい。環状オレフィンは、単環式オレフィンであってもよく、多環式オレフィンであってもよい。
(Cyclic olefin resin)
The cyclic olefin-based resin may be a resin having at least a polymerizable cyclic olefin having an ethylenic double bond in the ring as a polymerization component. The cyclic olefin may be a monocyclic olefin or a polycyclic olefin.
代表的な環状オレフィンとしては、例えば、ノルボルネン類、シクロペンタジエン類又はジシクロペンタジエン類、ノルボルネン類とシクロペンタジエンとの縮合により得られる１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン類、ヘキサシクロ［６．６．１．１．１．０．０］ヘプタデセン−４類、１−ブテンとシクロペンタジエンとから合成される６−エチルビシクロ［２．２．１］ヘプト−２−エンなどの多環式オレフィンが例示できる。 Typical cyclic olefins include, for example, norbornenes, cyclopentadiene or dicyclopentadiene, 1,4,5,8-dimethano-1,2,3,4 obtained by condensation of norbornenes and cyclopentadiene. , 4a, 5,8,8a-octahydronaphthalenes, hexacyclo [6.6.1.1.1.1.0.0] heptadecene-4s, 6-ethylbicyclo synthesized from 1-butene and cyclopentadiene [2.2.1] Polycyclic olefins such as hept-2-ene can be exemplified.
また、環状オレフィンは、置換基｛例えば、炭化水素基［例えば、アルキル基（例えば、メチル基などのＣ１−１０アルキル基、好ましくはＣ１−５アルキル基）、シクロアルキル基（例えば、シクロヘキシル基などのＣ５−１０シクロアルキル基）、アリール基（例えば、フェニル基などのＣ６−１０アリール基）、アルケニル基（例えば、プロペニル基などのＣ２−１０アルケニル基など）、シクロアルケニル基（例えば、シクロペンテニル基、シクロヘキセニル基などのＣ５−１０シクロアルケニル基など）、アルキリデン基（例えば、エチリデン基などのＣ２−１０アルキリデン基、好ましくはＣ２−５アルキリデン基など）など］、アルコキシ基（例えば、メトキシ基などのＣ１−１０アルコキシ基、好ましくはＣ１−６アルコキシ基）、アシル基（例えば、アセチル基などのＣ２−５アシル基など）、アルコキシカルボニル基（例えば、メトキシカルボニル基などのＣ１−１０アルコキシ−カルボニル基）、ヒドロキシル基、カルボキシル基、アミノ基、置換アミノ基、ハロゲン原子、ハロアルキル基、ニトロ基、シアノ基、オキソ基（＝Ｏ）、複素環基（ピリジル基などの窒素原子含有複素環基など）など｝を有していてもよい。環状オレフィンは、単独で又は２種以上組みあわせて置換基を有していてもよい。 In addition, the cyclic olefin includes a substituent {eg, a hydrocarbon group [eg, an alkyl group (eg, a C 1-10 alkyl group such as a methyl group, preferably a C 1-5 alkyl group), a cycloalkyl group (eg, cyclohexyl group]). A C 5-10 cycloalkyl group such as a group), an aryl group (eg, a C 6-10 aryl group such as a phenyl group), an alkenyl group (eg, a C 2-10 alkenyl group such as a propenyl group), a cycloalkenyl group (For example, C 5-10 cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group), alkylidene group (for example, C 2-10 alkylidene group such as ethylidene group, preferably C 2-5 alkylidene group, etc.) An alkoxy group (for example, a C 1-10 alkoxy group such as a methoxy group, preferably a C 1-6 Lucoxy group), acyl group (for example, C 2-5 acyl group such as acetyl group), alkoxycarbonyl group (for example, C 1-10 alkoxy-carbonyl group such as methoxycarbonyl group), hydroxyl group, carboxyl group, amino group Group, substituted amino group, halogen atom, haloalkyl group, nitro group, cyano group, oxo group (═O), heterocyclic group (nitrogen atom-containing heterocyclic group such as pyridyl group), etc.} . The cyclic olefin may have a substituent alone or in combination of two or more.
具体的な環状オレフィンとしては、単環式オレフィン類［例えば、シクロアルケン（例えば、シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテンなどのシクロＣ３−１０アルケンなど）、シクロアルカジエン（例えば、シクロペンタジエンなどのシクロＣ３−１０アルカジエン）など］；二環式オレフィン類｛例えば、ビシクロアルケン［例えば、ノルボルネン類（例えば、２−ノルボルネン、５−メチル−２−ノルボルネン、５，５又は５，６−ジメチル−２−ノルボルネン、５−エチリデン−２−ノルボルネン、５−シアノ−２−ノルボルネン、５−メトキシカルボニル−２−ノルボルネン、５−フェニル−２−ノルボルネン、５−メチル−５−メトキシカルボニル−２−ノルボルネン、５，６−ジメトキシカルボニル−２−ノルボルネン、５，６−ジ（トリフルオロメチル）−２−ノルボルネン、７−オキソ−２−ノルボルネンなど）などのＣ４−２０ビシクロアルケンなど］、ビシクロアルカジエン［例えば、ノルボルナジエン類（例えば、２，５−ノルボルナジエン、５−メチル−２，５−ノルボルナジエン、５−シアノ−２，５−ノルボルナジエン、５−メトキシカルボニル−２，５−ノルボルナジエン、５−フェニル−２，５−ノルボルナジエン、５，６−ジメチル−２，５−ノルボルナジエン、５，６−ジ（トリフルオロメチル）−２，５−ノルボルナジエン、７−オキソ−２−ノルボルナジエンなど）など］など｝、三環式オレフィン類｛例えば、トリシクロアルケン［例えば、ジヒドロジシクロペンタジエン類（ジヒドロジシクロペンタジエンなど）などのＣ６−２５トリシクロアルケンなど］、トリシクロアルカジエン［例えば、ジシクロペンタジエン類（ジシクロペンタジエン、メチルジシクロペンタジエンなど）、トリシクロ［４．４．０．１２，５］ウンデカ−３，７−ジエン、トリシクロ［４．４．０．１２，５］ウンデカ−３，８−ジエンなどのＣ６−２５トリシクロアルカジエンなど］など｝、四環以上の多環式オレフィン類｛例えば、四環式オレフィン［例えば、テトラシクロアルケン（例えば、テトラシクロ［４．４．０．１２，５．１７，１０］−３−ドデセン、８−メチルテトラシクロ［４．４．０．１２，５．１７，１０］−３−ドデセン、８，９−ジメチルテトラシクロ［４．４．０．１２，５．１７，１０］−３−ドデセンなどのＣ８−３０テトラシクロアルケンなど）など］、五環式オレフィン［例えば、ペンタシクロアルカジエン（例えば、トリシクロペンタジエンなどのＣ１０−３５ペンタシクロアルカジエン）など］、六環式オレフィン［例えば、ヘキサシクロアルケン（例えば、ヘキサシクロ［６．６．１．１３，６．０２，７．０９，１４］−４−ヘプタデセンなどのＣ１２−４０ヘキサシクロアルケン）など］など｝などの多環式オレフィン類などが挙げられる。 Specific cyclic olefins include monocyclic olefins [eg, cycloalkenes (eg, cyclo C 3-10 alkenes such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, etc.), cycloalkadienes (eg, cyclopentadiene, etc. Cyclocyclo 3-10 alkadiene etc.]; bicyclic olefins {e.g. bicycloalkenes [e.g. norbornenes (e.g. 2-norbornene, 5-methyl-2-norbornene, 5,5 or 5,6-dimethyl- 2-norbornene, 5-ethylidene-2-norbornene, 5-cyano-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5,6-dimethoxycarbonyl 2-norbornene, 5,6-di (trifluoromethyl) -2-norbornene, 7-oxo-2-norbornene, etc.) C 4-20 bicycloalkane such as, bicyclo alkadiene [e.g., norbornadiene (e.g., 2,5-norbornadiene, 5-methyl-2,5-norbornadiene, 5-cyano-2,5-norbornadiene, 5-methoxycarbonyl-2,5-norbornadiene, 5-phenyl-2,5-norbornadiene, 5,6 -Dimethyl-2,5-norbornadiene, 5,6-di (trifluoromethyl) -2,5-norbornadiene, 7-oxo-2-norbornadiene, etc.)], etc.], tricyclic olefins {eg, tricyclo Alkenes [eg dihydrodicyclopentadiene (dihydrodicyclopentadiene Etc.) C 6-25 tricycloalkyl alkenes, etc.], tri cycloalkadiene [e.g., a dicyclopentadiene compound (dicyclopentadiene, methyl dicyclopentadiene, etc.), tricyclo [4.4.0.12,5] undec -3,7-diene, C 6-25 tricycloalkadiene such as tricyclo [4.4.0.12,5] undeca-3,8-diene, etc.]}, polycyclic olefins having four or more rings {E.g., tetracyclic olefins [e.g., tetracycloalkenes (e.g., tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8-methyltetracyclo [4.4.0.12 , 5.17,10] -3-dodecene, 8,9-dimethyl-tetracyclo [4.4.0.12,5.17,10] -3-dodecene C 8-30 Tetorashi such Chloroalkene etc.)], pentacyclic olefins [eg pentacycloalkadiene (eg C 10-35 pentacycloalkadiene such as tricyclopentadiene) etc.], hexacyclic olefins [eg hexacycloalkene (eg hexacyclo [6.6.1.13,6.02,7.09,14] -4- C 12-40 hexa cycloalkene), etc., such as heptadecene] and the like polycyclic olefins such as such}.
これらの環状オレフィンは単独で又は二種以上組み合わせて使用できる。これらの環状オレフィンのうち、ノルボルネン類などの多環式オレフィンが好ましい。 These cyclic olefins can be used alone or in combination of two or more. Of these cyclic olefins, polycyclic olefins such as norbornenes are preferred.
環状オレフィン系樹脂は、環状オレフィンの単独又は共重合体（例えば、単環式オレフィンと多環式オレフィンとの共重合体など）であってもよく、環状オレフィンと共重合性単量体との共重合体であってもよい。 The cyclic olefin-based resin may be a cyclic olefin homopolymer or a copolymer (for example, a copolymer of a monocyclic olefin and a polycyclic olefin), and a cyclic olefin and a copolymerizable monomer. A copolymer may also be used.
共重合性単量体としては、共重合可能な限り特に限定されないが、鎖状オレフィン［アルケン（例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、３−メチル−１−ブテン、２−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセンなどのＣ２−２０アルケン）、アルカジエン（例えば、１，４−ヘキサジエン、４−メチル−１，４−ヘキサジエン、５−メチル−１，４−ヘキサジエン、１，７−オクタジエンなどの非共役Ｃ５−２０アルカジエン）など］などが例示できる。これらの共重合性単量体は単独で又は二種以上組み合わせて使用できる。共重合性単量体は、α−オレフィン類（例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセンなどのＣ２−１０α−オレフィン類、特にＣ２−６α−オレフィン類）であってもよい。 The copolymerizable monomer is not particularly limited as long as it can be copolymerized, but a chain olefin [alkene (for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene) 2-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1 C 2 such as -pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene -20 alkene), alkadienes (eg, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene) Non-conjugated C 5-20 alkadiene, etc.]. These copolymerizable monomers can be used alone or in combination of two or more. Copolymerizable monomers include α-olefins (for example, C 2-10 α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, in particular C 2-6 α-olefins. ).
さらに、本発明の目的を損なわない範囲内で、共重合性単量体として、重合性ニトリル化合物（例えば、（メタ）アクリロニトリルなど）、（メタ）アクリル系単量体（例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルなどの（メタ）アクリル酸エステル類、（メタ）アクリル酸など）、不飽和ジカルボン酸又はその誘導体（無水マレイン酸など）、ビニルエステル類（例えば、酢酸ビニル、プロピオン酸ビニルなど）、共役ジエン類（ブタジエン、イソプレンなど）などを用いてもよい。これらの共重合性単量体も単独で又は２種以上組み合わせて使用してもよい。 Furthermore, as long as the object of the present invention is not impaired, a polymerizable nitrile compound (for example, (meth) acrylonitrile), a (meth) acrylic monomer (for example, (meth) acrylic) is used as a copolymerizable monomer. Methyl methacrylate, (meth) acrylic acid esters such as ethyl (meth) acrylate, (meth) acrylic acid, etc.), unsaturated dicarboxylic acids or derivatives thereof (such as maleic anhydride), vinyl esters (eg, vinyl acetate, Vinyl propionate, etc.), conjugated dienes (butadiene, isoprene, etc.) and the like may be used. These copolymerizable monomers may be used alone or in combination of two or more.
好ましい環状オレフィン系樹脂は、環状オレフィンと鎖状オレフィンとの共重合体や、多環式オレフィン（例えば、二乃至六環式オレフィンなど）を重合成分とする樹脂、特に、多環式オレフィン（前記ノルボルネン類や前記ジシクロペンタジエン類などのノルボルネン骨格を有する単量体）とα−オレフィンとの共重合体である。特に、環状オレフィンと鎖状オレフィンとの共重合体（例えば、エチレンとノルボルネン系単量体との共重合体などのα−Ｃ２−４オレフィンと多環式オレフィンとの共重合体など）は、オレフィン系重合体（エチレン系重合体など）と環状オレフィン重合体との性質を兼ね備えており、鎖状オレフィンの共重合比率を調整することにより、高分子量の重合体を得ることができる。 Preferred cyclic olefin-based resins include copolymers of cyclic olefins and chain olefins, and resins containing polycyclic olefins (for example, bi to hexacyclic olefins) as polymerization components, particularly polycyclic olefins (described above). A monomer having a norbornene skeleton such as norbornene or the above-mentioned dicyclopentadiene) and an α-olefin. In particular, a copolymer of a cyclic olefin and a chain olefin (for example, a copolymer of an α-C 2-4 olefin such as a copolymer of ethylene and a norbornene monomer and a polycyclic olefin) is used. The polymer has both the properties of an olefin polymer (such as an ethylene polymer) and a cyclic olefin polymer, and a high molecular weight polymer can be obtained by adjusting the copolymerization ratio of the chain olefin.
環状オレフィン系樹脂において環状オレフィン（特に多環式オレフィン）の割合は、１〜１００モル％程度の範囲から選択でき、機械的特性や成形性などの点から、例えば、２０〜８０モル％、好ましくは２５〜７０モル％、さらに好ましくは３０〜６０モル％程度である。特に、環状オレフィン系樹脂が、多環式オレフィンと鎖状オレフィン（例えば、エチレンなどのα−オレフィン類）との共重合体である場合、両者の割合（モル比）が、多環式オレフィン／鎖状オレフィン＝２０／８０〜８０／２０、好ましくは２５／７５〜７０／３０、さらに好ましくは３０／７０〜６０／４０程度である。 In the cyclic olefin-based resin, the ratio of the cyclic olefin (particularly polycyclic olefin) can be selected from the range of about 1 to 100 mol%. From the viewpoint of mechanical properties and moldability, for example, 20 to 80 mol%, preferably Is about 25 to 70 mol%, more preferably about 30 to 60 mol%. In particular, when the cyclic olefin-based resin is a copolymer of a polycyclic olefin and a chain olefin (for example, α-olefins such as ethylene), the ratio (molar ratio) between the two is the polycyclic olefin / Chain olefin = 20/80 to 80/20, preferably 25/75 to 70/30, more preferably about 30/70 to 60/40.
環状オレフィン系樹脂の軟化点は、７０℃以上であればよく、例えば、８０〜２５０℃、好ましくは１００〜２３０℃、さらに好ましくは１２０〜２２０℃（特に１３０〜２１０℃）程度である。なお、軟化点は、共重合成分の割合、分子量などを調整して制御することができる。 The softening point of cyclic olefin resin should just be 70 degreeC or more, for example, 80-250 degreeC, Preferably it is 100-230 degreeC, More preferably, it is about 120-220 degreeC (especially 130-210 degreeC) grade. The softening point can be controlled by adjusting the proportion of the copolymer component, the molecular weight, and the like.
環状オレフィン系樹脂の数平均分子量は、５０００〜３０００００程度の範囲から選択できるが、通常、１００００を超えており、例えば、１５０００〜２０００００、好ましくは２００００〜１０００００、さらに好ましくは３００００〜８００００（特に４００００〜７００００）程度である。 The number average molecular weight of the cyclic olefin-based resin can be selected from the range of about 5000 to 300000, but usually exceeds 10,000, for example, 15000 to 200000, preferably 20000 to 100000, more preferably 30000 to 80000 (particularly 40000). ~ 70,000).
環状オレフィン系樹脂は、付加重合により得られた樹脂であってもよく、開環重合（開環メタセシス重合など）により得られた樹脂であってもよい。また、環状オレフィン系樹脂（例えば、開環メタセシス重合により得られた樹脂など）は、水素添加された水添樹脂であってもよい。また、環状オレフィン系樹脂は、結晶性又は非晶性樹脂であってもよく、通常、非晶性樹脂であってもよい。なお、環状オレフィン系樹脂は、慣用の重合方法（例えば、チーグラー型触媒を用いた付加重合、メタロセン系触媒を用いた付加重合、メタセシス重合触媒を用いた開環メタセシス重合など）により調製してもよい。 The cyclic olefin-based resin may be a resin obtained by addition polymerization or a resin obtained by ring-opening polymerization (ring-opening metathesis polymerization or the like). In addition, the cyclic olefin-based resin (for example, a resin obtained by ring-opening metathesis polymerization) may be a hydrogenated hydrogenated resin. In addition, the cyclic olefin resin may be a crystalline or amorphous resin, and may usually be an amorphous resin. The cyclic olefin resin may be prepared by a conventional polymerization method (for example, addition polymerization using a Ziegler type catalyst, addition polymerization using a metallocene catalyst, ring-opening metathesis polymerization using a metathesis polymerization catalyst, etc.). Good.
（有機繊維）
有機繊維としては、天然又は再生繊維（例えば、セルロース、レーヨン繊維やアセテート繊維などのセルロース系繊維、シルク、羊毛繊維、タンパク質又はポリペプチド繊維、アルギン酸繊維など）、合成繊維（熱硬化性樹脂繊維、熱可塑性樹脂繊維など）などが挙げられる。これらの有機繊維は、単独で又は二種以上組み合わせて使用してもよい。
(Organic fiber)
Organic fibers include natural or regenerated fibers (for example, cellulose fibers such as cellulose, rayon fiber and acetate fiber, silk, wool fibers, protein or polypeptide fibers, alginic acid fibers, etc.), synthetic fibers (thermosetting resin fibers, Thermoplastic resin fibers, etc.). These organic fibers may be used alone or in combination of two or more.
熱硬化性樹脂繊維としては、例えば、エポキシ系繊維、フェノール系繊維、不飽和ポリエステル系繊維、ポリイミド系繊維、ポリアミドイミド系繊維、ポリベンゾイミダゾール（ＰＢＩ）系繊維、ポリウレタン系繊維などが挙げられる。これらの熱硬化性樹脂繊維は、単独で又は二種以上組み合わせて使用してもよい。 Examples of the thermosetting resin fiber include epoxy fiber, phenol fiber, unsaturated polyester fiber, polyimide fiber, polyamideimide fiber, polybenzimidazole (PBI) fiber, polyurethane fiber, and the like. These thermosetting resin fibers may be used alone or in combination of two or more.
熱可塑性樹脂繊維としては、例えば、ポリアミド系繊維（ポリアミド５、ポリアミド６、ポリアミド６６、ポリアミド６１０、ポリアミド１１、ポリアミド１２、ポリアミド６１２、ポリアミド６／６６、ポリアミド６／１１などの脂肪族ポリアミド系繊維；ポリアミド６Ｔ、ポリアミド９Ｔ、ポリアミドＭＸＤなどの芳香族ポリアミド系繊維；脂環族ポリアミド系繊維など）、ポリイミド系繊維（ポリエーテルイミド繊維、ポリアミドイミド繊維、ポリアミノビスマレイミド繊維、ビスマレイミドトリアジン繊維など）、ポリエステル系繊維（ポリエチレンテレフタレートやポリブチレンテレフタレートなどのポリＣ２−４アルキレンテレフタレート、ポリＣ２−４アルキレンナフタレート、これらのコポリエステルなどの芳香族ポリエステル系繊維、ポリアリレート系繊維、液晶性ポリエステル繊維など）、ポリカーボネート系繊維（ビスフェノールＡ型ポリカーボネートなどのビスフェノール型ポリカーボネート繊維、水添ビスフェノール型ポリカーボネート繊維など）、オレフィン系繊維［ポリエチレン繊維（低密度ポリエチレン繊維、高密度ポリエチレン繊維など）、ポリプロピレン繊維など］、アクリル系繊維（ポリメタクリル酸メチルなどのポリ（メタ）アクリル酸アルキルエステル繊維、ポリアクリロニトリルやアクリロニトリル−塩化ビニル共重合体などのアクリロニトリル系繊維など）、ビニル系繊維（塩化ビニル系繊維、酢酸ビニル系繊維など）、ポリフェニレンオキシド系繊維［ポリフェニレンオキシド繊維、変性ポリフェニレンオキシド（ポリスチレンとのブレンドなど）繊維など］、ポリフェニレンスルフィド系繊維（ポリフェニレンスルフィド繊維、ポリビフェニレンスルフィド繊維、ポリフェニレンスルフィドケトン繊維、ポリビフェニレンスルフィドスルホン繊維など）、ポリスルホン系繊維（ポリスルホン繊維、ポリエーテルスルホン繊維など）、ポリアセタール系繊維（ポリアセタール繊維など）、ポリエーテルケトン系繊維（ポリエーテルケトン繊維、ポリエーテルエーテルケトン繊維など）、ポリベンゾオキサゾール系繊維（ポリパラフェニレンベンズオキサゾール系繊維など）などが挙げられる。これらの熱可塑性樹脂繊維は、単独で又は二種以上組み合わせて使用してもよい。 Examples of the thermoplastic resin fibers include polyamide fibers (polyamide 5, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 612, polyamide 6/66, polyamide 6/11, and other aliphatic polyamide fibers. Aromatic polyamide fibers such as polyamide 6T, polyamide 9T, polyamide MXD; alicyclic polyamide fibers, etc.), polyimide fibers (polyetherimide fibers, polyamideimide fibers, polyamino bismaleimide fibers, bismaleimide triazine fibers, etc.) , polyester fibers (polyethylene terephthalate or polybutylene terephthalate such as poly C 2-4 alkylene terephthalate, poly C 2-4 alkylene naphthalate, aromatic such as these copolyesters polyether Tellurium fiber, polyarylate fiber, liquid crystalline polyester fiber, etc.), polycarbonate fiber (bisphenol type polycarbonate fiber such as bisphenol A type polycarbonate, hydrogenated bisphenol type polycarbonate fiber, etc.), olefin fiber [polyethylene fiber (low density polyethylene) Fibers, high-density polyethylene fibers, etc.), polypropylene fibers, etc.], acrylic fibers (poly (meth) acrylic acid alkyl ester fibers such as polymethyl methacrylate, acrylonitrile fibers such as polyacrylonitrile and acrylonitrile-vinyl chloride copolymers) ), Vinyl fibers (vinyl chloride fibers, vinyl acetate fibers, etc.), polyphenylene oxide fibers [polyphenylene oxide fibers, modified polyphenylene oxide (polystyrene) Etc.), polyphenylene sulfide fibers (polyphenylene sulfide fibers, polybiphenylene sulfide fibers, polyphenylene sulfide ketone fibers, polybiphenylene sulfide sulfone fibers, etc.), polysulfone fibers (polysulfone fibers, polyether sulfone fibers, etc.), Examples include polyacetal fibers (polyacetal fibers, etc.), polyether ketone fibers (polyether ketone fibers, polyether ether ketone fibers, etc.), polybenzoxazole fibers (polyparaphenylene benzoxazole fibers, etc.), and the like. These thermoplastic resin fibers may be used alone or in combination of two or more.
これらの繊維のうち、機械的特性及び耐熱性の点から、ポリエステル系繊維、ポリアミド系繊維、アクリロニトリル系繊維などのアクリル系繊維、レーヨン繊維などのセルロース系繊維、ポリベンズオキサゾール系繊維、特に、全芳香族ポリアミド系繊維（アラミド繊維）、アリレート系繊維（全芳香族ポリエステル系繊維）、ポリパラフェニレンベンズオキサゾール系繊維が好ましい。 Among these fibers, from the viewpoint of mechanical properties and heat resistance, polyester fibers, polyamide fibers, acrylic fibers such as acrylonitrile fibers, cellulosic fibers such as rayon fibers, polybenzoxazole fibers, especially all Aromatic polyamide fibers (aramid fibers), arylate fibers (fully aromatic polyester fibers), and polyparaphenylene benzoxazole fibers are preferred.
芳香族ポリアミド系繊維には、ジアミンとジカルボン酸とを重合成分とするポリアミド繊維であって、ジアミン成分およびジカルボン酸成分のうち、少なくとも一方の成分が芳香族化合物であるポリアミドや、芳香族アミノカルボン酸を主な重合成分とするポリアミド繊維などが含まれる。芳香族ポリアミド系繊維としては、芳香族ジアミン［例えば、フェニレンジアミン、ジアミノトルエン、キシリレンジアミン、ビフェニレンジアミン、ビス（４−アミノフェニル）エーテル、ビス（４−アミノフェニル）ケトン、ビス（４−アミノフェニル）スルホン、１，４−ナフタレンジアミン、ジアミノジフェニルメタン、ビス（４−アミノ−３−エチル）ジフェニルメタン、ビス（４−アミノ−３−メチルフェニル）メタン、２，２′−ビス（４−アミノフェニル）プロパンなど］と、芳香族ジカルボン酸（フタル酸、無水フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸など）とから得られる全芳香族ポリアミド繊維（アラミド繊維）などが好ましい。アラミド繊維としては、ノメクス繊維、ケブラー繊維、テクノーラ繊維などが上市されている。 The aromatic polyamide fiber is a polyamide fiber having diamine and dicarboxylic acid as polymerization components, and at least one of the diamine component and the dicarboxylic acid component is an aromatic compound or an aromatic aminocarboxylic acid. Polyamide fibers containing acid as the main polymerization component are included. Aromatic polyamide fibers include aromatic diamines [for example, phenylenediamine, diaminotoluene, xylylenediamine, biphenylenediamine, bis (4-aminophenyl) ether, bis (4-aminophenyl) ketone, bis (4-amino Phenyl) sulfone, 1,4-naphthalenediamine, diaminodiphenylmethane, bis (4-amino-3-ethyl) diphenylmethane, bis (4-amino-3-methylphenyl) methane, 2,2'-bis (4-aminophenyl) ) Propane, etc.] and wholly aromatic polyamide fibers (aramid fibers) obtained from aromatic dicarboxylic acids (phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) are preferred. As aramid fibers, Nomex fibers, Kevlar fibers, Technora fibers, etc. are marketed.
ポリアリレート系繊維には、芳香族ジオール成分と芳香族ジカルボン酸成分とを主な重合成分とするポリエステル繊維などが含まれる。ポリアリレート系繊維としては、芳香族ジオール［例えば、２，２−ビス（４−ヒドロキシフェニル）プロパン、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタンなどのビス（ヒドロキシアリール）Ｃ１−６アルカン、ビスフェノールＳなどのジ（ヒドロキシフェニル）スルホキシドなど］と、芳香族ジカルボン酸（フタル酸、無水フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸など）とから得られる全芳香族ポリエステルなどが好ましい。 Polyarylate fibers include polyester fibers having an aromatic diol component and an aromatic dicarboxylic acid component as main polymerization components. Polyarylate fibers include aromatic diols [for example, bis such as 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane. (Hydroxyaryl) C 1-6 alkane, di (hydroxyphenyl) sulfoxide, etc. such as bisphenol S] and an aromatic dicarboxylic acid (phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) Preferred are wholly aromatic polyesters.
ポリパラフェニレンベンズオキサゾール系繊維には、フェニレン骨格とベンズオキサゾール（特にベンズビスオキサゾール）骨格とを有するポリマーで構成された繊維が含まれる。ポリパラフェニレンベンズオキサゾール系繊維としては、ポリ（ｐ−フェニレン−２，６−ベンズビスオキサゾール）繊維であるザイロン繊維が上市されている。 The polyparaphenylene benzoxazole-based fiber includes a fiber composed of a polymer having a phenylene skeleton and a benzoxazole (particularly benzbisoxazole) skeleton. As the polyparaphenylene benzoxazole-based fiber, a xylon fiber that is a poly (p-phenylene-2,6-benzbisoxazole) fiber is marketed.
有機繊維の平均繊維長（繊維強化樹脂組成物中での繊維長）は、例えば、３〜５０ｍｍ、好ましくは４〜２５ｍｍ、さらに好ましくは６〜１５ｍｍ程度である。後述する引き抜き成形により繊維強化樹脂組成物を調製する場合は、ストランド状ペレットの長さと有機繊維の繊維長が略同じ長さとなる。繊維長がこのような範囲にあると、機械的特性と成形性とのバランスを向上できる。 The average fiber length of the organic fibers (fiber length in the fiber reinforced resin composition) is, for example, about 3 to 50 mm, preferably about 4 to 25 mm, and more preferably about 6 to 15 mm. When a fiber reinforced resin composition is prepared by pultrusion described later, the length of the strand pellets and the fiber length of the organic fibers are substantially the same. When the fiber length is in such a range, the balance between mechanical properties and moldability can be improved.
有機繊維の平均繊維径は、例えば、１〜２５μｍ、好ましくは２〜２０μｍ、さらに好ましくは５〜１８μｍ程度である。繊維径がこのような範囲にあると、樹脂中に有機繊維が均一に分散するため、機械的特性を向上できる。 The average fiber diameter of the organic fibers is, for example, 1 to 25 μm, preferably 2 to 20 μm, and more preferably about 5 to 18 μm. When the fiber diameter is in such a range, the organic fibers are uniformly dispersed in the resin, so that the mechanical characteristics can be improved.
有機繊維の弾性率（ＡＳＴＭ Ｄ８８５Ｍ）は、例えば、４００〜１２００ｇ／デニール、好ましくは４００〜１０００ｇ／デニール、さらに好ましくは５００〜１０００ｇ／デニール程度である。 The elastic modulus (ASTM D885M) of the organic fiber is, for example, about 400 to 1200 g / denier, preferably 400 to 1000 g / denier, and more preferably about 500 to 1000 g / denier.
環状オレフィン系樹脂と有機繊維との割合（重量比）は、環状オレフィン系樹脂／有機繊維＝３０／７０〜９５／５、好ましくは４０／６０〜９０／１０、さらに好ましくは５０／５０〜８５／１５程度である。両者の割合がこのような範囲にあると、環状オレフィン系樹脂の特性を損なうことなく、機械的強度を向上できる。 The ratio (weight ratio) between the cyclic olefin resin and the organic fiber is cyclic olefin resin / organic fiber = 30/70 to 95/5, preferably 40/60 to 90/10, and more preferably 50/50 to 85. / 15 or so. When the ratio of both is in such a range, mechanical strength can be improved without impairing the characteristics of the cyclic olefin resin.
（酸変性オレフィン系樹脂）
酸変性オレフィン系樹脂は、オレフィン系樹脂が酸で変性された樹脂であり、例えば、共重合、末端や側鎖の変性などにより、酸基を導入した変性体であってもよい。
(Acid-modified olefin resin)
The acid-modified olefin-based resin is a resin obtained by modifying an olefin-based resin with an acid, and may be, for example, a modified product having an acid group introduced by copolymerization, terminal or side chain modification.
オレフィン系樹脂は、前記環状オレフィン系樹脂の他、鎖状オレフィン（例えば、エチレン、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセンなどのＣ2-10オレフィンなど）を重合成分とする非環状オレフィン系樹脂であってもよい。非環状オレフィン系樹脂としては、例えば、ポリエチレン系樹脂［例えば、ポリエチレン、エチレン−プロピレン共重合体、エチレン−ブテン−１共重合体、エチレン−プロピレン−ブテン−１共重合体、エチレン−（４−メチルペンテン−１）共重合体など］、ポリプロピレン系樹脂（例えば、ポリプロピレン、プロピレン−エチレン共重合体、プロピレン−ブテン−１共重合体、プロピレン−エチレン−ブテン−１共重合体など）、ポリ（メチルペンテン−１）樹脂などが挙げられる。これらのオレフィン系樹脂のうち、環状オレフィン系樹脂が好ましい。 The olefin resin is a polymerization component of a chain olefin (for example, C 2-10 olefin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, etc.) in addition to the cyclic olefin resin. An acyclic olefin resin may be used. Examples of the acyclic olefin-based resin include polyethylene-based resins [for example, polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene- (4- Methylpentene-1) copolymer, etc.], polypropylene resin (eg, polypropylene, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer, etc.), poly ( And methylpentene-1) resin. Of these olefin resins, cyclic olefin resins are preferred.
変性剤となる共重合性単量体としては、カルボキシル基を有する単量体（例えば、（メタ）アクリル酸、クロトン酸などの脂肪族モノカルボン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸などの脂肪族ジカルボン酸など）、酸無水物基を有する単量体（例えば、無水マレイン酸、無水イタコン酸、無水シトラコン酸などの脂肪族ジカルボン酸無水物、無水フタル酸などの芳香族ジカルボン酸無水物など）などが挙げられる。これらの単量体はアルキルエステル（メチル、エチルなどのＣ１−４アルキルエステルなど）であってもよい。 Examples of the copolymerizable monomer that serves as a modifier include monomers having a carboxyl group (for example, aliphatic monocarboxylic acids such as (meth) acrylic acid and crotonic acid, maleic acid, fumaric acid, citraconic acid, and itaconic acid. An aliphatic dicarboxylic acid such as maleic anhydride, itaconic anhydride, citraconic anhydride, and the like, and aromatic dicarboxylic acid such as phthalic anhydride. Anhydride) and the like. These monomers may be alkyl esters (C 1-4 alkyl esters such as methyl and ethyl).
これらの共重合性単量体（変性剤）は、単独で又は二種以上組み合わせて使用できる。これらの共重合性単量体のうち、（メタ）アクリル酸、（無水）マレイン酸、フマル酸、（無水）イタコン酸などの（無水）不飽和カルボン酸が好ましい。本発明では、特に、このような不飽和カルボン酸又はその誘導体で、グラフト共重合などにより変性された酸変性オレフィン系樹脂であってもよい。 These copolymerizable monomers (modifiers) can be used alone or in combination of two or more. Of these copolymerizable monomers, (anhydro) unsaturated carboxylic acids such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, and (anhydrous) itaconic acid are preferred. In the present invention, in particular, an acid-modified olefin resin modified with such an unsaturated carboxylic acid or a derivative thereof by graft copolymerization may be used.
変性剤（共重合性単量体）の割合は、樹脂中５０重量％以下の範囲から選択でき、例えば、０．１〜４０重量％、好ましくは０．５〜３０重量％、さらに好ましくは１〜２０重量％程度である。 The ratio of the modifier (copolymerizable monomer) can be selected from the range of 50% by weight or less in the resin, for example, 0.1 to 40% by weight, preferably 0.5 to 30% by weight, more preferably 1 About 20% by weight.
酸変性オレフィン系樹脂の具体例は、酸変性非環状オレフィン系樹脂として、例えば、エチレンと不飽和カルボン酸又はそのエステルとの共重合体［例えば、エチレン−無水マレイン酸共重合体、エチレン−（メタ）アクリル酸−無水マレイン酸共重合体など］、（無水）不飽和カルボン酸でグラフト変性したポリオレフィン［例えば、無水マレイン酸グラフトポリプロピレンなど］、アイオノマーなどが挙げられ、酸変性環状オレフィン系樹脂として、例えば、エチレンとノルボルネン系単量体と不飽和カルボン酸又はそのエステルとの共重合体（例えば、エチレン−ノルボルネン−無水マレイン酸共重合体など）、（無水）不飽和カルボン酸でグラフト変性したエチレン−ノルボルネン系共重合体（例えば、無水マレイン酸グラフトエチレン−ノルボルネン共重合体など）などが挙げられる。これらの酸変性オレフィン系樹脂のうち、前記環状オレフィン系樹脂との相溶性などの点から、酸変性環状オレフィン系樹脂［特に、前記環状オレフィン系樹脂と同種（特に、同一）の環状オレフィン系樹脂骨格を有する酸変性環状オレフィン系樹脂］が好ましい。 Specific examples of the acid-modified olefin resin include, for example, a copolymer of ethylene and an unsaturated carboxylic acid or an ester thereof [for example, ethylene-maleic anhydride copolymer, ethylene- ( (Meth) acrylic acid-maleic anhydride copolymer], polyolefins graft-modified with (anhydrous) unsaturated carboxylic acid [for example, maleic anhydride grafted polypropylene, etc.], ionomers, etc. For example, a copolymer of ethylene, a norbornene monomer and an unsaturated carboxylic acid or an ester thereof (for example, an ethylene-norbornene-maleic anhydride copolymer), graft-modified with (anhydrous) unsaturated carboxylic acid Ethylene-norbornene copolymer (for example, maleic anhydride grafted ethylene Down - norbornene copolymer) and the like. Among these acid-modified olefin resins, from the viewpoint of compatibility with the cyclic olefin resin, acid-modified cyclic olefin resins [particularly, the same kind (particularly, the same) cyclic olefin resin as the cyclic olefin resin. An acid-modified cyclic olefin resin having a skeleton] is preferable.
酸変性オレフィン系樹脂の割合は、環状オレフィン系樹脂１００重量部に対して、例えば、０．０１〜２０重量部、好ましくは０．１〜１５重量部、さらに好ましくは０．５〜１０重量部程度である。酸変性オレフィン系樹脂をこのような割合で含有すると、環状オレフィン系樹脂と有機繊維との親和性を向上できるため、繊維強化樹脂の機械的特性が向上する。 The ratio of the acid-modified olefin resin is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the cyclic olefin resin. Degree. When the acid-modified olefin resin is contained in such a ratio, the affinity between the cyclic olefin resin and the organic fiber can be improved, so that the mechanical properties of the fiber reinforced resin are improved.
（繊維強化樹脂組成物）
本発明の繊維強化樹脂組成物は、環状オレフィン系樹脂の特性を損なわない範囲で、他の樹脂（例えば、ポリエチレン系樹脂やポリプロピレン系樹脂などのオレフィン系樹脂など）を含んでいてもよい。他の樹脂の割合は、例えば、環状オレフィン系樹脂１００重量部に対して５０重量％以下であり、好ましくは０．１〜３０重量部、さらに好ましくは１〜２０重量部程度である。
(Fiber reinforced resin composition)
The fiber reinforced resin composition of the present invention may contain other resins (for example, olefin resins such as polyethylene resins and polypropylene resins) as long as the properties of the cyclic olefin resins are not impaired. The ratio of other resin is 50 weight% or less with respect to 100 weight part of cyclic olefin resin, for example, Preferably it is 0.1-30 weight part, More preferably, it is about 1-20 weight part.
本発明の繊維強化樹脂組成物は、さらに、慣用の添加剤、例えば、滑剤（オレフィン系ワックスなどのワックス類、脂質類など）、可塑剤又は軟化剤、着色剤、分散剤、離型剤、安定化剤（ヒンダードフェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤などの酸化防止剤、紫外線吸収剤、熱安定化剤など）、帯電防止剤、難燃剤、アンチブロッキング剤、結晶核成長剤、カップリング剤、充填剤（シリカやタルクなどの粒状充填剤や、ガラス繊維や炭素繊維などの無機繊維状充填剤など）などを含んでいてもよい。これらの添加剤は、単独で又は二種以上組み合わせて使用できる。これらの添加剤の割合は、種類に応じて適宜選択でき、環状オレフィン系樹脂１００重量部に対して、例えば、０．０１〜３０重量部、好ましくは０．１〜２０重量部、さらに好ましくは０．５〜１０重量部程度である。 The fiber-reinforced resin composition of the present invention further includes conventional additives such as lubricants (waxes such as olefin waxes, lipids, etc.), plasticizers or softeners, colorants, dispersants, release agents, Stabilizers (hindered phenolic antioxidants, phosphorus antioxidants, antioxidants such as sulfur antioxidants, UV absorbers, heat stabilizers, etc.), antistatic agents, flame retardants, antiblocking agents , Crystal nucleus growth agents, coupling agents, fillers (particulate fillers such as silica and talc, inorganic fibrous fillers such as glass fibers and carbon fibers), and the like. These additives can be used alone or in combination of two or more. The ratio of these additives can be appropriately selected according to the type, and is, for example, 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the cyclic olefin resin. About 0.5 to 10 parts by weight.
さらに、本発明の繊維強化樹脂組成物は、前記成分で構成された成形用基材であればよく、その形態は特に限定されず、成形品の用途に応じて、様々な形態を選択することができる。具体的には、プリプレグ、マット、スタンパブルシート、ＳＭＣ（シートモールディングコンパウンド）、ペレット、フィラメント、クロスなどの形態であってもよい。これらの形態のうち、後述する引き抜き成形で得られる形態であるストランド状（又は棒状）ペレットが好ましい。本発明のストランド状ペレットは、ペレットの長さ方向に対して平行に配列した有機繊維を含有している。１本のペレット（ストランド）内の有機繊維の本数は、例えば、１〜２００００本、好ましくは１０〜１８０００本、さらに好ましくは２０〜１６０００本程度である。ストランド状ペレットの断面形状は、特に限定されず、例えば、円形状、楕円形状、三角又は四角などの多角形状、不定形状などである。なお、引き抜き成形で得られる形態は、ストランド状に限られず、テープ状やシート状などであってもよく、その場合には、ペレットの引き取り方向において、有機繊維が平行に配列している。 Furthermore, the fiber reinforced resin composition of the present invention may be a molding base material composed of the above components, and the form thereof is not particularly limited, and various forms are selected according to the use of the molded product. Can do. Specifically, it may be in the form of a prepreg, mat, stampable sheet, SMC (sheet molding compound), pellet, filament, cloth, or the like. Of these forms, strand (or rod-like) pellets that are obtained by pultrusion described later are preferable. The strand-shaped pellet of the present invention contains organic fibers arranged in parallel to the length direction of the pellet. The number of organic fibers in one pellet (strand) is, for example, 1 to 20000, preferably 10 to 18000, and more preferably about 20 to 16000. The cross-sectional shape of the strand-shaped pellet is not particularly limited, and examples thereof include a circular shape, an elliptical shape, a polygonal shape such as a triangle or a square, and an indefinite shape. In addition, the form obtained by pultrusion molding is not limited to a strand shape, and may be a tape shape or a sheet shape. In that case, organic fibers are arranged in parallel in the direction in which the pellets are taken.
ストランド状ペレットの平均長（ペレット長）は、例えば、３〜５０ｍｍ、好ましくは４〜２５ｍｍ、さらに好ましくは４〜１５ｍｍ程度であり、平均径は、例えば、０．１〜５ｍｍ、好ましくは０．３〜４ｍｍ、さらに好ましくは０．５〜３ｍｍ程度である。 The average length (pellet length) of the strand-shaped pellets is, for example, 3 to 50 mm, preferably 4 to 25 mm, more preferably about 4 to 15 mm, and the average diameter is, for example, 0.1 to 5 mm, preferably 0. It is about 3 to 4 mm, more preferably about 0.5 to 3 mm.
（繊維強化樹脂組成物の製造方法）
繊維強化樹脂組成物の製造方法は、前述のサイズを有する有機繊維を環状オレフィン系樹脂中に含有させることができれば、特に限定されず、環状オレフィン系樹脂と有機繊維とを混合して押出成形する方法などであってもよいが、二次成形に供しても繊維の破損が抑制され、繊維強化樹脂組成物の耐衝撃性及び耐熱性を向上できる点から、有機繊維のロービング（有機繊維束）を引き抜き成形する方法（プルトルージョン法）が好ましい。
(Method for producing fiber-reinforced resin composition)
The method for producing the fiber reinforced resin composition is not particularly limited as long as the organic fiber having the above-described size can be contained in the cyclic olefin resin, and the cyclic olefin resin and the organic fiber are mixed and extruded. Although it may be a method, organic fiber roving (organic fiber bundle) from the point of being able to improve the impact resistance and heat resistance of the fiber reinforced resin composition by suppressing fiber breakage even when subjected to secondary molding A method (pultrusion method) in which pultrusion is formed is preferable.
引き抜き成形法とは、数千〜数万本のフィラメントで構成された繊維ロービングを開繊して引き出しながら、樹脂を含浸させ、所望の長さ（前述の長さ）に切断してストランド状ペレットを形成する方法である。 The pultrusion method is a strand-shaped pellet which is impregnated with resin while being opened and pulled out from a fiber roving composed of thousands to tens of thousands of filaments and cut to a desired length (the above-mentioned length). It is a method of forming.
有機繊維（有機繊維束）に環状オレフィン系樹脂を含浸する方法としては、例えば、押出機などを用いて溶融した樹脂をダイ（クロスヘッドダイなど）に供給してダイ中で繊維に樹脂を含浸させる方法、樹脂のエマルジョン又は溶液を入れた含浸浴の中を繊維を通過させて含浸させる方法、樹脂の粉末を繊維に吹きつけや流動層などを利用して付着させる方法などが挙げられる。これらの方法のうち、本発明では、クロスヘッドダイを用いて、溶融した環状オレフィン系樹脂を有機繊維に含浸させる方法が好ましい。クロスヘッドダイは、一般的に一段式であるが、生産性を向上させる点などから、多段式であってもよい。環状オレフィン系樹脂が溶融する温度に加熱され、この温度は、例えば、１２０〜３２０℃、好ましくは１３０〜３００℃、さらに好ましくは１４０〜２８０℃程度である。 As a method of impregnating organic fiber (organic fiber bundle) with cyclic olefin resin, for example, molten resin is supplied to a die (crosshead die, etc.) using an extruder or the like, and the fiber is impregnated with resin in the die. For example, a method of impregnating a fiber through an impregnation bath containing a resin emulsion or solution, and a method of spraying resin powder onto the fiber or attaching it using a fluidized bed. Among these methods, in the present invention, a method of impregnating a molten cyclic olefin resin into an organic fiber using a crosshead die is preferable. The crosshead die is generally a single-stage type, but may be a multi-stage type from the viewpoint of improving productivity. It is heated to a temperature at which the cyclic olefin-based resin melts, and this temperature is, for example, about 120 to 320 ° C, preferably about 130 to 300 ° C, and more preferably about 140 to 280 ° C.
環状オレフィン系樹脂を含浸させた有機繊維を切断する方法は、冷却装置などによって切断可能な温度まで冷却された後、カッターなどにより切断する方法が利用できる。クロスヘッドダイを用いた方法では、通常、クロスヘッドの下流に形成された賦形ダイ（クロスヘッドの出口ダイ）を通して、所望のサイズ及び形状に賦形された後、冷却されて切断される。 As a method of cutting the organic fiber impregnated with the cyclic olefin resin, a method of cutting with a cutter or the like after being cooled to a temperature that can be cut with a cooling device or the like can be used. In the method using a crosshead die, it is usually formed into a desired size and shape through a shaping die (crosshead outlet die) formed downstream of the crosshead, and then cooled and cut.
引き抜き成形法については、慣用の方法、例えば、米国特許第３，０４２，５７０号公報、米国特許第３，１１９，７１８号公報、米国特許第３，５８６，５６０号公報、米国特許第３，９９３，７２６号公報、特開昭４６−４５４５号公報、特開昭４９−８６４２７号公報、特開昭５３−５０２７９号公報、特開平２−２６３９５号公報、特開平３−３１４４１７号公報、特開２００５−６０５４７号公報、特開２００５−３０５９３３号公報、特開２００６−１６７９８２号公報、特開２００６−２７２７７３号公報などに記載の方法を利用できる。 As for the pultrusion method, conventional methods such as US Pat. No. 3,042,570, US Pat. No. 3,119,718, US Pat. No. 3,586,560, US Pat. No. 993,726, JP-A No. 46-4545, JP-A No. 49-86427, JP-A No. 53-50279, JP-A No. 2-26395, JP-A No. 3-314417, The methods described in JP-A-2005-60547, JP-A-2005-305933, JP-A-2006-167982, JP-A-2006-272773, and the like can be used.
（成形体）
本発明の成形体は、少なくとも前記繊維強化樹脂組成物で形成されている。すなわち、本発明の成形体は、前記繊維強化樹脂組成物単独で構成されていてもよく、他の熱可塑性樹脂と組み合わせて構成されていてもよい。
(Molded body)
The molded body of the present invention is formed of at least the fiber reinforced resin composition. That is, the molded article of the present invention may be composed of the fiber reinforced resin composition alone or in combination with other thermoplastic resins.
他の熱可塑性樹脂と組み合わせる場合には、前記繊維強化樹脂組成物をマスターバッチとして利用し、他の熱可塑性樹脂として、繊維強化樹脂組成物と同種（特に、同一）の環状オレフィン系樹脂を使用してもよい。繊維強化樹脂組成物と他の熱可塑性樹脂との割合（重量比）は、成形体に要求される物性に応じて選択すればよいが、例えば、前者／後者＝１／９９〜９９／１、好ましくは５／９５〜９５／５、さらに好ましくは１０／９０〜９０／１０程度である。 When combining with other thermoplastic resins, use the fiber reinforced resin composition as a masterbatch, and use the same type (particularly the same) cyclic olefin resin as the fiber reinforced resin composition as the other thermoplastic resin. May be. The ratio (weight ratio) between the fiber reinforced resin composition and the other thermoplastic resin may be selected according to the physical properties required for the molded article. For example, the former / the latter = 1/99 to 99/1, Preferably it is 5 / 95-95 / 5, More preferably, it is about 10 / 90-90 / 10.
本発明の繊維強化樹脂組成物は、外観特性、耐薬品性、防湿性、機械的特性、電気特性などの種々の特性に優れるため、機械部品、電気又は電子部品、容器などの各種成形品、フィルム又はシート状成形品など、各種成形品として利用できる。このような成形品は、慣用の成形法、例えば、射出成形法、押出成形法、ブロー成形法、真空成形法、異型成形法、インジェクションプレス法、プレス成形法、ガス注入成形法、スタンピングモールド成形法、圧縮成形法、ビーズ成形法、トランスファー成形法などの成形法を利用して製造できる。 The fiber reinforced resin composition of the present invention is excellent in various characteristics such as appearance characteristics, chemical resistance, moisture resistance, mechanical characteristics, electrical characteristics, etc., so various molded products such as mechanical parts, electrical or electronic parts, containers, It can be used as various molded products such as film or sheet-shaped molded products. Such molded products are obtained by conventional molding methods such as injection molding methods, extrusion molding methods, blow molding methods, vacuum molding methods, profile molding methods, injection press methods, press molding methods, gas injection molding methods, stamping mold moldings. It can be manufactured using a molding method such as a method, a compression molding method, a bead molding method, or a transfer molding method.
特に、本発明の繊維強化樹脂組成物は、二次成形しても繊維の破損が抑制されるため、射出成形、ブロー成形、押出成形などにより、フィルムやシートなどの二次元形状の成形品に加えて、容器などの三次元形状の成形品を成形してもよい。特に、射出成形や押出成形などにおいて、有機繊維の破損を防止するため、スクリューの溝の深さが大きい長繊維用スクリューを使用するのが好ましい。 In particular, since the fiber reinforced resin composition of the present invention suppresses fiber breakage even after secondary molding, it can be formed into a two-dimensional molded product such as a film or sheet by injection molding, blow molding, extrusion molding, or the like. In addition, a three-dimensional shaped molded product such as a container may be molded. In particular, in injection molding or extrusion molding, it is preferable to use a long fiber screw having a large groove depth in order to prevent the organic fiber from being damaged.
本発明の繊維強化樹脂組成物は、透明性、耐薬品性、防湿性、機械的特性などに優れるため、電気又は電子用部品（コネクター、フィルム状コンデンサ、絶縁部材（絶縁層）、半導体用備品又は包装材料など）、医薬又は医療機器用品（薬品用容器、注射器、血液検査用セル、集尿ビン、ビーカー、シリンダー、シリンジなど）、実験器具（ビーカー、フラスコなど）、容器又は包装材料（食品や薬品などのブリスターパッケージ、飲料用タンク、化粧品容器用キャップなど）などとして利用できる。 Since the fiber reinforced resin composition of the present invention is excellent in transparency, chemical resistance, moisture resistance, mechanical properties, etc., electrical or electronic parts (connectors, film capacitors, insulating members (insulating layers), semiconductor equipment) Or packaging materials), pharmaceutical or medical device supplies (medicine containers, syringes, blood test cells, urine collection bottles, beakers, cylinders, syringes, etc.), laboratory instruments (beakers, flasks, etc.), containers or packaging materials (foods) And blister packages for chemicals and medicines, beverage tanks, cosmetic container caps, etc.).
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、実施例及び比較例で用いた材料は以下の通りであり、評価項目は以下の方法で測定した。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the material used by the Example and the comparative example is as follows, and the evaluation item was measured with the following method.
［原料成分］
ＣＯＣ１：ノルボルネン系モノマーとオレフィン系モノマーとの共重合体、Ｔｏｐａｓ Ａｄｖａｎｃｅｄ Ｐｏｌｙｍｅｒｓ ＧｍｂＨ社製、商品名「ＴＯＰＡＳ８００７Ｆ」
ＣＯＣ２：ノルボルネン系モノマーとオレフィン系モノマーとの共重合体、Ｔｏｐａｓ Ａｄｖａｎｃｅｄ Ｐｏｌｙｍｅｒｓ ＧｍｂＨ社製、商品名「ＴＯＰＡＳ６０１３Ｆ」
ＰＰ：ポリプロピレン、住友化学（株）製、商品名「ノーブレンＺ１０１Ａ」
酸変性ＣＯＣ：以下の製造例で得られた無水マレイン酸変性グラフト変性体
ＣＯＣ２（ＴＯＰＡＳ６０１３Ｆ）１００重量部に対し、無水マレイン酸３重量部、開始剤として１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン０．０８重量部及び安定剤（チバ・スペシャルティ・ケミカルズ（株）製、イルガノックス１０１０）０．１重量部をヘンシェルミキサーで均一に混合後、二軸押出機で温度２８０℃、平均滞留時間０．８分で溶融混合し、変性環状ポリオレフィン系樹脂を得た。
[Raw ingredient]
COC1: Copolymer of norbornene monomer and olefin monomer, manufactured by Topas Advanced Polymers GmbH, trade name “TOPAS 8007F”
COC2: copolymer of norbornene monomer and olefin monomer, manufactured by Topas Advanced Polymers GmbH, trade name “TOPAS 6013F”
PP: polypropylene, manufactured by Sumitomo Chemical Co., Ltd., trade name “Noblen Z101A”
Acid-modified COC: 3 parts by weight of maleic anhydride and 1,3-bis (t-butylperoxy) as an initiator with respect to 100 parts by weight of maleic anhydride-modified graft modified product COC2 (TOPAS 6013F) obtained in the following production examples Isopropyl) benzene 0.08 part by weight and stabilizer (Ciba Specialty Chemicals Co., Ltd., Irganox 1010) 0.1 part by weight are uniformly mixed with a Henschel mixer, and then at a temperature of 280 ° C. with a twin screw extruder, average The mixture was melt-mixed with a residence time of 0.8 minutes to obtain a modified cyclic polyolefin resin.
アラミド繊維：全芳香族ポリアミド繊維、帝人テクノーラ（株）製、商品名「Ｔ２４１Ｊ」
ＰＢＯ繊維：ポリパラフェニレンベンズオキサゾール繊維、ＺＹＬＯＮ ＨＭ
ガラス繊維：アミノシランカップリング剤で表面処理されたガラス繊維ロービング（繊維径１７μｍ）。
Aramid fiber: Totally aromatic polyamide fiber, manufactured by Teijin Technora Co., Ltd., trade name “T241J”
PBO fiber: Polyparaphenylene benzoxazole fiber, ZYLON HM
Glass fiber: Glass fiber roving (fiber diameter 17 μm) surface-treated with an aminosilane coupling agent.
［引張強さ］
ＩＳＯ ５２７−１に準拠して測定した。
[Tensile strength]
The measurement was performed according to ISO 527-1.
［曲げ強さ及び曲げ弾性率］
ＩＳＯ １７８に準拠して測定した。
[Bending strength and flexural modulus]
Measured according to ISO 178.
［シャルピー衝撃強度］
ＩＳＯ １７９／１ｅＡ（エッジワイズ）に準拠して測定した。
[Charpy impact strength]
Measurement was performed in accordance with ISO 179 / 1eA (edgewise).
［荷重たわみ温度］
ＩＳＯ ７５−１（１．８０ＭＰａ：フラットワイズ）に準拠して測定した。
[Load deflection temperature]
It measured based on ISO 75-1 (1.80 MPa: flatwise).
実施例１〜４及び比較例１〜３
連続繊維の通路を波状に加工したクロスヘッドを通して、表１に示す有機繊維又はガラス繊維ロービングを引きながら、表１に示す割合の環状オレフィン系樹脂又はポリプロピレンをクロスヘッドに接続された押出機から供給して、溶融状態（約２８０℃）で有機繊維又はガラス繊維に含浸させた後、賦形ダイを通してストランドとして引取って細断し、表１に示す所定の繊維含有量及び長さのペレットを得た。得られたストランド状ペレットを使用して、以下の条件で、射出成形によりＩＳＯ多目的試験片を採取し、物性測定を行った。結果を表１に示す。
Examples 1-4 and Comparative Examples 1-3
Feeding the cyclic olefin-based resin or polypropylene in the ratio shown in Table 1 from the extruder connected to the crosshead while drawing the organic fiber or glass fiber roving shown in Table 1 through the crosshead processed into a corrugated continuous fiber passage. Then, after impregnating organic fibers or glass fibers in a molten state (about 280 ° C.), they are taken as strands through a shaping die and chopped, and pellets having a predetermined fiber content and length shown in Table 1 are obtained. Obtained. Using the obtained strand pellets, an ISO multipurpose test piece was collected by injection molding under the following conditions, and physical properties were measured. The results are shown in Table 1.
（射出成形条件）
射出成形機：（株）日本製鋼所製、Ｊ−１５０ＥII
スクリュー：長繊維専用スクリュー
シリンダー温度：２８０℃（比較例１のみ２３５℃）
金型温度：６０℃（比較例１のみ５０℃）
(Injection molding conditions)
Injection molding machine: J-150EII manufactured by Nippon Steel Works
Screw: Screw for long fibers Cylinder temperature: 280 ° C (only Comparative Example 1 is 235 ° C)
Mold temperature: 60 ° C. (Comparative example 1 only 50 ° C.)
表１の結果から明らかなように、実施例の成形体は、引張特性、曲げ特性、耐衝撃性、耐熱性のバランスに優れている。これに対して、比較例１の成形体は、引張特性、曲げ特性が充分でない。さらに、比較例２及び３の成形体は、引張特性、曲げ特性、耐衝撃性が充分でない。 As is apparent from the results in Table 1, the molded articles of the examples are excellent in balance of tensile characteristics, bending characteristics, impact resistance, and heat resistance. On the other hand, the molded article of Comparative Example 1 has insufficient tensile characteristics and bending characteristics. Furthermore, the molded articles of Comparative Examples 2 and 3 are insufficient in tensile properties, bending properties, and impact resistance.
Claims (11)
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| JP2005139246A (en) * | 2003-11-05 | 2005-06-02 | Polyplastics Co | Polymer for reinforcing transparent resin and its composition |
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| JPH01138238A (en) * | 1987-11-24 | 1989-05-31 | Mitsui Petrochem Ind Ltd | Lowly dielectric laminate |
| JPH02160510A (en) * | 1988-12-15 | 1990-06-20 | Sekisui Chem Co Ltd | Production of fiber reinforced composite |
| JPH0762110A (en) * | 1993-08-23 | 1995-03-07 | Nippon Zeon Co Ltd | Molded polynorbornene resin product |
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| JP2003138031A (en) * | 2001-08-07 | 2003-05-14 | Ticona Gmbh | Long-fiber-reinforced polyolefin structure, process for its production, and molding produced therefrom |
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