JP4368651B2 - Polymer composition - Google Patents
Polymer composition Download PDFInfo
- Publication number
- JP4368651B2 JP4368651B2 JP2003358139A JP2003358139A JP4368651B2 JP 4368651 B2 JP4368651 B2 JP 4368651B2 JP 2003358139 A JP2003358139 A JP 2003358139A JP 2003358139 A JP2003358139 A JP 2003358139A JP 4368651 B2 JP4368651 B2 JP 4368651B2
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- polymer
- polymer composition
- mass
- acrylic resin
- 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.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims description 107
- 239000000203 mixture Substances 0.000 title claims description 79
- 229920001400 block copolymer Polymers 0.000 claims description 83
- 239000004925 Acrylic resin Substances 0.000 claims description 43
- 229920000178 Acrylic resin Polymers 0.000 claims description 43
- 238000012644 addition polymerization Methods 0.000 claims description 41
- -1 aromatic vinyl compound Chemical group 0.000 claims description 34
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 239000004902 Softening Agent Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 57
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 32
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 26
- 229920001971 elastomer Polymers 0.000 description 25
- 239000005060 rubber Substances 0.000 description 24
- 238000000465 moulding Methods 0.000 description 23
- 238000005299 abrasion Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 229920002725 thermoplastic elastomer Polymers 0.000 description 16
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 14
- 239000000178 monomer Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 229920000428 triblock copolymer Polymers 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229920000314 poly p-methyl styrene Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- JPSVCKGZBDBQPG-UHFFFAOYSA-N 1,3,5-tris(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC(CCl)=C(C=C)C(CCl)=C1 JPSVCKGZBDBQPG-UHFFFAOYSA-N 0.000 description 1
- MLWORXSNFFNDJF-UHFFFAOYSA-N 1,3-bis(chloromethyl)-5-ethenylbenzene Chemical compound ClCC1=CC(CCl)=CC(C=C)=C1 MLWORXSNFFNDJF-UHFFFAOYSA-N 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- BCQNXDFECRPAOT-UHFFFAOYSA-N 1-(dichloromethyl)-2-ethenylbenzene Chemical compound ClC(Cl)C1=CC=CC=C1C=C BCQNXDFECRPAOT-UHFFFAOYSA-N 0.000 description 1
- IAFVZVIHAMSEDL-UHFFFAOYSA-N 1-(dichloromethyl)-3-ethenylbenzene Chemical compound ClC(Cl)C1=CC=CC(C=C)=C1 IAFVZVIHAMSEDL-UHFFFAOYSA-N 0.000 description 1
- IQXRSGMWLOIESY-UHFFFAOYSA-N 1-(dichloromethyl)-4-ethenylbenzene Chemical compound ClC(Cl)C1=CC=C(C=C)C=C1 IQXRSGMWLOIESY-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- UBRFDRBFBYCBFS-UHFFFAOYSA-N 1-ethenyl-2,4-diethylbenzene Chemical compound CCC1=CC=C(C=C)C(CC)=C1 UBRFDRBFBYCBFS-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- CCYFATPNAXTAFW-UHFFFAOYSA-N 1-ethenyl-2,4-dipropylbenzene Chemical compound CCCC1=CC=C(C=C)C(CCC)=C1 CCYFATPNAXTAFW-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- XIYATWBVQHWJPH-UHFFFAOYSA-N 1-ethenyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C=C XIYATWBVQHWJPH-UHFFFAOYSA-N 0.000 description 1
- HVOKBODBWQEEGI-UHFFFAOYSA-N 1-ethenyl-3,5-diethylbenzene Chemical compound CCC1=CC(CC)=CC(C=C)=C1 HVOKBODBWQEEGI-UHFFFAOYSA-N 0.000 description 1
- XKMDZVINHIFHLY-UHFFFAOYSA-N 1-ethenyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(C=C)=C1 XKMDZVINHIFHLY-UHFFFAOYSA-N 0.000 description 1
- UTEYZSGHFLOAGG-UHFFFAOYSA-N 1-ethenyl-3,5-dipropylbenzene Chemical compound CCCC1=CC(CCC)=CC(C=C)=C1 UTEYZSGHFLOAGG-UHFFFAOYSA-N 0.000 description 1
- XGEAAAIRJFPUMU-UHFFFAOYSA-N 1-ethenyl-3-ethyl-5-methylbenzene Chemical compound CCC1=CC(C)=CC(C=C)=C1 XGEAAAIRJFPUMU-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- CYAOHDYNSBNYPZ-UHFFFAOYSA-N 1-ethenyl-3-propylbenzene Chemical compound CCCC1=CC=CC(C=C)=C1 CYAOHDYNSBNYPZ-UHFFFAOYSA-N 0.000 description 1
- MBJWTCLMJBDAGT-UHFFFAOYSA-N 1-ethenyl-4-ethyl-2-methylbenzene Chemical compound CCC1=CC=C(C=C)C(C)=C1 MBJWTCLMJBDAGT-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- DPYJMQGTOTVJBV-UHFFFAOYSA-N 2,2-difluoroethenylbenzene Chemical compound FC(F)=CC1=CC=CC=C1 DPYJMQGTOTVJBV-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- SZUWQQOPFFEVSI-UHFFFAOYSA-N 2-ethenyl-1,3,5-triethylbenzene Chemical compound CCC1=CC(CC)=C(C=C)C(CC)=C1 SZUWQQOPFFEVSI-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- ZWPBTHVXPHHNJX-UHFFFAOYSA-N 2-ethenyl-1,3,5-tripropylbenzene Chemical compound CCCC1=CC(CCC)=C(C=C)C(CCC)=C1 ZWPBTHVXPHHNJX-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- GCQZRSVHYPEACN-UHFFFAOYSA-N 2-methylideneoxolane Chemical compound C=C1CCCO1 GCQZRSVHYPEACN-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920005497 Acrypet® Polymers 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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Description
本発明は、炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレン由来構造単位（Ｉ）を３０質量％以上有する芳香族ビニル化合物単位を主体とする重合体ブロックＡをハードセグメントとする付加重合系ブロック共重合体である熱可塑性エラストマーおよびアクリル系樹脂を含有する重合体組成物に関する。
本発明の重合体組成物は、成形加工性、柔軟性、ゴム弾性、力学的特性、透明性などの諸性能に優れるのに加え、特に耐傷つき性、耐摩耗性に優れており、それらの特性を活かして広範な用途に有効に使用することができる。
The present invention provides a polymer block A mainly composed of an aromatic vinyl compound unit having 30 % by mass or more of an alkylstyrene-derived structural unit (I) in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring. The present invention relates to a polymer composition containing a thermoplastic elastomer which is an addition polymerization block copolymer as a hard segment and an acrylic resin.
The polymer composition of the present invention is excellent in various properties such as moldability, flexibility, rubber elasticity, mechanical properties, and transparency, and is particularly excellent in scratch resistance and abrasion resistance. It can be used effectively for a wide range of applications by utilizing its characteristics.
熱可塑性エラストマーは常温でゴム弾性を有し、かつ加熱により可塑化・溶融するので、成形加工が容易であり、しかもリサイクル使用が可能であることから、近年、自動車部品、家電製品部品、建材、玩具、スポーツ用品、日用品などの幅広い分野で使用されている。 Thermoplastic elastomers have rubber elasticity at room temperature and are plasticized and melted by heating, so they are easy to mold and can be recycled.In recent years, automotive parts, home appliance parts, building materials, It is used in a wide range of fields such as toys, sports equipment, and daily necessities.
熱可塑性エラストマーの中でも、ポリスチレン−ポリブタジエン−ポリスチレンブロック共重合体（ＳＢＳ）やポリスチレン−ポリイソプレン−ポリスチレンブロック共重合体（ＳＩＳ）およびそれらの水素添加物などのスチレン系熱可塑性エラストマーは、安価で、柔軟性、ゴム弾性、リサイクル性などに優れる点から広く使用されている。 Among thermoplastic elastomers, polystyrene-polybutadiene-polystyrene block copolymers (SBS), polystyrene-polyisoprene-polystyrene block copolymers (SIS) and hydrogenated products thereof are inexpensive, Widely used because of its excellent flexibility, rubber elasticity, recyclability, etc.
スチレン系熱可塑性エラストマーについては、種々の物性の改良を目的とした検討がなされている。例えば、〈１〉柔らかい感触および優れた耐傷つき性を有する成形品を得るための、スチレン系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマーなどを含有する粉末成形用熱可塑性エラストマー樹脂組成物（特許文献１参照）、〈２〉柔軟性、成形加工性および耐スクラッチ性に優れた組成物として、スチレン系熱可塑性エラストマー（水添ブロック共重合体）とアクリル系樹脂からなる組成物に対し、双方に相溶性を示す単位を有する共重合体を添加した熱可塑性エラストマー組成物（特許文献２参照）が提案されている。 With respect to styrene-based thermoplastic elastomers, studies have been conducted for the purpose of improving various physical properties. For example, <1> a thermoplastic elastomer resin composition for powder molding containing a styrene-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, etc. for obtaining a molded product having a soft feel and excellent scratch resistance (Patent Document 1) (2) As a composition excellent in flexibility, moldability and scratch resistance, a composition comprising a styrene thermoplastic elastomer (hydrogenated block copolymer) and an acrylic resin is compatible with both. A thermoplastic elastomer composition to which a copolymer having a soluble unit is added (see Patent Document 2) has been proposed.
また、アクリル系樹脂の持つ表面硬度などの表面特性、耐候性、透明感などを保持し、かつ柔軟性、低温特性などの性質を兼ね備えた熱可塑性樹脂組成物として、〈３〉特定の分子量を有する、ビニル芳香族化合物からなる重合体ブロックと、イソプレンまたはイソプレンとブタジエンからなる重合体ブロックを含有するブロック共重合体の水素添加物と、特定の固有粘度を有するアクリル系樹脂を特定割合で配合したアクリル系熱可塑性樹脂組成物（特許文献３参照）；〈４〉アクリル系樹脂に対して、芳香族ビニル単量体からなるブロックと、イソプレンおよび／またはブタジエンからなるブロックとから構成される特定の数平均分子量を有する３元ブロック共重合体の水素添加物を特定配合比で含有する熱可塑性樹脂組成物（特許文献４参照）が提案されている。さらに、柔軟性、耐候性に優れ、かつ外観特性の良好な組成物として、〈５〉ポリオレフィン系樹脂（ｉ）、芳香族ビニル単量体からなるブロックと、イソプレンおよび／またはブタジエンからなるブロックとから構成される熱可塑性ブロック共重合体の水素添加物（ｉｉ）、アクリル系樹脂（ｉｉｉ）、炭化水素系柔軟化剤（ｉｖ）および側鎖にアクリル系単量体の重合物を有する、芳香族ビニル単量体からなるブロックと、イソプレンおよび／またはブタジエンからなるブロックから構成される熱可塑性ブロック共重合体の水素添加物（ｖ）を含有してなる熱可塑性樹脂組成物（特許文献５参照）が提案されている。 Furthermore, <3> a specific molecular weight as a thermoplastic resin composition that retains the surface properties such as surface hardness, weather resistance, transparency, etc. possessed by acrylic resins, and also has properties such as flexibility and low temperature properties. Contains a polymer block composed of a vinyl aromatic compound, a hydrogenated block copolymer containing a polymer block composed of isoprene or isoprene and butadiene, and an acrylic resin having a specific intrinsic viscosity at a specific ratio. Acrylic thermoplastic resin composition (see Patent Document 3); <4> A specific configuration comprising an acrylic resin block composed of an aromatic vinyl monomer and a block composed of isoprene and / or butadiene. Thermoplastic resin composition containing a hydrogenation product of a ternary block copolymer having a number average molecular weight of a specific blending ratio (Patent Literature) Reference) has been proposed. Furthermore, as a composition having excellent flexibility and weather resistance and good appearance characteristics, <5> polyolefin resin (i), a block made of an aromatic vinyl monomer, and a block made of isoprene and / or butadiene A hydrogenated product of a thermoplastic block copolymer (ii), an acrylic resin (iii), a hydrocarbon softening agent (iv) and an aromatic monomer polymer in the side chain A thermoplastic resin composition containing a hydrogenated product (v) of a thermoplastic block copolymer composed of a block composed of an aromatic vinyl monomer and a block composed of isoprene and / or butadiene (see Patent Document 5) ) Has been proposed.
上記特許文献１の組成物は、耐傷つき性について、ポリウレタン系熱可塑性エラストマーには及ばないものの一応の改良がされているが、耐加水分解性や耐候性が不足していることから、成形品とした場合の性能低下、黄変などの問題を有している。上記特許文献２〜特許文献５の組成物は、アクリル系樹脂の持つ表面硬度などの表面特性、耐候性、透明感などを保持しつつ、柔軟性に富み、成形加工性、透明性などに優れた性質を有する。しかしながら、上記特許文献２の組成物に関しては、耐スクラッチ性としてカナキン３号布を摩擦布として用い５００ｇ荷重、摩擦回数１００回の条件でのＪＩＳ Ｚ ８７４１に準じたテスト前後の光沢残存率での評価結果が開示され、また上記特許文献５の組成物に関しては、ＪＩＳ Ｋ ５４００に準拠して鉛筆擦傷性の評価結果が開示されているが、耐傷つき性および耐摩耗性の評価結果としては充分に満足のいくものではない。また、上記特許文献３および特許文献４の組成物に関しては、その耐摩耗性について何ら記載されていない。これらの事情から、摩擦を高頻度で受ける部位や美観が重要視される用途などにおいて有効に使用できる熱可塑性重合体組成物が求められていた。 The composition of Patent Document 1 has a slight improvement in scratch resistance, which is inferior to polyurethane thermoplastic elastomers. However, since it has insufficient hydrolysis resistance and weather resistance, it is a molded product. In such a case, there are problems such as performance degradation and yellowing. The compositions of the above Patent Documents 2 to 5 are rich in flexibility and excellent in molding processability, transparency, etc. while maintaining the surface properties such as surface hardness, weather resistance, transparency, etc. possessed by the acrylic resin. Have the same properties. However, with respect to the composition of Patent Document 2 described above, the gloss remaining rate before and after the test in accordance with JIS Z 8741 under the conditions of 500 g load and 100 times of friction using Kanakin No. 3 as a friction cloth as scratch resistance. Evaluation results are disclosed, and with respect to the composition of Patent Document 5 above, pencil scratch resistance evaluation results are disclosed in accordance with JIS K 5400, but the scratch resistance and abrasion resistance evaluation results are sufficient. Not satisfied with. Moreover, regarding the composition of the said patent document 3 and the patent document 4, there is no description about the abrasion resistance. Under these circumstances, there has been a demand for a thermoplastic polymer composition that can be used effectively in a part that receives friction at a high frequency or an application in which aesthetics are important.
しかして、本発明の目的は、良好な成形加工性、柔軟性、ゴム弾性、力学的特性、透明性を兼ね備えており、かつポリウレタン系熱可塑性エラストマーやポリエステル系熱可塑性エラストマーに匹敵する耐傷つき性と耐摩耗性を有している重合体組成物を提供することにある。 Thus, the object of the present invention is to have good moldability, flexibility, rubber elasticity, mechanical properties, transparency, and scratch resistance comparable to polyurethane-based thermoplastic elastomers and polyester-based thermoplastic elastomers. And providing a polymer composition having abrasion resistance.
本発明者らは、上記の目的を達成すべく検討を重ねた。その結果、炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレン由来構造単位（Ｉ）を３０質量％以上有する芳香族ビニル化合物単位を主体とする重合体ブロックＡをハードセグメントとする付加重合系ブロック共重合体、アクリル系樹脂および必要に応じて軟化剤を含有する重合体組成物の配合割合を特定の範囲にすることで、炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレン由来構造単位（Ｉ）を３０質量％以上有する芳香族ビニル化合物単位を主体とする重合体ブロックＡをハードセグメントとする付加重合系ブロック共重合体が連続相（マトリックス）を形成し、その中にアクリル系樹脂が分散し、特定の海島形態の相構造（モルフォロジー）になることを見出した。
そして、上記した特定の相構造を有する重合体組成物およびかかる重合体組成物を成形体としたときの物性について検討した結果、該重合体組成物は成形加工性に優れ、また、柔軟性、ゴム弾性、力学的特性、透明性などの諸特性に優れるのに加え、特に耐傷つき性、耐摩耗性に優れており、しかもそれらの諸特性をバランスよく兼ね備えていること、それによって種々の用途に有効に使用し得ることを見出して本発明を完成した。
The present inventors have repeatedly studied to achieve the above object. As a result, a polymer block A mainly composed of an aromatic vinyl compound unit having 30 % by mass or more of an alkylstyrene-derived structural unit (I) in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring is hard. By setting the blending ratio of the addition polymerization block copolymer to be a segment, the acrylic resin, and the polymer composition containing a softener as necessary, within a specific range, at least of the alkyl group having 1 to 8 carbon atoms An addition polymerization type block copolymer having a polymer segment A mainly composed of an aromatic vinyl compound unit having at least 30 % by mass of an alkylstyrene-derived structural unit (I) bonded to a benzene ring as a hard segment is a continuous phase. (Matrix) is formed, and acrylic resin is dispersed in it, and it is found that it has a specific sea-island phase structure (morphology) It was.
And as a result of examining the polymer composition having the above-mentioned specific phase structure and the physical properties when such a polymer composition is formed into a molded body, the polymer composition is excellent in molding processability, flexibility, In addition to excellent properties such as rubber elasticity, mechanical properties, and transparency, it is particularly excellent in scratch resistance and wear resistance, and also has these properties in a well-balanced manner. And the present invention was completed.
すなわち、本発明は、炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレン由来構造単位（Ｉ）（以下、構造単位（Ｉ）と略称する）を３０質量％以上有する芳香族ビニル化合物単位を主体とする重合体ブロックＡを１個以上と、共役ジエン化合物単位からなる重合体ブロックＢを１個以上有するブロック共重合体およびその水素添加物から選ばれる少なくとも１種の、重量平均分子量が３００００〜２０００００の付加重合系ブロック共重合体（ａ）、アクリル系樹脂（ｂ）および（ｃ）軟化剤を、下記式〔１〕および〔２〕を満足する配合比（質量比）で含有する重合体組成物である。
０．１≦Ｗｂ／Ｗａ≦１．６ 〔１〕
Ｗｃ／（Ｗａ＋Ｗｂ＋Ｗｃ）≦０．５ 〔２〕
［式中、Ｗａ、ＷｂおよびＷｃは重合体組成物を構成する付加重合系ブロック共重合体（ａ）、アクリル系樹脂（ｂ）および軟化剤（ｃ）の各成分の含有量（質量）を示す。］
That is, the present invention has 30 mass% or more of an alkylstyrene-derived structural unit (I) (hereinafter abbreviated as structural unit (I)) in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring. At least one selected from a block copolymer having at least one polymer block A mainly composed of an aromatic vinyl compound unit, at least one polymer block B composed of a conjugated diene compound unit, and a hydrogenated product thereof. The addition polymerization block copolymer (a) having a weight average molecular weight of 30,000 to 200,000, the acrylic resin (b) and the softening agent (c) are blended in a ratio (mass) satisfying the following formulas [1] and [2] Ratio).
0.1 ≦ Wb / Wa ≦ 1.6 [1]
Wc / (Wa + Wb + Wc) ≦ 0.5 [2]
[Wa, Wb and Wc are the contents (mass) of each component of the addition polymerization block copolymer (a), the acrylic resin (b) and the softening agent (c) constituting the polymer composition. Show. ]
本発明によれば、良好な成形加工性、柔軟性、ゴム弾性、力学的特性、透明性を兼ね備えており、かつポリウレタン系熱可塑性エラストマーやポリエステル系熱可塑性エラストマーに匹敵する耐傷つき性と耐摩耗性を有する重合体組成物を得ることができる。 According to the present invention, it has good moldability, flexibility, rubber elasticity, mechanical properties, transparency, and has scratch resistance and abrasion resistance comparable to polyurethane-based thermoplastic elastomers and polyester-based thermoplastic elastomers. A polymer composition having properties can be obtained.
以下、本発明について詳細に説明する。
本発明の重合体組成物において使用する付加重合系ブロック共重合体（ａ）は、構造単位（Ｉ）を３０質量％以上有する芳香族ビニル化合物単位を主体とする重合体ブロックＡを１個以上と、共役ジエン化合物単位からなる重合体ブロックＢを１個以上有するブロック共重合体およびその水素添加物から選ばれる少なくとも１種の、重量平均分子量が３００００〜２０００００の付加重合系ブロック共重合体である。
Hereinafter, the present invention will be described in detail.
The addition polymerization block copolymer (a) used in the polymer composition of the present invention has at least one polymer block A mainly composed of an aromatic vinyl compound unit having a structural unit (I) of 30 % by mass or more. A block copolymer having at least one polymer block B composed of conjugated diene compound units and a hydrogenated product thereof, and an addition polymerization block copolymer having a weight average molecular weight of 30,000 to 200,000. is there.
構造単位（Ｉ）を構成する炭素数１〜８のアルキル基の少なくとも１個がベンゼン環に結合したアルキルスチレンとしては、例えばアルキル基の炭素数が１〜８である、ｏ−アルキルスチレン、ｍ−アルキルスチレン、ｐ−アルキルスチレン、２，４−ジアルキルスチレン、３，５−ジアルキルスチレン、２，４，６−トリアルキルスチレン、前記したアルキルスチレン類におけるアルキル基の水素原子の１個または２個以上がハロゲン原子で置換されたハロゲン化アルキルスチレン類などを挙げることができる。より具体的には、構造単位（Ｉ）を構成するアルキルスチレンとしては、例えばｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン、３，５−ジメチルスチレン、２，４，６−トリメチルスチレン、ｏ−エチルスチレン、ｍ−エチルスチレン、ｐ−エチルスチレン、２，４−ジエチルスチレン、３，５−ジエチルスチレン、２，４，６−トリエチルスチレン、ｏ−プロピルスチレン、ｍ−プロピルスチレン、ｐ−プロピルスチレン、２，４−ジプロピルスチレン、３，５−ジプロピルスチレン、２，４，６−トリプロピルスチレン、２−メチル−４−エチルスチレン、３−メチル−５−エチルスチレン、ｏ−クロロメチルスチレン、ｍ−クロロメチルスチレン、ｐ−クロロメチルスチレン、２，４−ビス（クロロメチル）スチレン、３，５−ビス（クロロメチル）スチレン、２，４，６−トリ（クロロメチル）スチレン、ｏ−ジクロロメチルスチレン、ｍ−ジクロロメチルスチレン、ｐ−ジクロロメチルスチレンなどを挙げることができる。 Examples of the alkylstyrene in which at least one alkyl group having 1 to 8 carbon atoms constituting the structural unit (I) is bonded to a benzene ring include, for example, o-alkylstyrene having 1 to 8 carbon atoms in the alkyl group, m -Alkyl styrene, p-alkyl styrene, 2,4-dialkyl styrene, 3,5-dialkyl styrene, 2,4,6-trialkyl styrene, one or two hydrogen atoms of the alkyl group in the aforementioned alkyl styrenes Examples thereof include halogenated alkylstyrenes substituted with a halogen atom. More specifically, examples of the alkylstyrene constituting the structural unit (I) include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2 , 4,6-trimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4,6-triethylstyrene, o-propylstyrene M-propyl styrene, p-propyl styrene, 2,4-dipropyl styrene, 3,5-dipropyl styrene, 2,4,6-tripropyl styrene, 2-methyl-4-ethyl styrene, 3-methyl- 5-ethylstyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, 2,4- (Chloromethyl) styrene, 3,5-bis (chloromethyl) styrene, 2,4,6-tri (chloromethyl) styrene, o-dichloromethylstyrene, m-dichloromethylstyrene, p-dichloromethylstyrene, etc. Can be mentioned.
重合体ブロックＡは、構造単位（Ｉ）として前記したアルキルスチレンおよびハロゲン化アルキルスチレンのうちの１種または２種以上からなる単位を有することができる。そのうちでも、構造単位（Ｉ）として、ｐ−メチルスチレンに基づく構造単位が好ましい。 The polymer block A can have a unit composed of one or more of the aforementioned alkylstyrene and halogenated alkylstyrene as the structural unit (I). Among these, as the structural unit (I), a structural unit based on p-methylstyrene is preferable.
重合体ブロックＡにおける構造単位（Ｉ）の割合は、付加重合系ブロック共重合体（ａ）を構成する重合体ブロックＡの質量［付加重合系ブロック共重合体（ａ）が２個以上の重合体ブロックＡを有する場合はその合計質量］に対し３０質量％以上であり、５０質量％以上であるのがより好ましく、さらにすべての単位が構造単位（Ｉ）からなっていてもよい。構造単位（Ｉ）の割合が１質量％未満であると、アクリル系樹脂（ｂ）との充分な親和性が発現しない。重合体ブロックＡにおける構造単位（Ｉ）とそれ以外の芳香族ビニル化合物単位との結合形態は、ランダム、ブロック、テーパードなどのいずれの形態であってもよい。 The proportion of the structural unit (I) in the polymer block A is the mass of the polymer block A constituting the addition polymerization block copolymer (a) [the weight of the addition polymerization block copolymer (a) is two or more weights. polymer block Ri der 3 0 wt% or more against its total mass] If with a, and more preferably at least 50 wt%, still all the unit may be made of the structural units (I) . When the proportion of the structural unit (I) is less than 1% by mass, sufficient affinity with the acrylic resin (b) is not exhibited. The bonding form of the structural unit (I) and the other aromatic vinyl compound unit in the polymer block A may be any form such as random, block, and tapered.
重合体ブロックＡを構成する構造単位（Ｉ）以外の芳香族ビニル化合物単位としては、例えばスチレン、α−メチルスチレン、β−メチルスチレン、ｔ−ブチルスチレン、モノフルオロスチレン、ジフルオロスチレン、モノクロロスチレン、ジクロロスチレン、メトキシスチレン、ビニルナフタレン、ビニルアントラセン、インデン、アセトナフチレンなどからなる単位を挙げることができ、これらの１種または２種以上の単位を有することができる。なかでも、芳香族ビニル化合物単位としてはスチレンに基づく単位が好ましい。 Examples of aromatic vinyl compound units other than the structural unit (I) constituting the polymer block A include styrene, α-methylstyrene, β-methylstyrene, t-butylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, Examples include units composed of dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene, indene, acetonaphthylene, and the like, and may have one or more of these units. Among these, as the aromatic vinyl compound unit, a unit based on styrene is preferable.
付加重合系ブロック共重合体（ａ）において、重合体ブロックＡは構造単位（Ｉ）のみで構成されているのが特に好ましい。但し、本発明の目的および効果の妨げにならない限り、重合体ブロックＡは構造単位（Ｉ）および芳香族ビニル化合物単位以外の不飽和単量体単位、例えばブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエン、イソブチレン、メタクリル酸メチル、ビニルメチルエーテル、Ｎ−ビニルカルバゾール、β−ピネン、８，９−ｐ−メンテン、ジペンテン、メチレンノルボルネン、２−メチレンテトラヒドロフランなどに由来する構造単位の１種または２種以上を少量、好ましくは重合体ブロックＡの質量に対する割合として１０質量％以下の範囲で有していてもよい。 In the addition polymerization block copolymer (a), the polymer block A is particularly preferably composed of only the structural unit (I). However, the polymer block A is an unsaturated monomer unit other than the structural unit (I) and the aromatic vinyl compound unit , for example, butadiene, isoprene, 2,3-dimethyl- unless the purpose and effect of the present invention are hindered. 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, vinyl methyl ether, N-vinylcarbazole, β-pinene, 8,9-p-mentene, dipentene, methylene norbornene, One or more structural units derived from 2-methylenetetrahydrofuran or the like may be contained in a small amount, preferably in a range of 10% by mass or less as a ratio to the mass of the polymer block A.
付加重合系ブロック共重合体（ａ）における重合体ブロックＡの含有量は、重合体組成物から得られる成形体のゴム弾性および柔軟性の観点から、５〜４５質量％の範囲内であることが好ましく、１５〜４０質量％の範囲内であることがより好ましい。なお、付加重合系ブロック共重合体（ａ）における重合体ブロックＡの含有量は、例えば１Ｈ−ＮＭＲスペクトルなどにより求めることができる。 The content of the polymer block A in the addition polymerization block copolymer (a) is within the range of 5 to 45% by mass from the viewpoint of rubber elasticity and flexibility of the molded product obtained from the polymer composition. Is preferable, and it is more preferable that it exists in the range of 15-40 mass%. The content of the polymer block A in the addition polymerization-based block copolymer (a), for example, can be determined by such 1 H-NMR spectrum.
一方、付加重合系ブロック共重合体（ａ）における共役ジエン化合物単位を主体とする重合体ブロックＢを構成する共役ジエン化合物としては、例えばブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエンなどが挙げられる。重合体ブロックＢはこれらの化合物の１種類のみから構成されていてもよいし、２種以上から構成されていてもよく、中でもブタジエン、イソプレン、またはブタジエンとイソプレンの混合物から構成されているのが好ましい。 On the other hand, examples of the conjugated diene compound constituting the polymer block B mainly composed of the conjugated diene compound unit in the addition polymerization block copolymer (a) include butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. 1,3-pentadiene, 1,3-hexadiene and the like. The polymer block B may be composed of only one kind of these compounds, or may be composed of two or more kinds, among which butadiene, isoprene, or a mixture of butadiene and isoprene. preferable.
重合体ブロックＢが共役ジエン化合物から構成される場合において、共役ジエン化合物に由来する構造単位のミクロ構造は特に制限されないが、例えば重合体ブロックＢがブタジエンから構成されている場合は、その１，２−結合単位の割合が５〜９０モル％であることが好ましく、２０〜７０モル％であるのがより好ましい。また、重合体ブロックＢがイソプレンから構成されているか、またはブタジエンとイソプレンの混合物から構成されている場合は、その１，２−結合単位および３，４−結合単位の合計が５〜８０モル％であることが好ましく、１０〜６０モル％であるのがより好ましい。 When the polymer block B is composed of a conjugated diene compound, the microstructure of the structural unit derived from the conjugated diene compound is not particularly limited. For example, when the polymer block B is composed of butadiene, The proportion of 2-bond units is preferably from 5 to 90 mol%, more preferably from 20 to 70 mol%. When the polymer block B is composed of isoprene or a mixture of butadiene and isoprene, the total of 1,2-bond units and 3,4-bond units is 5 to 80 mol%. It is preferable that it is 10-60 mol%.
また、重合体ブロックＢが２種以上の共役ジエン化合物（例えばブタジエンとイソプレン）から構成されている場合は、それらの結合形態には特に制限はなく、ランダム、ブロック、テーパードまたはそれらの２種以上の組み合わせからなることができる。 When the polymer block B is composed of two or more kinds of conjugated diene compounds (for example, butadiene and isoprene), there is no particular limitation on the bonding form thereof, random, block, tapered or two or more kinds thereof. Can be a combination of
重合体ブロックＢは、共役ジエン化合物からなる構造単位とともに、必要に応じて他の重合性単量体からなる構造単位を少量有していてもよい。その場合の他の重合性単量体の割合は、付加重合系ブロック共重合体（ａ）を構成する重合体ブロックＢの質量［付加重合系ブロック共重合体（ａ）が２個以上の重合体ブロックＢを有する場合はその合計質量］に基づいて３０質量％以下であることが好ましく、１０質量％以下であることがより好ましい。その場合の他の重合性単量体としては、例えばスチレン、α−メチルスチレン、構造単位（Ｉ）を構成する前記したアルキルスチレン（好適にはｐ−メチルスチレン）などを挙げることができる。 The polymer block B may have a small amount of a structural unit composed of another polymerizable monomer as necessary, together with a structural unit composed of a conjugated diene compound. In this case, the ratio of the other polymerizable monomer is the mass of the polymer block B constituting the addition polymerization block copolymer (a) [the addition polymerization block copolymer (a) has two or more weights. When the combined block B is included, the total mass] is preferably 30% by mass or less, and more preferably 10% by mass or less. Examples of the other polymerizable monomer in that case include styrene, α-methylstyrene, and the above-described alkylstyrene (preferably p-methylstyrene) constituting the structural unit (I).
付加重合系ブロック共重合体（ａ）は、重合体ブロックＡと重合体ブロックＢとが結合している限りは、その結合形式は限定されず、直鎖状、分岐状、放射状、またはそれらの２つ以上が組合わさった結合形式のいずれでもよい。それらのうちでも、重合体ブロックＡと重合体ブロックＢの結合形式は直鎖状であることが好ましく、その例としては重合体ブロックＡをＡで、また重合体ブロックＢをＢで表したときに、Ａ−Ｂ−Ａで示されるトリブロック共重合体、Ａ−Ｂ−Ａ−Ｂで示されるテトラブロック共重合体、Ａ−Ｂ−Ａ−Ｂ−Ａで示されるペンタブロック共重合体などを挙げることができる。それらのうちでも、トリブロック共重合体（Ａ−Ｂ−Ａ）が、付加重合系ブロック共重合体（ａ）の製造の容易性、柔軟性などの点から好ましく用いられる。 As long as the polymer block A and the polymer block B are bonded to the addition polymerization block copolymer (a), the bonding type is not limited, and is linear, branched, radial, or those Any of two or more combined forms may be used. Among them, it is preferable that the bond form of the polymer block A and the polymer block B is a linear form, for example, when the polymer block A is represented by A and the polymer block B is represented by B. Further, a triblock copolymer represented by A-B-A, a tetrablock copolymer represented by A-B-A-B, a pentablock copolymer represented by A-B-A-B-A, etc. Can be mentioned. Among these, a triblock copolymer (ABA) is preferably used from the viewpoints of ease of production of the addition polymerization block copolymer (a) and flexibility.
付加重合系ブロック共重合体（ａ）の重量平均分子量は、３００００〜２０００００の範囲である必要があり、より好ましくは５００００〜１５００００の範囲である。付加重合系ブロック共重合体（ａ）の重量平均分子量が３００００未満である場合には、重合体組成物から得られる成形体の耐傷つき性、耐摩耗性、力学的特性が低下し、一方、２０００００を超える場合には重合体組成物の成形加工性および重合体組成物から得られる成形体の耐傷つき性、耐摩耗性が劣る。
なお、ここでいう重量平均分子量とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によって求めたポリスチレン換算の重量平均分子量を意味する。
The weight average molecular weight of the addition polymerization block copolymer (a) needs to be in the range of 30,000 to 200,000, more preferably in the range of 50,000 to 150,000. When the weight average molecular weight of the addition polymerization block copolymer (a) is less than 30000, the scratch resistance, wear resistance, and mechanical properties of the molded product obtained from the polymer composition are reduced, If it exceeds 200,000, the molding processability of the polymer composition and the scratch resistance and wear resistance of the molded article obtained from the polymer composition are inferior.
In addition, a weight average molecular weight here means the weight average molecular weight of polystyrene conversion calculated | required by the gel permeation chromatography (GPC) measurement.
付加重合系ブロック共重合体（ａ）は、本発明の趣旨を損なわない限り、分子鎖中および／または分子末端に、カルボキシル基、水酸基、酸無水物基、アミノ基、エポキシ基などの官能基を１種または２種以上有していてもよい。また、付加重合系ブロック共重合体（ａ）として、前記した官能基を有する付加重合系ブロック共重合体（ａ）と官能基を有さない付加重合系ブロック共重合体（ａ）を混合して使用してもよい。 The addition polymerization block copolymer (a) is a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular end unless the purpose of the present invention is impaired. You may have 1 type, or 2 or more types. Further, as the addition polymerization block copolymer (a), the addition polymerization block copolymer (a) having the functional group described above and the addition polymerization block copolymer (a) having no functional group are mixed. May be used.
付加重合系ブロック共重合体（ａ）は、例えば、次のような公知のアニオン重合法によって製造することができる。すなわち、アルキルリチウム化合物などを開始剤として、ｎ−ヘキサン、シクロヘキサンなどの重合反応に不活性な有機溶媒中で、構造単位（Ｉ）を構成するアルキルスチレン、または構造単位（Ｉ）を構成するアルキルスチレンと芳香族ビニル化合物の混合物、ブタジエン、イソプレンなどの共役ジエン化合物を逐次重合させてブロック共重合体（未水添の付加重合系ブロック共重合体（ａ）に相当）を形成する。 The addition polymerization block copolymer (a) can be produced, for example, by the following known anionic polymerization method. That is, alkyl styrene constituting the structural unit (I) or alkyl constituting the structural unit (I) in an organic solvent inert to the polymerization reaction such as n-hexane and cyclohexane using an alkyl lithium compound as an initiator. A block copolymer (corresponding to an unhydrogenated addition polymerization block copolymer (a)) is formed by sequentially polymerizing a mixture of styrene and an aromatic vinyl compound and a conjugated diene compound such as butadiene and isoprene.
また、得られた該ブロック共重合体は、必要に応じてさらに水素添加される。かかる水素添加反応は、例えば、上記で得られた該ブロック共重合体をシクロヘキサンなどの飽和炭化水素溶媒中で、ラネーニッケル；Ｐｔ、Ｐｄ、Ｒｕ、Ｒｈ、Ｎｉ等の金属をカーボン、アルミナ、硅藻土等の担体に担持させた不均一触媒；コバルト、ニッケルなどの第９族または第１０族の金属からなる有機金属化合物とトリエチルアルミニウム、トリイソブチルアルミニウムなどの有機アルミニウム化合物または有機リチウム化合物等の組み合わせからなるチーグラー系の触媒；チタン、ジルコニウム、ハフニウムなどの遷移金属のビス（シクロペンタジエニル）化合物とリチウム、ナトリウム、カリウム、アルミニウム、亜鉛またはマグネシウムなどからなる有機金属化合物の組み合わせからなるメタロセン系触媒などの水素添加触媒の存在下で、通常、反応温度として２０〜１００℃の範囲で、水素圧力０．１〜１０ＭＰａの範囲の条件下で行うことができ、該ブロック共重合体の水素添加物（水素添加された付加重合系ブロック共重合体（ａ）に相当）を得ることができる。水素添加率は、本発明の重合体組成物に要求される物性に応じて適宜調整することができるが、耐熱性、耐候性および耐オゾン性を重視する場合、かかるブロック共重合体を構成する重合体ブロックＢの共役ジエン化合物に由来する炭素−炭素二重結合の７０％以上が水素添加されていることが好ましく、８５％以上であることがより好ましく、９５％以上が水素添加されていることが更に好ましい。 Moreover, the obtained block copolymer is further hydrogenated as necessary. Such a hydrogenation reaction is carried out, for example, by using the block copolymer obtained above in a saturated hydrocarbon solvent such as cyclohexane, Raney nickel; metals such as Pt, Pd, Ru, Rh, and Ni as carbon, alumina, and diatoms. Heterogeneous catalyst supported on a support such as earth; a combination of an organometallic compound composed of a Group 9 or Group 10 metal such as cobalt or nickel and an organoaluminum compound or organolithium compound such as triethylaluminum or triisobutylaluminum Ziegler catalyst comprising: a metallocene catalyst comprising a combination of a bis (cyclopentadienyl) compound of a transition metal such as titanium, zirconium or hafnium and an organometallic compound comprising lithium, sodium, potassium, aluminum, zinc or magnesium Hydrogen addition touch In general, the reaction temperature can be 20 to 100 ° C. under a hydrogen pressure of 0.1 to 10 MPa, and the hydrogenated block copolymer (hydrogenated) Addition polymerization block copolymer (a)). The hydrogenation rate can be appropriately adjusted according to the physical properties required for the polymer composition of the present invention. However, when importance is attached to heat resistance, weather resistance and ozone resistance, such a block copolymer is constituted. 70% or more of the carbon-carbon double bonds derived from the conjugated diene compound of the polymer block B are preferably hydrogenated, more preferably 85% or more, and 95% or more hydrogenated. More preferably.
なお、重合体ブロックＢの共役ジエン化合物に由来する炭素−炭素二重結合の水素添加率は、ヨウ素価滴定、赤外分光光度計、核磁気共鳴などの測定手段により水素添加反応前後における重合体ブロックＢ中の炭素−炭素二重結合の量を測定し、その測定値から算出することができる。 The hydrogenation rate of the carbon-carbon double bond derived from the conjugated diene compound of the polymer block B is determined by the polymer before and after the hydrogenation reaction by measuring means such as iodine titration, infrared spectrophotometer, nuclear magnetic resonance. The amount of the carbon-carbon double bond in the block B can be measured and calculated from the measured value.
本発明の重合体組成物において使用するアクリル系樹脂（ｂ）は、メタクリル酸メチルの単独重合体、またはメタクリル酸メチルを主成分として他の共重合性を有する単量体を共重合させた共重合体である。他の共重合性を有する単量体としては、例えばアクリル酸またはその金属塩；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸ｓ−ブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシルなどのアクリル酸エステル；メタクリル酸またはその金属塩；メタクリル酸エチル、メタクリル酸ｎ−ブチル、メタクリル酸ｓ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−ヒドロキシエチル、メタクリル酸グリシジル、メタクリル酸シクロヘキシルなどのメタクリル酸エステル；酢酸ビニル；スチレン、α−メチルスチレン、ｐ−メチルスチレンなどの芳香族ビニル化合物；無水マレイン酸、Ｎ−メチルマレイミド、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミドなどのマレイミド系化合物などが挙げられる。これらをメタクリル酸メチルと共重合させる場合は、１種類を単独で使用してもよいし、２種以上の化合物を併用して共重合させてもよい。メタクリル酸メチルと他の共重合性を有する単量体を共重合させた共重合体においては、他の共重合性を有する単量体の比率はアクリル系樹脂の持つ性質を大きく変化させない比率であることが好ましく、３０質量％以下であるのが好ましく、２５質量％以下であるのがより好ましい。 The acrylic resin (b) used in the polymer composition of the present invention is a copolymer of methyl methacrylate or a copolymer obtained by copolymerizing methyl methacrylate as a main component and another copolymerizable monomer. It is a polymer. Examples of other copolymerizable monomers include acrylic acid or a metal salt thereof; methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, acrylic acid 2 -Acrylic esters such as ethylhexyl; methacrylic acid or metal salts thereof; ethyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl; Vinyl acetate; Aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; Maleimides such as maleic anhydride, N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide Compounds etc. It is below. When these are copolymerized with methyl methacrylate, one type may be used alone, or two or more types of compounds may be used in combination. In a copolymer obtained by copolymerizing methyl methacrylate and another copolymerizable monomer, the ratio of the other copolymerizable monomer is a ratio that does not significantly change the properties of the acrylic resin. It is preferably 30% by mass or less, and more preferably 25% by mass or less.
アクリル系樹脂（ｂ）は、溶液重合、乳化重合、懸濁重合などの一般の重合手法によって製造が可能であり、その製造方法には特に制限はない。また、本発明では、アクリル系樹脂（ｂ）として公知のものを特に制限なく用いることもできる。例えば、三菱レイヨン（株）製の「アクリペット（ＡＣＲＹＰＥＴ）」（商品名）、旭化成（株）製の「デルペット（ＤＥＬＰＥＴ）」（商品名）、住友化学工業（株）製の「スミペックス（ＳＵＭＩＰＥＸ）」（商品名）、（株）クラレ製の「パラペット（ＰＡＲＡＰＥＴ）」（商品名）などを挙げることができる。 The acrylic resin (b) can be produced by a general polymerization technique such as solution polymerization, emulsion polymerization, suspension polymerization, and the production method is not particularly limited. Moreover, in this invention, a well-known thing can also be used without a restriction | limiting especially as acrylic resin (b). For example, “ACRYPET” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “DELPET” (trade name) manufactured by Asahi Kasei Co., Ltd., “Sumipex” manufactured by Sumitomo Chemical Co., Ltd. (SUMIPEX) "(trade name)," PARAPET "(trade name) manufactured by Kuraray Co., Ltd., and the like.
本発明の重合体組成物において必要に応じて使用する軟化剤（ｃ）としては、例えばパラフィン系、ナフテン系、芳香族系などの炭化水素系油；流動パラフィン；落花生油、ロジンなどの植物油；リン酸エステル；低分子量ポリエチレングリコール；低分子量ポリエチレン、エチレン−α−オレフィン共重合オリゴマー、液状ポリブテン、液状ポリイソプレンまたはその水素添加物、液状ポリブタジエンまたはその水素添加物などの炭化水素系合成油などの公知の軟化剤を用いることができる。これらは１種類を単独で、または２種類以上を併用してもよい。これらの中でも、本発明においては、軟化剤（ｃ）としてパラフィン系の炭化水素系油やエチレン−α−オレフィン共重合オリゴマーなどの炭化水素系合成油が好適に使用される。 Examples of the softening agent (c) used as necessary in the polymer composition of the present invention include hydrocarbon oils such as paraffinic, naphthenic, and aromatic; liquid paraffin; vegetable oils such as peanut oil and rosin; Low molecular weight polyethylene glycol; low molecular weight polyethylene, ethylene-α-olefin copolymer oligomer, liquid polybutene, liquid polyisoprene or hydrogenated product thereof, hydrocarbon-based synthetic oil such as liquid polybutadiene or hydrogenated product, etc. A known softening agent can be used. These may be used alone or in combination of two or more. Among these, in the present invention, hydrocarbon-based synthetic oils such as paraffin-based hydrocarbon oils and ethylene-α-olefin copolymer oligomers are preferably used as the softening agent (c).
本発明の重合体組成物では、付加重合系ブロック共重合体（ａ）、アクリル系樹脂（ｂ）および軟化剤（ｃ）は、重合体組成物を構成する付加重合系ブロック共重合体（ａ）、アクリル系樹脂（ｂ）、軟化剤（ｃ）各成分の含有量（質量）をそれぞれＷａ、Ｗｂ、Ｗｃとするとき、下記式〔１〕および式〔２〕を満足する配合比（質量比）で含有することが必要である。
０．１≦Ｗｂ／Ｗａ≦１．６ 〔１〕
Ｗｃ／（Ｗａ＋Ｗｂ＋Ｗｃ）≦０．５ 〔２〕
In the polymer composition of the present invention, the addition polymerization block copolymer (a), the acrylic resin (b) and the softening agent (c) are added to the addition polymerization block copolymer (a ), Acrylic resin (b), softener (c) When the content (mass) of each component is Wa, Wb, and Wc, respectively, the blending ratio (mass satisfying the following formula [1] and formula [2]) Ratio).
0.1 ≦ Wb / Wa ≦ 1.6 [1]
Wc / (Wa + Wb + Wc) ≦ 0.5 [2]
Ｗｂ／Ｗａの値、すなわち重合体組成物における付加重合系ブロック共重合体（ａ）に対するアクリル系樹脂（ｂ）の含有量の比（質量比）が０．０５未満であると、重合体組成物およびそれからなる成形体の耐摩耗性や耐傷つき性などが不十分になり、一方、２を超えると重合体組成物およびそれからなる成形体の柔軟性、ゴム弾性、力学的特性などが不良になる。Ｗｂ／Ｗａの値の範囲は０．１〜１．６である。 When the value of Wb / Wa, that is, the ratio (mass ratio) of the content of the acrylic resin (b) to the addition polymerization block copolymer (a) in the polymer composition is less than 0.05, the polymer composition The wear resistance and scratch resistance of the molded product and the molded product made thereof are insufficient. On the other hand, when it exceeds 2, the flexibility, rubber elasticity, mechanical properties, etc. of the polymer composition and the molded product made of the polymer composition are poor. Become. The range of the value of Wb / Wa is 0.1 to 1.6.
また、Ｗｃ／（Ｗａ＋Ｗｂ＋Ｗｃ）の値、すなわち付加重合系ブロック共重合体（ａ）、アクリル系樹脂（ｂ）および軟化剤（ｃ）の合計含有量に対する軟化剤（ｃ）の含有量の比（質量比）が０．５を超えると、重合体組成物およびそれからなる成形体の耐傷つき性、耐摩耗性、力学的特性などが不良となる。 The value of Wc / (Wa + Wb + Wc), that is, the ratio of the content of the softener (c) to the total content of the addition polymerization block copolymer (a), the acrylic resin (b) and the softener (c) ( When the mass ratio is more than 0.5, the polymer composition and the molded article made from the polymer composition have poor scratch resistance, wear resistance, mechanical properties, and the like.
本発明の重合体組成物では、付加重合系ブロック共重合体（ａ）、アクリル系樹脂（ｂ）および軟化剤（ｃ）が前記した式〔１〕および式〔２〕を満足する量で含有することにより、相構造（モルフォロジー）において、付加重合系ブロック共重合体（ａ）が連続相（マトリックス）を形成し、その中に、アクリル系樹脂（ｂ）が分散した海島構造を有することが特徴である。かかる重合体組成物は、付加重合系ブロック共重合体（ａ）がマトリックスを形成することによって、柔軟性と高度なゴム弾性が発揮される。また、付加重合系ブロック共重合体（ａ）のマトリックス中に、優れた透明性と耐傷付き性、耐摩耗性とを併せ持つアクリル系樹脂（ｂ）が分散粒子相として存在することによって、付加重合系ブロック共重合体（ａ）の柔軟性と高度なゴム弾性を保持しながら、成形加工性、透明性、そして耐傷付き性と耐摩耗性が付加重合系ブロック共重合体（ａ）単独の場合に比べて格段に向上する。 In the polymer composition of the present invention, the addition polymerization block copolymer (a), the acrylic resin (b) and the softening agent (c) are contained in an amount satisfying the above-mentioned formulas [1] and [2]. Thus, in the phase structure (morphology), the addition polymerization block copolymer (a) forms a continuous phase (matrix), and has an island-island structure in which the acrylic resin (b) is dispersed. It is a feature. Such a polymer composition exhibits flexibility and high rubber elasticity when the addition polymerization block copolymer (a) forms a matrix. Further, in the matrix of the addition polymerization block copolymer (a), an acrylic resin (b) having both excellent transparency, scratch resistance, and abrasion resistance is present as a dispersed particle phase, so that addition polymerization is performed. When the block copolymer (a) alone has molding processability, transparency, scratch resistance and wear resistance while maintaining the flexibility and high rubber elasticity of the block copolymer (a) Compared to, it will be much improved.
本発明の重合体組成物において、付加重合系ブロック共重合体（ａ）がマトリックスを構成し、アクリル系樹脂（ｂ）が分散粒子相を構成していることは、例えば、透過電子顕微鏡で観察して確認することができる。
すなわち、例えば射出成形により厚さ２ｍｍの重合体組成物のシート状物を成形し、それを凍結条件下でミクロトームにより切断して、切片をルテニウム酸で染色した後、破断面を透過電子顕微鏡で観察することによって、付加重合系ブロック共重合体（ａ）がマトリックスを構成しアクリル系樹脂（ｂ）が分散粒子相を構成していることを確認できる。また、アクリル系樹脂（ｂ）の平均分散粒子径は、顕微鏡写真で観察することができる分散粒子の長径をものさしで計測し、その長さを顕微鏡写真撮影倍率で割った値の１００個の平均値をとることにより求めることができる。
In the polymer composition of the present invention, it is observed with a transmission electron microscope, for example, that the addition polymerization block copolymer (a) constitutes a matrix and the acrylic resin (b) constitutes a dispersed particle phase. Can be confirmed.
That is, for example, a sheet of polymer composition having a thickness of 2 mm is formed by injection molding, cut with a microtome under freezing conditions, and the section is stained with ruthenic acid, and then the fracture surface is examined with a transmission electron microscope. By observing, it can be confirmed that the addition polymerization block copolymer (a) constitutes a matrix and the acrylic resin (b) constitutes a dispersed particle phase. Further, the average dispersed particle size of the acrylic resin (b) was measured by measuring the major axis of the dispersed particles that can be observed with a micrograph, and the average of 100 values obtained by dividing the length by the micrograph magnification. It can be obtained by taking a value.
本発明の重合体組成物は、本発明の主旨を損なわない範囲であれば、必要に応じて、上記の付加重合系ブロック共重合体（ａ）やアクリル系樹脂（ｂ）とは異なる熱可塑性重合体や、ゴム補強剤または充填剤をさらに含有していてもよい。 If the polymer composition of the present invention is within a range that does not impair the gist of the present invention, the thermoplastic polymer different from the above addition polymerization block copolymer (a) and acrylic resin (b) as necessary. It may further contain a polymer, a rubber reinforcing agent or a filler.
他の熱可塑性重合体としては、例えば、各種ポリエチレン、各種ポリプロピレン、エチレン−プロピレンランダム共重合体やエチレン−酢酸ビニル共重合体などのポリオレフィン系樹脂；ポリスチレン、ポリ（α−メチルスチレン）、ポリ（ｐ−メチルスチレン）、スチレン−アクリロニトリル共重合体などのスチレン系樹脂；付加重合系ブロック共重合体（ａ）とは異なる、スチレンからなるブロックをハードセグメントとするスチレン系ブロック共重合体；ポリフェニレンオキシド、ポリカーボネート、熱可塑性ポリオレフィンエラストマー、架橋型の熱可塑性ポリオレフィンエラストマーなどを挙げることができる。これらは１種を単独で、また２種以上を併用してもよい。他の熱可塑性重合体を含有させる場合、その含有量は重合体組成物に対して１０質量％以下であるのが好ましい。 Examples of the other thermoplastic polymer include polyolefin resins such as various polyethylenes, various polypropylenes, ethylene-propylene random copolymers and ethylene-vinyl acetate copolymers; polystyrene, poly (α-methylstyrene), poly ( p-methylstyrene), styrene-based resins such as styrene-acrylonitrile copolymer; styrene-based block copolymer having a hard segment as a block made of styrene, which is different from addition-polymerized block copolymer (a); polyphenylene oxide , Polycarbonate, thermoplastic polyolefin elastomer, and cross-linked thermoplastic polyolefin elastomer. These may be used alone or in combination of two or more. When other thermoplastic polymer is contained, the content thereof is preferably 10% by mass or less based on the polymer composition.
一方、ゴム補強剤または充填剤としては、例えばカーボンブラック、炭酸カルシウム、タルク、シリカ、珪藻土などの無機充填剤；ゴム粉末、木粉などの有機充填剤などを挙げることができる。これらは１種を単独で、また２種以上を併用してもよい。ゴム補強剤または充填剤を含有させる場合、その含有量は重合体組成物に対して３０質量％以下であるのが好ましい。 On the other hand, examples of the rubber reinforcing agent or filler include inorganic fillers such as carbon black, calcium carbonate, talc, silica, and diatomaceous earth; and organic fillers such as rubber powder and wood powder. These may be used alone or in combination of two or more. When the rubber reinforcing agent or filler is contained, the content thereof is preferably 30% by mass or less with respect to the polymer composition.
また、本発明の重合体組成物は、本発明の主旨を損なわない範囲であれば、必要に応じて、熱安定剤、酸化防止剤、光安定剤、難燃剤、発泡剤、帯電防止剤、顔料、架橋剤などをさらに含有していてもよい。 Further, the polymer composition of the present invention is a heat stabilizer, an antioxidant, a light stabilizer, a flame retardant, a foaming agent, an antistatic agent, if necessary, as long as it does not impair the gist of the present invention. It may further contain a pigment, a crosslinking agent and the like.
本発明の重合体組成物は、従来の慣用の方法で得られる。例えば、一軸押出機、二軸押出機、バンバリーミキサー、ブラベンダー、オープンロール、ニーダーなどの混練機を使用して、上記した付加重合系ブロック共重合体（ａ）、アクリル系樹脂（ｂ）、必要に応じて軟化剤（ｃ）、その他の任意添加成分を所定の割合で混練して本発明の重合体組成物を得る。その際の混練温度としては、一般に１６０〜２８０℃の範囲が好ましく、１９０〜２６０℃の範囲がより好ましい。 The polymer composition of the present invention can be obtained by a conventional method. For example, by using a kneader such as a single screw extruder, twin screw extruder, Banbury mixer, Brabender, open roll, kneader, etc., the above addition polymerization block copolymer (a), acrylic resin (b), If necessary, the polymer composition of the present invention is obtained by kneading the softener (c) and other optional additive components at a predetermined ratio. In general, the kneading temperature is preferably in the range of 160 to 280 ° C, more preferably in the range of 190 to 260 ° C.
上記混練に際しては、例えば［１］重合体組成物を構成する全ての成分を、混練する前にヘンシェルミキサーやタンブラーのような混合機を用いて予めドライブレンドしておき、一括混練する方法；［２］軟化剤（ｃ）を除く他の成分を予め混練した後、サイドフィーダーなどを用いて混練機内に所定量の軟化剤（ｃ）を添加する方法；［３］アクリル系樹脂（ｂ）を除く他の成分を予め混練した後、サイドフィーダーなどを用いて混練機内に所定量のアクリル系樹脂（ｂ）を添加する方法などが挙げられ、いずれの方法を採用してもよい。 In the above kneading, for example, [1] A method in which all the components constituting the polymer composition are dry-blended in advance using a mixer such as a Henschel mixer or a tumbler before kneading, and then batch kneading; 2) A method of previously kneading other components excluding the softener (c) and then adding a predetermined amount of the softener (c) into the kneader using a side feeder or the like; [3] Acrylic resin (b) A method of adding a predetermined amount of the acrylic resin (b) into the kneader using a side feeder or the like after kneading the other components to be removed in advance, and any method may be adopted.
本発明の重合体組成物は、例えば、押出成形、射出成形、中空成形、圧縮成形、プレス成形、カレンダー成形などの従来公知の方法を用いて、シート、フィルム、チューブ、中空成形体、型成形体、その他の各種成形体に成形することができる。また、二色成形法により他の部材（例えば、ポリエチレン、ポリプロピレン、オレフィン系エラストマー、ＡＢＳ樹脂、ポリアミドなどの高分子材料、金属、木材、布など）と複合化することができる。 The polymer composition of the present invention can be obtained by using a conventionally known method such as extrusion molding, injection molding, hollow molding, compression molding, press molding, calendar molding, and the like, for example, a sheet, a film, a tube, a hollow molded body, and a mold molding. Body and other various shaped bodies. Moreover, it can be compounded with other members (for example, polymer materials such as polyethylene, polypropylene, olefin elastomer, ABS resin, polyamide, metal, wood, cloth, etc.) by a two-color molding method.
本発明の重合体組成物から得られる成形体が特に耐摩耗性に優れることは、具体的には、厚さ２ｍｍのシート状成形体として、ＪＩＳ Ｋ ６２６４に準じて、Ｈ−２２摩耗輪を用い、１ｋｇ荷重、１０００回転の条件下で測定したときのテーバー摩耗量が１００ｍｍ３以下、好ましくは５０ｍｍ３以下であることから実証される（実施例参照）。かかる条件で測定したテーバー摩耗量が前記した値以下であることにより、本発明の重合体組成物は、使用時における耐久性、使用材料を低減できるという省資源の観点から好ましい材料である。 The molded product obtained from the polymer composition of the present invention is particularly excellent in abrasion resistance. Specifically, a sheet-shaped molded product having a thickness of 2 mm is provided with an H-22 worn wheel according to JIS K 6264. It is demonstrated from the fact that the Taber wear amount when measured under the conditions of 1 kg load and 1000 revolutions is 100 mm 3 or less, preferably 50 mm 3 or less (see Examples). When the amount of Taber abrasion measured under such conditions is not more than the above-mentioned value, the polymer composition of the present invention is a preferable material from the viewpoint of resource saving that durability during use and material used can be reduced.
以下、実施例などにより本発明について具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではない。
なお、実施例および比較例における、重合体組成物から得られる成形体の耐傷つき性、耐摩耗性、透明性、ゴム弾性、柔軟性、力学的特性、並びに重合体組成物の成形加工性の測定または評価は、以下の方法によって行った。
EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited at all by these Examples.
In Examples and Comparative Examples, scratch resistance, abrasion resistance, transparency, rubber elasticity, flexibility, mechanical properties of molded products obtained from the polymer compositions, and molding processability of the polymer compositions are obtained. Measurement or evaluation was performed by the following method.
ａ）耐傷つき性
実施例１〜８および比較例１〜７で得られた重合体組成物のシートより、縦５ｃｍ×横１１ｃｍ×厚さ０．２ｃｍの試験片を作製し、該試験片上を、ＡＳＴＭ Ｄ２１９７に従って、２００ｇ荷重を加えたクロスカット試験用針状治具で１ｃｍ／秒の速度で引っ掻き、試験片に生じた傷の深さを表面粗さ計で測定し、傷の深さが浅いほど耐傷つき性が優れるとした。
a) Scratch resistance From the sheets of the polymer compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 7, a test piece having a length of 5 cm, a width of 11 cm, and a thickness of 0.2 cm was prepared. In accordance with ASTM D2197, the cross-cut test needle jig with a load of 200 g was scratched at a speed of 1 cm / second, and the depth of the scratch generated on the test piece was measured with a surface roughness meter. The shallower the surface, the better the scratch resistance.
ｂ）耐摩耗性
実施例１〜８および比較例１〜７で得られた重合体組成物のシートより、縦１１ｃｍ×横１１ｃｍ×厚さ０．２ｃｍの試験片を作製し、該試験片を用いて、ＪＩＳ Ｋ ６２６４に準じて、Ｈ−２２摩耗輪を用い、１ｋｇ荷重、１０００回転の条件下でテーバー摩耗量を測定した。
b) Abrasion resistance From the sheet | seat of the polymer composition obtained in Examples 1-8 and Comparative Examples 1-7, the test piece of length 11cm x width 11cm x thickness 0.2cm was produced, and this test piece was prepared. In accordance with JIS K 6264, the amount of Taber wear was measured under the conditions of 1 kg load and 1000 revolutions using an H-22 wear wheel.
ｃ）透明性
実施例１〜８および比較例１〜７で得られた重合体組成物のシートより、縦１１ｃｍ×横１１ｃｍ×厚さ０．２ｃｍの試験片を作製し、該試験片の可視光線の吸収スペクトルより全光線透過率を求めた。全光線透過率が高いほど透明性に優れる。
c) Transparency A test piece having a length of 11 cm, a width of 11 cm, and a thickness of 0.2 cm was prepared from the sheets of the polymer compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 7, and the test piece was visible. The total light transmittance was determined from the light absorption spectrum. The higher the total light transmittance, the better the transparency.
ｄ）ゴム弾性
実施例１〜８および比較例１〜７で得られた重合体組成物のシートからダンベル状１号形の試験片を打ち抜き、ＪＩＳ Ｋ ６２６２に準じて１００％伸長して２４時間保持した後、解放して、引張り永久伸び（％）を測定して、ゴム弾性の指標とした。引張り永久伸びが小さいほどゴム弾性が優れている。
d) Rubber elasticity A test piece of dumbbell-shaped No. 1 was punched out from the sheet of the polymer composition obtained in Examples 1 to 8 and Comparative Examples 1 to 7, and it was stretched 100% according to JIS K 6262 and 24 hours. After being held, it was released and the tensile elongation (%) was measured and used as an index of rubber elasticity. The smaller the tensile elongation, the better the rubber elasticity.
ｅ）柔軟性（硬度）
実施例１〜８および比較例１〜７で得られた重合体組成物のシートより、縦１１ｃｍ×横１１ｃｍ×厚さ０．２ｃｍの試験片を作製し、該試験片を用いて、ＪＩＳ Ｋ ６２５３に準じて、タイプＡデュロメータで硬度を測定して、柔軟性の指標とした。
e) Flexibility (hardness)
From the sheet | seat of the polymer composition obtained in Examples 1-8 and Comparative Examples 1-7, the test piece of length 11cm x width 11cm x thickness 0.2cm was produced, and JIS K was used using this test piece. According to 6253, the hardness was measured with a type A durometer and used as an index of flexibility.
ｆ）力学的特性
実施例１〜８および比較例１〜７で得られた重合体組成物のシートからダンベル状５号形試験片を打ち抜き、ＪＩＳ Ｋ ６２５１に準じて引張り試験を行い、破断強度および破断伸度を測定して、力学的特性の指標とした。
f) Mechanical properties A dumbbell-shaped No. 5 test piece was punched out from the sheets of the polymer compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 7, a tensile test was performed according to JIS K 6251, and a breaking strength was obtained. The elongation at break was measured and used as an index of mechanical properties.
ｇ）成形加工性
実施例１〜８および比較例１〜７で得られたペレット状の重合体組成物を用いて、ＪＩＳ Ｋ ７２１０に準じて、２３０℃、２．１６ｋｇ荷重におけるメルトフローレート（ＭＦＲ）を測定した。ＭＦＲの値が高いほど成形加工性に優れるとした。
g) Molding processability Melt flow rate at 230 ° C. and 2.16 kg load according to JIS K 7210 using the pellet-shaped polymer compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 7 ( MFR) was measured. The higher the MFR value, the better the moldability.
また、以下の実施例および比較例で使用した各成分の内容は以下のとおりである。
（ａ）付加重合系ブロック共重合体
重合例１
撹拌装置付き耐圧容器中に、シクロヘキサン５０ｋｇ、ｓｅｃ−ブチルリチウム（１１質量％、シクロヘキサン溶液）２６５ｍｌを加え、この溶液にｐ−メチルスチレン２．２５ｋｇを３０分かけて加えて５０℃で１２０分間重合し、次いでテトラヒドロフラン（ＴＨＦ）を８０ｇ添加してから、ブタジエン１０．５ｋｇを６０分かけて加え、５０℃で３０分間重合した後、さらにｐ−メチルスチレン２．２５ｋｇを３０分かけて加え、５０℃で３０分間重合し、ポリｐ−メチルスチレン−ポリブタジエン−ポリｐ−メチルスチレントリブロック共重合体を含む反応混合液を得た。得られたブロック共重合体の重量平均分子量は７６４００であり、１Ｈ−ＮＭＲによって測定したｐ−メチルスチレン含有量は３０質量％であった。
かかるブロック共重合体を含む反応混合液に、オクチル酸ニッケル（６４質量％、シクロヘキサン溶液）１３０ｇにトリイソプロピルアルミニウム（２０質量％、シクロヘキサン溶液）４００ｇを加えて別途調製した水素添加触媒を添加し、８０℃、１ＭＰａの水素雰囲気下で水素添加反応を行うことで、ポリｐ−メチルスチレン−ポリブタジエン−ポリｐ−メチルスチレントリブロック共重合体の水素添加物（以下、これをブロック共重合体１と称する）を得た。得られたブロック共重合体１の重量平均分子量は７７０００であり、１Ｈ−ＮＭＲによって測定したｐ−メチルスチレン含有量および水素添加率はそれぞれ２９質量％、９７％であった。
The contents of each component used in the following examples and comparative examples are as follows.
(A) Addition polymerization block copolymer polymerization example 1
In a pressure vessel equipped with a stirrer, 50 kg of cyclohexane and 265 ml of sec-butyllithium (11% by mass, cyclohexane solution) are added, and 2.25 kg of p-methylstyrene is added to this solution over 30 minutes, and polymerization is carried out at 50 ° C. for 120 minutes. Next, 80 g of tetrahydrofuran (THF) was added, 10.5 kg of butadiene was added over 60 minutes, polymerized at 50 ° C. for 30 minutes, and then 2.25 kg of p-methylstyrene was added over 30 minutes. Polymerization was carried out at a temperature of 30 ° C. for 30 minutes to obtain a reaction mixture containing poly p-methylstyrene-polybutadiene-poly p-methylstyrene triblock copolymer. The weight average molecular weight of the obtained block copolymer was 76400, and the p-methylstyrene content measured by 1 H-NMR was 30% by mass.
A hydrogenation catalyst prepared separately by adding 400 g of triisopropylaluminum (20% by mass, cyclohexane solution) to 130 g of nickel octylate (64% by mass, cyclohexane solution) is added to the reaction mixture containing the block copolymer, By performing a hydrogenation reaction in a hydrogen atmosphere at 80 ° C. and 1 MPa, a hydrogenated product of poly (p-methylstyrene-polybutadiene-poly (p-methylstyrene) triblock copolymer (hereinafter referred to as block copolymer 1). Obtained). The weight average molecular weight of the obtained block copolymer 1 was 77000, and the p-methylstyrene content and the hydrogenation rate measured by 1 H-NMR were 29% by mass and 97%, respectively.
重合例２
撹拌装置付き耐圧容器中に、シクロヘキサン５０ｋｇ、ｓｅｃ−ブチルリチウム（１１質量％、シクロヘキサン溶液）２６５ｍｌを加え、この溶液にｐ−メチルスチレンとスチレンの混合液（ｐ−メチルスチレン／スチレン＝５０／５０（質量比））２．２５ｋｇを３０分かけて加えて５０℃で１２０分間重合し、次いでＴＨＦを８０ｇ添加してから、ブタジエン１０．５ｋｇを６０分かけて加え、５０℃で３０分間重合した後、さらにｐ−メチルスチレンとスチレンの混合液（ｐ−メチルスチレン／スチレン＝５０／５０（質量比））２．２５ｋｇを３０分かけて加え、５０℃で３０分間重合し、ポリ（ｐ−メチルスチレン／スチレン）−ポリブタジエン−ポリ（ｐ−メチルスチレン／スチレン）共重合体を含む反応混合液を得た。得られたブロック共重合体の重量平均分子量は７６４００であり、１Ｈ−ＮＭＲによって測定したｐ−メチルスチレンとスチレンを合わせた含有量は３０質量％であった。
かかるブロック共重合体を含む反応混合液に、オクチル酸ニッケル（６４質量％、シクロヘキサン溶液）１３０ｇにトリイソプロピルアルミニウム（２０質量％、シクロヘキサン溶液）４００ｇを加えて別途調製した水素添加触媒を添加し、８０℃、１ＭＰａの水素雰囲気下で水素添加反応を行うことで、ポリ（ｐ−メチルスチレン／スチレン）−ポリブタジエン−ポリ（ｐ−メチルスチレン／スチレン）トリブロック共重合体の水素添加物（以下、これをブロック共重合体２と称する）を得た。得られたブロック共重合体１の重量平均分子量は７７０００であり、１Ｈ−ＮＭＲによって測定したｐ−メチルスチレンとスチレンを合わせた含有量および水素添加率はそれぞれ２９質量％、９７％であった。
Polymerization example 2
In a pressure vessel equipped with a stirrer, 50 kg of cyclohexane and 265 ml of sec-butyllithium (11% by mass, cyclohexane solution) are added, and a mixed liquid of p-methylstyrene and styrene (p-methylstyrene / styrene = 50/50) is added to this solution. (Mass ratio)) 2.25 kg was added over 30 minutes and polymerized at 50 ° C. for 120 minutes, then 80 g of THF was added, and then 10.5 kg of butadiene was added over 60 minutes and polymerized at 50 ° C. for 30 minutes. Thereafter, 2.25 kg of a mixed solution of p-methylstyrene and styrene (p-methylstyrene / styrene = 50/50 (mass ratio)) was added over 30 minutes, and polymerization was performed at 50 ° C. for 30 minutes. A reaction mixture containing a methylstyrene / styrene) -polybutadiene-poly (p-methylstyrene / styrene) copolymer was obtained. The weight average molecular weight of the obtained block copolymer was 76400, and the combined content of p-methylstyrene and styrene measured by 1 H-NMR was 30% by mass.
A hydrogenation catalyst prepared separately by adding 400 g of triisopropylaluminum (20% by mass, cyclohexane solution) to 130 g of nickel octylate (64% by mass, cyclohexane solution) is added to the reaction mixture containing the block copolymer, By performing a hydrogenation reaction in a hydrogen atmosphere at 80 ° C. and 1 MPa, a hydrogenated poly (p-methylstyrene / styrene) -polybutadiene-poly (p-methylstyrene / styrene) triblock copolymer (hereinafter, This was referred to as block copolymer 2). The obtained block copolymer 1 had a weight average molecular weight of 77000, and the combined content of p-methylstyrene and styrene and the hydrogenation rate measured by 1 H-NMR were 29% by mass and 97%, respectively. .
重合例３
撹拌装置付き耐圧容器中に、シクロヘキサン５０ｋｇ、ｓｅｃ−ブチルリチウム（１１質量％、シクロヘキサン溶液）２６５ｍｌを加え、この溶液にスチレン２．２５ｋｇを３０分かけて加えて５０℃で１２０分間重合し、次いでＴＨＦを８０ｇ添加してから、ブタジエン１０．５ｋｇを６０分かけて加え、５０℃で３０分間重合した後、さらにスチレン２．２５ｋｇを３０分かけて加え、５０℃で３０分間重合し、ポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体を含む反応混合液を得た。得られたブロック共重合体の重量平均分子量は７６４００であり、スチレン含有量は３０質量％であった。
かかるブロック共重合体を含む反応混合液に、オクチル酸ニッケル（６４質量％、シクロヘキサン溶液）１３０ｇにトリイソプロピルアルミニウム（２０質量％、シクロヘキサン溶液）４００ｇを加えて別途調製した水素添加触媒を添加し、８０℃、１ＭＰａの水素雰囲気下で水素添加反応を行うことで、ポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体の水素添加物（以下、これをブロック共重合体３と称する）を得た。得られたブロック共重合体３の重量平均分子量は７７０００であり、１Ｈ−ＮＭＲによって測定したスチレン含有量および水素添加率はそれぞれ２９質量％、９７％であった。
Polymerization example 3
In a pressure-resistant vessel equipped with a stirrer, 50 kg of cyclohexane and 265 ml of sec-butyllithium (11% by mass, cyclohexane solution) are added, and 2.25 kg of styrene is added to this solution over 30 minutes, followed by polymerization at 50 ° C. for 120 minutes, After adding 80 g of THF, 10.5 kg of butadiene was added over 60 minutes, polymerized at 50 ° C. for 30 minutes, further added with 2.25 kg of styrene over 30 minutes, polymerized at 50 ° C. for 30 minutes, polystyrene- A reaction mixture containing a polybutadiene-polystyrene triblock copolymer was obtained. The weight average molecular weight of the obtained block copolymer was 76400, and the styrene content was 30% by mass.
A hydrogenation catalyst prepared separately by adding 400 g of triisopropylaluminum (20% by mass, cyclohexane solution) to 130 g of nickel octylate (64% by mass, cyclohexane solution) is added to the reaction mixture containing the block copolymer, A hydrogenation reaction of polystyrene-polybutadiene-polystyrene triblock copolymer (hereinafter referred to as block copolymer 3) was obtained by performing a hydrogenation reaction at 80 ° C. in a hydrogen atmosphere of 1 MPa. The weight average molecular weight of the obtained block copolymer 3 was 77000, and the styrene content and hydrogenation rate measured by 1 H-NMR were 29% by mass and 97%, respectively.
（ｂ）アクリル系樹脂
重合例４
還流冷却管を備えた容量１０００ｍｌの三口フラスコに純水５００ｇを仕込み、充分に窒素置換した後、メタクリル酸メチル４２５ｇ、アクリル酸メチル５５ｇ、ラウリルパーオキサイド２．５ｇおよびラウリルメルカプタン４ｇの混合液を仕込み、８０℃で４時間重合を行い、アクリル系樹脂（以下、これをアクリル系樹脂１と称する）を得た。得られたアクリル系樹脂１の２０℃、クロロホルム中での固有粘度は０．３０１ｄｌ／ｇであった。
(B) Acrylic resin polymerization example 4
A 1000 ml three-necked flask equipped with a reflux condenser was charged with 500 g of pure water and thoroughly purged with nitrogen, and then charged with a mixed solution of 425 g of methyl methacrylate, 55 g of methyl acrylate, 2.5 g of lauryl peroxide and 4 g of lauryl mercaptan. Polymerization was carried out at 80 ° C. for 4 hours to obtain an acrylic resin (hereinafter referred to as “acrylic resin 1”). The obtained acrylic resin 1 had an intrinsic viscosity of 0.301 dl / g in chloroform at 20 ° C.
（ｃ）軟化剤
ダイアナプロセスＰＷ−３８０（商品名、出光石油化学株式会社製；パラフィン系プロセスオイル）
(C) Softener Diana Process PW-380 (trade name, manufactured by Idemitsu Petrochemical Co., Ltd .; paraffinic process oil)
≪実施例１〜８≫
（１）ブロック共重合体１、ブロック共重合体２、アクリル系樹脂１および軟化剤を、下記の表１に示す配合に従って、ヘンシェルミキサーを使用して予め一括して混合し、二軸押出し機（東芝機械株式会社製、ＴＥＭ−３５Ｂ）に供給して２３０℃で混練した後、ストランド状に押出し、切断して、ペレット状の重合体組成物を調製した。得られた重合体組成物のＭＦＲを上記の方法で測定したところ、下記表１に示すとおりであった。
（２）上記（１）で得られたペレット状の重合体組成物を使用して、プレス成形（成形温度２３０℃、プレス圧力１０ＭＰａ、プレス時間３分）により厚さ０．２ｃｍのシートを作製し、上記の方法で耐傷つき性、耐摩耗性、透明性、ゴム弾性、柔軟性、力学的特性を測定したところ、下記の表１に示すとおりであった。
<< Examples 1 to 8 >>
(1) The block copolymer 1, the block copolymer 2, the acrylic resin 1 and the softening agent are mixed together in advance using a Henschel mixer according to the formulation shown in Table 1 below, and a twin screw extruder (Toshiba Machine Co., Ltd. make, TEM-35B) knead | mixed at 230 degreeC, Then, it extruded in the shape of a strand, cut | disconnected, and prepared the pellet-shaped polymer composition. When MFR of the obtained polymer composition was measured by the above method, it was as shown in Table 1 below.
(2) Using the pellet-shaped polymer composition obtained in (1) above, a sheet having a thickness of 0.2 cm is produced by press molding (molding temperature 230 ° C., press pressure 10 MPa, press time 3 minutes). When the scratch resistance, abrasion resistance, transparency, rubber elasticity, flexibility, and mechanical properties were measured by the above methods, they were as shown in Table 1 below.
≪比較例１〜７≫
（１）ブロック共重合体１、ブロック共重合体３、アクリル系樹脂１および軟化剤を、下記の表２に示す配合に従って、ヘンシェルミキサーを使用して予め一括して混合し、二軸押出し機（東芝機械株式会社製、ＴＥＭ−３５Ｂ）に供給して２３０℃で混練した後、ストランド状に押出し、切断して、ペレット状の重合体組成物を調製した。得られた重合体組成物のＭＦＲを上記の方法で測定したところ、下記表２に示すとおりであった。
（２）上記（１）で得られたペレット状の重合体組成物を使用して、プレス成形（成形温度２３０℃、プレス圧力１０ＭＰａ、プレス時間３分）により厚さ０．２ｃｍのシートを作製し、上記の方法で耐傷つき性、耐摩耗性、透明性、ゴム弾性、柔軟性、力学的特性を測定したところ、下記の表２に示すとおりであった。
≪Comparative Examples 1-7≫
(1) A block copolymer 1, a block copolymer 3, an acrylic resin 1 and a softening agent are mixed together in advance using a Henschel mixer according to the formulation shown in Table 2 below, and a twin screw extruder (Toshiba Machine Co., Ltd. make, TEM-35B) knead | mixed at 230 degreeC, Then, it extruded in the shape of a strand, cut | disconnected, and prepared the pellet-shaped polymer composition. When the MFR of the obtained polymer composition was measured by the above method, it was as shown in Table 2 below.
(2) Using the pellet-shaped polymer composition obtained in (1) above, a sheet having a thickness of 0.2 cm is produced by press molding (molding temperature 230 ° C., press pressure 10 MPa, press time 3 minutes). When the scratch resistance, abrasion resistance, transparency, rubber elasticity, flexibility, and mechanical properties were measured by the above methods, they were as shown in Table 2 below.
≪参考例１≫
ポリウレタン系熱可塑性エラストマー（「クラミロンＵ３１９０」（商品名、株式会社クラレ製））を単独で用いて、プレス成形（成形温度２００℃、プレス圧力１０ＭＰａ、プレス時間３分）により厚さ０．２ｃｍのシートを作製し、耐傷つき性および耐摩耗性を上記と同様な方法で測定または評価したところ、下記の表３に示すとおりであった。
≪Reference Example 1≫
A polyurethane-based thermoplastic elastomer ("Kramilon U3190" (trade name, manufactured by Kuraray Co., Ltd.)) was used alone, and the thickness was 0.2 cm by press molding (molding temperature 200 ° C, press pressure 10 MPa, press time 3 minutes). When a sheet was prepared and scratch resistance and abrasion resistance were measured or evaluated by the same method as described above, the results were as shown in Table 3 below.
≪参考例２≫
ポリエステル系熱可塑性エラストマー（「ハイトレル４０５７」（商品名、東レ・デュポン株式会社製））を単独で用いて、プレス成形（成形温度２００℃、プレス圧力１０ＭＰａ、プレス時間３分）により厚さ０．２ｃｍのシートを作製し、耐傷つき性および耐摩耗性を上記と同様な方法で測定または評価したところ、下記の表３に示すとおりであった。
≪Reference example 2≫
A polyester thermoplastic elastomer (“Hytrel 4057” (trade name, manufactured by Toray DuPont Co., Ltd.)) was used alone, and the thickness was reduced to 0. 0 mm by press molding (molding temperature 200 ° C., press pressure 10 MPa, press time 3 minutes). When a 2 cm sheet was prepared and scratch resistance and abrasion resistance were measured or evaluated by the same method as described above, the results were as shown in Table 3 below.
表１の結果から、ブロック共重合体１、ブロック共重合体２とアクリル系樹脂１の配合比（質量比）が式〔１〕の範囲を満足し、軟化剤の配合比（質量比）が式〔２〕の範囲を満足している実施例１〜８の重合体組成物およびそれからなる成形体は、成形加工性、耐傷つき性および耐摩耗性に優れ、しかも透明性、ゴム弾性、柔軟性および力学的特性をバランス良く兼ね備えていることがわかる。 From the results in Table 1, the blending ratio (mass ratio) of the block copolymer 1, the block copolymer 2 and the acrylic resin 1 satisfies the range of the formula [1], and the blending ratio (mass ratio) of the softener is The polymer compositions of Examples 1 to 8 satisfying the range of the formula [2] and the molded products made thereof are excellent in molding processability, scratch resistance and abrasion resistance, and are transparent, rubber elastic and flexible. It can be seen that it has a good balance of sex and mechanical properties.
これに対して、比較例１の重合体組成物は、ブロック共重合体１に対するアクリル系樹脂１の配合比（質量比）が２．３４であって式〔１〕の範囲を満足していないため、ゴム弾性や柔軟性が乏しく、しかも、耐傷つき性、耐摩耗性および力学的特性が劣っている。
比較例２の重合体組成物は軟化剤を式〔２〕の範囲で含有するが、ブロック共重合体１に対するアクリル系樹脂１の配合比（質量比）が比較例１と同じ２．３４であって式〔１〕の範囲を満足していないため、耐傷つき性、耐摩耗性および力学的特性が劣っている。
In contrast, in the polymer composition of Comparative Example 1, the blending ratio (mass ratio) of the acrylic resin 1 with respect to the block copolymer 1 is 2.34 and does not satisfy the range of the formula [1]. Therefore, the rubber elasticity and flexibility are poor, and the scratch resistance, wear resistance and mechanical properties are inferior.
The polymer composition of Comparative Example 2 contains a softener in the range of the formula [2], but the blending ratio (mass ratio) of the acrylic resin 1 to the block copolymer 1 is 2.34, which is the same as that of Comparative Example 1. Since the range of the formula [1] is not satisfied, the scratch resistance, wear resistance and mechanical properties are inferior.
比較例３の重合体組成物はブロック共重合体１に対するアクリル系樹脂１の配合比（質量比）が０であるため、耐傷つき性および耐摩耗性が劣っている。
比較例４の重合体組成物は軟化剤の配合比（質量比）が式〔２〕の範囲を満足していないことにより、耐傷つき性、耐摩耗性および力学的特性が劣っている。
Since the blending ratio (mass ratio) of the acrylic resin 1 to the block copolymer 1 is 0, the polymer composition of Comparative Example 3 is inferior in scratch resistance and wear resistance.
The polymer composition of Comparative Example 4 is inferior in scratch resistance, abrasion resistance and mechanical properties because the blending ratio (mass ratio) of the softener does not satisfy the range of the formula [2].
比較例５〜７の重合体組成物は、ブロック共重合体３を構成する重合体ブロックＡがポリスチレンのため、ブロック共重合体３とアクリル系樹脂１の配合比（質量比）が式〔１〕の範囲を満足し、かつ軟化剤の配合比（質量比）が式〔２〕の範囲を満足していても、耐傷つき性、耐摩耗性および力学的特性が劣っている。 In the polymer compositions of Comparative Examples 5 to 7, since the polymer block A constituting the block copolymer 3 is polystyrene, the blending ratio (mass ratio) of the block copolymer 3 and the acrylic resin 1 is expressed by the formula [1 ] And the blending ratio (mass ratio) of the softener satisfies the range of the formula [2], the scratch resistance, wear resistance and mechanical properties are inferior.
本発明の重合体組成物は、成形加工性、柔軟性、ゴム弾性、力学的特性、透明性などの諸特性に加え、特に耐傷つき性、耐摩耗性に優れている。そして、それらの特性を活かして、例えばバンパー、サイドモール、ウェザーストリップ、マットガード、エンブレム、レザーシート、フロアーマット、アームレスト、エアバッグカバー、ステアリングホイール被覆、ベルトラインモール、フラッシュマウントなどの自動車用内外装材部品；冷蔵庫用ガスケット、洗濯機ホース、掃除機バンパー、携帯電話保護フィルム、防水ボディーなどの家電部品；コピー機紙送りローラー、巻き取りローラーなどの事務機部品；ソファーやチェアーシートなどの家具；スイッチカバー、キャスター、ストッパー、足ゴムなどの部品；履物；被覆鋼板、被覆合板などの建材；水中眼鏡、スノーケル、スキーストックグリップなどのスポーツ用品；シリンジガスケット、ローリングチューブなどの医療用品；コンベアーベルト、電動ベルト、ペレタイザーロールなどの工業資材；おしめ、ハップ剤、包帯などの伸縮部材；文房具、玩具、日用雑貨などの幅広い用途に有効に使用することができる。
The polymer composition of the present invention is particularly excellent in scratch resistance and abrasion resistance in addition to various properties such as moldability, flexibility, rubber elasticity, mechanical properties, and transparency. And taking advantage of these characteristics, for example, bumpers, side moldings, weather strips, mat guards, emblems, leather seats, floor mats, armrests, airbag covers, steering wheel covers, belt line moldings, flush mounts, etc. Exterior parts: Home appliance parts such as refrigerator gaskets, washing machine hoses, vacuum cleaner bumpers, mobile phone protective films, waterproof bodies; office machine parts such as copier paper feed rollers and take-up rollers; furniture such as sofas and chair seats Parts such as switch covers, casters, stoppers and rubber feet; footwear; building materials such as coated steel sheets and coated plywood; sports equipment such as underwater glasses, snorkels and ski stock grips; medical supplies such as syringe gaskets and rolling tubes Conveyor belts, electric belts, industrial materials such as a pelletizer rolls; diaper, poultices, elastic members such as bandages; stationery, toys, can be effectively used in a wide range of applications such as daily goods.
Claims (2)
０．１≦Ｗｂ／Ｗａ≦１．６ 〔１〕
Ｗｃ／（Ｗａ＋Ｗｂ＋Ｗｃ）≦０．５ 〔２〕
［式中、Ｗａ、ＷｂおよびＷｃは重合体組成物を構成するブロック共重合体（ａ）、アクリル系樹脂（ｂ）および軟化剤（ｃ）の各成分の含有量（質量）を示す。］ 1 or more polymer blocks A mainly composed of an aromatic vinyl compound unit having 30 % by mass or more of an alkylstyrene-derived structural unit (I) in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring; An addition polymerization block copolymer having a weight average molecular weight of 30,000 to 200,000 selected from a block copolymer having at least one polymer block B mainly composed of a conjugated diene compound unit and a hydrogenated product thereof A polymer composition containing (a), an acrylic resin (b) and a softening agent (c) at a blending ratio (mass ratio) satisfying the following formulas [1] and [2].
0.1 ≦ Wb / Wa ≦ 1.6 [1]
Wc / (Wa + Wb + Wc) ≦ 0.5 [2]
[Wherein, Wa, Wb and Wc represent the contents (mass) of the respective components of the block copolymer (a), the acrylic resin (b) and the softener (c) constituting the polymer composition. ]
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