WO2019026891A1 - 熱可塑性樹脂組成物、ホットメルト接着剤、自動車部材、及び衛生材料部材 - Google Patents
熱可塑性樹脂組成物、ホットメルト接着剤、自動車部材、及び衛生材料部材 Download PDFInfo
- Publication number
- WO2019026891A1 WO2019026891A1 PCT/JP2018/028611 JP2018028611W WO2019026891A1 WO 2019026891 A1 WO2019026891 A1 WO 2019026891A1 JP 2018028611 W JP2018028611 W JP 2018028611W WO 2019026891 A1 WO2019026891 A1 WO 2019026891A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- thermoplastic resin
- block copolymer
- polymer
- hydrogenated block
- Prior art date
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 120
- 239000011342 resin composition Substances 0.000 title claims abstract description 119
- 239000004831 Hot glue Substances 0.000 title claims description 31
- 239000000463 material Substances 0.000 title claims description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 174
- 229920001400 block copolymer Polymers 0.000 claims abstract description 144
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 48
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 230000004927 fusion Effects 0.000 claims abstract description 13
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 71
- 229920000098 polyolefin Polymers 0.000 claims description 69
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 68
- 238000005259 measurement Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- 229920013639 polyalphaolefin Polymers 0.000 claims description 12
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 44
- 238000000034 method Methods 0.000 description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 32
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 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 12
- 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 12
- 229920001577 copolymer Polymers 0.000 description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 12
- 229920000428 triblock copolymer Polymers 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000012943 hotmelt Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920013640 amorphous poly alpha olefin Polymers 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 4
- 229920000359 diblock copolymer Polymers 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- 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
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical group COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical group CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- GCQZRSVHYPEACN-UHFFFAOYSA-N 2-methylideneoxolane Chemical compound C=C1CCCO1 GCQZRSVHYPEACN-UHFFFAOYSA-N 0.000 description 2
- OQEBBZSWEGYTPG-UHFFFAOYSA-N 3-aminobutanoic acid Chemical compound CC(N)CC(O)=O OQEBBZSWEGYTPG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical class CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- QWCKQJZIFLGMSD-UHFFFAOYSA-N alpha-aminobutyric acid Chemical compound CCC(N)C(O)=O QWCKQJZIFLGMSD-UHFFFAOYSA-N 0.000 description 2
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229930006722 beta-pinene Natural products 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- TXFONIGDXLPYOB-UHFFFAOYSA-N 1,3,5-trichloro-2-ethenylbenzene Chemical group ClC1=CC(Cl)=C(C=C)C(Cl)=C1 TXFONIGDXLPYOB-UHFFFAOYSA-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
- WRBCPVXVVDKWJW-UHFFFAOYSA-N 1,3-dichloro-2-(1-chloroethenyl)benzene Chemical group ClC(=C)C1=C(Cl)C=CC=C1Cl WRBCPVXVVDKWJW-UHFFFAOYSA-N 0.000 description 1
- RPTSDKNERZWQIA-UHFFFAOYSA-N 1,3-dichloro-2-(2-chloroethenyl)benzene Chemical group ClC=CC1=C(Cl)C=CC=C1Cl RPTSDKNERZWQIA-UHFFFAOYSA-N 0.000 description 1
- YJCVRMIJBXTMNR-UHFFFAOYSA-N 1,3-dichloro-2-ethenylbenzene Chemical compound ClC1=CC=CC(Cl)=C1C=C YJCVRMIJBXTMNR-UHFFFAOYSA-N 0.000 description 1
- MYXGLEOAVQTFAK-UHFFFAOYSA-N 1,3-dimethyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=C(C)C=CC=C1C MYXGLEOAVQTFAK-UHFFFAOYSA-N 0.000 description 1
- QICPIQJTGZXQQJ-UHFFFAOYSA-N 1,3-dimethyl-2-prop-1-enylbenzene Chemical compound CC=CC1=C(C)C=CC=C1C QICPIQJTGZXQQJ-UHFFFAOYSA-N 0.000 description 1
- IZXSWEQCVDBMOL-UHFFFAOYSA-N 1-(bromomethyl)-2-ethenylbenzene Chemical group BrCC1=CC=CC=C1C=C IZXSWEQCVDBMOL-UHFFFAOYSA-N 0.000 description 1
- WFCJSNUJPWSKNE-UHFFFAOYSA-N 1-(bromomethyl)-3-ethenylbenzene Chemical group BrCC1=CC=CC(C=C)=C1 WFCJSNUJPWSKNE-UHFFFAOYSA-N 0.000 description 1
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical group BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical group ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical group ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical group ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- KAWKOONCEXAZMZ-UHFFFAOYSA-N 1-chloro-2-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=CC=CC=C1Cl KAWKOONCEXAZMZ-UHFFFAOYSA-N 0.000 description 1
- XKPCIGDIOQKJEB-UHFFFAOYSA-N 1-chloro-2-(2-chloroethenyl)benzene Chemical compound ClC=CC1=CC=CC=C1Cl XKPCIGDIOQKJEB-UHFFFAOYSA-N 0.000 description 1
- VCRHUWNATPGGTO-UHFFFAOYSA-N 1-chloro-3-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=CC=CC(Cl)=C1 VCRHUWNATPGGTO-UHFFFAOYSA-N 0.000 description 1
- XJCQFMIXTZNXMF-UHFFFAOYSA-N 1-chloro-3-(2-chloroethenyl)benzene Chemical compound ClC=CC1=CC=CC(Cl)=C1 XJCQFMIXTZNXMF-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- VLEPDKZOJYVEMK-UHFFFAOYSA-N 1-chloro-4-(1-chloroethenyl)benzene Chemical compound ClC(=C)C1=CC=C(Cl)C=C1 VLEPDKZOJYVEMK-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical group COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-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
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 1
- CZUZGUCIXCUKSC-UHFFFAOYSA-N 1-methyl-2-prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1C CZUZGUCIXCUKSC-UHFFFAOYSA-N 0.000 description 1
- XXTQHVKTTBLFRI-UHFFFAOYSA-N 1-methyl-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C)=C1 XXTQHVKTTBLFRI-UHFFFAOYSA-N 0.000 description 1
- UUOANSACYXAAOU-UHFFFAOYSA-N 1-methyl-3-prop-1-enylbenzene Chemical compound CC=CC1=CC=CC(C)=C1 UUOANSACYXAAOU-UHFFFAOYSA-N 0.000 description 1
- FAMJUFMHYAFYNU-UHFFFAOYSA-N 1-methyl-4-(propan-2-yl)cyclohex-1-ene Chemical compound CC(C)C1CCC(C)=CC1 FAMJUFMHYAFYNU-UHFFFAOYSA-N 0.000 description 1
- LSMSSYSRCUNIFX-UHFFFAOYSA-N 1-methyl-4-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(C)C=C1 LSMSSYSRCUNIFX-UHFFFAOYSA-N 0.000 description 1
- LUECERFWADIZPD-UHFFFAOYSA-N 1-tert-butyl-2-ethenylbenzene Chemical group CC(C)(C)C1=CC=CC=C1C=C LUECERFWADIZPD-UHFFFAOYSA-N 0.000 description 1
- SMSKIVCCLIQXFD-UHFFFAOYSA-N 1-tert-butyl-3-ethenylbenzene Chemical group CC(C)(C)C1=CC=CC(C=C)=C1 SMSKIVCCLIQXFD-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical group 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
- PKUQHKARGJFSRA-UHFFFAOYSA-N 2,4-dichloro-1-(1-chloroethenyl)benzene Chemical group ClC(=C)C1=CC=C(Cl)C=C1Cl PKUQHKARGJFSRA-UHFFFAOYSA-N 0.000 description 1
- XWEMGFGRWJFXST-UHFFFAOYSA-N 2,4-dichloro-1-(2-chloroethenyl)benzene Chemical group ClC=CC1=CC=C(Cl)C=C1Cl XWEMGFGRWJFXST-UHFFFAOYSA-N 0.000 description 1
- QIDIFDCCFHVZOR-UHFFFAOYSA-N 2,4-dimethyl-1-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(C)C=C1C QIDIFDCCFHVZOR-UHFFFAOYSA-N 0.000 description 1
- BOMOHWDVLAJWEI-UHFFFAOYSA-N 2,4-dimethyl-1-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(C)C=C1C BOMOHWDVLAJWEI-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-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
- OWRKXOZFTROHSH-UHFFFAOYSA-N 2-ethenyl-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1C=C OWRKXOZFTROHSH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-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
- VUBQYTCIOHLJGQ-UHFFFAOYSA-N acetylene;4-tert-butylphenol Chemical group C#C.CC(C)(C)C1=CC=C(O)C=C1 VUBQYTCIOHLJGQ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical group COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000001259 polydextrose Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 150000003440 styrenes Chemical group 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920003046 tetrablock copolymer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/225—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
- A61L15/585—Mixtures of macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
Definitions
- the present invention relates to a thermoplastic resin composition, a hot melt adhesive, an automobile member, and a sanitary material member.
- EVA ethylene-vinyl acetate copolymer
- EEA ethylene-ethyl acrylate copolymer
- EAA ethylene-acrylic acid copolymer
- EMMA EMMA (ethylene-acrylic acid copolymer)
- Ethylene-based copolymers such as ethylene-methyl methacrylate copolymer
- olefin-based resins such as polyethylene, polypropylene, APAO (amorphous poly ⁇ -olefin), POE (polyolefin elastomer), olefin block copolymer (OBC), etc.
- polyester resin polyamide resin, urethane resin, etc.
- urethane resin etc.
- a pressure-sensitive adhesive composition using the above-mentioned base polymer for example, a non-pressure-sensitive adhesive composition comprising a blend of poly ⁇ -olefin, a low viscosity styrenic block copolymer and a tackifying resin, and a specific non-crystalline composition
- a specific non-crystalline composition There have been proposed pressure-sensitive adhesive compositions containing an ⁇ -olefin copolymer and a specific styrenic block copolymer (see Patent Documents 1 to 3).
- hot melt adhesive has the property (hot melt adhesion) that solidifies and adheres by cooling after pressure bonding in a heated and molten state (solvent-free, high safety, instant bonding and high-speed bonding possible) As such, it is used in a wide range of fields such as paper processing, woodworking, sanitary materials and electronics.
- the hot melt adhesive to be used is required to have elasticity.
- the stretchability is not sufficient.
- the present invention has been made in view of such circumstances, and provides a thermoplastic resin composition excellent in stretchability, having high adhesive strength and transparency, a hot melt adhesive, an automobile member, and a sanitary material member.
- the purpose is to
- thermoplastic resin composition comprising an olefin polymer (a) and a hydrogenated block copolymer (b), wherein the heating rate in differential scanning calorimetry of the olefin polymer (a) is 10
- the content of A) is 1 to 60% by mass, and the proportion of the vinyl bond of the polymer block (B) is 50 to 95% by mol, and the hydrogenated block copolymer in the thermoplastic resin composition is United ( Content of
- ⁇ H heat of crystal fusion
- the olefin polymer (a) is at least one olefin polymer selected from non-crystalline or low crystalline poly ⁇ -olefin and polyolefin elastomers Thermoplastic resin composition.
- thermoplastic resin composition according to any one of the above [1] to [3], wherein the olefin polymer (a) is an amorphous or low crystalline poly ⁇ -olefin.
- olefin polymer (a) is an amorphous or low crystalline poly ⁇ -olefin.
- weight average molecular weight of the hydrogenated block copolymer (b) is 30,000 to 500,000.
- molecular weight distribution of the hydrogenated block copolymer (b) is 1.0 to 1.5.
- the above-mentioned hydrogenated block copolymer (b) has a melt flow rate of 0.1 to 90 g / 10 min measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K 7210-1: 2014.
- the polymer block (B) of the hydrogenated block copolymer (b) is a polymer block mainly composed of structural units derived from a mixture of isoprene and butadiene, and the mixing ratio of isoprene and butadiene
- the thermoplastic resin composition according to any one of the above [1] to [8], wherein [isoprene / butadiene] (molar ratio) is 10/90 to 90/10.
- the number of maximum peaks of loss elastic modulus (G ′ ′) in the temperature range of ⁇ 70 to 0 ° C. is one, the above [1] ]
- the thermoplastic resin composition in any one of-[9].
- thermoplastic resin composition according to any one of the above [1] to [10], further comprising a tackifier.
- a hot melt adhesive comprising the thermoplastic resin composition of any one of the above [1] to [11].
- An automobile member comprising the hot melt adhesive according to the above [12].
- a hygienic material member comprising the hot melt adhesive according to the above [12].
- thermoplastic resin composition which is excellent in stretchability and has high adhesion and transparency, a hot melt adhesive, an automobile member, and a sanitary material member.
- 5 is a dynamic viscoelasticity measurement chart of the thermoplastic resin composition sheet of Example 1. It is a dynamic-viscoelasticity measurement chart of the thermoplastic resin composition sheet of comparative example 2. 5 is a SEM photograph of the surface of the thermoplastic resin composition sheet of Example 1. FIG. It is a SEM photograph of the thermoplastic resin composition sheet surface of comparative example 2. It is a SPM observation result of the thermoplastic resin composition sheet
- the thermoplastic resin composition of the present invention is a thermoplastic resin composition containing an olefin polymer (a) and a hydrogenated block copolymer (b),
- the heat of crystal fusion ( ⁇ H) measured at a heating rate of 10 ° C./min in differential scanning calorimetry is less than 80 J / g
- the hydrogenated block copolymer (b) is a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a polymer block mainly composed of a structural unit derived from a conjugated diene compound (B)
- the proportion of the vinyl bond content of is 50 to 95 mol%
- the content of the hydrogenated block copolymer (b) is 50 to 95 mol%
- thermoplastic resin composition of the present invention comprises the olefin polymer (a) and the water by containing the hydrogenated block copolymer (b) in a specific ratio together with the olefin polymer (a).
- the polymer block (B) of the block copolymer (b) is compatible at the molecular level.
- the olefin polymer (a) and the polymer block (B) of the hydrogenated block copolymer (b) are compatible at the molecular level is, for example, the olefin polymer (a) and A sheet having a thickness of 1 mm obtained by heat-pressing a thermoplastic resin composition comprising a hydrogenated block copolymer (b) is immersed in tetrahydrofuran for 5 minutes for etching, and then the sheet surface is subjected to a scanning electron microscope ( It can confirm by observing by SEM).
- the surface of the thermoplastic resin composition sheet becomes a uniform surface with few irregularities even after the etching treatment.
- the hydrogenated block copolymer (b) is dissolved and removed by the etching treatment, so that the long side is 10 ⁇ m or more on the surface of the thermoplastic resin composition sheet surface.
- An indentation of the height occurs.
- seat surface of Example 1 is shown in FIG. When a 200 ⁇ m ⁇ 150 ⁇ m area on the surface of the thermoplastic resin composition sheet is observed, no concave portion having a long side of 10 ⁇ m or more is observed, and it can be seen that the sheet surface is uniform.
- seat surface of the comparative example 2 is shown in FIG. When an area of 200 ⁇ m ⁇ 150 ⁇ m on the surface of the thermoplastic resin composition sheet was observed, a large number of concave portions having a long side of 10 ⁇ m or more were observed.
- the size of the long side of the recess is less than 10 ⁇ m. .
- the size of the long side of the recess is preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 1 ⁇ m or less, because the adhesive strength, stretchability and haze of the thermoplastic resin composition become good.
- the lower limit of the size of the long side of the recess is not particularly limited, but may be 0.1 ⁇ m or more.
- thermoplastic resin composition sheet by the etching process is not substantially changed, and no concave portion is observed in the SEM photograph, and in this state, the molecular level compatibility is the best. .
- the thermoplastic resin composition of the present invention When the thermoplastic resin composition of the present invention is used as, for example, an adhesive, generally, the thermoplastic resin composition may be blended with a compound such as a tackifier, oil, or wax, Even in such a case, in the present invention, the thermoplastic resin composition and the compound may not necessarily be compatible at the molecular level, and the olefin polymer (a) and the above-mentioned hydrogenation may be used. If the polymer block (B) of the block copolymer (b) is compatible at the molecular level, good physical properties can be imparted even after the compounding.
- a compound such as a tackifier, oil, or wax
- the compound which is not compatible at the molecular level is observed as a recess having a size of 10 ⁇ m or more in a long side
- good physical properties can be obtained if the olefin polymer (a) and the polymer block (B) of the hydrogenated block copolymer (b) are compatible at the molecular level. Is obtained.
- the compound is not included, This can be confirmed by SEM observation of a thermoplastic resin composition consisting of only the olefin polymer (a) and the hydrogenated block copolymer (b).
- the olefin polymer (a) and the hydrogenated block copolymer (b) are compatible at the molecular level with the olefin polymer (a) and the hydrogenated polymer (a). It may be observable also by a scanning probe microscope (SPM) of a thermoplastic resin composition comprising the block copolymer (b).
- SPM scanning probe microscope
- the SPM observation result of the thermoplastic resin composition sheet of Example 1 is shown in FIG. 5, and the SPM observation result of the thermoplastic resin composition sheet of Comparative Example 2 is shown in FIG.
- FIG. 6 which is not compatible at the molecular level, the islands of the olefin polymer (a) and the islands of the hydrogenated block copolymer (b) are separately distinguished and observed, while they are compatible at the molecular level.
- FIG. 5 where it is seen, the whole is observed as a uniform state.
- the compatibility of the olefin polymer (a) with the polymer block (B) of the hydrogenated block copolymer (b) at the molecular level allows the dynamics of the thermoplastic resin composition of the present invention to be obtained.
- the number of maximum peaks of loss elastic modulus (G ′ ′) in the temperature range of ⁇ 70 to 0 ° C. tends to be 1. This corresponds to the olefin polymer (a) and the olefin polymer (a).
- the compatibility of the hydrogenated block copolymer (b) with the polymer block (B) at the molecular level allows the olefin to be observed in the temperature range of -70 to 0 ° C by temperature dispersion measurement of dynamic viscoelasticity.
- olefin polymer (a) and the polymer block (B) of the hydrogenated block copolymer (b) on a molecular level
- the olefin polymer (a) and the hydrogenated block Type of copolymer (b) adjustment of amount used, adjustment of vinyl bond ratio of polymer block (B), viscosity of olefin polymer (a) and viscosity of hydrogenated block copolymer (b) Regulation and the like.
- control of the proportion of the vinyl bond content is particularly effective for compatibilization at the molecular level.
- the polymer block (B) is a polymer block mainly composed of structural units derived from a mixture of isoprene and butadiene, and the mixing ratio of isoprene to butadiene [isoprene / butadiene] (molar ratio) is 10 / 90 to 90/10, the ratio of the vinyl bond content of the polymer block (B) is 50 to 95 mol%, and the hydrogenation ratio of the polymer block (B) is 85 mol% or more
- the compatibility between the olefin polymer (a) and the polymer block (B) is enhanced, and the polymer block (B) of the olefin polymer (a) and the hydrogenated block copolymer (b) It can be more easily compatible at the molecular level.
- the mixing ratio [isoprene / butadiene] (molar ratio) of the isoprene and butadiene and the ratio of the vinyl bond of the polymer block (B) determine the solubility parameter (SP value) of the polymer block (B) It can be adjusted to the indicator.
- SP value of the polymer block (B) is preferably 17.25MPa 1/2 or less, 17.15MPa 1/2 or less Is more preferable, 17.13 MPa 1/2 or less is further preferable, and 17.11 MPa 1/2 or less is particularly preferable.
- SP value of the polymer block (B) may also be 16.00MPa 1/2 or more, may also be 16.40MPa 1/2 or more, even 16.85MPa 1/2 or more It may be 17.00 MPa 1/2 or more.
- the SP value can be calculated by the Hoy method based on the structure of the polymer. The Hoy method is described in detail in “Properties of Polymers (4th Edition): DW van Krevelen, Klaas te Nijenhuis; Elsevier Science, 2009". In addition, when the calculation can not be performed by the Hoy method, the solubility parameter can be calculated by an experimental method by determining whether the polymer is dissolved in a known solvent. The experimental method is described in detail in "Polymer handbook (4th Edition): J. Brandrup, EH Immergut, EA Grulke (Eds.); Wiley, New York, 1999”.
- the olefin polymer (a) used in the present invention has a heat of crystal fusion ( ⁇ H) of less than 80 J / g as measured at a heating rate of 10 ° C./minute in differential scanning calorimetry.
- ⁇ H heat of crystal fusion
- the ⁇ H of the olefin polymer (a) may be appropriately set in the range of less than 80 J / g from the viewpoints of stretchability, heat resistance, etc.
- ⁇ H is preferably 1 J / g.
- ⁇ H is preferably 5 to 70 J / g, more preferably 10 to 60 J / g, and still more preferably 15 to 50 J / g.
- the heat of crystal fusion ( ⁇ H) is obtained by heating the sample from 30 ° C. to 180 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC) (heating step 1) and melting from 180 ° C. Analysis of the endothermic peak in the heating step 2 which occurs upon cooling to 70 ° C. for crystallization (cooling step) and further heating from ⁇ 70 ° C. to 180 ° C. at a heating rate of 10 ° C./min (heating step 2) It is.
- DSC differential scanning calorimeter
- the olefin-based polymer (a) is not particularly limited as long as the heat of crystal fusion ( ⁇ H) is less than 80 J / g, but adhesion is increased when the thermoplastic resin composition is used as a hot melt adhesive
- at least one olefin polymer selected from non-crystalline or low crystalline poly ⁇ -olefin (amorphous poly ⁇ -olefin) and polyolefin elastomer is preferable, and non-crystalline or low crystalline poly ⁇ More preferred is an olefin.
- noncrystalline or low crystalline poly ⁇ -olefin for example, propylene homopolymer, ethylene-propylene copolymer, propylene-1-butene random copolymer, propylene-ethylene-1-butene random copolymer, etc. Can be mentioned. Among them, propylene homopolymers and ethylene-propylene copolymers are preferable from the viewpoint of transparency.
- amorphous or low crystalline poly alpha-olefin for example, REXtac RT2115, RT2180, RT2215, RT2280, RT2304, RT2315, RT2535, RT2535, RT2535 made by REXtac RT2730, RT2780, RT2788, RT6825, E101, RT9720; Vestoplast 508, 703, 704, 708, 750, 751, 792, 828, 888, EP X55; Eastoflex E1016 PL-1, P1010, manufactured by EASTAN. P1023, E1060, E1200, D-178, M1058 can be mentioned.
- APAO amorphous poly alpha-olefin
- polyolefin elastomer As a polyolefin elastomer (POE), a polyethylene-type elastomer, a polypropylene-type elastomer, etc. are mentioned, for example.
- the polyethylene-based elastomer refers to an elastomer containing 50% by mass or more of ethylene
- the polypropylene-based elastomer refers to an elastomer containing 50% by mass or more of propylene.
- the use of a polyethylene elastomer is excellent in low temperature characteristics.
- heat resistance it is preferable to use a polypropylene-based elastomer.
- modified polyolefin elastomers obtained by copolymerizing copolymerizable monomers such as ⁇ -olefin, vinyl acetate, and alkyl (meth) acrylate can be used.
- Commercial products of polyolefin elastomer (POE) include, for example, ENGAGE 8000 series and 7000 series manufactured by Dow Chemical Company; AFFINITY GA 1900, 1950, 1875, 1000R manufactured by Dow Chemical Company; Vistamaxx 8380, 8780 manufactured by ExxonMobil 8880, 6102, 6202, 6502, 3000, 3020, 3588 FL, 3980 FL; TAFMER DF series, A series, P series, XM series manufactured by Mitsui Chemicals, Inc.
- the content of the olefin polymer (a) is preferably 5 to 99 parts by mass, more preferably 10 to 90 parts by mass, still more preferably 20 to 80 parts by mass, based on the total amount of the thermoplastic resin composition. Still more preferably, it is 25 to 75 parts by mass.
- the content of the olefin polymer (a) is preferably 70 to 99 parts by mass, more preferably 100 parts by mass in total of the olefin polymer (a) and the hydrogenated block copolymer (b). Is 75 to 98 parts by mass, more preferably 75 to 95 parts by mass, still more preferably 78 to 95 parts by mass, and particularly preferably 80 to 95 parts by mass.
- the thermoplastic resin composition is excellent in hot melt coatability when used as a hot melt adhesive.
- the hydrogenated block copolymer (b) used in the present invention is a polymer block mainly composed of a structural unit derived from an aromatic vinyl compound and a polymer block mainly composed of a structural unit derived from a conjugated diene compound It is a hydrogenated substance of the block copolymer consisting of (B).
- the polymer block (A) is mainly composed of a structural unit derived from an aromatic vinyl compound (hereinafter sometimes abbreviated as “aromatic vinyl compound unit”).
- aromatic vinyl compound unit a structural unit derived from an aromatic vinyl compound (hereinafter sometimes abbreviated as “aromatic vinyl compound unit”).
- the term "mainly” as used herein refers to containing more than 50% by mass of aromatic vinyl compound units based on the total mass of the polymer block (A).
- the content of the aromatic vinyl compound unit in the polymer block (A) is a polymer block (A) from the viewpoint that the stretchability of the thermoplastic resin composition becomes high and the haze is reduced to be excellent in transparency. 70 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, still more preferably 95 mass% or more, substantially 100 mass%, based on the total mass of May be
- aromatic vinyl compound examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, ⁇ -methyl-o-methylstyrene, ⁇ -methyl-m-methylstyrene, ⁇ -methyl-p-methylstyrene, ⁇ -methyl-o-methylstyrene, ⁇ -methyl-m-methylstyrene, ⁇ -methyl-p -Methylstyrene, 2,4,6-trimethylstyrene, ⁇ -methyl-2,6-dimethylstyrene, ⁇ -methyl-2,4-dimethylstyrene, ⁇ -methyl-2,6-dimethylstyrene, ⁇ -methyl- 2,4-Dimethylstyrene
- aromatic vinyl compounds may be used alone or in combination of two or more.
- styrene, ⁇ -methylstyrene, p-methylstyrene, and a mixture thereof are preferable, and styrene is more preferable, from the viewpoint of production cost and balance of physical properties.
- the polymer block (A) is a structural unit derived from another unsaturated monomer other than the aromatic vinyl compound (hereinafter referred to as “other unsaturated monomer”, as long as the objects and effects of the present invention are not hindered. May be abbreviated as “the unit”) may be contained in a proportion of 50% by mass or less.
- the other unsaturated monomer include isoprene, butadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene, 1,3-cyclopentadiene, and the like.
- Conjugated diene compounds such as 1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene; methacrylic esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; methyl acrylate, acrylic Ethyl esters, acrylic acid esters such as butyl acrylate; at least one selected from the group consisting of methyl vinyl ether, N-vinyl carbazole, isobutylene, ⁇ -pinene, mentenes, dipentene, methylene norbornene, 2-methylene tetrahydrofuran and the like
- the bonding form is not particularly limited, and may be random, tapered or completely alternating.
- the content of the structural unit derived from the other unsaturated monomer in the polymer block (A) is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and further more Preferably it is 0 mass%.
- the block copolymer may have at least one of the polymer block (A).
- the polymer blocks (A) may be the same or different.
- a polymer block is different means a monomer unit constituting a polymer block, a weight average molecular weight, stereoregularity, and a ratio and co It means that at least one of the forms of polymerization (random, tapered, completely alternating) is different.
- the weight average molecular weight (Mw) of the said polymer block (A) which the said block copolymer has does not have a restriction
- the weight average molecular weight of the block (A) is preferably 2,000 to 60,000, more preferably 4,000 to 50,000.
- the block copolymer exhibits the stretchability of the thermoplastic resin composition by having at least one polymer block (A) having a weight average molecular weight within the above range.
- weight average molecular weights are the weight average molecular weights of standard polystyrene conversion calculated
- the weight average molecular weight of each polymer block (A) which a block copolymer has can be calculated
- the weight average molecular weight of the first polymer block A1 is the polymer block It can be determined by GPC measurement of the liquid sampled when the polymerization of A1 is completed.
- the weight average molecular weight of the polymer block B is determined by GPC measurement of the liquid sampled when the polymerization of the polymer block B is completed to determine the weight average molecular weight of the diblock copolymer having the A1-B structure, and It can obtain
- the weight average molecular weight of the polymer block A2 is obtained by GPC measurement of the liquid sampled when the polymerization of the polymer block A2 is completed to determine the weight average molecular weight of the triblock copolymer having the A1-B-A2 structure.
- the value can be determined by subtracting the weight average molecular weight of the diblock copolymer having the A1-B structure determined by the above method from the value.
- a polymer in the triblock copolymer confirmed by the weight average molecular weight of the triblock copolymer and 1 H-NMR measurement
- the weight average molecular weight of the total of the polymer block (A) is calculated from the total content of the block (A), and then the polymer block A1 identified as a trace amount of deactivated component in the GPC measurement of the triblock copolymer
- the weight average molecular weight of the polymer block A2 can also be determined by calculating the weight average molecular weight and subtracting this from the total weight average molecular weight of the polymer blocks (A) determined by the above method.
- the content of the polymer block (A) in the block copolymer is 1 to 60% by mass.
- the content of the polymer block (A) is less than 1% by mass, the cohesion of the thermoplastic resin composition is reduced, the restorability after deformation is reduced, or the thermoplastic resin composition is hot-melted. Adhesiveness may be reduced when used as an adhesive. On the other hand, if it exceeds 60% by mass, the stretchability of the thermoplastic resin composition is reduced, and when using the thermoplastic resin composition as a hot melt adhesive, the adhesion to the adherend may be reduced.
- the content of the polymer block (A) is preferably 2 to 40% by mass, more preferably 3 to 20% by mass, still more preferably 4 to 15% by mass, still more preferably 5 to 9 % By mass, particularly preferably 6 to 9% by mass.
- the content of the polymer block (A) is preferably 3 to 15% by mass, more preferably 3 to 9% by mass, and still more preferably 3 It is ⁇ 5% by mass.
- the content of the polymer block (A) in the block copolymer is a value determined by 1 H-NMR measurement, and more specifically, it is a value determined according to the method described in the examples.
- the polymer block (B) is mainly composed of a structural unit derived from a conjugated diene compound (hereinafter sometimes abbreviated as “conjugated diene compound unit”).
- conjugated diene compound unit a conjugated diene compound derived from a conjugated diene compound.
- the term "mainly” as used herein means that the conjugated diene compound unit is contained in an amount of more than 50% by mass based on the total mass of the polymer block (B).
- the content of the conjugated diene compound unit in the polymer block (B) is such that the compatibility between the olefin polymer (a) which is a component of the thermoplastic resin composition and the polymer block (B) is enhanced, From the viewpoint of improving the stretchability and the adhesive strength when the plastic resin composition is used as a hot melt adhesive, it is preferably 70% by mass or more, more preferably 80% by mass, based on the total mass of the polymer block (B). % Or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and may be substantially 100% by mass.
- conjugated diene compound examples include isoprene, butadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene, 1,3-cyclopentadiene, and 1,3-cyclohexadiene. And 1,3-cycloheptadiene, 1,3-cyclooctadiene and the like.
- isoprene, butadiene, isoprene and butadiene from the viewpoint of compatibilizing the olefin polymer (a) and the polymer block (B) of the hydrogenated block copolymer (b) at the molecular level to improve the stretchability.
- mixtures of isoprene and butadiene are more preferable. Further, from the viewpoint of improving the transparency, a mixture of isoprene and butadiene is preferable.
- the mixing ratio [isoprene / butadiene] (molar ratio) is not particularly limited, but preferably 10/90 to 90/10, more preferably 30/70 to 80/20, More preferably, it is 40/60 to 70/30, still more preferably 45/55 to 60/40, and particularly preferably 45/55 to 50/50.
- the bonding form thereof can be random, tapered, completely alternating, or a combination of two or more thereof.
- the bonding form of isoprene and butadiene is 1,2 in the case of butadiene.
- the bond may be a 1,4-bond, and in the case of isoprene, a 1,2-bond, a 3,4-bond or a 1,4-bond.
- the proportion of the sum of the contents of 3,4-linked units and 1,2-linked units in the polymer block (B) is 50 to 95 mol%.
- the proportion of the vinyl bond is less than 50 mol%, the compatibility between the olefin polymer (a) and the polymer block (B) is low, and when the thermoplastic resin composition is used as a hot melt adhesive It is not possible to improve sex and adhesion. This is because the SP value (dissolution parameter) of the polymer block (B) and the olefin polymer (a) becomes close to each other by setting the ratio of the vinyl bond amount to 50 mol% or more, which contributes to the compatibility. It is guessed that. In addition, when the proportion of the vinyl bond content exceeds 95 mol%, the glass transition temperature of the polymer block (B) becomes high, and the flexibility at room temperature decreases.
- the proportion of the vinyl bond amount is preferably 55 to 90 mol%, more preferably 56 to 80 mol%, and still more preferably 58 to 70 mol%.
- the ratio of the amount of vinyl bond is a value calculated by 1 H-NMR measurement according to the method described in the examples.
- the content of the polymer block (B) in the block copolymer is preferably 40 to 99% by mass.
- the content of the polymer block (B) exceeds 99% by mass, the cohesion of the thermoplastic resin composition is reduced, the restorability after deformation is reduced, or the thermoplastic resin composition is hot-melt adhered. Adhesion may decrease when used as an agent.
- the content is less than 40% by mass, the stretchability of the thermoplastic resin composition may be reduced, and the adhesiveness to the adherend may be reduced when used as a thermoplastic resin composition hot melt adhesive.
- the content of the polymer block (B) is preferably 60 to 98% by mass, more preferably 80 to 97% by mass, still more preferably 85 to 96% by mass, still more preferably 91 to 95 % By mass, particularly preferably 91 to 94% by mass. Further, from the viewpoint of improving the transparency of the thermoplastic resin composition, the content of the polymer block (B) is preferably 85 to 97% by mass, more preferably 91 to 97% by mass, and still more preferably 95%. It is ⁇ 97 mass%.
- the content of the polymer block (B) in the block copolymer is a value determined by 1 H-NMR measurement, and more specifically, it is a value determined according to the method described in the examples.
- the polymer block (B) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound, as long as the object and effects of the present invention are not hindered.
- the content of structural units derived from other polymerizable monomers other than the conjugated diene compound is preferably 50% by mass or less, more preferably 40% by mass or less, and further Preferably it is 30 mass% or less, more preferably 20 mass% or less.
- the lower limit of the content of structural units derived from other polymerizable monomers other than conjugated diene compounds is not particularly limited, but it may be 0 mol% or 5 mol%. And 10 mol%.
- Examples of such other polymerizable monomers include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyl Aromatic vinyl compounds such as naphthalene and vinyl anthracene; methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; methyl vinyl ether, N- Preferred is at least one compound selected from the group consisting of vinylcarbazole, isobutylene, ⁇ -pinene, menthene, dipentene, methylene norbornene, 2-methylene tetrahydrofuran and the like.
- the polymer block (B) contains a structural unit derived from another polymerizable monomer other than a conjugated diene compound, as a specific combination thereof, preferably isoprene and styrene, butadiene and styrene, It is isoprene and butadiene and styrene, more preferably isoprene and styrene, isoprene and butadiene and styrene, and still more preferably isoprene and styrene.
- the bonding mode is not particularly limited, and may be random, tapered or completely alternating. Good, but random is preferred.
- the block copolymer may have at least one of the polymer blocks (B).
- the polymer blocks (B) may be the same or different.
- the type of bonding of the block copolymer is not limited, and may be linear, branched, radial or two of them. Any of the combination modes combined above may be used.
- the bonding form of the polymer block (A) and the polymer block (B) is preferably linear, and as an example, the polymer block (A) is A, and the polymer block (B) is A diblock copolymer represented by A-B, a triblock copolymer represented by A-B-A or B-A-B when represented by B, A-B-A-B, A-B A tetrablock copolymer represented by -BA, BABA or AABA, shown by AABA or BABA.
- pentablock copolymers, (AB) nX type copolymer (X represents a coupling agent residue, n represents an integer of 3 or more), and the like.
- a linear triblock copolymer or a diblock copolymer is preferable, and an ABA type triblock copolymer is preferably used from the viewpoints of flexibility, easiness of production, and the like.
- the entire bonded polymer block is treated as one polymer block.
- the said hydrogenated block copolymer (b) is a hydrogenated substance of the said block copolymer. From the viewpoint of increasing the compatibility between the olefin polymer (a) and the polymer block (B) of the hydrogenated block copolymer (b), 50 moles of the carbon-carbon double bond of the polymer block (B) % Or more is preferably hydrogenated (hereinafter, may be abbreviated as hydrogenation), more preferably 70 mol% or more is hydrogenated, and 80 mol% or more is hydrogenated It is more preferable that 85 mol% or more be hydrogenated and still more preferable that 90 mol% or more be hydrogenated. In addition, this value may be called a hydrogenation rate (hydrogenation rate).
- the upper limit value of the hydrogenation rate is not particularly limited, but the upper limit value may be 99 mol% or 98 mol%.
- the above-mentioned hydrogenation rate is a value determined by 1 H-NMR measurement after hydrogenation of the content of carbon-carbon double bond in the structural unit derived from the conjugated diene compound in the polymer block (B). More specifically, it is a value measured according to the method described in the examples.
- the weight average molecular weight (Mw) determined in terms of standard polystyrene equivalent by gel permeation chromatography of the above-mentioned hydrogenated block copolymer (b) is preferably 30,000 to 500,000, more preferably 50,000 to 400, 000, more preferably 80,000 to 300,000, still more preferably 100,000 to 200,000, and 150,000 to 200,000 is particularly preferable.
- the stretchability of the thermoplastic resin composition becomes high, and if it is 500,000 or less, the olefin polymer (a) and The compatibility of the hydrogenated block copolymer (b) with the polymer block (B) is high, and when the thermoplastic resin composition is used as a hot melt adhesive, the hot melt coatability is excellent.
- the molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (b) becomes high in heat resistance, and bleeds to the adherend. From the viewpoint of reducing the out (smearing out), it is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, still more preferably 1.0 to 1.2, and particularly preferably It is 1.0 to 1.1, and most preferably 1.0 to 1.05.
- the molecular weight distribution (Mw / Mn) is a value calculated from a polystyrene-equivalent weight average molecular weight Mw and a number average molecular weight Mn measured by gel permeation chromatography (GPC).
- the melt flow rate (MFR) of the hydrogenated block copolymer (b) measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K 7210-1: 2014 is an olefin polymer (a)
- the compatibility of the polymer block (B) with the polymer block (B) of the hydrogenated block copolymer (b) is high, and when the thermoplastic resin composition is used as a hot melt adhesive, from the viewpoint of excellent hot melt coatability, It is preferably 0.1 to 90 g / 10 min, more preferably 1 to 80 g / 10 min, still more preferably 2 to 60 g / 10 min, still more preferably 5 to 40 g / 10 min, particularly preferably 10 to 30 g It is 10 minutes.
- the hydrogenated block copolymer (b) can be produced by a solution polymerization method, an emulsion polymerization method, a solid phase polymerization method, or the like.
- the solution polymerization method is preferable, and for example, known methods such as ion polymerization methods such as anion polymerization and cation polymerization and radical polymerization method can be applied.
- the anionic polymerization method is preferred.
- a block copolymer is obtained by adding an aromatic vinyl compound and a conjugated diene compound in the presence of a solvent, an anionic polymerization initiator, and optionally a Lewis base to obtain a block copolymer, and, if necessary, a cup
- a hydrogenated block copolymer (b) can be obtained by adding and reacting a ring agent and then hydrogenating the block copolymer.
- the content of the hydrogenated block copolymer (b) contained in the thermoplastic resin composition of the present invention is a total of 100 mass of the olefin polymer (a) and the hydrogenated block copolymer (b). 1 to 30 parts by mass with respect to the part.
- the content of the hydrogenated block copolymer (b) is less than 1 part by mass, the stretchability can not be enhanced, and when it exceeds 30 parts by mass, the thermoplastic resin composition is adhered when used as a hot melt adhesive The power is reduced.
- the content of the hydrogenated block copolymer (b) is preferably 2 to 25 parts by mass, more preferably 5 to 25 parts by mass, and still more preferably 5 to 22 parts by mass. And particularly preferably 5 to 20 parts by mass.
- the thermoplastic resin composition of the present invention preferably further contains a tackifier from the viewpoint of enhancing the adhesion.
- tackifiers include coumarone resins such as coumarone and indene resin; p-t-butylphenol acetylene resin, phenol formaldehyde resin, terpene phenol resin, polyterpene resin, phenol resin such as xylene formaldehyde resin, and terpene Resins; petroleum resins such as aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, modified alicyclic petroleum resins, etc .; pentaerythritol esters of rosin and glycerol esters of rosin Etc., rosin ester represented by rosin, hydrogenated rosin, methyl ester of hydrogenated rosin, pentaerythritol ester of polymerized rosin, hydrogenated rosin ester, high melting point este
- the softening point of the tackifier is preferably 70 to 160 ° C., more preferably 80 to 140 ° C., and still more preferably 85 to 120 ° C.
- the softening point of the tackifier is 70 ° C. or higher, the heat resistance becomes high when the thermoplastic resin composition is used as a hot melt adhesive, and bleeding out to the adherend (bleeding out) occurs. If the temperature is 160 ° C. or less, the hot melt coatability and the processability tend to be good.
- the compounding amount thereof is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, with respect to the total amount of the thermoplastic resin composition. Preferably, it is 10 to 30 parts by mass.
- thermoplastic resin composition of the present invention may further contain, if necessary, a plasticizer such as paraffinic oil, a wax, a coloring agent, a flame retardant, an ultraviolet light absorber, an antioxidant, as long as the object of the present invention is not impaired.
- a plasticizer such as paraffinic oil, a wax, a coloring agent, a flame retardant, an ultraviolet light absorber, an antioxidant, as long as the object of the present invention is not impaired.
- Various additives such as hydrolysis resistance improvers, fungicides, antibacterial agents, stabilizers, etc .; various fibers such as glass fibers, polyester fibers; fillers such as talc, silica, wood powder etc. It may be
- thermoplastic resin composition of this invention can prepare using a well-known means.
- a blender such as a Henschel mixer, V blender, ribbon blender, tumbler blender, conical blender, etc.
- Manufacture by mixing, or thereafter melt-kneading or melt-mixing at 80 to 250 ° C. using a kneader such as a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a roll, or a stirring mixer.
- thermoplastic resin composition of the present invention can be prepared.
- the respective components are dissolved in a solvent in which the respective components [at least an olefin polymer (a) and a hydrogenated block copolymer (b)] are soluble and mixed, and the solvent is removed to remove the solvent.
- a solvent in which the respective components [at least an olefin polymer (a) and a hydrogenated block copolymer (b)] are soluble and mixed, and the solvent is removed to remove the solvent.
- thermoplastic resin composition Physical properties of thermoplastic resin composition
- a mixture of a tackifier, oil, wax and the like is blended with a thermoplastic resin composition according to the purpose of the user, and the physical properties are adjusted appropriately and used.
- the thermoplastic resin composition of the present invention good physical properties possessed by the thermoplastic resin composition are reflected even if a compound is blended, and physical properties after compounding of the compound are also favorable.
- the glass transition temperature (Tg) of the thermoplastic resin composition of the present invention is preferably -15 to -50.degree. C., more preferably -20 to -40.degree.
- Tg glass transition temperature
- a glass transition temperature (Tg) can be measured by the method as described in an Example.
- the haze of the thermoplastic resin composition of the present invention is preferably 80% or less, more preferably 60% or less, still more preferably 30% or less, still more preferably 27% or less, particularly preferably 25 from the viewpoint of transparency. % Or less.
- the haze can be measured by a method in accordance with JIS K7136: 2000.
- the thermoplastic resin composition of the present invention preferably has an adhesive strength of 25 N / 25 mm or more, more preferably 30 N / 25 mm or more, in which the peel strength is measured by a T-type peel test according to JIS L1086: 2013. More preferably, it is 40 N / 25 mm or more.
- the hot melt adhesive of the present invention comprises the above-mentioned thermoplastic resin composition.
- the hot melt adhesive is excellent in stretchability and has high adhesion and transparency.
- the hot melt adhesive of the present invention can be used in various applications. For example, painted outer panels, wheels, mirrors, windows, lights, light covers, decorative films for interiors, decorative films for exteriors, door moldings, ceilings, dashboards, instrument panels, seats, rear trays, seat seats, interior skin members Bonding or sealing of automotive parts such as floor mats, trunk floors, sound absorbing members such as dash silencers, head lamps and tail lamps; bonding applications of sanitary materials such as disposable diapers, sanitary napkins for women, non-woven fabrics, polyethylene films; Packaging materials such as heat-sealable packaging films; Hot melt adhesive sheets for clothing; Applications for bonding or sealing of architectural members such as wallpaper, carpets, tiles, plywood panels, roofing materials such as roofing materials, outer walls, heat insulating materials; Carton case etc.
- ⁇ Applications air conditioning, air purifier pleating applications and frame fixing applications such as air purifiers, surface protection film applications (for example, resin for binder layer in the middle of substrate and adhesive layer, resin for adhesive layer, etc.) surgery Medical devices such as drapes; Food trays; Adhesive and adhesive products such as tapes and labels; Resins for adhesive layers of laminates; Appliances such as liquid crystal displays; Adhesives for bookbinding; Adhesives for woodworking; Asphalt for pavements Modifiers: Non-slip materials of mats such as floor mats and bath mats; Adhesives for packaging such as straw attachments of beverage packs; Heat sealing layers such as heat sealable packaging films etc.
- Olefin-based polymer (a) The olefin polymer described below was used.
- ⁇ Olefin-based polymer (a) -1 Propylene homopolymer (RT 2180, manufactured by REXtac, poly ⁇ -olefin having a heat of crystal fusion ⁇ H of 23.7 J / g)
- Olefin-based polymer (a) -2 ethylene-propylene copolymer (RT 2280, manufactured by REXtac, poly ⁇ -olefin which is a low ethylene copolymer and has a heat of crystal melting ⁇ H of 16.0 J / g)
- Olefin-based polymer (a) -3 ethylene-propylene copolymer (RT 2585, manufactured by REXtac, poly- ⁇ -olefin which is a high ethylene copolymer and has a heat of crystal melting ⁇ H of 6.8 J / g) ⁇ Olefin-based
- Comparative Production Example 3 Production of Comparative Hydrogenated Block Copolymer (x) -3
- the use of N, N, N ′, N′-tetramethylethylenediamine instead of tetrahydrofuran, and the amounts of raw materials used are shown in Table 1
- Comparative hydrogenated block copolymer (x) -3 was produced in the same manner as in Production Example 1 except that it was changed as described in -3.
- the analysis and physical property evaluation of the obtained comparative hydrogenated block copolymer (x) -3 were carried out according to the following method. The results are shown in Table 1-3.
- Peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn) The polystyrene top equivalent peak top molecular weight (Mp) of each copolymer, polymer block (A) and polymer block (B) was determined by gel permeation chromatography (GPC) measurement under the following conditions.
- the molecular weight distribution (Mw / Mn) was calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined as a standard polystyrene equivalent molecular weight by gel permeation chromatography (GPC).
- Ratio of vinyl bond amount of polymer block (B) The block copolymer before hydrogenation is dissolved in CDCl 3 and the apparatus: "ULTRASHIELD 400 PLUS" (manufactured by Bruker) measurement temperature: 50 The 1 H-NMR spectrum is measured in ° C., and the total peak area of the structural units derived from isoprene and butadiene, and the 3,4- and united 1,2- bonding units in the isoprene structural unit and the 1,2 in the butadiene structural unit From the ratio of the total peak area of bonding units, the ratio of the amount of vinyl bonds (the sum of the contents of 3,4-linked units and 1,2-linked units) was calculated.
- Melt flow rate According to JIS K 7210-1: 2014, it measured on temperature 230 degreeC, and the conditions of 2.16 kg of loads using the melt indexer (TAKARA L241, Techno seven company make).
- Solubility parameter (SP value) of polymer block (B) Based on the structure of the polymer block (B), the solubility parameter of the polymer block (B) by the Hoy method described in "Properties of Polymers (4th Edition): DW van Krevelen, Klaas te Nijenhuis; Elsevier Science, 2009" (SP value) was calculated.
- Examples 1 to 16 Comparative Examples 2, 3, and 8
- Thermoplastic resin by melt-kneading each component of the type and blending amount described in Tables 3 to 6 using a mixer (Plastograph EC, manufactured by Brabender) at a temperature of 170 ° C. and a rotation number of 80 rpm for 30 minutes
- the composition was obtained.
- Physical property evaluation was performed according to the following method about the obtained thermoplastic resin composition. The results are shown in Tables 3 to 6. In Tables 3 to 6, blanks indicate no blending.
- Comparative Examples 1 and 4 to 7 The physical properties of the olefin polymers (a) used in Comparative Examples 1 and 4 to 7 were evaluated according to the following method. The results are shown in Tables 3, 4 and 6.
- thermoplastic resin composition was heat pressed under the conditions of a temperature of 180 ° C., a pressure of 10 MPa and a pressing time of 2 minutes to produce sheets of 1 mm, 300 ⁇ m and 100 ⁇ m in thickness.
- thermoplastic resin composition was heat pressed under the conditions of a temperature of 140 ° C., a pressure of 10 MPa and a pressing time of 2 minutes to produce sheets of 1 mm, 300 ⁇ m and 100 ⁇ m in thickness.
- Heating step 1 heating from 30 ° C. to 180 ° C. at heating rate 10 ° C./min Cooling step: cooling from 180 ° C. to ⁇ 70 ° C. at cooling rate 10 ° C./min Heating step 2: heat rate at 10 ° C./min Heating from -70 ° C to 180 ° C
- the hysteresis loss determined from the first stress-strain curve is defined as hysteresis loss-1 by the calculation method described in 11.2.4 of JIS K7312: 1996, and the hysteresis loss determined from the second stress-strain curve is the hysteresis It is loss -2. Further, a stress of 100% strain at the first stress-strain curve is set to M100. The lower the hysteresis loss value, the better the elasticity.
- Adhesiveness A test piece of 25 mm ⁇ 150 mm ⁇ 100 ⁇ m in thickness is cut out of the sheet (100 ⁇ m in thickness) of the thermoplastic resin composition obtained by the above-mentioned method, and it is cut into two cloths T-shirts, 66% cotton, 34% polyester) were bonded under the following bonding conditions.
- Examples 1, 2 and 9 in which the conjugated diene compound is a mixture of isoprene and butadiene are compared with Example 8 in which the conjugated diene compound is isoprene
- Examples 1, 2 and 9 are more transparent. It turns out that it is excellent.
- the polymer block (B) of the olefin polymer (a) -2 and the hydrogenated block copolymer (b) -1 or (b) -4 It is understood that is compatible at the molecular level, and the stretchability, adhesiveness and transparency are all improved relative to Comparative Example 4 of the olefin polymer (a) -2 alone.
- the olefin polymer (a) -3 and the hydrogenated block copolymer (b) -1 or (b) -4 polymer block (B) are at the molecular level. It can be seen that both the stretchability, the adhesiveness and the transparency are improved as compared with Comparative Example 5 of the olefin polymer (a) -3 alone.
- the olefin polymer (a) -4 and the hydrogenated block copolymer (b) -1 or the polymer block (B) of (b) -4 are at the molecular level.
- the olefin polymer (a) and the polymer block (B) of the hydrogenated block copolymer (b) are compatible with each other. It was shown to be excellent in stretchability and to have high adhesion and transparency. In particular, when the conjugated diene compound is a mixture of isoprene and butadiene, it is understood that in addition to the stretchability and the adhesive strength, the transparency is more excellent.
Abstract
Description
しかしながら、上述の特許文献1乃至3に記載の粘接着剤組成物では、伸縮性は十分なものではなかった。
[1]オレフィン系重合体(a)及び水添ブロック共重合体(b)を含有する熱可塑性樹脂組成物であって、前記オレフィン系重合体(a)において、示差走査熱量測定における加熱速度10℃/分で測定される結晶融解熱量(ΔH)が80J/g未満であり、前記水添ブロック共重合体(b)が、芳香族ビニル化合物に由来する構造単位を主体とする重合体ブロック(A)及び共役ジエン化合物に由来する構造単位を主体とする重合体ブロック(B)からなるブロック共重合体の水素添加物であり、前記水添ブロック共重合体(b)における前記重合体ブロック(A)の含有量が1~60質量%であり、前記重合体ブロック(B)のビニル結合量の割合が50~95モル%であり、前記熱可塑性樹脂組成物中の前記水添ブロック共重合体(b)の含有量が、前記オレフィン系重合体(a)及び前記水添ブロック共重合体(b)の合計100質量部に対して1~30質量部であり、前記オレフィン系重合体(a)と前記水添ブロック共重合体(b)の重合体ブロック(B)とが分子レベルで相溶している、熱可塑性樹脂組成物。
[2]前記オレフィン系重合体(a)の前記結晶融解熱量(ΔH)が1J/g以上80J/g未満である、上記[1]の熱可塑性樹脂組成物。
[3]前記オレフィン系重合体(a)が、非晶性又は低結晶性ポリα-オレフィン及びポリオレフィンエラストマーから選ばれる少なくとも1種のオレフィン系重合体である、上記[1]又は[2]の熱可塑性樹脂組成物。
[4]前記オレフィン系重合体(a)が、非晶性又は低結晶性ポリα-オレフィンである、上記[1]~[3]のいずれかの熱可塑性樹脂組成物。
[5]前記水添ブロック共重合体(b)の重量平均分子量が30,000~500,000である、上記[1]~[4]のいずれかの熱可塑性樹脂組成物。
[6]前記水添ブロック共重合体(b)の分子量分布が1.0~1.5である、上記[1]~[5]のいずれかの熱可塑性樹脂組成物。
[7]前記水添ブロック共重合体(b)の、JIS K7210-1:2014に準拠し、温度230℃、荷重2.16kgの条件で測定したメルトフローレートが0.1~90g/10分である、上記[1]~[6]のいずれかの熱可塑性樹脂組成物。
[8]前記水添ブロック共重合体(b)における前記重合体ブロック(A)の含有量が5~9質量%である、上記[1]~[7]のいずれかの熱可塑性樹脂組成物。
[9]前記水添ブロック共重合体(b)の重合体ブロック(B)が、イソプレンとブタジエンとの混合物に由来する構造単位を主体とする重合体ブロックであり、イソプレンとブタジエンとの混合比率[イソプレン/ブタジエン](モル比)が10/90~90/10である、上記[1]~[8]のいずれかに記載の熱可塑性樹脂組成物。
[10]前記熱可塑性樹脂組成物の動的粘弾性の温度分散測定において、-70~0℃の温度範囲にある損失弾性率(G”)の極大ピーク数が1つである、上記[1]~[9]のいずれかの熱可塑性樹脂組成物。
[11]粘着付与剤をさらに含む、上記[1]~[10]のいずれかの熱可塑性樹脂組成物。
[12]上記[1]~[11]のいずれかの熱可塑性樹脂組成物を含むホットメルト接着剤。
[13]上記[12]のホットメルト接着剤を含有してなる自動車部材。
[14]上記[12]のホットメルト接着剤を含有してなる衛生材料部材。
本発明の熱可塑性樹脂組成物は、オレフィン系重合体(a)及び水添ブロック共重合体(b)を含有する熱可塑性樹脂組成物であって、
前記オレフィン系重合体(a)において、示差走査熱量測定における加熱速度10℃/分で測定される結晶融解熱量(ΔH)が80J/g未満であり、
前記水添ブロック共重合体(b)が、芳香族ビニル化合物に由来する構造単位を主体とする重合体ブロック(A)及び共役ジエン化合物に由来する構造単位を主体とする重合体ブロック(B)からなるブロック共重合体の水素添加物であり、前記水添ブロック共重合体(b)における前記重合体ブロック(A)の含有量が1~60質量%であり、前記重合体ブロック(B)のビニル結合量の割合が50~95モル%であり、
前記熱可塑性樹脂組成物中の前記水添ブロック共重合体(b)の含有量が、前記オレフィン系重合体(a)及び前記水添ブロック共重合体(b)の合計100質量部に対して1~30質量部であり、前記オレフィン系重合体(a)と前記水添ブロック共重合体(b)の重合体ブロック(B)とが分子レベルで相溶していることを特徴とする。
図3に実施例1の熱可塑性樹脂組成物シート表面のSEM写真を示す。該熱可塑性樹脂組成物シート表面の200μm×150μmの領域を観察したところ、長辺が10μm以上の大きさの凹部は観察されず、該シート表面は均一であることが分かる。また、図4に比較例2の熱可塑性樹脂組成物シート表面のSEM写真を示す。該熱可塑性樹脂組成物シート表面の200μm×150μmの領域を観察したところ、長辺が10μm以上の大きさの凹部が多数観察された。
例えば本発明の熱可塑性樹脂組成物と配合物との混合物を上記と同様にSEM観察した場合、分子レベルで相溶していない配合物が長辺10μm以上の大きさの凹部として観察されることがあるが、この場合であっても、オレフィン系重合体(a)と前記水添ブロック共重合体(b)の重合体ブロック(B)とが分子レベルで相溶していれば良好な物性が得られる。
例えば、オレフィン系重合体(a)と前記水添ブロック共重合体(b)の重合体ブロック(B)とが分子レベルで相溶していることを確認する場合は、配合物を含まない、オレフィン系重合体(a)及び水添ブロック共重合体(b)のみからなる熱可塑性樹脂組成物をSEM観察することにより、確認することができる。
特に、前記重合体ブロック(B)が、イソプレンとブタジエンとの混合物に由来する構造単位を主体とする重合体ブロックであり、イソプレンとブタジエンとの混合比率[イソプレン/ブタジエン](モル比)が10/90~90/10であり、前記重合体ブロック(B)のビニル結合量の割合が50~95モル%であり、前記重合体ブロック(B)の水素添加率が85モル%以上である場合に、オレフィン系重合体(a)と重合体ブロック(B)の相溶性が特に高まり、前記オレフィン系重合体(a)と前記水添ブロック共重合体(b)の重合体ブロック(B)をより容易に分子レベルで相溶させることができる。
前記SP値は、重合体の構造に基づいてHoy法によって算出することができる。前記Hoy法については、詳しくは「Properties of Polymers(4th Edition): D.W. van Krevelen, Klaas te Nijenhuis; Elsevier Science, 2009」に記載されている。また、前記Hoy法により計算できない場合は、重合体が既知の溶媒に対して溶解するか否かの判定による実験法で溶解度パラメータを算出することができる。前記実験法については、詳しくは「Polymer handbook (4th Edition): J. Brandrup, E.H. Immergut, E.A. Grulke (Eds.); Wiley, New York, 1999」に記載されている。
本発明で用いるオレフィン系重合体(a)は、示差走査熱量測定における加熱速度10℃/分で測定される結晶融解熱量(ΔH)が80J/g未満である。ΔHが80J/g以上では熱可塑性樹脂組成物の伸縮性がなくなり、また、熱可塑性樹脂組成物をホットメルト接着剤として使用する際に接着力が低くなる。オレフィン系重合体(a)のΔHは、伸縮性や耐熱性などそれぞれの観点から80J/g未満の範囲において適宜設定してもよく、例えば伸縮性を高める観点からは、ΔHは好ましくは1J/g以上80J/g未満、より好ましくは2~40J/g、さらに好ましくは5~25J/gである。また、耐熱性の観点からは、ΔHは好ましくは5~70J/g、より好ましくは10~60J/g、さらに好ましくは15~50J/gである。
上記結晶融解熱量(ΔH)は、示差走査熱量計(DSC)により試料を加熱速度10℃/分で30℃から180℃まで昇温して(加熱工程1)融解させた後、180℃から-70℃まで冷却して結晶化させ(冷却工程)、さらに加熱速度10℃/分で-70℃から180℃まで昇温する(加熱工程2)際に現れる加熱工程2における吸熱ピークを解析したものである。
また、非晶性又は低結晶性ポリα-オレフィン(APAO、アモルファスポリα-オレフィン)の市販品としては、例えば、REXtac社製のREXtac RT2115、RT2180、RT2215、RT2280、RT2304、RT2315、RT2535、RT2585、RT2730、RT2780、RT2788、RT6825、E101、RT9720;EVONIK社製のVestoplast 508、703、704、708、750、751、792、828、888、EP X55;EASTMAN社製のEastoflex E1016PL-1、P1010、P1023、E1060、E1200、D-178、M1058が挙げられる。
ポリオレフィンエラストマー(POE)の市販品としては、例えば、Dow Chemical Company製のENGAGE 8000番台シリーズ、7000番台シリーズ;Dow Chemical Company製のAFFINITY GA 1900、1950、1875、1000R;ExxonMobil社製のVistamaxx 8380、8780、8880、6102、6202、6502、3000、3020、3588FL、3980FL;三井化学社製のTAFMER DFシリーズ、Aシリーズ、Pシリーズ、XMシリーズが挙げられる。
また、前記オレフィン系重合体(a)及び水添ブロック共重合体(b)の合計100質量部に対するオレフィン系重合体(a)の含有量は、好ましくは70~99質量部であり、より好ましくは75~98質量部であり、さらに好ましくは75~95質量部であり、よりさらに好ましくは78~95質量部であり、特に好ましくは80~95質量部である。オレフィン系重合体(a)の含有量が上記範囲内であれば、熱可塑性樹脂組成物をホットメルト接着剤として使用する際にホットメルト塗工性に優れる。
本発明で用いる水添ブロック共重合体(b)は、芳香族ビニル化合物に由来する構造単位を主体とする重合体ブロック(A)及び共役ジエン化合物に由来する構造単位を主体とする重合体ブロック(B)からなるブロック共重合体の水素添加物である。
重合体ブロック(A)は、芳香族ビニル化合物に由来する構造単位(以下、「芳香族ビニル化合物単位」と略称することがある。)を主体とする。ここで言う「主体とする」とは、重合体ブロック(A)の合計質量に基づいて芳香族ビニル化合物単位を50質量%を超えて含むことをいう。該重合体ブロック(A)中の芳香族ビニル化合物単位の含有量は、熱可塑性樹脂組成物の伸縮性が高くなり、また、ヘーズが低下して透明性に優れる観点から、重合体ブロック(A)の合計質量に基づいて、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは90質量%以上、よりさらに好ましくは95質量%以上であり、実質的に100質量%であってもよい。
中でも、製造コストと物性バランスの観点から、スチレン、α-メチルスチレン、p-メチルスチレン、及びこれらの混合物が好ましく、スチレンがより好ましい。
重合体ブロック(A)における前記他の不飽和単量体に由来する構造単位の含有量は、好ましくは30質量%以下、より好ましくは10質量%以下、さらに好ましくは5質量%以下、よりさらに好ましくは0質量%である。
なお、ブロック共重合体における重合体ブロック(A)の含有量は、1H-NMR測定により求めた値であり、より詳細には実施例に記載の方法に従って測定した値である。
前記重合体ブロック(B)は、共役ジエン化合物に由来する構造単位(以下、「共役ジエン化合物単位」と略称することがある。)を主体とする。ここで言う「主体とする」とは、重合体ブロック(B)の合計質量に基づいて共役ジエン化合物単位を50質量%を超えて含むことをいう。該重合体ブロック(B)中の共役ジエン化合物単位の含有量は、熱可塑性樹脂組成物の成分であるオレフィン系重合体(a)と該重合体ブロック(B)との相溶性が高まり、熱可塑性樹脂組成物をホットメルト接着剤として使用した際に伸縮性と接着力が向上する観点から、重合体ブロック(B)の合計質量に基づいて、好ましくは70質量%以上、より好ましくは80質量%以上、さらに好ましくは90質量%以上、よりさらに好ましくは95質量%以上であり、実質的に100質量%であってもよい。
ブロック共重合体において、重合体ブロック(B)中の3,4-結合単位及び1,2-結合単位の含有量の合計(ビニル結合量)の割合は、50~95モル%である。ビニル結合量の割合が50モル%未満ではオレフィン系重合体(a)と該重合体ブロック(B)との相溶性が低くなり、熱可塑性樹脂組成物をホットメルト接着剤として使用した際に伸縮性と接着力を高めることができない。これは、ビニル結合量の割合を50モル%以上とすることで、該重合体ブロック(B)とオレフィン系重合体(a)とのSP値(溶解パラメータ)が近くなり、相溶性に寄与するためと推測される。また、ビニル結合量の割合が95モル%を超えると該重合体ブロック(B)のガラス転移温度が高くなり、室温での柔軟性が低下する。このような観点から、ビニル結合量の割合は好ましくは55~90モル%、より好ましくは56~80モル%、さらに好ましくは58~70モル%である。
ここで、ビニル結合量の割合は、実施例に記載の方法に従って、1H-NMR測定によって算出した値である。
なお、重合体ブロック(B)がブタジエンのみからなる場合には、前記の「3,4-結合単位及び1,2-結合単位の含有量」とは「1,2-結合単位の含有量」と読み替えて適用する。
なお、ブロック共重合体における重合体ブロック(B)の含有量は、1H-NMR測定により求めた値であり、より詳細には実施例に記載の方法に従って測定した値である。
該他の重合性の単量体としては、例えばスチレン、α-メチルスチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、p-t-ブチルスチレン、2,4-ジメチルスチレン、ビニルナフタレン及びビニルアントラセンなどの芳香族ビニル化合物;メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル等のメタクリル酸エステル;アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル;メチルビニルエーテル、N-ビニルカルバゾール、イソブチレン、β-ピネン、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からなる群から選択される少なくとも1種の化合物が好ましく挙げられる。中でも、スチレン、α-メチルスチレン、p-メチルスチレンが好ましく、スチレンがより好ましい。
重合体ブロック(B)が、共役ジエン化合物以外の他の重合性の単量体に由来する構造単位を含有する場合、その具体的な組み合わせとしては、好ましくは、イソプレンとスチレン、ブタジエンとスチレン、イソプレンとブタジエンとスチレンであり、より好ましくはイソプレンとスチレン、イソプレンとブタジエンとスチレンであり、さらに好ましくは、イソプレンとスチレンである。
重合体ブロック(B)が、共役ジエン化合物以外の他の重合性の単量体に由来する構造単位を含有する場合、その結合形態は特に制限はなく、ランダム、テーパー状、完全交互のいずれでもよいが、ランダムが好ましい。
ブロック共重合体は、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、またはこれらの2つ以上が組合わさった結合様式のいずれでもよい。中でも、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で示されるジブロック共重合体、A-B-AまたはB-A-Bで示されるトリブロック共重合体、A-B-A-B、A-B-B-A、B-A-A-BまたはA-A-B-Bで示されるテトラブロック共重合体、A-B-A-B-AまたはB-A-B-A-Bで示されるペンタブロック共重合体、(A-B)nX型共重合体(Xはカップリング剤残基を表し、nは3以上の整数を表す)などを挙げることができる。中でも、直鎖状のトリブロック共重合体、またはジブロック共重合体が好ましく、A-B-A型のトリブロック共重合体が、柔軟性、製造の容易性などの観点から好ましく用いられる。
ここで、本明細書においては、同種の重合体ブロックが二官能のカップリング剤などを介して直線状に結合している場合、結合している重合体ブロック全体は一つの重合体ブロックとして取り扱われる。これに従い、上記例示も含め、本来、厳密にはY-X-Y(Xはカップリング残基を表す)と表記されるべき重合体ブロックは、特に単独の重合体ブロックYと区別する必要がある場合を除き、全体としてYと表示される。本明細書においては、カップリング剤残基を含むこの種の重合体ブロックを上記のように取り扱うので、例えば、カップリング剤残基を含み、厳密にはA-B-X-B-A(Xはカップリング剤残基を表す)と表記されるべきブロック共重合体はA-B-Aと表記され、トリブロック共重合体の一例として取り扱われる。
オレフィン系重合体(a)と水添ブロック共重合体(b)の重合体ブロック(B)との相溶性が高まる観点から、重合体ブロック(B)が有する炭素-炭素二重結合の50モル%以上が水素添加(以下、水添と略称することがある。)されていることが好ましく、70モル%以上が水添されていることがより好ましく、80モル%以上が水添されていることがさらに好ましく、85モル%以上が水添されていることがよりさらに好ましく、90モル%以上が水添されていることが特に好ましい。なお、該値を水素添加率(水添率)と称することがある。水素添加率の上限値に特に制限はないが、上限値は99モル%であってもよく、98モル%であってもよい。
なお、上記の水素添加率は、重合体ブロック(B)中の共役ジエン化合物由来の構造単位中の炭素-炭素二重結合の含有量を、水素添加後の1H-NMR測定によって求めた値であり、より詳細には実施例に記載の方法に従って測定した値である。
本発明において、分子量分布(Mw/Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定したポリスチレン換算の重量平均分子量Mw及び数平均分子量Mnより算出した値である。
前記水添ブロック共重合体(b)は、溶液重合法、乳化重合法または固相重合法などにより製造することができる。中でも溶液重合法が好ましく、例えば、アニオン重合、カチオン重合などのイオン重合法、ラジカル重合法などの公知の方法を適用できる。中でも、アニオン重合法が好ましい。アニオン重合法では、溶媒、アニオン重合開始剤、及び必要に応じてルイス塩基の存在下、芳香族ビニル化合物と、共役ジエン化合物とを添加して、ブロック共重合体を得、必要に応じてカップリング剤を添加して反応させ、次いでブロック共重合体を水素添加することにより、水添ブロック共重合体(b)を得ることができる。
粘着付与剤としては、例えば、クマロン・インデン樹脂等のクマロン樹脂;p-t-ブチルフェノール・アセチレン樹脂、フェノール・ホルムアルデヒド樹脂、テルペン・フェノール樹脂、ポリテルペン樹脂、キシレン・ホルムアルデヒド樹脂等のフェノール系樹脂及びテルペン系樹脂;芳香族系石油樹脂、脂肪族系石油樹脂、脂環式系石油樹脂、芳香族系石油樹脂、変性脂環式系石油樹脂等の石油樹脂;ロジンのペンタエリスリトールエステル及びロジンのグリセロールエステル等に代表されるロジンエステル、水素添加ロジン、水素添加ロジンのメチルエステル、重合ロジンのペンタエリスリトールエステル、水素添加ロジンエステル、高融点エステル系樹脂、重合ロジン、硬化ロジン、特殊ロジンエステル等のロジン系樹脂などが挙げられる。中でも、テルペン系樹脂、石油樹脂、ロジン系樹脂が好ましく、石油樹脂がより好ましい。粘着付与剤は、1種を用いてもよく、2種以上を組み合わせて用いてもよい。
一般的に、例えばホットメルト接着剤は、使用者の目的に応じて、熱可塑性樹脂組成物に粘着付与剤やオイル、ワックスなどの配合物が配合され、適宜物性を調整して用いられる。本発明の熱可塑性樹脂組成物であれば、配合物が配合されても、該熱可塑性樹脂組成物の有する良好な物性が反映され、配合物配合後の物性も良好となる。
なお、ガラス転移温度(Tg)は、実施例に記載の方法により測定することができる。
また、本発明の熱可塑性樹脂組成物は、JIS L1086:2013に準拠してT型剥離試験によって剥離強さを測定した接着力が、好ましくは25N/25mm以上、より好ましくは30N/25mm以上、さらに好ましくは40N/25mm以上である。
本発明のホットメルト接着剤は上述の熱可塑性樹脂組成物を含む。これにより、該ホットメルト接着剤は、伸縮性に優れ、高い接着力及び透明性を有する。
本発明のホットメルト接着剤は種々の用途に使用できる。例えば、塗装外板、ホイール、ミラー、ウィンドウ、ライト、ライトカバー、内装用加飾フィルム、外装用加飾フィルム、ドアモール、天井、ダッシュボード、インストルメントパネル、シート、リアトレイ、座席シート、内装表皮部材、フロアマット、トランク床、ダッシュサイレンサーなどの吸音部材、ヘッドランプ、テールランプなどの自動車部材の接着又はシーリング用途;使い捨ておむつ、女性用サニタリーナプキン、不織布、ポリエチレン製フィルムなどの衛生材料部材の接着用途;ヒートシール性包装フィルム等の包装材料;衣料用ホットメルト接着シート;壁紙、カーペット、タイル、合板パネル、屋根葺き材等建築部材、外壁、断熱材等の建築部材の接着又はシーリング用途;ダンボール箱やカートンケースなどの製函・封緘用途;エアコン、空気清浄器等のエアフィルターのプリーツ加工用途及び枠固定用途;表面保護フィルム用途(例えば、基材と粘着層の中間にあるバインダー層用樹脂、粘着層用樹脂等);手術用ドレープ等の医療用具;食品トレイ;テープ、ラベル等の粘・接着製品;積層体の接着層用樹脂;液晶ディスプレイ等の電化製品;製本用接着剤;木工細工用接着剤;舗装道路用アスファルト改質剤;フロアマットやバスマット等のマットの滑り止め材;飲料パックのストローアタッチメント等の包装用接着剤;ヒートシール性包装用フィルム等のヒートシール層用樹脂等として好適に用いることができる。
下記に記載のオレフィン系重合体を用いた。
・オレフィン系重合体(a)-1:プロピレン単独重合体(RT2180、REXtac社製、結晶融解熱量ΔHが23.7J/gのポリα-オレフィン)
・オレフィン系重合体(a)-2:エチレン-プロピレン共重合体(RT2280、REXtac社製、低エチレンコポリマーであり結晶融解熱量ΔHが16.0J/gのポリα-オレフィン)
・オレフィン系重合体(a)-3:エチレン-プロピレン共重合体(RT2585、REXtac社製、高エチレンコポリマーであり結晶融解熱量ΔHが6.8J/gのポリα-オレフィン)
・オレフィン系重合体(a)-4:プロピレン-1-ブテンランダム共重合体(RT2780、REXtac社製、結晶融解熱量ΔHが4.7J/g未満のポリα-オレフィン)
・オレフィン系重合体(a)-5:エチレン-プロピレン共重合体(Vistamaxx 3588FL、ExxonMobil社製、エチレン含有量が4質量%のエチレンコポリマーであり結晶融解熱量ΔHが51.7J/gのポリオレフィンエラストマー)
・水添ブロック共重合体(b)-1:下記製造例1で製造した水添ブロック共重合体
・水添ブロック共重合体(b)-2:下記製造例2で製造した水添ブロック共重合体
・水添ブロック共重合体(b)-3:下記製造例3で製造した水添ブロック共重合体
・水添ブロック共重合体(b)-4:下記製造例4で製造した水添ブロック共重合体
・水添ブロック共重合体(x)-1:下記比較製造例1で製造した水添ブロック共重合体
・水添ブロック共重合体(x)-2:下記比較製造例2で製造した水添ブロック共重合体
・水添ブロック共重合体(x)-3:下記比較製造例3で製造した水添ブロック共重合体
乾燥した窒素で置換された耐圧容器に、シクロヘキサン及びスチレン(A1)を仕込んだ。この溶液に、sec-ブチルリチウム(10質量%、シクロヘキサン溶液)を加え、60℃で1時間重合させた。次いで、この反応混合物にテトラヒドロフランを加えた後、イソプレンとブタジエンの混合物を加えて2時間重合を行い、さらにスチレン(A2)を加えて1時間重合させることにより、ポリスチレン-ポリ(イソプレン/ブタジエン)-ポリスチレンのトリブロック共重合体を含む反応液を得た。前記反応に用いた原料の使用量を表1-1に示す。
この反応液に、オクチル酸ニッケル及びトリメチルアルミニウムから形成されるチーグラー系水添触媒を水素雰囲気下で添加し、水素圧力1.0MPa、80℃の条件で5時間反応させた。続いて反応液を放冷及び放圧させた後、水洗により上記触媒を除去し、真空乾燥させることにより、ポリスチレン-ポリ(イソプレン/ブタジエン)-ポリスチレントリブロック共重合体の水添物(以下、「水添ブロック共重合体(b)-1」ともいう)を得た。得られた水添ブロック共重合体(b)-1について、分析及び物性評価を後述の方法に従って行った。その結果を表1-1に示す。
原料の使用量を表1-1に記載のとおり変更したこと以外は、製造例1と同様にして、水添ブロック共重合体(b)-2、比較水添ブロック共重合体(x)-1及び(x)-2を製造した。得られた水添ブロック共重合体(b)-2、比較水添ブロック共重合体(x)-1及び(x)-2について、分析及び物性評価を後述の方法に従って行った。その結果を表1-1に示す。
原料の使用量を表1-2に記載のとおり変更したこと以外は、製造例1と同様にして、水添ブロック共重合体(b)-3、及び(b)-4を製造した。得られた水添ブロック共重合体(b)-3、及び(b)-4について、分析及び物性評価を後述の方法に従って行った。その結果を表1-2に示す。
テトラヒドロフランの代わりにN,N,N’,N’-テトラメチルエチレンジアミンを用いたことと、原料の使用量を表1-3に記載のとおり変更したこと以外は、製造例1と同様にして、比較水添ブロック共重合体(x)-3を製造した。得られた比較水添ブロック共重合体(x)-3について、分析及び物性評価を下記方法に従って行った。その結果を表1-3に示す。
(1)ピークトップ分子量(Mp)及び分子量分布(Mw/Mn)
下記条件のゲルパーミエーションクロマトグラフィー(GPC)測定により、各共重合体、重合体ブロック(A)及び重合体ブロック(B)のポリスチレン換算のピークトップ分子量(Mp)を求めた。また、分子量分布(Mw/Mn)は、ゲル浸透クロマトグラフィー(GPC)により標準ポリスチレン換算分子量として求めた重量平均分子量(Mw)及び数平均分子量(Mn)から算出した。
・装置 :GPC装置「HLC-8320」(東ソー株式会社製)
・分離カラム :カラム「TSKgel Super HZ4000」(東ソー株式会社製)を2本直列に接続
・溶離液 :テトラヒドロフラン
・溶離液流量 :0.35mL/分
・サンプル濃度:5mg/10mL
・カラム温度 :40℃
・検出器:示差屈折率(RI)検出器
・検量線:標準ポリスチレンを用いて作成
水素添加前のブロック共重合体をCDCl3に溶解して、装置:「ULTRASHIELD 400 PLUS」(Bruker社製)を用いて測定温度:50℃で、1H-NMRスペクトルを測定し、スチレンに由来するピーク面積とイソプレン及びブタジエンに由来するピーク面積の比率から重合体ブロック(A)及び重合体ブロック(B)の含有量を算出した。
水素添加前後のブロック共重合体をCDCl3に溶解して、装置:「ULTRASHIELD 400 PLUS」(Bruker社製)を用いて測定温度:50℃で、1H-NMRスペクトルを測定し、水素添加前後の共役ジエン重合体ブロックの炭素-炭素二重結合に由来するピーク面積比の減少率から水素添加率を求めた。
水素添加前のブロック共重合体をCDCl3に溶解して、装置:「ULTRASHIELD 400 PLUS」(Bruker社製)を用いて測定温度:50℃で、1H-NMRスペクトルを測定し、イソプレン及びブタジエン由来の構造単位の全ピーク面積と、イソプレン構造単位における3,4-結合単位と1,2-結合単位及びブタジエン構造単位における1,2-結合単位の全ピーク面積の比率からビニル結合量(3,4-結合単位と1,2-結合単位の含有量の合計)の割合を算出した。
JIS K7121:2012に準拠し、セイコー電子工業社製、示差走査型熱量計「DSC6200」を用いて、10℃/分の昇温速度にて-120℃から100℃まで昇温し、得られたDSC曲線からガラス転移温度を求めた。なお、水添ブロック共重合体(b)及び比較水添ブロック共重合体(x)の場合、重合体ブロック(B)に由来するガラス転移温度が観測される。
JIS K7210-1:2014に準拠し、メルトインデクサ(TAKARA L241、テクノ・セブン社製)を用いて、温度230℃、荷重2.16kgの条件で測定した。
重合体ブロック(B)の構造に基づいて、「Properties of Polymers(4th Edition): D.W. van Krevelen, Klaas te Nijenhuis; Elsevier Science, 2009」に記載のHoy法によって、重合体ブロック(B)の溶解度パラメータ(SP値)を算出した。
表3~6に記載の種類及び配合量の各成分をミキサー(ブラベンダー社製、プラストグラフEC)を用いて、温度170℃、回転数80rpmにて30分間溶融混練することにより、熱可塑性樹脂組成物を得た。得られた熱可塑性樹脂組成物について、物性評価を下記方法に従って行った。その結果を表3~6に示す。なお、表3~6中、空欄は配合なしを表す。
比較例1、4~7で用いたオレフィン系重合体(a)について、物性評価を下記方法に従って行った。その結果を表3、表4、及び表6に示す。
[実施例1~5、実施例8~10、実施例13、実施例14、比較例1~4、比較例8]
熱可塑性樹脂組成物を温度180℃、圧力10MPa、プレス時間2分間の条件で熱プレスし、厚さ1mm、300μm及び100μmのシートを作製した。
熱可塑性樹脂組成物を温度140℃、圧力10MPa、プレス時間2分間の条件で熱プレスし、厚さ1mm、300μm及び100μmのシートを作製した。
(1)損失弾性率(G”)
前記の方法で得られた熱可塑性樹脂組成物のシート(厚さ1mm)から直径8mm、厚さ1mmの円盤状に切り出した試験片について、ARES-G2レオメーター(TA Instruments社製)を用いて、下記条件で動的粘弾性測定を行い、-70℃~0℃の温度範囲にある損失弾性率(G”)の極大ピーク数及び極大ピーク温度を求めた。
なお、実施例1及び比較例2の動的粘弾性測定チャートを図1及び図2に示す。
・平行プレート:直径8mm
・振動モード :ねじり振動
・歪み量 :0.1%
・周波数 :1Hz
・測定温度 :-70~0℃
・昇温速度 :3℃/分
JIS K7121:2012及びJIS K7122:2012に準拠し、セイコー電子工業社製、示差走査型熱量計「DSC6200」を用いて、下記の加熱工程1、冷却工程、加熱工程2の順に温度を変化させて測定した。結晶化温度については、実施例1~6、実施例8~11、実施例13~16、比較例1~5、比較例7及び比較例8は、冷却工程で得られるDSC曲線から求め、実施例7、実施例12及び比較例6については、加熱工程2で得られるDSC曲線から求めた。また、ガラス転移温度、融点及び結晶融解熱量(ΔH)については、加熱工程2で得られるDSC曲線から求めた。
・加熱工程1:加熱速度10℃/分で30℃から180℃まで加熱
・冷却工程:冷却速度10℃/分で180℃から-70℃まで冷却
・加熱工程2:加熱速度10℃/分で-70℃から180℃まで加熱
前記の方法で得られた熱可塑性樹脂組成物のシート(厚さ300μm)から25mm×150mm×厚さ300μmの試験片を切り出し、引張試験機(インストロン社製、3345型)を用いて、チャック間距離40mm、300mm/分の速度で歪み100%まで伸ばし、直後に同じ速度にて元に戻す操作を同じ試験片に対して2回繰り返して行った。JIS K7312:1996の11.2.4に記載の計算方法により、1回目の応力-歪曲線から求めたヒステリシス損失をヒステリシス損失-1とし、2回目の応力-歪曲線から求めたヒステリシス損失をヒステリシス損失-2とした。また、1回目の応力-歪曲線での歪み100%の応力をM100とした。なお、ヒステリシス損失の数値が低いほど、伸縮性に優れる。
前記の方法で得られた熱可塑性樹脂組成物のシート(厚さ1mm)について、JIS K7136:2000に準拠して、ヘーズメーター(村上色彩研究所社製、HR-100)を用いて、ヘーズを求めた。
前記の方法で得られた熱可塑性樹脂組成物のシート(厚さ100μm)から25mm×150mm×厚さ100μmの試験片を切り出し、それを2枚の布地(ユニクロ社製、カラーTシャツ、綿66%、ポリエステル34%)で挟んで下記の接着条件にて接着した。
(接着条件)
実施例1~3、実施例8、実施例9、実施例13、実施例14、比較例1~3、比較例8:145℃、30秒、0.06MPa
実施例4、実施例5、実施例10、比較例4:135℃、30秒、0.06MPa
実施例6、実施例11、比較例5:105℃、30秒、0.06MPa
実施例7、実施例12、比較例6:85℃、30秒、0.06MPa
実施例15、実施例16、比較例7:158℃、30秒、0.06MPa
得られた布地/熱可塑性樹脂組成物/布地からなる積層体について、JIS L1086:2013に準拠してT型剥離試験によって剥離強さを測定して接着力を求めた。また、剥離試験後の試験片の剥離面を目視によって観察し、剥離面の状態を下記表2に示す判定基準により判定した。剥離試験の際に布地が破断した場合は、「基材破壊」と判定した。「基材破壊」は、基材の強度よりも強く接着していることを意味する。
前記の方法にて厚さ1mmのシートを溶剤のテトラヒドロフランに5分間浸漬してエッチング処理を行った後、走査型電子顕微鏡(SEM)(JEOL社製、JSM-6510)を用いてモルフォロジーを観察した。200μm×150μmの観察領域において、長辺が10μm以上の大きさの凹部が観察される場合を「非相溶」、観察されない場合を「相溶」と判定した。
なお、実施例1及び比較例2のSEM写真を図3及び図4に示す。
前記の方法にて作製した厚さ1mmのシートの中央部について、下記の断面作製条件にて面出しを行い、その1日後に下記のSPM測定条件にてSPM観察を行った。実施例1及び比較例2の観察結果を図5及び図6に示す。
(断面作製条件)
装置:Leica社製UC-7
試料・ナイフ・雰囲気:-100℃
切削厚み:150nm
スピード:0.3mm/s
使用ナイフ:ガラスナイフ
(SPM測定条件)
装置:エスアイアイ・ナノテクノロジー株式会社製走査型プローブ顕微鏡(SPM)
測定温度:25℃
測定モード:タッピングモード
カンチレバー:SI-DF20
また、共役ジエン化合物がイソプレンとブタジエンの混合物である実施例1、2、9と、共役ジエン化合物がイソプレンである実施例8とを比較すると、実施例1、2、9の方が透明性により優れることがわかる。
また、実施例4、5、10、14においては、オレフィン系重合体(a)-2と水添ブロック共重合体(b)-1、又は(b)-4の重合体ブロック(B)とが分子レベルで相溶しており、オレフィン系重合体(a)-2単体の比較例4に対して伸縮性、接着性及び透明性がいずれも改善されていることがわかる。
また、実施例6、11においては、オレフィン系重合体(a)-3と水添ブロック共重合体(b)-1、又は(b)-4の重合体ブロック(B)とが分子レベルで相溶しており、オレフィン系重合体(a)-3単体の比較例5に対して伸縮性、接着性及び透明性がいずれも改善されていることがわかる。
また、実施例7、12においては、オレフィン系重合体(a)-4と水添ブロック共重合体(b)-1、又は(b)-4の重合体ブロック(B)とが分子レベルで相溶しており、オレフィン系重合体(a)-4単体の比較例6に対して伸縮性及び接着性を改善しながら、透明性についても実用上問題の無い数値であった。
また、実施例15、16においては、オレフィン系重合体(a)-5と水添ブロック共重合体(b)-1、又は(b)-4の重合体ブロック(B)とが分子レベルで相溶しており、オレフィン系重合体(a)-5単体の比較例7に対して伸縮性、接着性及び透明性がいずれも改善されていることがわかる。
以上のことから、実施例1~16の熱可塑性樹脂組成物は、いずれもオレフィン系重合体(a)と水添ブロック共重合体(b)の重合体ブロック(B)とが相溶しており、伸縮性に優れるとともに、高い接着力及び透明性を有することが示された。特に、共役ジエン化合物がイソプレンとブタジエンとの混合物である場合、伸縮性及び接着力に加え透明性にもより優れることが分かる。
Claims (14)
- オレフィン系重合体(a)及び水添ブロック共重合体(b)を含有する熱可塑性樹脂組成物であって、
前記オレフィン系重合体(a)において、示差走査熱量測定における加熱速度10℃/分で測定される結晶融解熱量(ΔH)が80J/g未満であり、
前記水添ブロック共重合体(b)が、芳香族ビニル化合物に由来する構造単位を主体とする重合体ブロック(A)及び共役ジエン化合物に由来する構造単位を主体とする重合体ブロック(B)からなるブロック共重合体の水素添加物であり、前記水添ブロック共重合体(b)における前記重合体ブロック(A)の含有量が1~60質量%であり、前記重合体ブロック(B)のビニル結合量の割合が50~95モル%であり、
前記熱可塑性樹脂組成物中の前記水添ブロック共重合体(b)の含有量が、前記オレフィン系重合体(a)及び前記水添ブロック共重合体(b)の合計100質量部に対して1~30質量部であり、前記オレフィン系重合体(a)と前記水添ブロック共重合体(b)の重合体ブロック(B)とが分子レベルで相溶している、熱可塑性樹脂組成物。 - 前記オレフィン系重合体(a)の前記結晶融解熱量(ΔH)が1J/g以上80J/g未満である、請求項1に記載の熱可塑性樹脂組成物。
- 前記オレフィン系重合体(a)が、非晶性又は低結晶性ポリα-オレフィン及びポリオレフィンエラストマーから選ばれる少なくとも1種のオレフィン系重合体である、請求項1又は2に記載の熱可塑性樹脂組成物。
- 前記オレフィン系重合体(a)が、非晶性又は低結晶性ポリα-オレフィンである、請求項1~3のいずれかに記載の熱可塑性樹脂組成物。
- 前記水添ブロック共重合体(b)の重量平均分子量が30,000~500,000である、請求項1~4のいずれかに記載の熱可塑性樹脂組成物。
- 前記水添ブロック共重合体(b)の分子量分布が1.0~1.5である、請求項1~5のいずれかに記載の熱可塑性樹脂組成物。
- 前記水添ブロック共重合体(b)の、JIS K7210-1:2014に準拠し、温度230℃、荷重2.16kgの条件で測定したメルトフローレートが0.1~90g/10分である、請求項1~6のいずれかに記載の熱可塑性樹脂組成物。
- 前記水添ブロック共重合体(b)における前記重合体ブロック(A)の含有量が5~9質量%である、請求項1~7のいずれかに記載の熱可塑性樹脂組成物。
- 前記水添ブロック共重合体(b)の重合体ブロック(B)が、イソプレンとブタジエンとの混合物に由来する構造単位を主体とする重合体ブロックであり、イソプレンとブタジエンとの混合比率[イソプレン/ブタジエン](モル比)が10/90~90/10である、請求項1~8のいずれかに記載の熱可塑性樹脂組成物。
- 前記熱可塑性樹脂組成物の動的粘弾性の温度分散測定において、-70~0℃の温度範囲にある損失弾性率(G”)の極大ピーク数が1つである、請求項1~9のいずれかに記載の熱可塑性樹脂組成物。
- 粘着付与剤をさらに含む、請求項1~10のいずれかに記載の熱可塑性樹脂組成物。
- 請求項1~11のいずれかに記載の熱可塑性樹脂組成物を含むホットメルト接着剤。
- 請求項12に記載のホットメルト接着剤を含有してなる自動車部材。
- 請求項12に記載のホットメルト接着剤を含有してなる衛生材料部材。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018563633A JP6621045B2 (ja) | 2017-07-31 | 2018-07-31 | 熱可塑性樹脂組成物、ホットメルト接着剤、自動車部材、及び衛生材料部材 |
EP18841020.3A EP3663350B1 (en) | 2017-07-31 | 2018-07-31 | Thermoplastic resin composition, hot melt adhesive, automobile member, and hygienic material member |
US16/627,482 US11015046B2 (en) | 2017-07-31 | 2018-07-31 | Thermoplastic resin composition, hot melt adhesive, automobile member, and hygienic material member |
KR1020197037038A KR102522227B1 (ko) | 2017-07-31 | 2018-07-31 | 열가소성 수지 조성물, 핫멜트 접착제, 자동차 부재, 및 위생 재료 부재 |
CA3067000A CA3067000A1 (en) | 2017-07-31 | 2018-07-31 | Thermoplastic resin composition, hot melt adhesive, automobile member, and hygienic material member |
CN201880048965.4A CN110914358B (zh) | 2017-07-31 | 2018-07-31 | 热塑性树脂组合物、热熔粘接剂、汽车构件、和卫生材料构件 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017148460 | 2017-07-31 | ||
JP2017-148460 | 2017-07-31 | ||
JP2018015593 | 2018-01-31 | ||
JP2018-015593 | 2018-01-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019026891A1 true WO2019026891A1 (ja) | 2019-02-07 |
Family
ID=65233782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/028611 WO2019026891A1 (ja) | 2017-07-31 | 2018-07-31 | 熱可塑性樹脂組成物、ホットメルト接着剤、自動車部材、及び衛生材料部材 |
Country Status (8)
Country | Link |
---|---|
US (1) | US11015046B2 (ja) |
EP (1) | EP3663350B1 (ja) |
JP (1) | JP6621045B2 (ja) |
KR (1) | KR102522227B1 (ja) |
CN (1) | CN110914358B (ja) |
CA (1) | CA3067000A1 (ja) |
TW (1) | TWI759518B (ja) |
WO (1) | WO2019026891A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023195539A1 (ja) * | 2022-04-08 | 2023-10-12 | 積水フーラー株式会社 | ホットメルト組成物 |
JP7366647B2 (ja) | 2019-08-29 | 2023-10-23 | 日東シンコー株式会社 | ホットメルト接着シート |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115011177A (zh) * | 2022-07-14 | 2022-09-06 | 江苏锐剑科技有限公司 | 一种三元乙丙防水卷材用环保底涂的制备方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS601685B2 (ja) | 1977-03-17 | 1985-01-17 | キヤノン株式会社 | 磁気記録方法 |
JPS6028442A (ja) * | 1983-07-26 | 1985-02-13 | Mitsui Petrochem Ind Ltd | ポリ4−メチル−1−ペンテンフイルム |
JPS6039693B2 (ja) | 1982-09-21 | 1985-09-07 | 日本電信電話株式会社 | 感光性樹脂及びその製造方法 |
WO2001085818A1 (fr) * | 2000-05-09 | 2001-11-15 | Asahi Kasei Kabushiki Kaisha | Copolymere bloc et composition contenant ce copolymere |
JP2003503553A (ja) * | 1999-06-25 | 2003-01-28 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | ホットメルト感圧位置決め接着剤(iii) |
JP2004250563A (ja) * | 2003-02-20 | 2004-09-09 | Mitsuboshi Belting Ltd | スラッシュ成形用熱可塑性エラストマー組成物、粉末物およびこれを用いた表皮体 |
WO2011040586A1 (ja) * | 2009-09-30 | 2011-04-07 | 株式会社クラレ | 熱可塑性エラストマー組成物、成形体および医療用シーリング材 |
WO2012067609A1 (en) * | 2010-11-17 | 2012-05-24 | Kraton Polymers Us, Llc | Thermaoplastic elastomer composition with improved compression set values |
JP2012236895A (ja) | 2011-05-11 | 2012-12-06 | Sumitomo Chemical Co Ltd | 樹脂組成物、並びにその樹脂組成物からなる成形品及び粘着フィルム |
JP2014111711A (ja) * | 2012-11-12 | 2014-06-19 | Sekisui Fuller Co Ltd | ホットメルト接着剤及び使い捨て製品 |
JP2014169437A (ja) * | 2013-02-08 | 2014-09-18 | Sumitomo Chemical Co Ltd | オレフィン系樹脂組成物、これからなるフィルム及び医療用包装容器 |
WO2016136760A1 (ja) * | 2015-02-24 | 2016-09-01 | 株式会社クラレ | 水添ブロック共重合体、樹脂組成物、粘着剤、接着剤、成形体、液体包装容器、医療用具、医療用チューブ、ウェザーシール用コーナー部材及びウェザーシール |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003083003A1 (en) * | 2002-03-22 | 2003-10-09 | Exxonmobil Chemical Patents Inc. | Adhesives |
US7348376B2 (en) * | 2004-04-13 | 2008-03-25 | Kraton Polymers U.S. Llc | Adhesive composition |
KR101281896B1 (ko) * | 2008-09-18 | 2013-07-03 | 미쓰이 가가쿠 가부시키가이샤 | 접착제 조성물 및 이것으로 이루어지는 접착제 |
US9771473B2 (en) * | 2012-02-24 | 2017-09-26 | Kraton Polymers U.S. Llc | High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications |
US20130225020A1 (en) | 2012-02-24 | 2013-08-29 | Kraton Polymers Us Llc | High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications |
EP2947127B1 (en) | 2013-01-18 | 2020-03-18 | Nichiban Company Limited | Self-adhesive composition, self-adhesive sheet, method for producing self-adhesive sheets and use of a self-adhesive sheet |
JP6423276B2 (ja) * | 2013-02-06 | 2018-11-14 | 株式会社クラレ | 熱可塑性重合体組成物、シューズおよびアウターソール |
JP6607182B2 (ja) * | 2016-12-27 | 2019-11-20 | 横浜ゴム株式会社 | ホットメルト組成物 |
WO2019204545A1 (en) * | 2018-04-20 | 2019-10-24 | The Procter & Gamble Company | Absorbent article comprising an adhesive composition |
-
2018
- 2018-07-31 TW TW107126529A patent/TWI759518B/zh active
- 2018-07-31 EP EP18841020.3A patent/EP3663350B1/en active Active
- 2018-07-31 JP JP2018563633A patent/JP6621045B2/ja active Active
- 2018-07-31 WO PCT/JP2018/028611 patent/WO2019026891A1/ja unknown
- 2018-07-31 US US16/627,482 patent/US11015046B2/en active Active
- 2018-07-31 KR KR1020197037038A patent/KR102522227B1/ko active IP Right Grant
- 2018-07-31 CA CA3067000A patent/CA3067000A1/en active Pending
- 2018-07-31 CN CN201880048965.4A patent/CN110914358B/zh active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS601685B2 (ja) | 1977-03-17 | 1985-01-17 | キヤノン株式会社 | 磁気記録方法 |
JPS6039693B2 (ja) | 1982-09-21 | 1985-09-07 | 日本電信電話株式会社 | 感光性樹脂及びその製造方法 |
JPS6028442A (ja) * | 1983-07-26 | 1985-02-13 | Mitsui Petrochem Ind Ltd | ポリ4−メチル−1−ペンテンフイルム |
JP2003503553A (ja) * | 1999-06-25 | 2003-01-28 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | ホットメルト感圧位置決め接着剤(iii) |
WO2001085818A1 (fr) * | 2000-05-09 | 2001-11-15 | Asahi Kasei Kabushiki Kaisha | Copolymere bloc et composition contenant ce copolymere |
JP2004250563A (ja) * | 2003-02-20 | 2004-09-09 | Mitsuboshi Belting Ltd | スラッシュ成形用熱可塑性エラストマー組成物、粉末物およびこれを用いた表皮体 |
WO2011040586A1 (ja) * | 2009-09-30 | 2011-04-07 | 株式会社クラレ | 熱可塑性エラストマー組成物、成形体および医療用シーリング材 |
WO2012067609A1 (en) * | 2010-11-17 | 2012-05-24 | Kraton Polymers Us, Llc | Thermaoplastic elastomer composition with improved compression set values |
JP2012236895A (ja) | 2011-05-11 | 2012-12-06 | Sumitomo Chemical Co Ltd | 樹脂組成物、並びにその樹脂組成物からなる成形品及び粘着フィルム |
JP2014111711A (ja) * | 2012-11-12 | 2014-06-19 | Sekisui Fuller Co Ltd | ホットメルト接着剤及び使い捨て製品 |
JP2014169437A (ja) * | 2013-02-08 | 2014-09-18 | Sumitomo Chemical Co Ltd | オレフィン系樹脂組成物、これからなるフィルム及び医療用包装容器 |
WO2016136760A1 (ja) * | 2015-02-24 | 2016-09-01 | 株式会社クラレ | 水添ブロック共重合体、樹脂組成物、粘着剤、接着剤、成形体、液体包装容器、医療用具、医療用チューブ、ウェザーシール用コーナー部材及びウェザーシール |
Non-Patent Citations (3)
Title |
---|
"Polymer handbook", 1999, WILEY |
D.W. VAN KREVELENKLAAS TE NIJENHUIS: "Properties of Polymers", 2009, ELSEVIER SCIENCE |
See also references of EP3663350A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7366647B2 (ja) | 2019-08-29 | 2023-10-23 | 日東シンコー株式会社 | ホットメルト接着シート |
WO2023195539A1 (ja) * | 2022-04-08 | 2023-10-12 | 積水フーラー株式会社 | ホットメルト組成物 |
Also Published As
Publication number | Publication date |
---|---|
CN110914358A (zh) | 2020-03-24 |
CA3067000A1 (en) | 2019-02-07 |
JP6621045B2 (ja) | 2019-12-18 |
EP3663350A4 (en) | 2021-04-07 |
US20200157326A1 (en) | 2020-05-21 |
TWI759518B (zh) | 2022-04-01 |
KR102522227B1 (ko) | 2023-04-14 |
TW201920424A (zh) | 2019-06-01 |
EP3663350B1 (en) | 2023-07-05 |
KR20200037138A (ko) | 2020-04-08 |
EP3663350A1 (en) | 2020-06-10 |
CN110914358B (zh) | 2022-05-24 |
US11015046B2 (en) | 2021-05-25 |
JPWO2019026891A1 (ja) | 2019-08-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10214600B2 (en) | Amorphpus propylene-ethylene copolymers | |
US9879160B2 (en) | Pressure-sensitive hot melt adhesive compositions | |
US9109143B2 (en) | Polypropylene-based adhesive compositions | |
JP3556224B2 (ja) | 接着剤用多ブロック水素化ポリマー | |
US20060229411A1 (en) | Hot melt pressure sensitive adhesives based on blends of styrene/butadiene copolymers | |
JP2014514390A (ja) | 伸縮性フィルム積層接着剤 | |
JP6283029B2 (ja) | 粘着剤組成物及び粘着剤シート | |
US10647795B2 (en) | Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins | |
JP6621045B2 (ja) | 熱可塑性樹脂組成物、ホットメルト接着剤、自動車部材、及び衛生材料部材 | |
US11390701B2 (en) | Amorphous propylene-ethylene copolymers | |
US20200317833A1 (en) | Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer | |
US11267916B2 (en) | Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins | |
JP6328536B2 (ja) | 粘接着剤組成物 | |
JPH083526A (ja) | ホットメルト組成物 | |
WO2020085299A1 (ja) | ホットメルト接着剤 | |
JP2023505302A (ja) | 改善された特性プロファイルを有する熱可塑性成形材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018563633 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18841020 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 3067000 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2018841020 Country of ref document: EP Effective date: 20200302 |