JP2020176202A - Solvent type pressure sensitive adhesive composition and pressure sensitive adhesive sheet - Google Patents
Solvent type pressure sensitive adhesive composition and pressure sensitive adhesive sheet Download PDFInfo
- Publication number
- JP2020176202A JP2020176202A JP2019079185A JP2019079185A JP2020176202A JP 2020176202 A JP2020176202 A JP 2020176202A JP 2019079185 A JP2019079185 A JP 2019079185A JP 2019079185 A JP2019079185 A JP 2019079185A JP 2020176202 A JP2020176202 A JP 2020176202A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- solvent
- mass
- meth
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 239000002904 solvent Substances 0.000 title claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 122
- 229920005989 resin Polymers 0.000 claims abstract description 100
- 239000011347 resin Substances 0.000 claims abstract description 100
- -1 acrylic ester Chemical class 0.000 claims abstract description 58
- 229920001577 copolymer Polymers 0.000 claims abstract description 52
- 235000007586 terpenes Nutrition 0.000 claims abstract description 46
- 150000003505 terpenes Chemical class 0.000 claims abstract description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims description 88
- 230000001070 adhesive effect Effects 0.000 claims description 88
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 47
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 17
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- 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 claims 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 claims description 12
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- 125000001931 aliphatic group Chemical group 0.000 claims description 11
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- 235000005128 Sapium sebiferum Nutrition 0.000 claims description 2
- 244000057114 Sapium sebiferum Species 0.000 claims description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 239000004593 Epoxy Substances 0.000 description 4
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- 125000003545 alkoxy group Chemical group 0.000 description 3
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- 239000004744 fabric Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- REJKHFKLPFJGAQ-UHFFFAOYSA-N oxiran-2-ylmethanethiol Chemical compound SCC1CO1 REJKHFKLPFJGAQ-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- FQYWWLSIKWDAEC-UHFFFAOYSA-N tributoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCOCC1CO1 FQYWWLSIKWDAEC-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、溶剤型粘着剤組成物および粘着シートに関する。 The present invention relates to solvent-based pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets.
粘着剤組成物から形成した粘着剤層を有する粘着シートは、接着剤と比べて取り扱いが容易であることから、表示用ラベルや固定用テープとして幅広い分野で使用されている。粘着シートをプラスチックや金属等の容器の内容物を表示するラベルとして使用することは多々あるが、特に使用環境が低温の場合、ラベルが被着体から浮いたり剥がれが生じたりするという問題があった。 An adhesive sheet having an adhesive layer formed from an adhesive composition is easier to handle than an adhesive, and is therefore used in a wide range of fields as a display label and a fixing tape. Adhesive sheets are often used as labels to display the contents of containers such as plastic and metal, but there is a problem that the label may float or peel off from the adherend, especially when the usage environment is low temperature. It was.
特許文献１には、２０質量％以上のｎ−オクチルアクリレートを含む炭素数１〜１４のアルキル基を有する１種以上のアルキルアクリレートと共重合可能な官能性モノマーとを主成分とし、溶剤中で共重合して得られたアクリル系溶剤型粘着剤が開示されている。しかし、実施例に記載されているアクリル系共重合体と併用するタッキファイヤが液状ロジンであり、これでは低温タックは発現するものの、加工性が不足しているという問題があった。
また、特許文献２には、（メタ）アクリル共重合体１００質量部及び粘着付与樹脂５〜３０質量部を含有する感圧接着剤組成物において、上記粘着付与樹脂が（Ａ）２０℃で粘稠体である粘着付与樹脂の少なくとも一種及び（Ｂ）２０℃で固体である粘着付与樹脂の少なくとも一種を含有し、且つ該（Ａ）成分の含有量と該（Ｂ）成分の含有量との質量比Ａ／Ｂが０．１〜９であることを特徴とする感圧接着剤組成物が開示されている。しかし、低温環境下では十分にタック性が発現しないという問題があった。
Patent Document 1 contains, as a main component, a functional monomer copolymerizable with one or more alkyl acrylates having an alkyl group having 1 to 14 carbon atoms including 20% by mass or more of n-octyl acrylate, and in a solvent. An acrylic solvent-based pressure-sensitive adhesive obtained by copolymerization is disclosed. However, the tack fire used in combination with the acrylic copolymer described in the examples is liquid rosin, which has a problem that low-temperature tack is exhibited but processability is insufficient.
Further, in Patent Document 2, in a pressure-sensitive adhesive composition containing 100 parts by mass of a (meth) acrylic copolymer and 5 to 30 parts by mass of a tackifier resin, the tackifier resin is (A) sticky at 20 ° C. The content of the component (A) and the content of the component (B), which contain at least one of the cohesive tackifier resin and (B) at least one of the tackifier resin which is solid at 20 ° C. A pressure-sensitive adhesive composition having a mass ratio of A / B of 0.1 to 9 is disclosed. However, there is a problem that tackiness is not sufficiently developed in a low temperature environment.
本発明が解決しようとする課題は、低温〜常温（−１０〜２５℃程度）での粘着力とタック性に優れると共に、高温（４０℃以上）での保持力と加工性に優れた溶剤型粘着剤組成物を提供することである。 The problem to be solved by the present invention is a solvent type having excellent adhesive strength and tackiness at low temperature to normal temperature (about −10 to 25 ° C.) and excellent holding power and workability at high temperature (40 ° C. or higher). The purpose is to provide a pressure-sensitive adhesive composition.
本発明者らは上記課題を解決すべく鋭意検討を重ねた結果、以下に示す溶剤型粘着剤組成物により、上記目的が達成できることを見出し、本発明を完成するに至った。
即ち、本発明の実施態様は、共重合体、硬化剤、粘着付与樹脂、および有機溶剤を含む溶剤型粘着剤組成物であって、前記共重合体が、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）、およびカルボキシル基を有するモノマー（Ｂ）を含むモノマー混合物の共重合体であり、前記粘着付与樹脂がテルペン樹脂を含み、溶剤型粘着剤組成物の硬化物である粘着剤層１００質量％中、前記共重合体の含有量が４０質量％以上である、溶剤型粘着剤組成物である。
As a result of diligent studies to solve the above problems, the present inventors have found that the above object can be achieved by the solvent-type pressure-sensitive adhesive composition shown below, and have completed the present invention.
That is, an embodiment of the present invention is a solvent-type pressure-sensitive adhesive composition containing a copolymer, a curing agent, a tackifier resin, and an organic solvent, wherein the copolymer has an alkyl group having 8 to 12 carbon atoms. It is a copolymer of a monomer mixture containing the (meth) acrylic acid ester monomer (A) and the monomer (B) having a carboxyl group, and the tackifier resin contains a terpene resin, and the solvent-type pressure-sensitive adhesive composition is cured. It is a solvent-type pressure-sensitive adhesive composition in which the content of the copolymer is 40% by mass or more in 100% by mass of the pressure-sensitive adhesive layer which is a product.
また本発明は、前記粘着付与樹脂は、さらに脂肪族系石油樹脂、芳香族系石油樹、脂脂肪族／芳香族系石油樹脂およびロジン誘導体からなる群より選ばれる少なくとも１種の粘着付与樹脂を含む、前記溶剤型粘着剤組成物に関する。 Further, in the present invention, the tackifier resin is at least one tackifier resin selected from the group consisting of an aliphatic petroleum resin, an aromatic petroleum tree, an aliphatic / aromatic petroleum resin and a rosin derivative. The present invention relates to the solvent-type pressure-sensitive adhesive composition.
また本発明は、前記テルペン樹脂の含有量は、前記粘着付与樹脂の合計１００質量％中、５０質量％以上である、前記溶剤型粘着剤組成物に関する。 The present invention also relates to the solvent-based pressure-sensitive adhesive composition, wherein the content of the terpene resin is 50% by mass or more in a total of 100% by mass of the pressure-sensitive adhesive resin.
また本発明は、前記テルペン樹脂が、構造単位としてテルペンのみからなる樹脂である、前記溶剤型粘着剤組成物に関する。 The present invention also relates to the solvent-based pressure-sensitive adhesive composition, wherein the terpene resin is a resin composed of only terpenes as a structural unit.
また本発明は、前記有機溶剤が、炭化水素系溶剤である、前記溶剤型粘着剤組成物に関する。 The present invention also relates to the solvent-type pressure-sensitive adhesive composition in which the organic solvent is a hydrocarbon-based solvent.
また本発明は、前記カルボキシル基を有するモノマー（Ｂ）が、（メタ）アクリル酸２‐カルボキシエチルを含む、前記溶剤型粘着剤組成物に関する。 The present invention also relates to the solvent-based pressure-sensitive adhesive composition, wherein the monomer (B) having a carboxyl group contains 2-carboxyethyl (meth) acrylate.
また本発明は、前記（メタ）アクリル酸２‐カルボキシエチルの含有量は、カルボキシル基を有するモノマー（Ｂ）の合計１００質量％中、５０質量％以上である、前記溶剤型粘着剤組成物に関する。 The present invention also relates to the solvent-based pressure-sensitive adhesive composition, wherein the content of 2-carboxyethyl (meth) acrylic acid is 50% by mass or more based on 100% by mass of the total of the monomer (B) having a carboxyl group. ..
また本発明は、カルボキシル基を有するモノマー（Ｂ）が、（メタ）アクリル酸および（メタ）アクリル酸２‐カルボキシエチルを含む、前記溶剤型粘着剤組成物に関する。 The present invention also relates to the solvent-based pressure-sensitive adhesive composition, wherein the monomer (B) having a carboxyl group contains (meth) acrylic acid and 2-carboxyethyl (meth) acrylic acid.
また本発明は、前記モノマー混合物が、さらにアルキル基の炭素数が１〜３の（メタ）アクリル酸エステルモノマー（Ｃ）または炭素数１〜３のカルボン酸のビニルエステルモノマー（Ｄ）を含む、前記溶剤型粘着剤組成物に関する。 Further, in the present invention, the monomer mixture further contains a (meth) acrylic acid ester monomer (C) having an alkyl group having 1 to 3 carbon atoms or a vinyl ester monomer (D) having a carboxylic acid having 1 to 3 carbon atoms. The present invention relates to the solvent type pressure-sensitive adhesive composition.
また本発明は、前記モノマー混合物１００質量％中、前記アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）を８０〜９７質量％含む、前記溶剤型粘着剤組成物に関する。 The present invention also relates to the solvent-based pressure-sensitive adhesive composition containing 80 to 97% by mass of a (meth) acrylic acid ester monomer (A) having an alkyl group having 8 to 12 carbon atoms in 100% by mass of the monomer mixture. ..
また本発明は、基材、および前記溶剤型粘着剤組成物の硬化物である粘着剤層を備える、粘着シートに関する。 The present invention also relates to a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer which is a cured product of the solvent-based pressure-sensitive adhesive composition.
また、本発明の実施態様は、基材、および上記溶剤型粘着剤組成物の硬化物である粘着剤層を備える、粘着シートである。 Further, an embodiment of the present invention is a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer which is a cured product of the solvent-based pressure-sensitive adhesive composition.
本発明によって、低温〜常温（−１０〜２５℃程度）での粘着力とタック性に優れると共に、高温（４０℃以上）での保持力と加工性に優れた溶剤型粘着剤組成物を提供することができるようになった。 INDUSTRIAL APPLICABILITY According to the present invention, a solvent-type pressure-sensitive adhesive composition having excellent adhesive strength and tackiness at low temperature to normal temperature (about −10 to 25 ° C.) and excellent holding power and processability at high temperature (40 ° C. or higher) is provided. You can now do it.
本発明の説明の前に用語を定義する。本明細書では、「被着体」とは、粘着シートを貼り付ける対象物をいう。「テープ」、「フィルム」、「シート」は同義である。また「（メタ）アクリル酸エステルモノマー」とは、アクリル酸エステルモノマー及びメタクリル酸エステルモノマーを表し、単にモノマーと表記する場合もある。本明細書において、特に明記しない限り、「分子量」は、重量平均分子量（Ｍｗ）を意味する。 Terms are defined before the description of the present invention. In the present specification, the “adhesive body” refers to an object to which the adhesive sheet is attached. "Tape", "film" and "sheet" are synonymous. Further, the "(meth) acrylic acid ester monomer" represents an acrylic acid ester monomer and a methacrylic acid ester monomer, and may be simply referred to as a monomer. In the present specification, unless otherwise specified, "molecular weight" means weight average molecular weight (Mw).
≪溶剤型粘着剤組成物≫
本発明の溶剤型粘着剤組成物は、共重合体、硬化剤、粘着付与樹脂、および有機溶剤を含む溶剤型粘着剤組成物であって、前記共重合体が、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）、およびカルボキシル基を有するモノマー（Ｂ）を含むモノマー混合物の共重合体であり、前記粘着付与樹脂がテルペン樹脂を含み、溶剤型粘着剤組成物の硬化物である粘着剤層１００質量％中、前記共重合体の含有量が４０質量％以上である。
≪Solvent type adhesive composition≫
The solvent-type pressure-sensitive adhesive composition of the present invention is a solvent-type pressure-sensitive adhesive composition containing a copolymer, a curing agent, a tackifier resin, and an organic solvent, and the copolymer has an alkyl group having 8 carbon atoms. A copolymer of a monomer mixture containing the (meth) acrylic acid ester monomer (A) and the monomer (B) having a carboxyl group, wherein the tackifier resin contains a terpene resin, and is a solvent-type pressure-sensitive adhesive composition. The content of the copolymer is 40% by mass or more in 100% by mass of the pressure-sensitive adhesive layer which is the cured product of.
＜共重合体＞
本発明で用いられる共重合体は、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）およびカルボキシル基を有するモノマー（Ｂ）を含むモノマー混合物を重合して得ることができる。共重合体の重合方法は、低温環境下の粘着力、タック性と加工性、保持力の両立の点で、溶液重合が好ましい。なお本明細書で溶液重合は、紫外線重合、塊状重合等の溶媒に水を含まない重合方法を包含している。
<Copolymer>
The copolymer used in the present invention can be obtained by polymerizing a monomer mixture containing a (meth) acrylic acid ester monomer (A) having an alkyl group having 8 to 12 carbon atoms and a monomer (B) having a carboxyl group. it can. As a polymerization method of the copolymer, solution polymerization is preferable from the viewpoint of achieving both adhesive strength, tackiness and processability, and holding power in a low temperature environment. In the present specification, solution polymerization includes a polymerization method in which water is not contained in a solvent such as ultraviolet polymerization and bulk polymerization.
本発明では、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）およびカルボキシル基を有するモノマー（Ｂ）含むモノマー混合物の共重合体、硬化剤、ならびにテルペン樹脂を併用することで、低温環境下の粘着力、タック性と加熱環境下での加工性、保持力の両立を実現できた。一般に（メタ）アクリル酸アルキルエステルモノマーを主成分としたアクリル共重合体を含む溶剤型粘着剤組成物を使用した粘着シートは、低温環境下での粘着力を付与するためにアルキル基の炭素数の長いモノマーを使用することで、共重合体のガラス転移温度を低くする手法、粘着付与樹脂を添加する手法が用いられる。
しかし、アルキル基の炭素数の長いモノマーを使用することで凝集力が不足し、加工性の悪化や粘着付与樹脂を添加することでタック性が低下する問題が生じる。そこで本発明ではアルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）とカルボキシル基を有するモノマー（Ｂ）を併用することで加熱環境下での加工性の悪化を抑制し、十分な保持力を発現させた。また粘着付与樹脂にテルペン樹脂を選定することで低温環境化でも良好な粘着力とタック性を得ることができた。
In the present invention, a copolymer, a curing agent, and a terpene resin of a monomer mixture containing a (meth) acrylic acid ester monomer (A) having an alkyl group having 8 to 12 carbon atoms and a monomer (B) having a carboxyl group are used in combination. As a result, it was possible to achieve both adhesive strength and tackiness in a low temperature environment and processability and holding power in a heating environment. In general, a pressure-sensitive adhesive sheet using a solvent-based pressure-sensitive adhesive composition containing an acrylic copolymer containing a (meth) acrylic acid alkyl ester monomer as a main component has the number of carbon atoms of the alkyl group in order to impart adhesive strength in a low-temperature environment. A method of lowering the glass transition temperature of the copolymer and a method of adding a tackifier resin are used by using a long monomer.
However, the use of a monomer having a long number of carbon atoms of an alkyl group causes a problem that the cohesive force is insufficient, the processability is deteriorated, and the tackiness is lowered by adding a tackifier resin. Therefore, in the present invention, the deterioration of processability in a heating environment is suppressed by using the (meth) acrylic acid ester monomer (A) having an alkyl group having 8 to 12 carbon atoms and the monomer (B) having a carboxyl group in combination. , Sufficient holding power was expressed. In addition, by selecting a terpene resin as the tackifying resin, good adhesive strength and tackiness could be obtained even in a low temperature environment.
［アルキル鎖の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー］
本発明においてアルキル鎖の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）は、炭素数が８〜１２の範囲にあることで共重合体のガラス転移温度を低くすることができ、低温環境下で良好な粘着力とタック性を得ることができる。具体的には、例えば、（メタ）アクリル酸オクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシルなどが挙げられる。アルキル基の構造は、直鎖構造、分岐構造のいずれの構造を有しても良い。さらに、これらの中でも（メタ）アクリル酸オクチル、特に分岐構造を有するアクリル酸オクチルは、低温環境下での粘着力、タック性が優れるためより好ましい。これらのモノマーは、単独または２種以上を併用できる。
[(Meta) acrylic acid ester monomer having 8 to 12 carbon atoms in the alkyl chain]
In the present invention, the (meth) acrylic acid ester monomer (A) having an alkyl chain having 8 to 12 carbon atoms can lower the glass transition temperature of the copolymer when the carbon number is in the range of 8 to 12. , Good adhesive strength and tackiness can be obtained in a low temperature environment. Specific examples thereof include octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecylic (meth) acrylate, and dodecyl (meth) acrylate. The structure of the alkyl group may have either a linear structure or a branched structure. Further, among these, octyl (meth) acrylate, particularly octyl acrylate having a branched structure, is more preferable because it has excellent adhesive strength and tackiness in a low temperature environment. These monomers can be used alone or in combination of two or more.
アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）は、共重合に使用するモノマー混合物１００質量％中、７０〜９７質量％を含むことが好ましく、８０〜９７質量％がより好ましく、９０〜９７質量％が特に好ましい。７０質量％以上であれば低温環境で良好な粘着力、タック性が得やすくなる。９７質量％以下であれば加熱環境下での加工性、保持力が良好となる。 The (meth) acrylic acid ester monomer (A) having an alkyl group having 8 to 12 carbon atoms preferably contains 70 to 97% by mass, preferably 80 to 97% by mass, based on 100% by mass of the monomer mixture used for copolymerization. Is more preferable, and 90 to 97% by mass is particularly preferable. If it is 70% by mass or more, good adhesive strength and tackiness can be easily obtained in a low temperature environment. If it is 97% by mass or less, the workability and holding power in a heating environment are good.
［カルボキシル基を有するモノマー（Ｂ）］
カルボキシル基を有するモノマー（Ｂ）は、カルボキシル基を含有することで粘着力、タック性、加工性のバランスの優れた共重合体を得ることができる。
具体的には、例えば、（メタ）アクリル酸、（メタ）アクリル酸２‐カルボキシエチル、（メタ）アクリル酸２−サクシノイルオキシエチル、マレイン酸、モノエチルマレイン酸、イタコン酸、シトラコン酸、フマル酸などが挙げられる。さらにこれらのなかでも（メタ）アクリル酸、（メタ）アクリル酸２‐カルボキシエチルが共重合性の面で好ましい。
これらのモノマーは、単独または２種以上を併用でき、（メタ）アクリル酸２‐カルボキシエチルを含むことがタック性の面で特に好ましい。
[Monomer having a carboxyl group (B)]
Since the monomer (B) having a carboxyl group contains a carboxyl group, a copolymer having an excellent balance of adhesive strength, tackiness and processability can be obtained.
Specifically, for example, (meth) acrylic acid, (meth) acrylic acid 2-carboxyethyl, (meth) acrylic acid 2-succinoyloxyethyl, maleic acid, monoethylmaleic acid, itaconic acid, citraconic acid, fumaric acid. Examples include acid. Further, among these, (meth) acrylic acid and 2-carboxyethyl (meth) acrylic acid are preferable in terms of copolymerizability.
These monomers can be used alone or in combination of two or more, and it is particularly preferable that they contain 2-carboxyethyl (meth) acrylate in terms of tackiness.
（メタ）アクリル酸２‐カルボキシエチルの比率はカルボキシル基を有するモノマー（Ｂ）の合計１００質量％中、５０質量％以上であることが好ましく、５０〜９０質量％含むことがより好ましく、さらに好ましくは６０〜９０重量％である。５０質量％以上含むことで低温時の粘着力、タックがより良好となる。 The ratio of 2-carboxyethyl (meth) acrylate is preferably 50% by mass or more, more preferably 50 to 90% by mass, still more preferably, out of a total of 100% by mass of the monomer (B) having a carboxyl group. Is 60 to 90% by weight. By containing 50% by mass or more, the adhesive strength and tack at low temperature become better.
カルボキシル基を有するモノマー（Ｂ）は重合に使用するモノマー混合物１００質量％中、０．５〜１０質量％含むことが好ましく、１〜８質量％がより好ましく、１．５〜６質量％が更に好ましく、２〜５質量％が特に好ましい。０．５質量％以上であれば加熱環境下で十分な加工性、保持力が得られ、１０質量％以下であれば低温環境下での粘着力、タック性を維持することができる。 The monomer (B) having a carboxyl group preferably contains 0.5 to 10% by mass, more preferably 1 to 8% by mass, and further 1.5 to 6% by mass in 100% by mass of the monomer mixture used for polymerization. It is preferable, and 2 to 5% by mass is particularly preferable. If it is 0.5% by mass or more, sufficient processability and holding power can be obtained in a heating environment, and if it is 10% by mass or less, adhesive strength and tackiness in a low temperature environment can be maintained.
［アルキル基の炭素数が１〜３の（メタ）アクリル酸エステルモノマー（Ｃ）
および炭素数が１〜３のカルボン酸のビニルエステルモノマー（Ｄ）］
本発明においてアルキル基の炭素数が１〜３の（メタ）アクリル酸エステルモノマー（Ｃ）および炭素数が１〜３のカルボン酸のビニルエステルモノマー（Ｄ）は、炭素数が１〜３の範囲にあることで共重合体に凝集力を付与することができ、加熱環境下で良好な加工性を得ることができる。
具体的には、アルキル基の炭素数が１〜３の（メタ）アクリル酸エステルモノマー（Ｃ）は、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピルなどが挙げられる。炭素数１〜３のカルボン酸ビニルモノマー（Ｄ）は、例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニルなどが挙げられる。
炭素数が１〜３のカルボン酸のビニルエステルモノマー（Ｄ）のアルキル基の構造は、直鎖構造、分岐構造のいずれの構造を有しても良い。さらに、これらの中でも（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、酢酸ビニルは高い凝集力を付与することができるためより好ましい。
これらのモノマーは、単独または２種以上を併用できる。
[(Meta) acrylic acid ester monomer (C) having 1 to 3 carbon atoms in the alkyl group
And vinyl ester monomer (D) of carboxylic acid having 1 to 3 carbon atoms]
In the present invention, the (meth) acrylic acid ester monomer (C) having an alkyl group having 1 to 3 carbon atoms and the vinyl ester monomer (D) having a carboxylic acid having 1 to 3 carbon atoms have a carbon number in the range of 1 to 3. It is possible to impart a cohesive force to the copolymer and obtain good processability in a heating environment.
Specifically, the (meth) acrylate monomer (C) having an alkyl group having 1 to 3 carbon atoms includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and the like. Can be mentioned. Examples of the vinyl carboxylate monomer (D) having 1 to 3 carbon atoms include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
The structure of the alkyl group of the vinyl ester monomer (D) of the carboxylic acid having 1 to 3 carbon atoms may have either a linear structure or a branched structure. Further, among these, methyl (meth) acrylate, ethyl (meth) acrylate, and vinyl acetate are more preferable because they can impart high cohesive force.
These monomers can be used alone or in combination of two or more.
アルキル基の炭素数が１〜３の（メタ）アクリル酸エステルモノマー（Ｃ）および炭素数が１〜３のカルボン酸のビニルエステルモノマー（Ｄ）は、共重合に使用するモノマー混合物１００質量％中、合計で１〜４０質量％を含むことが好ましく、２〜２０質量％がより好ましく、２〜１５質量％が更に好ましく、２〜１０質量％が特に好ましい。１質量％以上を含むことで共重合体に凝集力を付与することができ、４０質量％以下にすることで低温環境下での粘着力、タック性を維持することができる。 The (meth) acrylic acid ester monomer (C) having an alkyl group having 1 to 3 carbon atoms and the vinyl ester monomer (D) having a carboxylic acid having 1 to 3 carbon atoms are contained in 100% by mass of the monomer mixture used for copolymerization. , 1 to 40% by mass in total, more preferably 2 to 20% by mass, further preferably 2 to 15% by mass, and particularly preferably 2 to 10% by mass. When it contains 1% by mass or more, the cohesive force can be imparted to the copolymer, and when it contains 40% by mass or less, the adhesive force and tackiness in a low temperature environment can be maintained.
［その他モノマー］
本発明では共重合体の合成にその他モノマーを使用することができる。その他モノマーとは、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）、カルボキシル基を有するモノマー（Ｂ）、アルキル基の炭素数が１〜３の（メタ）アクリル酸エステルモノマー（Ｃ）または炭素数が１〜３のカルボン酸のビニルエステルモノマー（Ｄ）以外の共重合可能なモノマーを指す。
[Other monomers]
In the present invention, other monomers can be used for the synthesis of the copolymer. Other monomers include a (meth) acrylic acid ester monomer (A) having an alkyl group having 8 to 12 carbon atoms, a monomer (B) having a carboxyl group, and a (meth) acrylic acid having an alkyl group having 1 to 3 carbon atoms. Refers to a copolymerizable monomer other than the ester monomer (C) or the vinyl ester monomer (D) of a carboxylic acid having 1 to 3 carbon atoms.
具体的には、反応性官能基含有モノマー、アルキル基の炭素数が４〜２０の（メタ）アクリル酸アルキルエステルモノマー（ただし、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）を除く）、芳香環含有モノマー、アルコキシ（ポリ）アルキレンオキサイド含有モノマーおよびその他ビニルモノマーが好ましい。
反応性官能基含有モノマーとしては、水酸基含有モノマー、アミド結合含有モノマー、エポキシ基含有モノマー、アミノ基含有モノマー等が好ましい。
Specifically, a reactive functional group-containing monomer, a (meth) acrylic acid ester monomer having an alkyl group having 4 to 20 carbon atoms (however, a (meth) acrylic acid ester monomer having an alkyl group having 8 to 12 carbon atoms). (Excluding (A)), aromatic ring-containing monomer, alkoxy (poly) alkylene oxide-containing monomer and other vinyl monomer are preferable.
As the reactive functional group-containing monomer, a hydroxyl group-containing monomer, an amide bond-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer and the like are preferable.
アルキル基の炭素数が４〜２０の（メタ）アクリル酸アルキルエステルモノマー（ただし、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）を除く）としては、例えば、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸イコシルなどが挙げられる。 Examples of the (meth) acrylic acid alkyl ester monomer having 4 to 20 carbon atoms in the alkyl group (excluding the (meth) acrylic acid ester monomer (A) having 8 to 12 carbon atoms in the alkyl group) include ( Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, (meth) ) Icocil acrylate and the like can be mentioned.
アルキル基の炭素数が４〜２０の（メタ）アクリル酸アルキルエステルモノマー（ただし、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）を除く）は、モノマー混合物１００質量％中、１〜１５質量部含むことが好ましい。 The (meth) acrylic acid alkyl ester monomer having 4 to 20 carbon atoms in the alkyl group (excluding the (meth) acrylic acid ester monomer (A) having 8 to 12 carbon atoms in the alkyl group) has 100 mass by mass of the monomer mixture. It is preferable to contain 1 to 15 parts by mass in%.
水酸基含有モノマーとしては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸３−ヒドロキシブチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル、（メタ）アクリル酸８−ヒドロキシオクチルなどの（メタ）アクリル酸ヒドロキシアルキルエステルや、ポリエチレングリコールモノ（メタ）アクリル酸エステル、ポリプロピレングリコールモノ（メタ）アクリル酸エステル、１，４−シクロヘキサンジメタノールモノ（メタ）アクリル酸エステルなどのグリコールモノ（メタ）アクリル酸エステル、カプロラクトン変性（メタ）アクリル酸エステル、ヒドロキシエチルアクリルアミドなどが挙げられる。これらの中でも、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸４−ヒドロキシブチルが好ましい。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (meth) acrylic. (Meta) acrylate hydroxyalkyl esters such as 3-hydroxybutyl acid, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and polyethylene glycol mono Glycol mono (meth) acrylic acid ester such as (meth) acrylic acid ester, polypropylene glycol mono (meth) acrylic acid ester, 1,4-cyclohexanedimethanol mono (meth) acrylic acid ester, caprolactone-modified (meth) acrylic acid ester , Hydroxyethyl acrylamide and the like. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.
水酸基含有モノマーは、モノマー混合物１００質量％中、０．１〜８質量％を含むことが好ましく、０．２〜６質量％がより好ましい。０．１〜８質量％含むことで硬化剤との架橋密度を適切な範囲に調整し易くなる。 The hydroxyl group-containing monomer preferably contains 0.1 to 8% by mass, more preferably 0.2 to 6% by mass, based on 100% by mass of the monomer mixture. By containing 0.1 to 8% by mass, it becomes easy to adjust the crosslink density with the curing agent within an appropriate range.
アミド結合含有モノマーとしては、（メタ）アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ、Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、ジアセトンアクリルアミド、Ｎ−(ヒドロキシメチル)アクリルアミド、Ｎ−(ブトキシメチル)アクリルアミド、などの（メタ）アクリルアミド系の化合物、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、アクリロイルモルホリンなどの複素環を含有した化合物、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニル−Ｎ−メチルアセトアミドなどが挙げられる。 Examples of the amide bond-containing monomer include (meth) acrylamide, N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and diacetone. (Meta) acrylamide-based compounds such as acrylamide, N- (hydroxymethyl) acrylamide, N- (butoxymethyl) acrylamide, compounds containing heterocycles such as N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholin, N -Vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamamide and the like can be mentioned.
エポキシ基含有モノマーとしては、（メタ）アクリル酸グリシジル、（メタ）アクリル酸メチルグリシジル、（メタ）アクリル酸３，４−エポキシシクロヘキシルメチル、（メタ）アクリル酸６−メチル−３，４−エポキシシクロヘキシルメチルなどが挙げられる。 Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 6-methyl-3,4-epoxycyclohexyl (meth) acrylate. Examples include methyl.
アミノ基含有モノマーとしては、（メタ）アクリル酸モノメチルアミノエチル、（メタ）アクリル酸モノエチルアミノエチル、（メタ）アクリル酸モノメチルアミノプロピル、（メタ）アクリル酸モノエチルアミノプロピルなどの（メタ）アクリル酸モノアルキルアミノエステルなどが挙げられる。 Examples of the amino group-containing monomer include (meth) acrylics such as monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate. Examples include acid monoalkylamino ester.
アミド結合含有モノマー、エポキシ基含有モノマーおよびアミノ基含有モノマーは、モノマー混合物１００質量％中、それぞれ０．１〜１５質量％含むことが好ましい。反応性官能基含有モノマーは、単独または２種以上を併用できる。 The amide bond-containing monomer, the epoxy group-containing monomer, and the amino group-containing monomer are preferably contained in an amount of 0.1 to 15% by mass in 100% by mass of the monomer mixture. The reactive functional group-containing monomer may be used alone or in combination of two or more.
芳香環含有モノマーとしては、（メタ）アクリル酸フェニル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェノキシジエチレングリコール、（メタ）アクリル酸エチレンオキサイド変性ノニルフェノール、（メタ）アクリル酸ビフェニル、スチレン、ビニルトルエン、α-メチルスチレンなどが挙げられる。芳香環含有モノマーは、モノマー混合物１００質量％中、１〜１５質量％含むことが好ましい。 Examples of the aromatic ring-containing monomer include phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, and (meth). Examples thereof include biphenyl acrylate, styrene, vinyl toluene, and α-methylstyrene. The aromatic ring-containing monomer is preferably contained in an amount of 1 to 15% by mass based on 100% by mass of the monomer mixture.
アルコキシ（ポリ）アルキレンオキサイド含有モノマーとしては、アクリル酸２−メトキシエチル、アクリル酸２−エトキシエチル、アクリル酸２−フェノキシエチル、メトキシポリエチレングリコール（メタ）アクリル酸エステル、エトキシポリエチレングリコール（メタ）アクリル酸エステル、メトキシポリプロピレングリコール（メタ）アクリル酸エステル、エトキシポリプロピレングリコール（メタ）アクリル酸エステル、フェノキシポリエチレングリコール（メタ）アクリル酸エステル、フェノキシポリプロピレングリコール（メタ）アクリル酸エステルなどが挙げられる。アルコキシ（ポリ）アルキレンオキサイド含有モノマーは、モノマー混合物１００質量％中、１〜１５質量％含むことが好ましい。 Examples of the alkoxy (poly) alkylene oxide-containing monomer include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth) acrylic acid ester, and ethoxypolyethylene glycol (meth) acrylic acid. Examples thereof include esters, methoxypolypropylene glycol (meth) acrylic acid esters, ethoxypolypropylene glycol (meth) acrylic acid esters, phenoxypolyethylene glycol (meth) acrylic acid esters, and phenoxypolyethylene glycol (meth) acrylic acid esters. The alkoxy (poly) alkylene oxide-containing monomer is preferably contained in an amount of 1 to 15% by mass based on 100% by mass of the monomer mixture.
その他ビニルモノマーは、スチレン、アクリロニトリルなどが挙げられる。これら以外の共重合可能なモノマーを適宜選択することができる。その他ビニルモノマーは、モノマー混合物１００質量％中、１〜１５質量％含むことが好ましい。 Other vinyl monomers include styrene and acrylonitrile. Copolymerizable monomers other than these can be appropriately selected. The other vinyl monomer is preferably contained in an amount of 1 to 15% by mass based on 100% by mass of the monomer mixture.
［共重合体の製造方法］
共重合体は、モノマー混合物に重合開始剤を加え、溶液重合、塊状重合、各種ラジカル重合などの公知の製造方法を適宜選択して行うことができる。これらの中でも、溶液重合が、共重合体の重量平均分子量の調整が容易である点から好ましい。
[Method for producing copolymer]
The copolymer can be carried out by adding a polymerization initiator to the monomer mixture and appropriately selecting a known production method such as solution polymerization, bulk polymerization, and various radical polymerizations. Among these, solution polymerization is preferable because it is easy to adjust the weight average molecular weight of the copolymer.
溶液重合で使用できる溶媒は、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、トルエン、キシレン、ヘキサン、シクロヘキサン、メチルシクロヘキサン、ヘプタン、アセトン、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、プロパノール、およびイソプロパノール等が好ましい。これらは単独また２種類以上を適宜選択できる。溶剤は、トルエン、キシレン、ヘキサン、シクロヘキサン、メチルシクロヘキサン、ヘプタンといった炭化水素系溶剤を含有することが好ましい。また炭化水素系溶剤のなかでも環境規制の観点からヘキサン、ヘプタンといった芳香環を有さない炭化水素系溶剤が特に好ましい。 Solvents that can be used in solution polymerization include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, toluene, xylene, hexane, cyclohexane, methylcyclohexane, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, and isopropanol. Is preferable. These can be selected individually or two or more types as appropriate. The solvent preferably contains a hydrocarbon solvent such as toluene, xylene, hexane, cyclohexane, methylcyclohexane and heptane. Among the hydrocarbon solvents, hydrocarbon solvents such as hexane and heptane which do not have an aromatic ring are particularly preferable from the viewpoint of environmental regulation.
炭化水素系溶剤は、共重合に使用するモノマー混合物１００質量部に対して、１０〜２００質量部含むことが好ましい。１０〜２００質量部含むことで共重合体とテルペン樹脂の相溶性を向上させることができる。 The hydrocarbon solvent is preferably contained in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the monomer mixture used for the copolymerization. By containing 10 to 200 parts by mass, the compatibility between the copolymer and the terpene resin can be improved.
溶液重合は、モノマー混合物の合計１００質量部に対して、重合開始剤を０．００１〜１質量部用いるのが好ましい。通常、重合反応は、窒素気流下で、５０℃〜９０℃程度の温度で６時間〜２０時間行うことができる。また、重合反応に連鎖移動剤を使用して共重合体の重量平均分子量を適宜調整することができる。 For solution polymerization, it is preferable to use 0.001 to 1 part by mass of the polymerization initiator with respect to 100 parts by mass in total of the monomer mixture. Usually, the polymerization reaction can be carried out at a temperature of about 50 ° C. to 90 ° C. for 6 hours to 20 hours under a nitrogen stream. In addition, the weight average molecular weight of the copolymer can be appropriately adjusted by using a chain transfer agent in the polymerization reaction.
本発明において共重合体の重量平均分子量は、２０万〜１２０万が好ましく、４０万〜１００万がより好ましく、５０万〜９０万がさらに好ましく、５０万〜８０万が特に好ましい。重量平均分子量を２０万〜１２０万の範囲にすることで、粘着物性と塗工性のバランスを両立することができる。 In the present invention, the weight average molecular weight of the copolymer is preferably 200,000 to 1.2 million, more preferably 400,000 to 1,000,000, further preferably 500,000 to 900,000, and particularly preferably 500,000 to 800,000. By setting the weight average molecular weight in the range of 200,000 to 1.2 million, it is possible to achieve both adhesive physical properties and coatability.
連鎖移動剤は、例えば、ｎ−ドデシルメルカプタン、メルカプトイソブチルアルコール、メルカプト酢酸、２−メルカプトエタノール、チオグリコール酸、チオグルコール酸２−エチルヘキシル、２，３−ジメルカプト−１−プロパノール、グリシジルメルカプタン、α−メチルスチレンダイマー、四塩化炭素、クロロホルム、ハイドロキノン等が挙げられる。 Chain transfer agents include, for example, n-dodecyl mercaptan, mercaptoisobutyl alcohol, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglucolate, 2,3-dimercapto-1-propanol, glycidyl mercaptan, α-methyl. Examples thereof include styrene dimer, carbon tetrachloride, chloroform, hydroquinone and the like.
重合開始剤は、アゾ系化合物、有機過酸化物が一般的である。アゾ系化合物は、例えば、２，２'−アゾビスイソブチロニトリル、２，２'−アゾビス（２−メチルブチロニトリル）、１，１'−アゾビス（シクロヘキサン１−カルボニトリル）、２，２'−アゾビス（２，４−ジメチルバレロニトリル）、２，２'−アゾビス（２，４−ジメチル−４−メトキシバレロニトリル）、ジメチル２，２'−アゾビス（２−メチルプロピオネート）、４，４'−アゾビス（４−シアノバレリック酸）、２，２'−アゾビス（２−ヒドロキシメチルプロピオニトリル）、２，２'−アゾビス（２−（２−イミダゾリン−２−イル）プロパン）等が挙げられる。 The polymerization initiator is generally an azo compound or an organic peroxide. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis (2- (2-imidazolin-2-yl) propane) ) Etc. can be mentioned.
有機過酸化物は、例えば、過酸化ベンゾイル、ｔ−ブチルパーベンゾエイト、クメンヒドロパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ（２−エトキシエチル）パーオキシジカーボネート、ｔ−ブチルパーオキシネオデカノエート、ｔ−ブチルパーオキシビバレート、（３，５，５−トリメチルヘキサノイル）パーオキシド、ジプロピオニルパーオキシド、ジアセチルパーオキシド等が挙げられる。これら重合開始剤は単独または２種以上を併用できる。 Organic peroxides include, for example, benzoyl peroxide, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxydi. Examples thereof include carbonate, t-butylperoxyneodecanoate, t-butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.
共重合体は、溶剤型粘着剤組成物の硬化物である粘着剤層１００質量％中、前記共重合体の含有量が４０質量％以上である。また、１００質量％未満であることが好ましい。前記共重合体の含有量は６０〜９９質量％がより好ましく、７０〜９９質量％が特に好ましい。含有量がこの範囲にあることで、より良好なタック性と加工性を発現することができるとともに、透明な塗膜を得ることができるために好ましい。 The copolymer has a content of 40% by mass or more of the copolymer in 100% by mass of the pressure-sensitive adhesive layer which is a cured product of the solvent-type pressure-sensitive adhesive composition. Further, it is preferably less than 100% by mass. The content of the copolymer is more preferably 60 to 99% by mass, and particularly preferably 70 to 99% by mass. When the content is in this range, better tackiness and processability can be exhibited, and a transparent coating film can be obtained, which is preferable.
＜硬化剤＞
本発明において硬化剤は、イソシアネート系化合物、エポキシ系化合物、エチレンイミン系化合物、金属キレート系化合物、アミン系化合物などが好ましく、加熱環境下での加工性の観点からエポキシ系化合物が特に好ましい。
<Hardener>
In the present invention, the curing agent is preferably an isocyanate compound, an epoxy compound, an ethyleneimine compound, a metal chelate compound, an amine compound or the like, and an epoxy compound is particularly preferable from the viewpoint of processability in a heating environment.
イソシアネート系化合物は、例えばトリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルイソシアネートなどのイソシアネートモノマーとトリメチロールプロパン等のポリオール化合物とのアダクト体、ビュレット体またはイソシアヌレート体、およびこれらイソシアネートモノマーと公知のポリエーテルポリオールまたはポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール等とのアダクト体などの分子内に３個以上のイソシアネート基を有する化合物、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルイソシアネート等のイソシアネートモノマー、ヘキサメチレンジイソシアネートのアロファネート体（コロネート２７７０：日本ポリウレタン工業社製）などの分子内に２個のイソシアネート基を有する化合物などが挙げられる。中でも、トリレンジイソシアネートのトリメチロールプロパンアダクト体が、粘着物性を容易に調整できるため好ましい。なお、イソシアネート基の個数は平均個数である。 Examples of isocyanate-based compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. Adducts, bullets or isocyanurates of isocyanate monomers such as polymethylene polyphenyl isocyanate and polyol compounds such as trimethylolpropane, and these isocyanate monomers and known polyether polyols or polyester polyols, acrylic polyols, polybutadiene polyols, poly Compounds having three or more isocyanate groups in the molecule such as an adduct with isoprene polyol, etc., tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate , Tetramethylxylylene diisocyanate, Naphthalene diisocyanate, Triphenylmethane triisocyanate, Polymethylenepolyphenylisocyanate and other isocyanate monomers, Hexamethylene diisocyanate allophanate (Coronate 2770: manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. Examples thereof include compounds having an isocyanate group. Of these, the trimethylolpropane adduct body of tolylene diisocyanate is preferable because the adhesive physical properties can be easily adjusted. The number of isocyanate groups is an average number.
エポキシ系化合物は、例えばビスフェノールＡ−エピクロロヒドリン型のエポキシ系樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラグリシジル−ｍ−キシリレンジアミン、１、３−ビス（Ｎ、Ｎ’−ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ'，Ｎ'−テトラグリシジルアミノフェニルメタン等が挙げられる。 Epoxy compounds include, for example, bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether. , Trimethylol Propane triglycidyl ether, diglycidyl aniline, N, N, N', N'-tetraglycidyl-m-xylylene diamine, 1,3-bis (N, N'-diglycidyl aminomethyl) cyclohexane, N , N, N', N'-tetraglycidylaminophenylmethane and the like.
エチレンイミン系化合物は、例えばＮ，Ｎ’−ジフェニルメタン−４，４'−ビス（１−アジリジンカルボキサイト）、Ｎ，Ｎ’−トルエン−２，４−ビス（１−アジリジンカルボキサイト）、ビスイソフタロイル−１−（２−メチルアジリジン）、トリ−１−アジリジニルホスフィンオキサイド、Ｎ，Ｎ’−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキサイト）、２，２’−ビスヒドロキシメチルブタノール−トリス［３−（１−アジリジニル）プロピオネート］、トリメチロールプロパントリ−β−アジリジニルプロピオネート、テトラメチロールメタントリ−β−アジリジニルプロピオネート、トリス−２，４，６−（１−アジリジニル）−１、３、５−トリアジン等が挙げられる。 The ethyleneimine compounds include, for example, N, N'-diphenylmethane-4,4'-bis (1-aziridinecarbokisite), N, N'-toluene-2,4-bis (1-aziridinecarbokisite), and bisiso. Phtaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N'-hexamethylene-1,6-bis (1-aziridinecarbokisite), 2,2'-bishydroxy Methylbutanol-tris [3- (1-aziridinyl) propionate], trimethylpropantri-β-aziridinyl propionate, tetramethylolmethanetri-β-aziridinyl propionate, tris-2,4,6 -(1-Aziridineyl) -1,3,5-triazine and the like can be mentioned.
金属キレート系化合物は、例えばアルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロムおよびジルコニウムなどの多価金属と、アセチルアセトンまたはアセト酢酸エチルとの配位化合物などが挙げられる。 Examples of the metal chelate compound include a coordination compound of a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium with acetylacetone or ethyl acetoacetate. Be done.
アミン系化合物は、例えばヘキサメチレンジアミン、トリエチルジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチルテトラミン、イソホロンジアミン、アミノ樹脂およびメチレン樹脂などが挙げられる。
これら硬化剤は、単独または２種以上を併用できる。
Examples of the amine compound include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine, amino resin and methylene resin.
These curing agents may be used alone or in combination of two or more.
硬化剤は、共重合体１００質量部に対して、０．００５〜１５質量部を含むことが好ましく、０．０１〜１０質量部がより好ましく、０．０２〜５質量部が更に好ましく、０．０３〜３質量部が特に好ましい。０．００５〜１５質量部を含むと粘着剤層の凝集力と粘着力のバランスを取ることが容易になる。 The curing agent preferably contains 0.005 to 15 parts by mass, more preferably 0.01 to 10 parts by mass, further preferably 0.02 to 5 parts by mass, and 0, based on 100 parts by mass of the copolymer. .03 to 3 parts by mass is particularly preferable. If it contains 0.005 to 15 parts by mass, it becomes easy to balance the cohesive force and the adhesive force of the pressure-sensitive adhesive layer.
＜粘着付与樹脂＞
本発明の溶剤型粘着剤組成物は、粘着付与樹脂として、テルペン樹脂を含有する。
また、テルペン樹脂以外の粘着付与樹脂を併用してもよい。その他粘着付与樹脂を含むことで、粘着力をより向上させることができる。
粘着付与樹脂が、テルペン樹脂とその他粘着付与樹脂である場合、テルペン樹脂の含有量は、粘着付与樹脂合計１００質量％中、５０質量％以上であることが好ましく、６０〜９８質量％がより好ましく、７０〜９８質量％が特に好ましい。５０質量％以上であることにより、低温時のポリオレフィンに対する粘着力がより良好になる。
本発明の粘着剤組成物は、テルペン樹脂とその他粘着付与樹脂とを含有することにより、極性の高いポリオレフィンに対する粘着力に優れており、とくに上記含有量である場合、ポリプロピレンだけでなく、より粘着力を高くすることが困難なポリエチレンであっても、高い粘着力を維持できるという効果を有することができるために好ましい。
<Adhesive-imparting resin>
The solvent-based pressure-sensitive adhesive composition of the present invention contains a terpene resin as a pressure-imparting resin.
Further, a tackifier resin other than the terpene resin may be used in combination. By including the adhesive-imparting resin, the adhesive strength can be further improved.
When the tackifier resin is a terpene resin and other tackifier resins, the content of the terpene resin is preferably 50% by mass or more, more preferably 60 to 98% by mass, based on 100% by mass of the total tackifier resin. , 70-98% by mass is particularly preferable. When it is 50% by mass or more, the adhesive strength to the polyolefin at low temperature becomes better.
The pressure-sensitive adhesive composition of the present invention is excellent in adhesive strength to highly polar polyolefin by containing a terpene resin and other pressure-imparting resin, and particularly when the above content is used, not only polypropylene but also more adhesive Even polyethylene, which is difficult to increase in strength, is preferable because it can have the effect of maintaining high adhesive strength.
［テルペン樹脂］
本発明においてテルペン樹脂を添加することで、低温環境下の粘着性、タック性と加熱環境下での加工性を両立することができる。テルペン樹脂とは、イソプレンを構造単位として有する粘着付与樹脂を意味する。タック性の観点から、構造単位として、イソプレンを有し、テルペンのみからなる樹脂である、ポリテルペンが好ましい。すなわち、芳香族変性テルペン樹脂、テルペンフェノール樹脂、水添テルペンフェノール樹脂等のテルペン以外の構造単位を有するテルペン樹脂以外のテルペン樹脂が好ましい。
[Terpene resin]
By adding the terpene resin in the present invention, it is possible to achieve both adhesiveness and tackiness in a low temperature environment and processability in a heating environment. The terpene resin means a tackifier resin having isoprene as a structural unit. From the viewpoint of tackiness, polyterpenes, which have isoprene as a structural unit and are made of only terpenes, are preferable. That is, a terpene resin other than the terpene resin having a structural unit other than the terpene such as an aromatic-modified terpene resin, a terpene phenol resin, and a hydrogenated terpene phenol resin is preferable.
テルペン以外の構造単位を有するテルペン樹脂としては、芳香族変性テルペン樹脂、テルペンフェノール樹脂、水添テルペンフェノール樹脂を使用することができる。具体的には、イソプレンのみを構造単位とするテルペン樹脂は、例えばヤスハラケミカル（株）製のＹＳレジンＰＸ８００、ＹＳレジンＰＸ１０００、ＹＳレジンＰＸ１１５０、ＹＳレジンＰＸ１２５０やアリゾナケミカル社製のＳＹＬＶＡＲＥＳ ＴＲＡ９０、ＳＹＬＶＡＲＥＳ ＴＲＭ１１１５、ＳＹＬＶＡＲＥＳ ＴＲ７１２５などが挙げられる。芳香族変性テルペン樹脂としては、ヤスハラケミカル（株）製のＹＳレジンＴＯ１０５、ＹＳレジンＴＯ１１５、テルペンフェノール樹脂としては、ヤスハラケミカル（株）製のＹＳポリスターＴ１００、ＹＳポリスターＴ１１５、水添テルペンフェノール樹脂としては、ヤスハラケミカル（株）製のＹＳポリスターＵＨ１１５などが挙げられる。 As the terpene resin having a structural unit other than terpene, an aromatic-modified terpene resin, a terpene phenol resin, and a hydrogenated terpene phenol resin can be used. Specifically, terpene resins having only isoprene as a structural unit include, for example, YS Resin PX800, YS Resin PX1000, YS Resin PX1150, YS Resin PX1250 manufactured by Yasuhara Chemical Co., Ltd., and SYLVARES TRA90, SYLVARES TRM1115 manufactured by Arizona Chemical Co., Ltd. SYLVARES TR7125 and the like can be mentioned. The aromatic-modified terpene resin includes YS resin TO105 and YS resin TO115 manufactured by Yasuhara Chemical Co., Ltd., and the terpene phenol resin includes YS polystar T100 and YS polystar T115 manufactured by Yasuhara Chemical Co., Ltd. Examples include YS Polystar UH115 manufactured by Yasuhara Chemical Co., Ltd.
また、テルペン樹脂の軟化点は８０〜１３０℃の範囲内であることがより好ましい。軟化点を８０〜１３０℃にすることで低温環境下と加熱環境下の粘着剤層の凝集力と粘着力のバランスを取ることが容易になる。 Further, the softening point of the terpene resin is more preferably in the range of 80 to 130 ° C. By setting the softening point to 80 to 130 ° C., it becomes easy to balance the cohesive force and the adhesive force of the adhesive layer in the low temperature environment and the heated environment.
テルペン樹脂は、共重合体１００質量部に対して、２〜５０質量部を含むことが好ましく、５〜４０質量部がより好ましく、８〜３０質量部が更に好ましく、１０〜２８質量部が特に好ましい。２〜５０質量部含むと、粘着剤層の凝集力と粘着力のバランスを取ることが容易になる。これらは単独また２種類以上を適宜選択できる。 The terpene resin preferably contains 2 to 50 parts by mass, more preferably 5 to 40 parts by mass, further preferably 8 to 30 parts by mass, and particularly preferably 10 to 28 parts by mass with respect to 100 parts by mass of the copolymer. preferable. When it contains 2 to 50 parts by mass, it becomes easy to balance the cohesive force and the adhesive force of the pressure-sensitive adhesive layer. These can be selected individually or two or more types as appropriate.
［その他粘着付与樹脂］
本発明の溶剤型粘着剤組成物は、テルペン樹脂に加え、その他粘着付与樹脂を含むと粘着力がより向上することができる。
その他粘着付与樹脂は、例えば、脂肪族系石油樹脂、芳香族系石油樹脂、クマロン−インデン樹脂、フェノール樹脂、ロジン誘導体（ロジン、重合ロジン、水添ロジン、及びそれらのグリセリン、ペンタエリスリトール等とのエステル、樹脂酸ダイマー等）、アクリル樹脂など既存の全てのものが使用可能である。
これらは、単独または２種以上を併用できる。
[Other adhesive resins]
When the solvent-based pressure-sensitive adhesive composition of the present invention contains other tack-imparting resin in addition to the terpene resin, the adhesive strength can be further improved.
Other tackifier resins include, for example, aliphatic petroleum resins, aromatic petroleum resins, kumaron-inden resins, phenol resins, rosin derivatives (rosin, polymerized rosin, hydrogenated rosin, and their glycerin, pentaerythritol and the like. All existing products such as esters, rosin dimers, etc.) and acrylic resins can be used.
These can be used alone or in combination of two or more.
ポリプロピレン（ＰＰ）やポリエチレン（ＰＥ）のように一般的に粘着させることが困難な非極性な被着体に対する粘着力という観点から、その他粘着付与樹脂としては、脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族／芳香族系石油樹脂およびロジン誘導体からなる群より選ばれる少なくとも１種の粘着付与樹脂が好ましい。
より好ましくは、脂肪族系石油樹脂、芳香族系石油樹脂、またはロジン誘導体である。
From the viewpoint of adhesive strength to non-polar adherends that are generally difficult to adhere to, such as polypropylene (PP) and polyethylene (PE), other tackifying resins include aliphatic petroleum resins and aromatic resins. At least one tackifier resin selected from the group consisting of petroleum resins, aliphatic / aromatic petroleum resins and rosin derivatives is preferred.
More preferably, it is an aliphatic petroleum resin, an aromatic petroleum resin, or a rosin derivative.
脂肪族系石油樹脂としては、日本ゼオン（株）製のクイントンＢ１７０、芳香族系石油樹脂としては、ＪＸＴＧ（製）の日石ネオポリマーＬ−９０、脂肪族/芳香族系石油樹脂としては、三井化学（株）製のＦＴＲ６１００、ロジン誘導体としては、アリゾナケミカル社製のＳｙｌｖａｔａｃＲＥ８５、荒川化学工業（株）のスーパーエステルＡ−７５などが挙げられる。 As an aliphatic petroleum resin, Quinton B170 manufactured by Nippon Zeon Co., Ltd., as an aromatic petroleum resin, Nisseki Neopolymer L-90 manufactured by JXTG Co., Ltd., and as an aliphatic / aromatic petroleum resin, Examples of the FTR6100 manufactured by Mitsui Chemicals Co., Ltd., the rosin derivative include SylvatacRE85 manufactured by Arizona Chemical Co., Ltd., and Superester A-75 manufactured by Arakawa Chemical Industry Co., Ltd.
その他粘着付与樹脂は、共重合体１００質量部に対して、１〜１０質量部配合することが好ましく、１〜５質量部がより好ましい。１〜１０質量部含むことでＰＰに対して良好な粘着力を得ることができる。 The other tackifier resin is preferably blended in an amount of 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the copolymer. Good adhesive strength to PP can be obtained by containing 1 to 10 parts by mass.
＜有機溶剤＞
本発明の溶剤型粘着剤組成物は、有機溶剤を含有する。
有機溶剤は、共重合体を溶液重合する際の反応溶剤や、共重合体合成後の希釈溶剤であってもよく、粘着剤組成物を塗工する前に、添加することもできる。
<Organic solvent>
The solvent-based pressure-sensitive adhesive composition of the present invention contains an organic solvent.
The organic solvent may be a reaction solvent for solution polymerization of the copolymer or a diluting solvent after the copolymer synthesis, and may be added before the pressure-sensitive adhesive composition is applied.
有機溶剤としては、共重合体の製造方法で記載したものを用いることができる。
また、溶剤型粘着剤組成物を塗工する前に、例えば、トルエン、キシレン、ヘキサン、ヘプタン等の炭化水素系溶剤；酢酸エチル、酢酸ブチル等のエステル系溶剤；アセトン、メチルエチルケトン等のケトン系溶剤；ジクロロメタン、クロロホルム等のハロゲン化炭化水素系溶剤；ジエチルエーテル、メトキシトルエン、ジオキサン等のエーテル系溶剤等の有機溶剤を添加して、粘度を調整することもでき、これらの有機溶剤は、単独または２種類以上であってもよい。
なかでも、炭化水素系溶剤を含むことが好ましい。
粘着剤組成物中に炭化水素系溶剤を含むことで、溶液時のテルペン樹脂の相溶性が改善し、幅広い温度範囲で優れた経時安定性を発現することができる。炭化水素系溶剤のなかでも環境規制の観点からヘキサン、ヘプタンといった芳香環を有さない炭化水素系溶剤が特に好ましい。
As the organic solvent, those described in the method for producing a copolymer can be used.
Further, before applying the solvent-type pressure-sensitive adhesive composition, for example, a hydrocarbon solvent such as toluene, xylene, hexane, and heptane; an ester solvent such as ethyl acetate and butyl acetate; and a ketone solvent such as acetone and methyl ethyl ketone. The viscosity can be adjusted by adding an organic solvent such as a halogenated hydrocarbon solvent such as dichloromethane or chloroform; an ether solvent such as diethyl ether, methoxytoluene or dioxane, and these organic solvents can be used alone or. There may be two or more types.
Of these, it is preferable to contain a hydrocarbon solvent.
By including a hydrocarbon solvent in the pressure-sensitive adhesive composition, the compatibility of the terpene resin at the time of solution is improved, and excellent stability over time can be exhibited in a wide temperature range. Among the hydrocarbon solvents, hydrocarbon solvents such as hexane and heptane which do not have an aromatic ring are particularly preferable from the viewpoint of environmental regulation.
有機溶剤は、共重合体１００重量部に対して、１０〜５００質量部を含むことが好ましく、５０〜３００質量部がより好ましい。この範囲であることで合成、塗工時のハンドリング性により優れる。 The organic solvent preferably contains 10 to 500 parts by mass, more preferably 50 to 300 parts by mass, based on 100 parts by weight of the copolymer. Within this range, the handleability at the time of synthesis and coating is excellent.
＜シランカップリング剤＞
本発明の溶剤型粘着剤組成物は、さらにシランカップリング剤を含むこともできる。シランカップリング剤は、例えば、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルトリエトキシシラン、３−（メタ）アクリロキシプロピルトリプロポキシシラン、３−（メタ）アクリロキシプロピルトリブトキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン、３−（メタ）アクリロキシプロピルメチルジエトキシシランなどの（メタ）アクリロキシ基を有するアルコキシシラン化合物；
ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシランなどのビニル基を有するアルコキシシラン化合物；
３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリプロポキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルメチルジエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランなどのアミノ基を有するアルコキシシラン化合物；
３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルトリプロポキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルメチルジエトキシシランなどのメルカプト基を有するアルコキシシラン化合物；
３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルトリプロポキシシラン、３−グリシドキシプロピルトリブトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシ基を有するアルコキシシラン化合物；
テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどのテトラアルコキシシラン化合物；
３−クロロプロピルトリメトキシシラン、ｎ−ヘキシルトリメトキシシラン、ｎ−ヘキシルトリエトキシシラン、ｎ−デシルトリメトキシシラン、ｎ−デシルトリエトキシシラン、スチリルトリメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチルブチリデン）プロピルアミン、１，３，５−トリス（３−トリメトキシシリルプロピル）イソシアヌレート、３−イソシアネートプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシラン、ヘキサメチルジシラザン、分子内にアルコキシシリル基を有するシリコーンレジンなどが挙げられる。
<Silane coupling agent>
The solvent-based pressure-sensitive adhesive composition of the present invention may further contain a silane coupling agent. The silane coupling agent includes, for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxipropyltripropoxysilane, 3- (meth) acry. An alkoxysilane compound having a (meth) acryloxy group, such as loxypropyltributoxysilane, 3- (meth) acryloxipropylmethyldimethoxysilane, 3- (meth) acryloxipropylmethyldiethoxysilane;
Alkoxysilane compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane;
3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl)- 3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) An alkoxysilane compound having an amino group such as -3-aminopropylmethyldiethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane;
Alkoxysilane compounds having a mercapto group such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane;
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropylmethyldimethoxysilane, An alkoxysilane compound having an epoxy group such as 3-glycidoxypropylmethyldiethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;
Tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane;
3-Chloropropyltrimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, styryltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-Triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyl Examples thereof include triethoxysilane, hexamethyldisilazane, and silicone resins having an alkoxysilyl group in the molecule.
＜その他成分＞
本発明の溶剤型粘着剤組成物は、本発明の効果を損なわない範囲で、任意成分として、各種樹脂、硬化触媒、オイル、軟化剤、染料、顔料、酸化防止剤、紫外線吸収剤、耐候安定剤、可塑剤、充填剤、老化防止剤及び帯電防止剤等を配合しても良い。
<Other ingredients>
The solvent-based pressure-sensitive adhesive composition of the present invention has various resins, curing catalysts, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, and weather-resistant stable components as optional components as long as the effects of the present invention are not impaired. Agents, plasticizers, fillers, anti-aging agents, anti-static agents and the like may be blended.
本発明の溶剤型粘着剤組成物は、非極性被着体の貼り付け用として好適である他、一般ラベル・シール、粘着性光学フィルム、塗料、弾性壁材、塗膜防水材、床材、積層構造体用、シーリング剤、成形材料、表面改質用コーティング剤、バインダー（磁気記録媒体、インキバインダー、鋳物バインダー、焼成レンガバインダー、グラフト材、マイクロカプセル、グラスファイバーサイジング等）、ウレタンフォーム（硬質、半硬質、軟質）、ウレタンＲＩＭ、ＵＶ・ＥＢ硬化樹脂、ハイソリッド塗料、熱硬化型エラストマー、マイクロセルラー、繊維加工剤、可塑剤、吸音材料、制振材料、界面活性剤、ゲルコート剤、人工大理石用樹脂、人工大理石用耐衝撃性付与剤、インキ用樹脂、フィルム（ラミネート粘着剤、保護フィルム等）、合わせガラス用樹脂、反応性希釈剤、各種成形材料、弾性繊維、人工皮革、合成皮革等の原料として、又、各種樹脂添加剤およびその原料等としても非常に有用に使用できる。 The solvent-based pressure-sensitive adhesive composition of the present invention is suitable for attaching non-polar adherends, general labels / seals, adhesive optical films, paints, elastic wall materials, coating waterproof materials, floor materials, etc. For laminated structures, sealants, molding materials, coating agents for surface modification, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), urethane foam (hard) , Semi-hard, soft), urethane RIM, UV / EB curable resin, high solid paint, heat-curable elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coating agent, artificial Resin for marble, impact resistance imparting agent for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.), resin for laminated glass, reactive diluent, various molding materials, elastic fiber, artificial leather, synthetic leather It can be very usefully used as a raw material for the above, and also as various resin additives and their raw materials.
≪粘着シート≫
本発明の粘着シートは、基材と、本発明の溶剤型粘着剤組成物から形成した粘着剤層を備えていることが好ましい。また別の態様として、芯材の両面に粘着剤層を有する両面粘着シート、または基材および芯材を有さず粘着剤層のみで構成されたキャスト粘着シートも好ましい。粘着剤層は、粘着剤を基材上に塗工し、乾燥することで形成できる。または、粘着剤を剥離性シート上に塗工し、乾燥して粘着剤層を形成した後、基材を貼り合わせることで形成できる。なお粘着剤層の基材と接しない面に剥離性シートを貼り合わせることはいうまでもない。
≪Adhesive sheet≫
The pressure-sensitive adhesive sheet of the present invention preferably includes a base material and a pressure-sensitive adhesive layer formed from the solvent-based pressure-sensitive adhesive composition of the present invention. As another aspect, a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers on both sides of the core material, or a cast pressure-sensitive adhesive sheet having no base material and core material and composed only of the pressure-sensitive adhesive layer is also preferable. The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive onto a substrate and drying it. Alternatively, it can be formed by applying an adhesive on a peelable sheet, drying it to form an adhesive layer, and then laminating the base materials. Needless to say, the peelable sheet is attached to the surface of the pressure-sensitive adhesive layer that does not come into contact with the base material.
基材としては、例えば、セロハン、プラスチック、ゴム、発泡体、布帛、ゴムびき布、樹脂含浸布、ガラス、および木材等が好ましい。基材の形状は、板状およびフィルム状が選択できるが、取り扱いが容易であるフィルムが好ましい。基材は、単独または２種以上の積層体を使用できる。 As the base material, for example, cellophane, plastic, rubber, foam, cloth, rubberized cloth, resin-impregnated cloth, glass, wood and the like are preferable. The shape of the base material can be selected from a plate shape and a film shape, but a film that is easy to handle is preferable. As the base material, a single material or a laminate of two or more types can be used.
プラスチックは、例えば、ポリビニルアルコール、トリアセチルセルロース、ポリプロピレン、ポリエチレン、ポリシクロオレフィン、エチレン−酢酸ビニル共重合体などのポリオレフィン、ポリエチレンテレフタレート，ポリブチレンテレフタレート，ポリエチレンナフタレートなどのポリエステル、ポリカーボネート、ポリノルボルネン、ポリアリレート、ポリアクリル、ポリフェニレンサルファイドム、ポリスチレン、ポリアミド、ポリイミドのフィルム、エポキシなどが挙げられる。 Plastics include, for example, polyolefins such as polyvinyl alcohol, triacetyl cellulose, polypropylene, polyethylene, polycycloolefin, ethylene-vinyl acetate copolymer, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonate, polynorbornene, and the like. Examples thereof include polyarylate, polyacrylic, polyphenylene sulfide, polystyrene, polyamide, polyimide film, and epoxy.
溶剤型粘着剤組成物の塗工方法は、特に制限は無く、マイヤーバー、アプリケーター、刷毛、スプレー、ローラー、グラビアコーター、ダイコーター、リップコーター、コンマコーター、ナイフコーター、リバースコ−ター、スピンコーター等が挙げられる。乾燥方法には特に制限はなく、熱風乾燥、赤外線や減圧法を利用したものが挙げられる。乾燥条件としては硬化剤種、粘着剤層の厚さ、または溶剤種により、通常６０〜１６０℃程度の熱風加熱ができる。 The method of applying the solvent-based pressure-sensitive adhesive composition is not particularly limited, and is such as Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, spin coater, etc. Can be mentioned. The drying method is not particularly limited, and examples thereof include hot air drying, infrared rays, and decompression methods. As the drying conditions, hot air heating of about 60 to 160 ° C. is usually possible depending on the type of curing agent, the thickness of the pressure-sensitive adhesive layer, or the type of solvent.
粘着剤層の厚さは、０．１〜３００μｍが好ましく、１〜１００μｍがより好ましい。０．１〜３００μｍの範囲にあることで粘着物性を適切な範囲に調整できる。 The thickness of the pressure-sensitive adhesive layer is preferably 0.1 to 300 μm, more preferably 1 to 100 μm. The adhesive physical properties can be adjusted to an appropriate range by being in the range of 0.1 to 300 μm.
本発明の粘着シートは、ポリオレフィンを始めとするプラスチック、ガラス、ダンボール、および金属等といった高極性から低極性まで被着体を選ばずに様々な用途で使用できる。具体的には、冷凍、冷蔵環境下で保管する食料品ラベル用途や寒冷地等で使用するラベルで好ましく使用できる。 The adhesive sheet of the present invention can be used for various purposes regardless of the adherend from high polarity to low polarity such as plastics such as polyolefin, glass, cardboard, and metal. Specifically, it can be preferably used for food label applications stored in a frozen or refrigerated environment or for labels used in cold regions.
次に、本発明の実施例を示して詳細を説明するが、本発明はこれらによって限定されるものではない。例中、「部」とは「質量部」、「％」とは「質量％」をそれぞれ意味するものとする。 Next, examples of the present invention will be described in detail, but the present invention is not limited thereto. In the example, "part" means "parts by mass" and "%" means "% by mass".
（合成例１）
撹拌機、温度計、還流冷却管、滴下装置、窒素導入管を備えた反応容器（以下、単に「反応容器」と記述する。）に窒素雰囲気下、アクリル酸２−エチルヘキシル９０．４部、アクリル酸１．２部、アクリル酸２‐カルボキシエチル２．４部、アクリル酸メチル６部、酢酸エチル６０部、２，２'−アゾビスイソブチロニトリル（以下「ＡＩＢＮ」と記述する。）０．０３部を仕込んだ。撹拌しながら加熱を行い重合反応の開始を確認して還流温度で２時間反応した。次いで、ＡＩＢＮ ０．０３部を反応溶液に添加し６時間反応を継続した。その後、反応容器を冷却し酢酸エチル２５部、ヘキサン２５部を加え、重量平均分子量が８７万の共重合体１溶液を得た。
(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube (hereinafter, simply referred to as "reaction vessel"), under a nitrogen atmosphere, 90.4 parts of 2-ethylhexyl acrylate, acrylic. 1.2 parts of acid, 2.4 parts of 2-carboxyethyl acrylate, 6 parts of methyl acrylate, 60 parts of ethyl acetate, 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") 0 .03 copies were prepared. Heating was carried out with stirring to confirm the start of the polymerization reaction, and the reaction was carried out at the reflux temperature for 2 hours. Then, 0.03 part of AIBN was added to the reaction solution, and the reaction was continued for 6 hours. Then, the reaction vessel was cooled and 25 parts of ethyl acetate and 25 parts of hexane were added to obtain one solution of a copolymer having a weight average molecular weight of 870,000.
（合成例２〜２１）
モノマーの種類及び配合量を表１の記載に従った他は、合成例１と同様に行うことで合成例２〜２１の共重合体２〜２１溶液を得た。得られた共重合体溶液について、重量平均分子量を以下の方法に従って求めた。その結果を表１に示す。
(Synthesis Examples 2 to 21)
The copolymers 2 to 21 solutions of Synthesis Examples 2 to 21 were obtained by carrying out the same procedure as in Synthesis Example 1 except that the types and blending amounts of the monomers were as described in Table 1. The weight average molecular weight of the obtained copolymer solution was determined according to the following method. The results are shown in Table 1.
（合成例２２〜２５）
モノマーの種類及び配合量を表２の記載に従った他は、合成例１と同様に行うことで合成例２２〜２５の共重合体２〜２５溶液を得た。得られた共重合体溶液について、重量平均分子量を以下の方法に従って求めた。その結果を表２に示す。
(Synthesis Examples 22 to 25)
The copolymers 2 to 25 solutions of Synthesis Examples 22 to 25 were obtained by carrying out the same procedure as in Synthesis Example 1 except that the types and blending amounts of the monomers were as described in Table 2. The weight average molecular weight of the obtained copolymer solution was determined according to the following method. The results are shown in Table 2.
なお、表中の「β―ＣＥＡ／（Ｂ）」は、カルボキシル基を有するモノマー（Ｂ）１００質量％中のβ―ＣＥＡ（アクリル酸２‐カルボキシエチル）の含有量（質量％）であり、
「（Ａ）／共重合体」は、モノマー混合物１００質量％中の、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）の含有量（質量％）である。
In the table, "β-CEA / (B)" is the content (mass%) of β-CEA (2-carboxyethyl acrylate) in 100% by mass of the monomer (B) having a carboxyl group.
“(A) / copolymer” is the content (mass%) of the (meth) acrylic acid ester monomer (A) having 8 to 12 carbon atoms in the alkyl group in 100% by mass of the monomer mixture.
＜重量平均分子量の測定＞
重量平均分子量（Ｍｗ）の測定は島津製作所製ＧＰＣ「ＬＣ−ＧＰＣシステム」を用いた。ＧＰＣは溶媒（ＴＨＦ；テトラヒドロフラン）に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーであり、重量平均分子量の決定はポリスチレン換算で行った。
装置名 ： 島津製作所製、ＬＣ−ＧＰＣシステム「Ｐｒｏｍｉｎｅｎｃｅ」
カラム ： 東ソー（株）製ＧＭＨＸＬ ４本、東ソー（株）製ＨＸＬ-Ｈ １本を直列に連結した。
移動相溶媒 ： テトラヒドロフラン
流量 ： １．０ｍｌ／分
カラム温度 ： ４０℃
<Measurement of weight average molecular weight>
The weight average molecular weight (Mw) was measured by using a GPC "LC-GPC system" manufactured by Shimadzu Corporation. GPC is a liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in its molecular size, and the weight average molecular weight is determined in terms of polystyrene.
Device name: LC-GPC system "Prominence" manufactured by Shimadzu Corporation
Column: Four GMHXL manufactured by Tosoh Corporation and one HXL-H manufactured by Tosoh Corporation were connected in series.
Mobile phase solvent: Tetrahydrofuran flow rate: 1.0 ml / min Column temperature: 40 ° C
表１、２中の略号を以下に列記する。
２ＥＨＡ ： アクリル酸２−エチルヘキシル
２ＥＨＭＡ： メタクリル酸２−エチルヘキシル
ＬＭＡ ： メタクリル酸ラウリル
ＭＡ ： アクリル酸メチル
ＭＭＡ ： メタクリル酸メチル
ＥＡ ： アクリル酸エチル
ＡＡ ： アクリル酸
ＨＥＡ ： アクリル酸２−ヒドロキシエチル
β−ＣＥＡ： アクリル酸２‐カルボキシエチル
ＢＡ ： アクリル酸ブチル
ＶＡｃ ： 酢酸ビニル
The abbreviations in Tables 1 and 2 are listed below.
2EHA: 2-ethylhexyl acrylate 2EHMA: 2-ethylhexyl methacrylate LMA: lauryl methacrylate MA: methyl acrylate MMA: methyl methacrylate EA: ethyl acrylate AA: HEA acrylate: 2-hydroxyethyl acrylate β-CEA: 2-carboxyethyl acrylate BA: Butyl acrylate VAc: Vinyl acetate
（実施例１）
合成例１で得られた共重合体溶液中の共重合体１００部に対して、硬化剤としてＴＥＴＲＡＤ−Ｘ（Ｎ，Ｎ，Ｎ'，Ｎ'−テトラグリシジル−ｍ−キシリレンジアミン、三菱ガス化学（株）製）０．０３部（不揮発分換算）、テルペン樹脂としてＹＳレジンＰＸ１２５０（ヤスハラケミカル（株）製）１０部（不揮発分換算）、ロジン誘導体としてＳｙｌｖａｔａｃ ＲＥ８５（アリゾナケミカル社製）５部（不揮発分換算）を配合し、更に溶剤としてヘキサンを加え、不揮発分を３５％に調整して粘着剤溶液を得た。
粘着剤溶液を、厚さ３８μｍの剥離性シート（ポリエチレンテレフタレート（ＰＥＴ）製）上に、乾燥後の厚さが５０μｍになるようにコンマコーターで塗工を行い、１００℃で２分間乾燥することで粘着剤層を形成した。次いで、この粘着剤層に、厚さ５０μｍの基材（ポリエチレンテレフタレート製、以下、ＰＥＴシートという）を貼り合せ、温度２３℃相対湿度５０％の条件で１週間熟成することで「剥離性シート／粘着剤層／ＰＥＴシート」という構成の粘着シートを得た。
(Example 1)
TETRAD-X (N, N, N', N'-tetraglycidyl-m-xylylene diamine, Mitsubishi gas as a curing agent for 100 parts of the copolymer in the copolymer solution obtained in Synthesis Example 1. 0.03 parts (manufactured by Chemical Co., Ltd.), YS resin PX1250 (manufactured by Yasuhara Chemical Co., Ltd.) 10 parts (converted to non-volatile content) as terpen resin, 5 parts of Sylvatac RE85 (manufactured by Arizona Chemical Co., Ltd.) as rosin derivative (Consolidated content equivalent) was further added, and hexane was further added as a solvent to adjust the non-volatile content to 35% to obtain a pressure-sensitive adhesive solution.
The pressure-sensitive adhesive solution is coated on a removable sheet (made of polyethylene terephthalate (PET)) having a thickness of 38 μm with a comma coater so that the thickness after drying is 50 μm, and dried at 100 ° C. for 2 minutes. A pressure-sensitive adhesive layer was formed in. Next, a base material having a thickness of 50 μm (made of polyethylene terephthalate, hereinafter referred to as PET sheet) is attached to this pressure-sensitive adhesive layer and aged for one week at a temperature of 23 ° C. and a relative humidity of 50%. An adhesive sheet having a structure of "adhesive layer / PET sheet" was obtained.
（実施例２〜３９、比較例１〜４）
表３の材料及び配合に変更した以外は、実施例１と同様に行うことで実施例２〜３９および比較例１〜４の粘着剤溶液および粘着シートをそれぞれ得た。
(Examples 2-39, Comparative Examples 1-4)
The adhesive solutions and adhesive sheets of Examples 2 to 39 and Comparative Examples 1 to 4 were obtained by carrying out the same procedure as in Example 1 except that the materials and formulations shown in Table 3 were changed.
（実施例４０〜５８）
表４の材料及び配合に変更した以外は、実施例１と同様に行うことで実施例４０〜５８の粘着剤溶液および粘着シートをそれぞれ得た。
(Examples 40 to 58)
The pressure-sensitive adhesive solutions and pressure-sensitive adhesive sheets of Examples 40 to 58 were obtained in the same manner as in Example 1 except that the materials and formulations shown in Table 4 were changed.
なお、表中の「テルペン樹脂／粘着付与樹脂」は、粘着付与樹脂の合計１００質量％中のテルペン樹脂の含有量（質量％）であり、「共重合体／粘着剤層」は、粘着剤層１００質量％中の共重合体の含有量（質量％）である。 In the table, "terpene resin / tackifier resin" is the content (mass%) of terpene resin in the total 100% by mass of the tackifier resin, and "copolymer / pressure-sensitive adhesive layer" is a pressure-sensitive adhesive. The content (% by mass) of the copolymer in 100% by mass of the layer.
表３、４の略号を以下に記載する。
ＴＥＴＲＡＤ−Ｘ ：Ｎ，Ｎ，Ｎ'，Ｎ'−テトラグリシジル−ｍ−キシリレンジアミン（三菱ガス化学（株）製）
ＴＤＩ／ＴＭＰ ： トリレンジイソシアネートのトリメチロールプロパンアダクト体ＰＺ−３３：２，２’−ビスヒドロキシメチルブタノール−トリス［３−（１−アジリジニル）プロピオネート］（（株）日本触媒製）
ＰＸ１２５０ ：構造単位として、イソプレンを有し、テルペンのみからなる樹脂（ヤスハラケミカル（株）製）
ＰＸ８００ ：構造単位として、イソプレンを有し、テルペンのみからなる樹脂（ヤスハラケミカル（株）製）
ＴＯ１２５ ：芳香族変性テルペン樹脂（ヤスハラケミカル（株）製）
ＲＥ８５ ： ロジン誘導体 （アリゾナケミカル社製）
ＦＴＲ６１００ ：脂肪族/芳香族系石油樹脂（三井化学（株）製）
The abbreviations in Tables 3 and 4 are listed below.
TETRAD-X: N, N, N', N'-tetraglycidyl-m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.)
TDI / TMP: Trimethylolpropane adduct of tolylene diisocyanate PZ-33: 2,2'-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] (manufactured by Nippon Shokubai Co., Ltd.)
PX1250: Resin having isoprene as a structural unit and consisting only of terpenes (manufactured by Yasuhara Chemical Co., Ltd.)
PX800: Resin having isoprene as a structural unit and consisting only of terpenes (manufactured by Yasuhara Chemical Co., Ltd.)
TO125: Aromatic modified terpene resin (manufactured by Yasuhara Chemical Co., Ltd.)
RE85: Rosin derivative (manufactured by Arizona Chemical Co., Ltd.)
FTR6100: Aliphatic / aromatic petroleum resin (manufactured by Mitsui Chemicals, Inc.)
得られた粘着シートを以下の方法で評価した。結果を表３、４に示す。
（１）粘着力
得られた粘着シートを幅２５ｍｍ・縦１５０ｍｍの大きさに準備した。５℃または２３℃、相対湿度５０％雰囲気下、粘着シートから剥離性シートを剥がしてステンレス（ＳＵＳ）板に貼り付け、２ｋｇロールで１往復圧着した２４時間放置した後に引張試験機を用いて１８０度方向に３００ｍｍ／分の速度で引き剥がす１８０°ピール試験において粘着力を測定した。上記同様にポリプロピレン（ＰＰ）板、ポリエチレン（ＰＥ）板に対する粘着力を測定した。
評価基準
ＳＵＳ（２３℃）
◎：「粘着力が３６Ｎ／２５ｍｍ以上。非常に良好。」
○：「粘着力が３０Ｎ／２５ｍｍ以上３６Ｎ／２５ｍｍ未満。良好。」
△：「粘着力が２４Ｎ／２５ｍｍ以上３０Ｎ／２５ｍｍ未満。実用可能レベル。」
×：「粘着力が２４Ｎ／２５ｍｍ未満。実用不可。」
ＳＵＳ（５℃）
◎：「粘着力が１６Ｎ／２５ｍｍ以上。非常に良好。」
○：「粘着力が１３Ｎ／２５ｍｍ以上１６Ｎ／２５ｍｍ未満。良好。」
△：「粘着力が１０Ｎ／２５ｍｍ以上１３Ｎ／２５ｍｍ未満。実用可能レベル。」
×：「粘着力が１０Ｎ／２５ｍｍ未満。実用不可。」
ＰＰ（２３℃）
◎：「粘着力が１７Ｎ／２５ｍｍ以上。非常に良好。」
○：「粘着力が１４Ｎ／２５ｍｍ以上１７Ｎ／２５ｍｍ未満。良好。」
△：「粘着力が１１Ｎ／２５ｍｍ以上１４Ｎ／２５ｍｍ未満。実用可能レベル。」
×：「粘着力が１１Ｎ／２５ｍｍ未満。実用不可。」
ＰＰ（５℃）
◎：「粘着力が１６Ｎ／２５ｍｍ以上。非常に良好。」
○：「粘着力が１３Ｎ／２５ｍｍ以上１６Ｎ／２５ｍｍ未満。良好。」
△：「粘着力が１０Ｎ／２５ｍｍ以上１３Ｎ／２５ｍｍ未満。実用可能レベル。」
×：「粘着力が１０Ｎ／２５ｍｍ未満。実用不可。」
ＰＥ（２３℃）
◎：「粘着力が９Ｎ／２５ｍｍ以上。非常に良好。」
○：「粘着力が７Ｎ／２５ｍｍ以上９Ｎ／２５ｍｍ未満。良好。」
△：「粘着力が５Ｎ／２５ｍｍ以上７Ｎ／２５ｍｍ未満。実用可能レベル。」
×：「粘着力が５Ｎ／２５ｍｍ未満。実用不可。」
ＰＥ（５℃）
◎：「粘着力が８Ｎ／２５ｍｍ以上。非常に良好。」
○：「粘着力が６Ｎ／２５ｍｍ以上８Ｎ／２５ｍｍ未満。良好。」
△：「粘着力が４Ｎ／２５ｍｍ以上６Ｎ／２５ｍｍ未満。実用可能レベル。」
×：「粘着力が４Ｎ／２５ｍｍ未満。実用不可。」
The obtained adhesive sheet was evaluated by the following method. The results are shown in Tables 3 and 4.
(1) Adhesive Strength The obtained adhesive sheet was prepared to have a width of 25 mm and a length of 150 mm. In an atmosphere of 5 ° C. or 23 ° C. and a relative humidity of 50%, the peelable sheet was peeled off from the adhesive sheet, attached to a stainless steel (SUS) plate, crimped once with a 2 kg roll, left for 24 hours, and then 180 using a tensile tester. The adhesive strength was measured in a 180 ° peel test in which the material was peeled off at a speed of 300 mm / min in the degree direction. The adhesive strength to the polypropylene (PP) plate and the polyethylene (PE) plate was measured in the same manner as described above.
Evaluation standard SUS (23 ° C)
⊚: "Adhesive strength is 36N / 25mm or more. Very good."
◯: “Adhesive strength is 30 N / 25 mm or more and less than 36 N / 25 mm. Good.”
Δ: “Adhesive strength is 24 N / 25 mm or more and less than 30 N / 25 mm. Practical level.”
X: "Adhesive strength is less than 24N / 25mm. Not practical."
SUS (5 ° C)
⊚: "Adhesive strength is 16N / 25mm or more. Very good."
◯: “Adhesive strength is 13 N / 25 mm or more and less than 16 N / 25 mm. Good.”
Δ: “Adhesive strength is 10 N / 25 mm or more and less than 13 N / 25 mm. Practical level.”
X: "Adhesive strength is less than 10N / 25mm. Not practical."
PP (23 ° C)
⊚: "Adhesive strength is 17N / 25mm or more. Very good."
◯: “Adhesive strength is 14 N / 25 mm or more and less than 17 N / 25 mm. Good.”
Δ: “Adhesive strength is 11 N / 25 mm or more and less than 14 N / 25 mm. Practical level.”
X: "Adhesive strength is less than 11N / 25mm. Not practical."
PP (5 ° C)
⊚: "Adhesive strength is 16N / 25mm or more. Very good."
◯: “Adhesive strength is 13 N / 25 mm or more and less than 16 N / 25 mm. Good.”
Δ: “Adhesive strength is 10 N / 25 mm or more and less than 13 N / 25 mm. Practical level.”
X: "Adhesive strength is less than 10N / 25mm. Not practical."
PE (23 ° C)
⊚: "Adhesive strength is 9N / 25mm or more. Very good."
◯: “Adhesive strength is 7N / 25mm or more and less than 9N / 25mm. Good.”
Δ: “Adhesive strength is 5N / 25mm or more and less than 7N / 25mm. Practical level.”
X: "Adhesive strength is less than 5N / 25mm. Not practical."
PE (5 ° C)
⊚: "Adhesive strength is 8N / 25mm or more. Very good."
◯: “Adhesive strength is 6N / 25mm or more and less than 8N / 25mm. Good.”
Δ: “Adhesive strength is 4N / 25mm or more and less than 6N / 25mm. Practical level.”
X: "Adhesive strength is less than 4N / 25mm. Not practical."
（２）保持力
得られた粘着シートを幅２５ｍｍ・縦１５０ｍｍの大きさに準備した。粘着シートから剥離性シートを剥がして研磨した幅３０ｍｍ・縦１５０ｍｍのステンレス板の下端部幅２５ｍｍ・横２５ｍｍの部分に粘着剤層を貼着し、２ｋｇロールで１往復圧着した後、４０℃雰囲気で１ｋｇの荷重をかけ、７万秒放置することで保持力を測定した。評価は、粘着シート貼付面上端部が下にずれた長さを測定した。
評価基準
◎：「ずれがみられなかった。非常に良好。」
○：「ずれが発生し、ずれた長さが２ｍｍ未満である。良好。」
△：「ずれた長さが２ｍｍ以上５ｍｍ未満である。実用可能レベル。」
×：「ずれた長さが５ｍｍ以上である。実用不可。」
(2) Holding power The obtained adhesive sheet was prepared to have a width of 25 mm and a length of 150 mm. An adhesive layer is attached to the lower end of a stainless steel plate with a width of 30 mm and a length of 150 mm and a width of 25 mm and a width of 25 mm, which is obtained by peeling off the peelable sheet from the adhesive sheet and crimping it once with a 2 kg roll. The holding force was measured by applying a load of 1 kg and leaving it for 70,000 seconds. For the evaluation, the length at which the upper end of the adhesive sheet sticking surface was displaced downward was measured.
Evaluation Criteria ◎: “No deviation was observed. Very good.”
◯: “There is a deviation, and the length of the deviation is less than 2 mm. Good.”
Δ: “The displaced length is 2 mm or more and less than 5 mm. Practical level.”
X: "The offset length is 5 mm or more. It is not practical."
（３）ボールタック
得られた粘着シートを幅２５ｍｍ・縦２５０ｍｍの大きさに準備した。粘着シートから剥離性シートを剥がして傾斜角３０度の傾斜版に粘着面を上にして固定した。助走路用のＰＥＴフィルムを上部に貼り付け、助走１０ｃｍ糊面１０ｃｍとした試料にスチールボール（１/３２〜３２/３２インチ）を転がし、糊面の中央付近に停止するボールの径の番号を記録した。測定は５℃もしくは２３℃、相対湿度５０％雰囲気下で実施した。
５℃雰囲気下での評価基準
◎：「ボール径が１０以上。非常に良好。」
○：「ボール径が７から９。良好。」
△：「ボール径が４から６。実用可能レベル。」
×：「ボール径が３以下。実用不可。」
２３℃、相対湿度５０％雰囲気下での評価基準
◎：「ボール径が１９以上。非常に良好。」
○：「ボール径が１５から１８。良好。」
△：「ボール径が１１から１４。実用可能レベル。」
×：「ボール径が１０以下。実用不可。」
(3) Ball tack The obtained adhesive sheet was prepared to have a width of 25 mm and a length of 250 mm. The peelable sheet was peeled off from the adhesive sheet and fixed to an inclined plate having an inclination angle of 30 degrees with the adhesive side facing up. A PET film for the runway is pasted on the top, a steel ball (1/32 to 32/32 inch) is rolled on a sample with a run-up 10 cm glue surface 10 cm, and the number of the diameter of the ball that stops near the center of the glue surface is assigned. Recorded. The measurement was carried out in an atmosphere of 5 ° C. or 23 ° C. and a relative humidity of 50%.
Evaluation criteria in an atmosphere of 5 ° C ◎: "Ball diameter is 10 or more. Very good."
◯: “Ball diameter is 7 to 9. Good.”
Δ: “Ball diameter is 4 to 6. Practical level.”
X: "Ball diameter is 3 or less. Not practical."
Evaluation criteria in an atmosphere of 23 ° C and 50% relative humidity ◎: "Ball diameter is 19 or more. Very good."
◯: “Ball diameter is 15 to 18. Good.”
Δ: “Ball diameter is 11 to 14. Practical level.”
X: "Ball diameter is 10 or less. Not practical."
（４）加工性試験
得られた粘着シートを幅１０ｍｍ・縦１０ｍｍの大きさに準備した。粘着シートから剥離性シートを剥がして、上下を厚さ３８μｍの剥離性シート（ポリエチレンテレフタレート製）で挟み、プレス試験機を用いて４０℃の環境下、５０Ｋｇ／ｃｍ２の圧力を加え、２時間放置した。試験終了後サンプルを取り出し試験片端部からはみ出している糊の幅を（最大値）測定した。
評価基準
◎：「はみだしが０以上０．４ｍｍ未満。非常に良好。」
○：「はみだしが０．４以上０．６ｍｍ未満。良好。」
△：「はみだしが０．６以上０．８ｍｍ未満。実用可能レベル。」
×：「はみだしが０．８ｍｍ以上である。実用不可。」
(4) Workability test The obtained adhesive sheet was prepared to have a width of 10 mm and a length of 10 mm. Peel off the peelable sheet from the adhesive sheet, sandwich the top and bottom with a removable sheet (made of polyethylene terephthalate) with a thickness of 38 μm, and apply a pressure of 50 kg / cm 2 in an environment of 40 ° C. using a press tester for 2 hours. I left it. After the test was completed, the sample was taken out and the width (maximum value) of the glue protruding from one end of the test was measured.
Evaluation criteria ◎: "Extrusion is 0 or more and less than 0.4 mm. Very good."
◯: “The protrusion is 0.4 or more and less than 0.6 mm. Good.”
Δ: “The protrusion is 0.6 or more and less than 0.8 mm. Practical level.”
X: "The protrusion is 0.8 mm or more. It is not practical."
（４）塗膜外観
得られた粘着シートをスライドガラスに貼り付けヘーズメーター（日本電色工業（株）社製 ＮＤＨ ５０００）で測定した。
評価基準
◎：「ヘーズが７未満。非常に良好。」
○：「ヘーズが７以上１１未満。良好。」
△：「ヘーズが１１以上１５未満。実用可能レベル。」
×：「ヘーズが１５以上。実用不可。」
(4) Appearance of coating film The obtained adhesive sheet was attached to a slide glass and measured with a haze meter (NDH 5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.).
Evaluation Criteria ◎: “Haze is less than 7. Very good.”
◯: “Haze is 7 or more and less than 11. Good.”
Δ: “Haze is 11 or more and less than 15. Practical level.”
X: "Haze is 15 or more. Not practical."
表３、４の実施例に示すように、本発明の溶剤型粘着剤組成物は、低温、常温環境下での粘着力、ボールタック、高温下での保持力、加工性、塗膜外観に優れていることが明らかとなった。これに対して、比較例では、いずれかの項目が不良となっており、実用不可であることが明らかとなった。 As shown in Examples of Tables 3 and 4, the solvent-based pressure-sensitive adhesive composition of the present invention has adhesive strength at low temperature and normal temperature environment, ball tack, holding power at high temperature, processability, and coating film appearance. It turned out to be excellent. On the other hand, in the comparative example, it became clear that one of the items was defective and could not be put into practical use.
（実施例２〜３９、比較例１〜４）
表３の材料及び配合に変更した以外は、実施例１と同様に行うことで実施例２〜３９および比較例１〜４の粘着剤溶液および粘着シートをそれぞれ得た。
ただし、実施例１５〜３９は参考例である。
(Examples 2-39, Comparative Examples 1-4)
The adhesive solutions and adhesive sheets of Examples 2 to 39 and Comparative Examples 1 to 4 were obtained by carrying out the same procedure as in Example 1 except that the materials and formulations shown in Table 3 were changed.
However, Examples 15 to 39 are reference examples.
（実施例２〜３９、比較例１〜４）
表３の材料及び配合に変更した以外は、実施例１と同様に行うことで実施例２〜３９および比較例１〜４の粘着剤溶液および粘着シートをそれぞれ得た。
ただし、実施例１５〜３９、５５〜５８は参考例である。
(Examples 2-39, Comparative Examples 1-4)
The adhesive solutions and adhesive sheets of Examples 2 to 39 and Comparative Examples 1 to 4 were obtained by carrying out the same procedure as in Example 1 except that the materials and formulations shown in Table 3 were changed.
However, Examples 15 to 39 and 55 to 58 are reference examples.
Claims (11)
前記共重合体が、アルキル基の炭素数が８〜１２の（メタ）アクリル酸エステルモノマー（Ａ）、およびカルボキシル基を有するモノマー（Ｂ）を含むモノマー混合物の共重合体であり、
前記粘着付与樹脂がテルペン樹脂を含み、
溶剤型粘着剤組成物の硬化物である粘着剤層１００質量％中、前記共重合体の含有量が４０質量％以上である、溶剤型粘着剤組成物。 A solvent-based pressure-sensitive adhesive composition containing a copolymer, a curing agent, a tackifier resin, and an organic solvent.
The copolymer is a copolymer of a monomer mixture containing a (meth) acrylic acid ester monomer (A) having an alkyl group having 8 to 12 carbon atoms and a monomer (B) having a carboxyl group.
The tackifier resin contains a terpene resin and contains
A solvent-type pressure-sensitive adhesive composition in which the content of the copolymer is 40% by mass or more in 100% by mass of the pressure-sensitive adhesive layer which is a cured product of the solvent-type pressure-sensitive adhesive composition.
A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer which is a cured product of the solvent-based pressure-sensitive adhesive composition according to any one of claims 1 to 10.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022118678A1 (en) * | 2020-12-01 | 2022-06-09 | 日東電工株式会社 | Adhesive composition and adhesive tape |
| WO2022118676A1 (en) * | 2020-12-01 | 2022-06-09 | 日東電工株式会社 | Adhesive composition and adhesive tape |
| WO2022118677A1 (en) * | 2020-12-01 | 2022-06-09 | 日東電工株式会社 | Adhesive composition and adhesive tape |
| JP7311695B1 (en) | 2022-03-29 | 2023-07-19 | 日東電工株式会社 | Adhesive sheet |
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| JP6994689B2 (en) * | 2019-12-18 | 2022-01-14 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition and adhesive sheet |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310852A (en) * | 1992-05-14 | 1993-11-22 | Sekisui Chem Co Ltd | Photopolymerizable composition and production of viscoelastic product |
| JPH08283683A (en) * | 1995-04-14 | 1996-10-29 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition |
| JP2006348143A (en) * | 2005-06-15 | 2006-12-28 | Dainippon Ink & Chem Inc | Water dispersion type acrylic adhesive composition and adhesive sheet using the same |
| JP2007186588A (en) * | 2006-01-13 | 2007-07-26 | Harima Chem Inc | Tackifier resin emulsion |
| JP2014034652A (en) * | 2012-08-09 | 2014-02-24 | Dic Corp | Thermally conductive tacky-adhesive tape |
| WO2015064283A1 (en) * | 2013-10-29 | 2015-05-07 | 日東電工株式会社 | Surface-protecting sheet |
-
2019
- 2019-04-18 JP JP2019079185A patent/JP6614383B1/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310852A (en) * | 1992-05-14 | 1993-11-22 | Sekisui Chem Co Ltd | Photopolymerizable composition and production of viscoelastic product |
| JPH08283683A (en) * | 1995-04-14 | 1996-10-29 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition |
| JP2006348143A (en) * | 2005-06-15 | 2006-12-28 | Dainippon Ink & Chem Inc | Water dispersion type acrylic adhesive composition and adhesive sheet using the same |
| JP2007186588A (en) * | 2006-01-13 | 2007-07-26 | Harima Chem Inc | Tackifier resin emulsion |
| JP2014034652A (en) * | 2012-08-09 | 2014-02-24 | Dic Corp | Thermally conductive tacky-adhesive tape |
| WO2015064283A1 (en) * | 2013-10-29 | 2015-05-07 | 日東電工株式会社 | Surface-protecting sheet |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022118678A1 (en) * | 2020-12-01 | 2022-06-09 | 日東電工株式会社 | Adhesive composition and adhesive tape |
| WO2022118676A1 (en) * | 2020-12-01 | 2022-06-09 | 日東電工株式会社 | Adhesive composition and adhesive tape |
| WO2022118677A1 (en) * | 2020-12-01 | 2022-06-09 | 日東電工株式会社 | Adhesive composition and adhesive tape |
| JP7311695B1 (en) | 2022-03-29 | 2023-07-19 | 日東電工株式会社 | Adhesive sheet |
| WO2023188482A1 (en) * | 2022-03-29 | 2023-10-05 | 日東電工株式会社 | Adhesive sheet |
| JP2023147166A (en) * | 2022-03-29 | 2023-10-12 | 日東電工株式会社 | adhesive sheet |
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