JP5925676B2 - Manufacturing method of adhesive sheet - Google Patents
Manufacturing method of adhesive sheet Download PDFInfo
- Publication number
- JP5925676B2 JP5925676B2 JP2012509622A JP2012509622A JP5925676B2 JP 5925676 B2 JP5925676 B2 JP 5925676B2 JP 2012509622 A JP2012509622 A JP 2012509622A JP 2012509622 A JP2012509622 A JP 2012509622A JP 5925676 B2 JP5925676 B2 JP 5925676B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- adhesive sheet
- resin
- mass
- 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.)
- Active
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- 239000000853 adhesive Substances 0.000 title claims description 52
- 230000001070 adhesive effect Effects 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 98
- 239000000463 material Substances 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 39
- 229920006243 acrylic copolymer Polymers 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 23
- 125000003277 amino group Chemical group 0.000 claims description 17
- 239000004014 plasticizer Substances 0.000 claims description 17
- 239000002736 nonionic surfactant Substances 0.000 claims description 16
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 14
- 229920005990 polystyrene resin Polymers 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 229920005668 polycarbonate resin Polymers 0.000 claims description 12
- 239000004431 polycarbonate resin Substances 0.000 claims description 12
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229920006026 co-polymeric resin Polymers 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 2
- -1 polyoxyethylene Polymers 0.000 description 51
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000000123 paper Substances 0.000 description 13
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 150000003505 terpenes Chemical class 0.000 description 11
- 235000007586 terpenes Nutrition 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 241000282320 Panthera leo Species 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000003973 alkyl amines Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011086 glassine Substances 0.000 description 3
- 125000005702 oxyalkylene group Chemical group 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- KATAXDCYPGGJNJ-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethoxy)propan-2-ol Chemical compound C1OC1COCC(O)COCC1CO1 KATAXDCYPGGJNJ-UHFFFAOYSA-N 0.000 description 1
- KQSMCAVKSJWMSI-UHFFFAOYSA-N 2,4-dimethyl-1-n,1-n,3-n,3-n-tetrakis(oxiran-2-ylmethyl)benzene-1,3-diamine Chemical compound CC1=C(N(CC2OC2)CC2OC2)C(C)=CC=C1N(CC1OC1)CC1CO1 KQSMCAVKSJWMSI-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 1
- VHNJXLWRTQNIPD-UHFFFAOYSA-N 3-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(O)CCOC(=O)C(C)=C VHNJXLWRTQNIPD-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 125000001117 oleyl 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])=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
- 125000006353 oxyethylene group Chemical group 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
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2425/00—Presence of styrenic polymer
- C09J2425/006—Presence of styrenic polymer in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2455/00—Presence of ABS
- C09J2455/006—Presence of ABS in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2469/00—Presence of polycarbonate
- C09J2469/006—Presence of polycarbonate in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、粘着シートの製造方法に関し、詳しくは家電や電子機器の樹脂製筺体に貼付後に剥離でき、また、必要に応じて該筺体に貼付したままリサイクルできる再剥離粘着シートの製造方法に関する。 The present invention relates to a method for producing a pressure-sensitive adhesive sheet, and more particularly, to a method for producing a re-peelable pressure-sensitive adhesive sheet that can be peeled off after being attached to a resin casing of home appliances and electronic devices, and can be recycled while being attached to the casing as necessary.
従来から、家電や電子機器の樹脂製筺体に、その商品名や、商品説明、使用方法などを表面に記載した粘着シートを貼付し、展示、販売することが行われている。
近年、省資源の観点から、使用済みの家電や電子機器の樹脂製筺体を回収し、粉砕して再利用するリサイクルが行われている。
家電や電子機器の樹脂製筺体をリサイクルする際に、該樹脂製筺体に粘着シートが貼付されている場合、その粘着シートを剥がしてリサイクルすることもあれば、その粘着シートを貼付したままリサイクルすることもある。
2. Description of the Related Art Conventionally, an adhesive sheet having a product name, a product description, a usage method, and the like attached to a resin casing of a home appliance or an electronic device is attached to the surface and displayed and sold.
In recent years, from the viewpoint of resource saving, recycling is performed by collecting, crushing, and reusing resin housings of used home appliances and electronic devices.
When recycling resin housings for home appliances and electronic devices, if the adhesive sheet is affixed to the resin housing, the adhesive sheet may be peeled off for recycling or recycled with the adhesive sheet still attached. Sometimes.
該樹脂製筺体から粘着シートを剥がしてリサイクルする場合には、該樹脂製筺体に貼付している間は強固に固定されているように十分な粘着力が求められ、該樹脂製筺体から剥がすときには容易に剥離できるような再剥離性も粘着シートに求められている。また、該樹脂製筺体に粘着シートを貼付したままリサイクルする場合、粘着シートの表面基材と該樹脂製筺体の材質が同じであることが要求されている。
すなわち、粘着シートには、樹脂製筺体などの被着体への粘着力と、被着体からの再剥離性が要求され、さらには被着体と同じ材質から成る表面基材であることが要求され、これらを満たすことが望まれている。
When the adhesive sheet is peeled off from the resin casing and recycled, sufficient adhesive force is required to be firmly fixed while being attached to the resin casing, and when peeling from the resin casing, The releasability that can be easily peeled is also required for the pressure-sensitive adhesive sheet. Moreover, when recycling with the adhesive sheet attached to the resin casing, it is required that the surface base material of the adhesive sheet and the material of the resin casing are the same.
That is, the pressure-sensitive adhesive sheet is required to have an adhesive force to an adherend such as a resin casing and a removability from the adherend, and is a surface substrate made of the same material as the adherend. It is required and desired to meet these requirements.
一方、再剥離性粘着シートの粘着剤としては、環境問題の観点から、溶剤系粘着剤から水系粘着剤へ移行している。水系粘着剤の場合、被着体からの剥離性を容易にすると、同素材である表面基材との密着力も低下し、被着体に粘着剤層が残留することが生じる問題があった。
従来、紙、金属、プラスチック類などの被着体に対し、良好な接着性を有し、かつ粘着ラベルを被着体から剥がす際に粘着剤成分が被着体に残留することがなく、再剥離可能であることを目的とする粘着シートとして、表面基材の表面に、粘着性微粒子（Ａ）および必要に応じてバインダー（Ｂ）を含有する水性粘着剤組成物に可塑剤としてポリオキシエチレンノニルフェニルエーテルなどの界面活性剤系可塑剤を添加した粘着剤組成物層を積層した粘着シートが提案されている（特許文献１）。
On the other hand, the pressure-sensitive adhesive for the releasable pressure-sensitive adhesive sheet has shifted from a solvent-based pressure-sensitive adhesive to a water-based pressure-sensitive adhesive from the viewpoint of environmental problems. In the case of the water-based pressure-sensitive adhesive, when the peelability from the adherend is facilitated, there is a problem that the adhesive force with the surface base material, which is the same material, is reduced, and the pressure-sensitive adhesive layer remains on the adherend.
Conventionally, it has good adhesion to adherends such as paper, metal and plastics, and the adhesive component does not remain on the adherend when the adhesive label is peeled off from the adherend. As an adhesive sheet intended to be peelable, an aqueous adhesive composition containing adhesive fine particles (A) and, if necessary, a binder (B) on the surface of a surface substrate, polyoxyethylene as a plasticizer A pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive composition layer added with a surfactant-based plasticizer such as nonylphenyl ether has been proposed (Patent Document 1 ) .
特許文献１には、界面活性剤系可塑剤として、実施例にはポリオキシエチレンノニルフェニルエーテルのみが使用されており、その他の具体例としてはその段落［００５８］にポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンジ（ステアリル）エーテル等のポリオキシアルキレンアルキルまたはアルケニルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンジ（ノニル）フェニルエーテル、ポリオキシエチレンジ（ノニルフェニル）エーテル等のポリオキシアルキルフェニルエーテルのみが記載されている。 In Patent Document 1, as a surfactant-based plasticizer, only polyoxyethylene nonylphenyl ether is used in the examples, and other specific examples include polyoxyethylene lauryl ether, polyoxyethylene lauryl ether in paragraph [0058]. Polyoxyalkylene alkyl or alkenyl ethers such as oxyethylene stearyl ether, polyoxyethylene di (stearyl) ether, polyoxyethylene octyl phenyl ether, polyoxyethylene di (nonyl) phenyl ether, polyoxyethylene di (nonylphenyl) ether Only polyoxyalkylphenyl ethers are described.
しかし、これらの界面活性剤系可塑剤を配合した粘着剤を使用した粘着シートは、被着体から剥がす際に、表面基材と粘着剤層の粘着力が十分でなく、粘着剤成分が被着体に残留する糊残りが生じることがあり、再剥離性が必ずしも十分とは言えないという問題点があった。 However, the pressure-sensitive adhesive sheet using a pressure-sensitive adhesive containing these surfactant plasticizers does not have sufficient adhesive strength between the surface base material and the pressure-sensitive adhesive layer when peeled off from the adherend, and the pressure-sensitive adhesive component is not covered. There is a problem in that adhesive residue remaining on the adherend may be generated, and re-peelability is not always sufficient.
本発明は、上記従来技術の状況に鑑みてなされたものであり、表面基材と粘着剤層とが優れた密着性を有し、かつ被着体への粘着性にも優れ、さらに、被着体に長期間貼付後に剥離しても被着体に糊残りが生じない粘着シートの製造方法を提供することを目的とする。 The present invention has been made in view of the above-described prior art. The surface base material and the pressure-sensitive adhesive layer have excellent adhesion, and are excellent in adhesion to an adherend. It is an object of the present invention to provide a method for producing a pressure-sensitive adhesive sheet in which no adhesive residue is produced on an adherend even if the adherend is peeled off after being applied for a long time.
本発明者らは、上記課題を解決するために、特定のアクリル系共重合体を含む水分散型粘着性組成物に、可塑剤としてのアミノ基含有ノニオン系界面活性剤を特定量添加して調製した水分散型粘着剤を塗布して得られる粘着剤層を、表面基材の裏面に設けることにより上記課題が解決できることを見出し、この知見に基づいて本発明を完成するに至った。 In order to solve the above-mentioned problems, the inventors added a specific amount of an amino group-containing nonionic surfactant as a plasticizer to a water-dispersed adhesive composition containing a specific acrylic copolymer. It has been found that the above problem can be solved by providing a pressure-sensitive adhesive layer obtained by applying the prepared water-dispersed pressure-sensitive adhesive on the back surface of the surface base material, and the present invention has been completed based on this finding.
すなわち、本発明は、表面基材と該表面基材の裏面に設けられている粘着剤層を含む粘着シートの製造方法であって、該粘着剤層が、２−エチルヘキシルアクリレート及びエチレン性不飽和カルボン酸を乳化重合してエマルションの形態で得られる平均粒子径が１００ｎｍ以上、かつ５００ｎｍ未満であるアクリル系共重合体を含む水分散型粘着性組成物に、可塑剤としてのアミノ基含有ノニオン系界面活性剤を前記アクリル系共重合体１００質量部に対して、０．１５〜１．５質量部添加して調製された水分散型粘着剤を塗布して形成されていることを特徴とする粘着シートの製造方法を提供するものである。 That is, this invention is a manufacturing method of the adhesive sheet containing the surface base material and the adhesive layer provided in the back surface of this surface base material, Comprising: This adhesive layer is 2-ethylhexyl acrylate and ethylenic unsaturated An amino group-containing nonion as a plasticizer in an aqueous dispersion-type adhesive composition containing an acrylic copolymer having an average particle size of 100 nm or more and less than 500 nm obtained by emulsion polymerization of a carboxylic acid It is formed by applying a water-dispersed adhesive prepared by adding 0.15 to 1.5 parts by mass of a surfactant to 100 parts by mass of the acrylic copolymer. The manufacturing method of an adhesive sheet is provided.
また、本発明は、上記粘着シートの製造方法において、前記表面基材が粘着シートを貼付する被着体の素材と同一の素材で構成されている粘着シートの製造方法を提供するものである。
また、本発明は、上記粘着シートの製造方法において、前記表面基材がポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂、ポリカーボネート樹脂、又は前記樹脂の２種以上の混合物により構成されている粘着シートの製造方法を提供するものである。
また、本発明は、上記粘着シートの製造方法において、前記アクリル系共重合体が、２−エチルヘキシルアクリレート及びエチレン性不飽和カルボン酸、さらに必要に応じて共重合可能なその他の不飽和単量体を乳化重合して得られるアクリル系共重合体である粘着シートの製造方法を提供するものである。
Further, the present invention provides the method of manufacturing a pressure-sensitive adhesive sheet, in which the surface substrate to provide a method for manufacturing a pressure-sensitive adhesive sheet is composed of the same material as the material of the adherend sticking the adhesive sheet.
Further, the present invention provides the pressure-sensitive adhesive sheet manufacturing method , wherein the surface substrate is composed of a polystyrene resin, an acrylonitrile-butadiene-styrene copolymer resin, a polycarbonate resin, or a mixture of two or more of the resins. A method for manufacturing a sheet is provided.
Further, the present invention provides the method for producing an adhesive sheet, wherein the acrylic copolymer is 2-ethylhexyl acrylate and an ethylenically unsaturated carboxylic acid, and other unsaturated monomers copolymerizable as necessary. The present invention provides a method for producing a pressure-sensitive adhesive sheet which is an acrylic copolymer obtained by emulsion polymerization.
また、本発明は、上記粘着シートの製造方法において、前記アミノ基含有ノニオン系界面活性剤が、式（１）で表されるポリオキシアルキレンアミンである粘着シートの製造方法を提供するものである。 Further, the present invention provides a method for producing the adhesive sheet, the amino group-containing nonionic surfactant, there is provided a method of manufacturing the pressure-sensitive adhesive sheet is a polyoxyalkylene amine represented by the formula (1) .
（式中、Ｒは炭素数が３〜３０のアルキル基、アルケニル基又はアシル基であり、Ａ１及びＡ２は炭素数２〜４のアルキレン基であり、ｘ及びｙは０又は正整数であり、ｘ＋ｙは２〜４０であり、ｘが２以上の場合に複数のＡ１は同一であっても良いし、異なっても良く、ｙが２以上の場合に複数のＡ２は同一であっても良いし、異なっても良い。）
また、本発明は、上記粘着シートの製造方法において、前記アミノ基含有ノニオン系界面活性剤のＨＬＢ値が８〜２０である粘着シートの製造方法を提供するものである。
また、本発明は、上記粘着シートの製造方法において、前記アクリル系共重合体の平均粒子径が１５０〜４００ｎｍである粘着シートの製造方法を提供するものである。
(Wherein R is an alkyl group, alkenyl group or acyl group having 3 to 30 carbon atoms, A 1 and A 2 are alkylene groups having 2 to 4 carbon atoms, and x and y are 0 or a positive integer. Yes, x + y is 2 to 40, and when x is 2 or more, the plurality of A 1 may be the same or different, and when y is 2 or more, the plurality of A 2 are the same. May be different or different.)
Further, the present invention provides a method for producing the adhesive sheet, HLB value of the amino group-containing nonionic surfactant is to provide a method of manufacturing the pressure-sensitive adhesive sheet 8 to 20.
Further, the present invention provides a method for producing the adhesive sheet, the average particle diameter of the acrylic copolymer is one that provides a method of producing a pressure-sensitive adhesive sheet is 150 to 400 nm.
本発明の粘着シートの製造方法により得られる粘着シートは、表面基材と粘着剤層とが優れた密着性を有し、かつ被着体への粘着性にも優れ、さらに、被着体に長期間貼付後に剥離しても被着体に糊残りが生じない。 The pressure-sensitive adhesive sheet obtained by the method for producing a pressure-sensitive adhesive sheet of the present invention has excellent adhesion to the surface base material and the pressure-sensitive adhesive layer, and also has excellent adhesion to the adherend. Even if it peels after sticking for a long time, adhesive residue does not occur on the adherend.
本発明において粘着剤層を形成するために用いられる水分散型粘着剤は、２−エチルヘキシルアクリレート及びエチレン性不飽和カルボン酸を乳化重合して得られるアクリル系共重合体を含む水分散型粘着性組成物に、可塑剤としてのアミノ基含有ノニオン系界面活性剤を添加して調製されたものである。
アクリル系共重合体は、本質的に２−エチルヘキシルアクリレート及びエチレン性不飽和カルボン酸からなる単量体を共重合させたものであっても良いし、さらに、これらの単量体と共重合可能なその他の不飽和単量体を共重合させたものであってもよい。好ましくは、本質的に２−エチルヘキシルアクリレート及びエチレン性不飽和カルボン酸からなる単量体を共重合させたものである。
The water-dispersed pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer in the present invention is a water-dispersed pressure-sensitive adhesive containing an acrylic copolymer obtained by emulsion polymerization of 2-ethylhexyl acrylate and ethylenically unsaturated carboxylic acid. The composition was prepared by adding an amino group-containing nonionic surfactant as a plasticizer.
The acrylic copolymer may be one obtained by copolymerizing monomers consisting essentially of 2-ethylhexyl acrylate and ethylenically unsaturated carboxylic acid, and can be copolymerized with these monomers. It is also possible to copolymerize other unsaturated monomers. Preferably, it is a copolymer of monomers consisting essentially of 2-ethylhexyl acrylate and an ethylenically unsaturated carboxylic acid.
エチレン性不飽和カルボン酸としては、アクリル酸、メタクリル酸などの（メタ）アクリル酸、イタコン酸、マレイン酸、無水マレイン酸、フマル酸、無水フマル酸等が挙げられ、好ましくは（メタ）アクリル酸である。エチレン性不飽和カルボン酸は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。エチレン性不飽和カルボン酸としては、特に好ましくはアクリル酸とメタクリル酸の併用である。アクリル酸とメタクリル酸を併用する場合、両者の重合割合は質量比で１／１０〜１０／１が好ましく、１／５〜５／１がより好ましく、１／３〜３／１がさらに好ましい。 Examples of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid such as acrylic acid and methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and fumaric anhydride, and preferably (meth) acrylic acid. It is. An ethylenically unsaturated carboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type. The ethylenically unsaturated carboxylic acid is particularly preferably a combination of acrylic acid and methacrylic acid. When acrylic acid and methacrylic acid are used in combination, the polymerization ratio of the two is preferably 1/10 to 10/1, more preferably 1/5 to 5/1, and still more preferably 1/3 to 3/1.
その他の不飽和単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸ラウリル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタクリル酸ラウリルなどのアルキル基の炭素数が１〜２０の（メタ）アクリル酸アルキルエステル、アクリル酸−２−ヒドロキシエチル、アクリル酸−２−ヒドロキシプロピル、アクリル酸−３−ヒドロキシプロピル、アクリル酸−３−ヒドロキシブチル、アクリル酸−４−ヒドロキシブチル、メタクリル酸−２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシプロピル、メタクリル酸−３−ヒドロキシプロピル、メタクリル酸−３−ヒドロキシブチル、メタクリル酸−４−ヒドロキシブチルなどの水酸基含有（メタ）アクリル酸アルキルエステルなどが挙げられる。その他の不飽和単量体は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Other unsaturated monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, (Meth) acrylic acid alkyl ester having 1 to 20 carbon atoms such as hexyl methacrylate and lauryl methacrylate, -2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, -3-hydroxypropyl acrylate 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, meta A hydroxyl group-containing (meth) acrylic acid alkyl esters such as acrylic acid-4-hydroxy-butyl. Another unsaturated monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
アクリル系共重合体におけるエチレン性不飽和カルボン酸に由来する単位の含有割合は、２−エチルヘキシルアクリレートに由来する単位の含有量１００質量部に対して０．１〜１０質量部が好ましく、０．３〜５質量部がより好ましい。また、アクリル系共重合体におけるその他の不飽和単量体に由来する単位の含有割合は、２−エチルヘキシルアクリレートに由来する単位の含有量１００質量部に対して０〜２０質量部が好ましく、０〜１５質量部がより好ましい。 The content ratio of the units derived from the ethylenically unsaturated carboxylic acid in the acrylic copolymer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the unit derived from 2-ethylhexyl acrylate. 3-5 mass parts is more preferable. The content ratio of units derived from other unsaturated monomers in the acrylic copolymer is preferably 0 to 20 parts by mass with respect to 100 parts by mass of units derived from 2-ethylhexyl acrylate. -15 mass parts is more preferable.
本発明においては、アクリル系共重合体は、乳化重合により得られる。乳化重合は、種々の乳化重合法により行うことができるが、一般的な乳化重合法でよい。具体的には、例えば、反応器内に２−エチルヘキシルアクリレート及びエチレン性不飽和カルボン酸、さらに、必要に応じてその他の不飽和単量体などの単量体、乳化剤、重合開始剤等を投入し、窒素等の不活性ガスで内部を置換した後、還流下で、水を分散媒として攪拌しながら昇温し、適当な重合温度、例えば４０〜１００℃程度の温度範囲にて、適当な重合時間、例えば１〜８時間程度乳化重合を行う方法が挙げられる。 In the present invention, the acrylic copolymer is obtained by emulsion polymerization. Emulsion polymerization can be performed by various emulsion polymerization methods, but may be a general emulsion polymerization method. Specifically, for example, 2-ethylhexyl acrylate and ethylenically unsaturated carboxylic acid, and other monomers such as an unsaturated monomer, an emulsifier, a polymerization initiator, etc. are charged into the reactor as necessary. Then, after the inside is replaced with an inert gas such as nitrogen, the temperature is raised with stirring using water as a dispersion medium under reflux, and an appropriate polymerization temperature, for example, within a temperature range of about 40 to 100 ° C. The method of performing emulsion polymerization for about 1 to 8 hours, for example, is mentioned.
乳化重合時に使用される乳化剤としては、特に限定されるものではなく、例えば、アニオン性乳化剤、ノニオン性乳化剤、反応性乳化剤などが挙げられる。ただし、乳化重合時に使用される乳化剤は、乳化重合後に添加される可塑剤としてのアミノ基含有ノニオン系界面活性剤とは異なるものである。
アニオン性乳化剤としては、例えば、オレイン酸カリウム、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、アルキルナフタレンスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルアリルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルアリルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンアルキルアリルエーテルリン酸エステルなどが挙げられる。
The emulsifier used at the time of emulsion polymerization is not particularly limited, and examples thereof include an anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier. However, the emulsifier used at the time of emulsion polymerization is different from the amino group-containing nonionic surfactant as a plasticizer added after the emulsion polymerization.
Examples of the anionic emulsifier include potassium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, Examples include ammonium polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate, and the like.
ノニオン性乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオキシプロピレンブロックコポリマー、ポリエチレングリコール脂肪酸エステル、ポリプロピレングリコールクレゾールエーテル、ポリオキシエチレンソルビタン脂肪酸エステルなどが挙げられる。 Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oxypropylene block copolymer, polyethylene glycol fatty acid ester, polypropylene glycol cresol ether, polyoxyethylene sorbitan fatty acid ester and the like.
反応性乳化剤としては、例えば、種々の分子量（エチレンオキサイド付加モル数の異なる）のポリエチレングリコールモノ（メタ）アクリレート、ポリオキシエチレンアルキルフェノールエーテル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルスルホン酸アンモニウム、ポリオキシエチレングリコールのモノマレイン酸エステルおよびその誘導体、（メタ）アクリロイルポリオキシアルキレンアルキルエーテルリン酸エステルなどが挙げられる。環境衛生面、特に環境ホルモン問題を生じない点で好ましい乳化剤は、上記うちで高級アルコール系誘導体の乳化剤である。
乳化剤は、１種単独で用いることもできるし、２種以上を組み合わせて用いることもできる。
Examples of reactive emulsifiers include polyethylene glycol mono (meth) acrylate, polyoxyethylene alkylphenol ether (meth) acrylate and ammonium 2- (meth) acryloyloxyethylsulfonate having various molecular weights (different number of moles of ethylene oxide added). And monomaleic acid ester of polyoxyethylene glycol and derivatives thereof, (meth) acryloyl polyoxyalkylene alkyl ether phosphate, and the like. Among the above, preferred emulsifiers from the viewpoint of environmental hygiene, particularly those that do not cause environmental hormone problems, are higher alcohol derivatives.
An emulsifier can also be used individually by 1 type and can also be used in combination of 2 or more type.
乳化剤の使用量は、通常、アクリル系共重合体１００質量部に対して、０．２〜１０質量部が好ましく、０．５〜５質量部がより好ましい。乳化剤の使用量が上記範囲にあることにより、凝固物を生じることなく、適度な粒子径のエマルションが得られる。 The amount of the emulsifier used is usually preferably 0.2 to 10 parts by mass and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the acrylic copolymer. When the amount of the emulsifier is in the above range, an emulsion having an appropriate particle size can be obtained without producing a coagulated product.
乳化重合により得られるアクリル系共重合体は、エマルションの形態で得られる。エマルション中に分散しているアクリル系共重合体の平均粒子径は、１００ｎｍ以上、かつ５００ｎｍ未満であり、より好ましくは１５０〜４００ｎｍであり、さらに好ましくは２００〜３５０ｎｍである。
アクリル系共重合体の重量平均分子量は、３０，０００〜１，５００，０００が好ましく、５０，０００〜１，０００，０００がより好ましく、１００，０００〜５００，０００が特に好ましい。なお、本明細書において、重量平均分子量とは、テトラヒドロフラン可溶成分をゲルパーミエーションクロマトグラフィー法により測定した標準ポリスチレン換算の値である。
The acrylic copolymer obtained by emulsion polymerization is obtained in the form of an emulsion. The average particle diameter of the acrylic copolymer dispersed in the emulsion is 100 nm or more and less than 500 nm, more preferably 150 to 400 nm, and still more preferably 200 to 350 nm.
The weight average molecular weight of the acrylic copolymer is preferably 30,000 to 1,500,000, more preferably 50,000 to 1,000,000, and particularly preferably 100,000 to 500,000. In addition, in this specification, a weight average molecular weight is the value of standard polystyrene conversion which measured the tetrahydrofuran soluble component by the gel permeation chromatography method.
本発明においては、上記乳化重合により、アクリル系共重合体を含む水分散型粘着性組成物が得られる。
本発明における水分散型粘着剤は、上記アクリル系共重合体を含む水分散型粘着性組成物に、可塑剤としてのアミノ基含有ノニオン系界面活性剤を添加して、混合することにより得られる。
アミノ基含有ノニオン系界面活性剤としては、ノニオン系界面活性剤にアミノ基が結合しているものであれば種々のものが使用できるが、アミノ基の数は、ノニオン系界面活性剤の１分子中に６個以下が好ましく、３個以下が好ましく、２個以下が特に好ましい。
In the present invention, a water-dispersed pressure-sensitive adhesive composition containing an acrylic copolymer is obtained by the emulsion polymerization.
The water-dispersed pressure-sensitive adhesive in the present invention is obtained by adding an amino group-containing nonionic surfactant as a plasticizer to the water-dispersed pressure-sensitive adhesive composition containing the acrylic copolymer and mixing them. .
As the amino group-containing nonionic surfactant, various types can be used as long as the amino group is bonded to the nonionic surfactant. The number of amino groups is one molecule of the nonionic surfactant. Among them, 6 or less are preferable, 3 or less are preferable, and 2 or less are particularly preferable.
アミノ基含有ノニオン系界面活性剤の好適な具体例としては、ポリオキシアルキレンアミンが挙げられ、ポリオキシアルキレンアルキルアミンがより好ましい。ポリオキシアルキレンアミンの具体例としては、例えば、式（１）で表されるポリオキシアルキレンアミンが挙げられる。 Preferable specific examples of the amino group-containing nonionic surfactant include polyoxyalkyleneamine, and polyoxyalkylenealkylamine is more preferable. Specific examples of the polyoxyalkylene amine include, for example, a polyoxyalkylene amine represented by the formula (1).
（式中、Ｒは炭素数が３〜３０のアルキル基、アルケニル基又はアシル基であり、Ａ１及びＡ２は炭素数２〜４のアルキレン基であり、ｘ及びｙは０又は正整数であり、ｘ＋ｙは２〜４０であり、ｘが２以上の場合に複数のＡ１は同一であっても良いし、異なっても良く、ｙが２以上の場合に複数のＡ２は同一であっても良いし、異なっても良い。） (Wherein R is an alkyl group, alkenyl group or acyl group having 3 to 30 carbon atoms, A 1 and A 2 are alkylene groups having 2 to 4 carbon atoms, and x and y are 0 or a positive integer. Yes, x + y is 2 to 40, and when x is 2 or more, the plurality of A 1 may be the same or different, and when y is 2 or more, the plurality of A 2 are the same. May be different or different.)
式（１）におけるＲの炭素数は４〜２４が好ましく、６〜２０がより好ましく、１０〜２０が特に好ましい。また、Ａ１及びＡ２はエチレン基、プロピレン基、ブチレン基が挙げられるが、エチレン基、プロピレン基が好ましく、エチレン基が更に好ましい。ｘ及びｙが２以上である場合の（Ａ１Ｏ）ｘ及び（Ａ２Ｏ）ｙは、ポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシブチレン基などのように１種類のオキシアルキレン基の連鎖であってもよいし、炭素数２〜４のオキシアルキレン基の２種以上の組み合わせからなるポリオキシアルキレン基であってもよい。炭素数２〜４のオキシアルキレン基の２種以上の組み合わせからなるポリオキシアルキレン基は、ランダム構造であってもよいし、ブロック構造であってもよい。また、ｘ＋ｙは２〜４０であるが、３〜２０が好ましく、４〜１７が特に好ましい。 4-24 are preferable, as for carbon number of R in Formula (1), 6-20 are more preferable, and 10-20 are especially preferable. A 1 and A 2 include an ethylene group, a propylene group, and a butylene group, but an ethylene group and a propylene group are preferable, and an ethylene group is more preferable. When x and y are 2 or more, (A 1 O) x and (A 2 O) y are one kind of oxyalkylene group such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group and the like. A chain may be sufficient and the polyoxyalkylene group which consists of 2 or more types of combinations of a C2-C4 oxyalkylene group may be sufficient. A polyoxyalkylene group composed of a combination of two or more kinds of oxyalkylene groups having 2 to 4 carbon atoms may have a random structure or a block structure. Moreover, although x + y is 2-40, 3-20 are preferable and 4-17 are especially preferable.
また、アミノ基含有ノニオン系界面活性剤は、ＨＬＢ値が８〜２０であることが好ましく、１０〜１６であることが特に好ましい。
アミノ基含有ノニオン系界面活性剤は、１種を用いてもよいし、２種以上を組み合わせて用いてもよい。２種以上を組み合わせる場合、上記特に好ましいものの２種以上を組み合わせることが特に好ましい。
可塑剤としてのアミノ基含有ノニオン系界面活性剤の添加量は、アクリル系共重合体１００質量部に対して、０．１５〜１．５質量部であり、０．２〜１．２質量部がさらに好ましい。
The amino group-containing nonionic surfactant preferably has an HLB value of 8 to 20, particularly preferably 10 to 16.
One type of amino group-containing nonionic surfactant may be used, or two or more types may be used in combination. When combining 2 or more types, it is particularly preferable to combine 2 or more of the above-mentioned particularly preferable types.
The addition amount of the amino group-containing nonionic surfactants as plasticizers for the acrylic copolymer 100 parts by weight, a 0.15 to 1.5 parts by weight, 0.2 to 1.2 parts by weight Is more preferable.
本発明の水分散型粘着剤には、アクリル系共重合体を架橋剤により架橋させるために、架橋剤を配合することが好ましい。
アクリル系共重合体を架橋するために用いられる架橋剤としては、エポキシ系架橋剤が好ましい。エポキシ系架橋剤としては、例えば、ネオペンチル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、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、フタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエーテル、トリグリシジルイソシアヌレート、ジグリセロールトリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ソルビトールテトラグリシジルエーテル、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、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’−テトラグリシジルジアミノジフェニルメタンなどのエポキシ系架橋剤が用いられる。
架橋剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
架橋剤の使用量は、アクリル系共重合体１００質量部に対して、０．０１〜１０質量部が好ましく、０．１〜５質量部がより好ましい。
The water-dispersed pressure-sensitive adhesive of the present invention preferably contains a crosslinking agent in order to crosslink the acrylic copolymer with a crosslinking agent.
As the crosslinking agent used for crosslinking the acrylic copolymer, an epoxy crosslinking agent is preferable. Examples of the epoxy crosslinking agent include neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phthalic acid diglycidyl ester, dimer acid diglycidyl ether, and triglycidyl isocyanurate. , Diglycerol triglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol tetraglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino) Epoxy crosslinking agents such as methyl) cyclohexane and N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane are used.
A crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.
0.01-10 mass parts is preferable with respect to 100 mass parts of acrylic copolymers, and, as for the usage-amount of a crosslinking agent, 0.1-5 mass parts is more preferable.
本発明の水分散型粘着剤には、増粘剤、粘着付与剤、安定剤などの各種添加剤を配合することができる。
増粘剤としては、ポリアクリル酸系重合体、ポリメタクリル酸系重合体、ポリ（メタ）アクリル酸エステル系重合体、ポリオレフィン系重合体などが挙げられる。増粘剤の配合割合は、水分散型粘着剤の粘度を塗布するために適度な粘度にできる量であればよく、水分散型粘着剤の粘度が１００〜１００００ｍＰａ・ｓ（ＢＭ型粘度計、２５℃、６０ｒｐｍ）の範囲になるような量であればよい。通常、アクリル系共重合体１００質量部に対して、０．１〜１０質量部が好ましく、１〜５質量部がより好ましい。
Various additives, such as a thickener, a tackifier, and a stabilizer, can be mix | blended with the water dispersion-type adhesive of this invention.
Examples of the thickener include polyacrylic acid polymers, polymethacrylic acid polymers, poly (meth) acrylic acid ester polymers, polyolefin polymers, and the like. The blending ratio of the thickener may be an amount that can be adjusted to an appropriate viscosity for applying the viscosity of the water-dispersed pressure-sensitive adhesive, and the viscosity of the water-dispersed pressure-sensitive adhesive is 100 to 10,000 mPa · s (BM type viscometer, The amount may be in a range of 25 ° C. and 60 rpm. Usually, 0.1-10 mass parts is preferable with respect to 100 mass parts of acrylic copolymers, and 1-5 mass parts is more preferable.
粘着付与剤としては、ロジン、ロジンエステル、水添ロジンエステルなどのロジンエステル系粘着付与剤、テルペンフェノール樹脂などのテルペン系粘着付与剤が挙げられる。粘着付与剤は、乳化重合時にアクリル系単量体と共存させておいてもよいし、公知の方法で乳化された粘着付与樹脂エマルションを乳化重合後に添加してもよく、両者を併用してもよい。粘着付与剤の配合割合は、通常、アクリル系共重合体１００質量部に対して、０．１〜２０質量部が好ましく、５〜１５質量部がより好ましい。粘着付与剤の配合割合を０．１質量部以上にすることにより、貼付中に剥がれることなく使用でき、粘着付与剤の配合割合を２０質量部以下にすることにより、被着体から糊残りなく容易に剥がすことができる。 Examples of the tackifier include rosin ester tackifiers such as rosin, rosin ester and hydrogenated rosin ester, and terpene tackifiers such as terpene phenol resin. The tackifier may be allowed to coexist with an acrylic monomer during emulsion polymerization, a tackifier resin emulsion emulsified by a known method may be added after emulsion polymerization, or both may be used in combination. Good. As for the compounding ratio of a tackifier, 0.1-20 mass parts is preferable with respect to 100 mass parts of acrylic copolymers normally, and 5-15 mass parts is more preferable. By making the blending ratio of the tackifier 0.1 parts by mass or more, it can be used without peeling during sticking, and by making the blending ratio of the tackifier 20 parts by mass or less, there is no adhesive residue from the adherend. Can be easily peeled off.
本発明における水分散型粘着性組成物は、樹脂固形分の含有量は、通常３０〜７０質量％であればよく、４０〜６０質量％が好ましい。
本発明の粘着シートの製造方法により得られる粘着シートは、表面基材と該表面基材の裏面に設けられている粘着剤層を含む粘着シートである。
In the water-dispersed pressure-sensitive adhesive composition of the present invention, the resin solid content is usually 30 to 70% by mass, preferably 40 to 60% by mass.
The pressure-sensitive adhesive sheet obtained by the method for producing a pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet including a surface base material and a pressure-sensitive adhesive layer provided on the back surface of the surface base material.
表面基材としては、種々のプラスチックのシート、フィルムが使用できる。表面基材の具体例としては、例えばポリエチレン樹脂、ポリプロピレン樹脂などのポリオレフィン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリブチレンテレフタレート樹脂などのポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂（ＡＢＳ樹脂）、ポリカーボネート樹脂、ポリアミド樹脂、ポリイミド樹脂、フッ素系樹脂、及びこれらの２種以上の混合物などの各種合成樹脂のシート、フィルムが挙げられ、特に、高強度であり安価であることから家電製品や電子機器の樹脂製筺体に使用されている樹脂の素材と同一の素材を用いることが好ましい。これらの表面基材としては、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂（ＡＢＳ樹脂）、ポリカーボネート樹脂、又は前記樹脂の２種以上の混合物により構成されているシート、フィルムが好ましい。表面基材は、単層であってもよいし、同種又は異種の２層以上の多層であってもよい。 As the surface substrate, various plastic sheets and films can be used. Specific examples of the surface substrate include, for example, polyolefin resins such as polyethylene resin and polypropylene resin, polyester resins such as polyethylene terephthalate resin, polyethylene naphthalate resin and polybutylene terephthalate resin, polyvinyl chloride resin, polystyrene resin, acrylonitrile-butadiene- Examples include sheets and films of various synthetic resins such as styrene copolymer resins (ABS resins), polycarbonate resins, polyamide resins, polyimide resins, fluorine resins, and mixtures of two or more of these, and particularly high strength. Since it is inexpensive, it is preferable to use the same material as the resin material used in the resin casing of home appliances and electronic devices. As these surface base materials, a sheet or film composed of polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, or a mixture of two or more of the above resins is preferable. The surface substrate may be a single layer, or may be a multilayer of two or more layers of the same type or different types.
表面基材の厚みは、特に制限ないが、通常１０〜３５０μｍが好ましく、１５〜３００μｍがより好ましく、２０〜２５０μｍが特に好ましい。
表面基材の表面には、印刷受容層を設けてもよい。表面基材の表面に印刷受容層を設けると、粘着剤層を表面基材の裏面に設けた後に、印刷することができる。
印刷受容層は、種々の印字用コート剤を塗布することにより設けることができる。印字用コート剤としては、好ましくはアクリル樹脂又はポリエステル樹脂、あるいはそれらを併用した印字用コート剤が挙げられる。
表面基材の裏面は、粘着剤層との密着力をさらに上げるために易接着処理を施してもよい。易接着処理としては、特に制限はないが、例えば、コロナ放電処理等が挙げられる。
Although the thickness of a surface base material does not have a restriction | limiting in particular, Usually, 10-350 micrometers is preferable, 15-300 micrometers is more preferable, and 20-250 micrometers is especially preferable.
A print receiving layer may be provided on the surface of the surface substrate. When a print receiving layer is provided on the surface of the surface substrate, printing can be performed after the pressure-sensitive adhesive layer is provided on the back surface of the surface substrate.
The print receiving layer can be provided by applying various printing coating agents. As the printing coating agent, an acrylic resin or a polyester resin, or a printing coating agent using them in combination is preferably used.
The back surface of the surface base material may be subjected to an easy adhesion treatment in order to further increase the adhesion with the pressure-sensitive adhesive layer. Although there is no restriction | limiting in particular as an easily bonding process, For example, a corona discharge process etc. are mentioned.
本発明の粘着シートの製造方法により得られる粘着シートにおいては、表面基材の裏面に、上記粘着剤組成物からなる粘着剤層が形成されている。
粘着剤層の厚みは、特に制限されないが、通常乾燥後の膜厚が３〜１５０μｍが好ましく、５〜１００μｍがより好ましく、１０〜６０μｍがさらに好ましい。
表面基材の裏面に、上記粘着剤組成物からなる粘着剤層を形成する方法としては、基材シートの裏面に、上記水分散型粘着剤を塗布して、乾燥する方法、予め剥離シートの剥離処理面に上記水分散型粘着剤を塗布して、乾燥し、形成された粘着剤層を表面基材の裏面に貼り合わせる方法などが挙げられる。
In the pressure-sensitive adhesive sheet obtained by the method for producing a pressure-sensitive adhesive sheet of the present invention, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is formed on the back surface of the surface base material.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, but the film thickness after drying is usually preferably 3 to 150 μm, more preferably 5 to 100 μm, further preferably 10 to 60 μm.
As a method of forming the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition on the back surface of the surface base material, a method of applying the water-dispersed pressure-sensitive adhesive to the back surface of the base material sheet and drying it, Examples include a method in which the water-dispersed pressure-sensitive adhesive is applied to the release treatment surface, dried, and the formed pressure-sensitive adhesive layer is bonded to the back surface of the surface substrate.
上記水分散型粘着剤の表面基材又は剥離シートへの塗布方法は、例えば、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法、カーテンコート法など従来公知の方法が挙げられる。
乾燥は、通常６０〜１３０℃で行うことが好ましく、８０〜１２０℃がより好ましい。乾燥時間は特に制限ないが、通常１０秒〜５分間で十分である。
Methods for applying the water-dispersed pressure-sensitive adhesive to the surface substrate or release sheet are conventionally known, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, and a curtain coating method. The method is mentioned.
It is preferable to perform drying normally at 60-130 degreeC, and 80-120 degreeC is more preferable. The drying time is not particularly limited, but usually 10 seconds to 5 minutes is sufficient.
剥離シートとしては、特に限定されるものではない。剥離シートの基材としては、例えば、紙、合成紙、合成樹脂フィルムなどが挙げられる。紙としては、例えば、上質紙、グラシン紙、コート紙などの紙基材、これらの紙基材にポリエチレン、ポリプロピレンなどの熱可塑性樹脂をラミネートしたラミネート紙のような紙基材、及び上質紙、グラシン紙、コート紙などにセルロース、澱粉、ポリビニルアルコール、アクリル−スチレン樹脂などで目止め処理した紙基材などが挙げられる。プラスチック合成樹脂フィルムとしては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂などのポリオレフィン樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂などのポリエステル樹脂からなるフィルム、及びこれらの合成樹脂フィルムに易接着処理を施したフィルムなどが挙げられ、これらに剥離剤を塗布したものであることが望ましい。 The release sheet is not particularly limited. Examples of the base material of the release sheet include paper, synthetic paper, and synthetic resin film. As the paper, for example, a paper base such as fine paper, glassine paper, coated paper, a paper base such as a laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene to these paper bases, and high-quality paper, Examples thereof include a paper base or the like that is subjected to a sealing treatment with glassine paper, coated paper, etc. with cellulose, starch, polyvinyl alcohol, acrylic-styrene resin, or the like. Examples of plastic synthetic resin films include films made of polyolefin resins such as polyethylene resins and polypropylene resins, films made of polyester resins such as polybutylene terephthalate resins and polyethylene terephthalate resins, and films obtained by subjecting these synthetic resin films to easy adhesion treatment. It is desirable that these are coated with a release agent.
剥離剤には、フッ素系樹脂、シリコーン系樹脂、長鎖アルキル基含有カルバメートなどが挙げられる。
本発明の粘着シートの製造方法により得られる粘着シートは、被着体貼付用粘着シートとして用いられ、被着体に貼付して使用され、その用途は限定されないが、特に、被着体をリサイクルして再利用する場合の被着体に貼付して使用されることが好ましい。
Examples of the release agent include fluorine resins, silicone resins, and long-chain alkyl group-containing carbamates.
The pressure-sensitive adhesive sheet obtained by the method for producing a pressure-sensitive adhesive sheet of the present invention is used as a pressure-sensitive adhesive sheet for sticking an adherend, and is used by being attached to an adherend, and its use is not limited, but in particular, the adherend is recycled. Then, it is preferably used by being attached to an adherend when reused.
本発明の粘着シートの製造方法により得られる粘着シートは、粘着シートの表面基材の材質と、被着体を構成する材質が同じである場合に、好適に適用することができる。
被着体を構成する材質としては、具体例として、ポリスチレン樹脂、ＡＢＳ樹脂、ポリカーボネート樹脂、又は前記樹脂の２種以上の混合物により構成されている被着体が挙げられる。
被着体の形状は、特に制限されるものではなく、種々の形状にすることができる。
The pressure-sensitive adhesive sheet obtained by the method for producing a pressure-sensitive adhesive sheet of the present invention can be suitably applied when the material of the surface base material of the pressure-sensitive adhesive sheet and the material constituting the adherend are the same.
Specific examples of the material constituting the adherend include an adherend composed of polystyrene resin, ABS resin, polycarbonate resin, or a mixture of two or more of the above resins.
The shape of the adherend is not particularly limited, and can be various shapes.
次に、本発明を実施例によりさらに具体的に説明する。なお、本発明は、これらの例によって何ら制限されるものではない。 Next, the present invention will be described more specifically with reference to examples. In addition, this invention is not restrict | limited at all by these examples.
（実施例１）
（１）水分散型粘着性組成物の調製
攪拌機、還流冷却器、温度計、窒素導入管及び滴下ロートを備えた反応容器に、２−エチルヘキシルアクリレート１００質量部、アクリル酸０．２質量部、メタクリル酸０．４質量部を仕込み、さらに、ポリオキシエチレンアルキルエーテル硫酸ナトリウム（界面活性剤、花王株式会社製、商品名「ラテムルＥ−１１８Ｂ」）０．５質量部、ポリオキシエチレンアルキルアリルエーテル硫酸アンモニウム（界面活性剤、第一工業製薬製、商品名「アクアロンＫＨ−０５」）０．１質量部、ポリオキシエチレンアルキルエーテル（界面活性剤、花王株式会社製、商品名「エマルゲン１０３」）１．０質量部、水添ロジンエステル系粘着付与剤（理化ファインテク製、商品名「リカタックＦ−１０５」）２．０質量部、テルペンフェノール系粘着付与剤（ヤスハラケミカル株式会社製、商品名「ＹＳポリエスターＮ−１２５」）０．５質量部と、イオン交換水８０質量部を投入して、室温で攪拌して不飽和単量体の混合物の乳化物を予め調製した。
Example 1
(1) Preparation of water-dispersed pressure-sensitive adhesive composition In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel, 100 parts by mass of 2-ethylhexyl acrylate, 0.2 parts by mass of acrylic acid, 0.4 parts by weight of methacrylic acid was charged, and 0.5 parts by weight of sodium polyoxyethylene alkyl ether sulfate (surfactant, trade name “Latemul E-118B”), polyoxyethylene alkyl allyl ether Ammonium sulfate (surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name “AQUALON KH-05”) 0.1 part by mass, polyoxyethylene alkyl ether (surfactant, manufactured by Kao Corporation, trade name “Emulgen 103”) 1 0.0 part by mass, hydrogenated rosin ester-based tackifier (Rika Finetech, trade name “Rekatak F-105”) 2.0 Parts, 0.5 parts by mass of a terpene phenol tackifier (manufactured by Yasuhara Chemical Co., Ltd., trade name “YS Polyester N-125”) and 80 parts by mass of ion-exchanged water were added and stirred at room temperature. An emulsion of a mixture of saturated monomers was prepared in advance.
別途、攪拌機、還流冷却器、温度計、窒素導入管及び滴下ロートを備えた反応容器に、イオン交換水２８質量部を入れ、窒素を封入して内温８０℃まで昇温し、その温度に保ちながら１０質量％の過硫酸アンモニウム水溶液０．５質量部を加えた。
次に、上記のように予め調製した不飽和単量体の混合物の乳化物を滴下ロートに移し、４時間かけて滴下した。これと併行して５質量％過硫酸アンモニウム水溶液４質量部を滴下して、内温８０℃で乳化重合を行った。
滴下終了後、８０℃で４時間熟成し、アクリル系共重合体エマルションを得た。その後、室温まで冷却し、アンモニア水で中和した後に水を加えて、固形分５０質量％、ｐＨ８．０の水分散型粘着剤組成物を得た。水分散型粘着剤組成物中のアクリル系共重合体の平均粒子径は２７０ｎｍであった。
Separately, in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube and a dropping funnel, 28 parts by mass of ion-exchanged water is enclosed, and the temperature is raised to an internal temperature of 80 ° C. by filling nitrogen. While maintaining, 0.5 part by mass of a 10% by mass aqueous ammonium persulfate solution was added.
Next, the emulsion of the mixture of unsaturated monomers prepared in advance as described above was transferred to a dropping funnel and dropped over 4 hours. At the same time, 4 parts by mass of a 5% by mass ammonium persulfate aqueous solution was dropped, and emulsion polymerization was carried out at an internal temperature of 80 ° C.
After completion of dropping, the mixture was aged at 80 ° C. for 4 hours to obtain an acrylic copolymer emulsion. Then, after cooling to room temperature and neutralizing with ammonia water, water was added to obtain a water-dispersed pressure-sensitive adhesive composition having a solid content of 50% by mass and a pH of 8.0. The average particle diameter of the acrylic copolymer in the water-dispersed pressure-sensitive adhesive composition was 270 nm.
（２）水分散型粘着剤の調製
上記（１）で得られた水分散型粘着剤組成物１００質量部に対して、エマルション型ロジンエステル系粘着付与剤（ハリマ化成社製、商品名「ハリエスターＳＫ−８１６」）３．０質量部、エマルション型テルペンフェノール系粘着付与剤（荒川化学株式会社製、商品名「タマノールＥ−１００」）５．３質量部と、可塑剤としてポリオキシエチレンアルキルアミン（ライオン・アクゾ株式会社製、商品名「エソミンＣ／２５」、式（１）におけるＲがヤシ油から得られる平均炭素数が１２のアルキル基であり、ｘ＋ｙが１５である。ＨＬＢ値１５．４）０．６質量部を添加し、さらに、ポリアクリル酸系増粘剤（ロームアンドハース社製、商品名「アクリゾールＡＳＥ−６０」）３．０質量部を添加して、粘度８０００ｍＰａ・ｓ（ＢＭ型粘度計、２５℃、６０ｒｐｍ）に増粘させて、水分散型粘着剤を得た。
(2) Preparation of water-dispersed pressure-sensitive adhesive For 100 parts by mass of the water-dispersed pressure-sensitive adhesive composition obtained in (1) above, an emulsion-type rosin ester-based tackifier (trade name “Harrie, manufactured by Harima Chemical Co., Ltd.” Star SK-816 ") 3.0 parts by mass, emulsion type terpene phenol tackifier (Arakawa Chemical Industries, trade name" Tamanol E-100 ") 5.3 parts by mass, and polyoxyethylene alkyl as a plasticizer Amine (product name “Esomin C / 25” manufactured by Lion Akzo Co., Ltd.), R in formula (1) is an alkyl group having an average carbon number of 12 obtained from coconut oil, and x + y is 15. HLB value 15 .4) Add 0.6 parts by weight, and further add 3.0 parts by weight of a polyacrylic acid thickener (Rohm and Haas, trade name “Acrysol ASE-60”). 000mPa · s (BM type viscometer, 25 ° C., 60 rpm) to thicken the, to obtain an aqueous dispersion adhesive.
（３）粘着シートの作成
上記（２）で得られた水分散型粘着剤１００質量部に、エポキシ系架橋剤（ナガセケムテックス社製、商品名「デナコールＥＸ−３１３」）０．５質量部を添加、混合したものを剥離シート（リンテック社製、シリコーン樹脂で剥離処理したグラシン紙、商品名「ＳＰ−８Ｋアオ」）の剥離処理面上にロールナイフコーターを用いて、乾燥後の塗布厚みが２０μｍになるように塗工し、９０℃で２分間乾燥し、粘着剤層を形成した。乾燥後、粘着剤層をポリスチレン樹脂フィルム（オージー株式会社製、商品名「ハイスチレンＰＳ６５」、厚み６５μｍ）と剥離シート上の粘着剤層とを貼り合わせて、表面基材がポリスチレン樹脂フィルムの再剥離性の粘着シートを作成した。
(3) Preparation of pressure-sensitive adhesive sheet To 100 parts by weight of the water-dispersed pressure-sensitive adhesive obtained in (2) above, 0.5 parts by weight of an epoxy-based crosslinking agent (trade name “Denacol EX-313” manufactured by Nagase ChemteX Corporation) The coating thickness after drying using a roll knife coater on the release-treated surface of a release sheet (made by Lintec Co., Ltd., glassine paper released by silicone resin, trade name “SP-8K Ao”) Was applied to a thickness of 20 μm and dried at 90 ° C. for 2 minutes to form an adhesive layer. After drying, the pressure-sensitive adhesive layer was bonded to a polystyrene resin film (manufactured by OG Co., Ltd., trade name “High Styrene PS65”, thickness 65 μm) and the pressure-sensitive adhesive layer on the release sheet, and the surface substrate was re-coated with the polystyrene resin film. A peelable adhesive sheet was prepared.
同様にして、表面基材として、ポリスチレン樹脂フィルムの代わりに、ＡＢＳ樹脂フィルム（信越ポリマー社製、商品名「ＰＳＺ９８０」、厚み８０μｍ）、ポリカーボネート樹脂フィルム（帝人社製、商品名「ピュアエースＣ−１１０−１００」、厚み１００μｍ）、ポリカーボネート樹脂−ＡＢＳ樹脂の混合樹脂からなるフィルム（帝人化成社製のポリカーボネート樹脂−ＡＢＳ樹脂系ポリマーアロイ「マルチロンＴ２７１１」をインフレーション製膜機を用いて、２４０℃で溶融させながら押出成形して得られた厚さ１００μｍのフィルム）、ポリカーボネート樹脂−ポリスチレン樹脂の混合樹脂からなるフィルム（ポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製の「ノバレックス７０２７Ｒ」）とポリスチレン樹脂（日本ポリスチレン社製の「Ｇ６９０Ｎ」）を等量ずつ混合し、インフレーション製膜機を用いて、２６０℃で溶融させながら押出成形して得られた厚さ１００μｍのフィルム）をそれぞれ用いて、表面基材がＡＢＳ樹脂フィルムの再剥離性の粘着シート、ポリカーボネート樹脂フィルムの再剥離性の粘着シート、ポリカーボネート樹脂−ＡＢＳ樹脂の混合樹脂からなるフィルムの再剥離性の粘着シート、ポリカーボネート樹脂−ポリスチレン樹脂の混合樹脂からなるフィルムの再剥離性の粘着シートを作成した。このように、表面基材が異なる５種類の粘着シートを作成した。 Similarly, as a surface base material, instead of polystyrene resin film, ABS resin film (manufactured by Shin-Etsu Polymer Co., Ltd., trade name “PSZ980”, thickness 80 μm), polycarbonate resin film (manufactured by Teijin Ltd., trade name “Pure Ace C-”) 110-100 ”, thickness 100 μm), a polycarbonate resin-ABS resin mixed film (Teijin Kasei's polycarbonate resin-ABS resin-based polymer alloy“ Multilon T2711 ”) using an inflation film forming machine at 240 ° C. 100 μm thick film obtained by extrusion while melting), a film made of a mixed resin of polycarbonate resin and polystyrene resin (polycarbonate resin (“NOVALEX 7027R” manufactured by Mitsubishi Engineering Plastics) and polystyrene resin “G690N” manufactured by Nippon Polystyrene Co., Ltd.) was mixed in equal amounts, and each film was obtained by extrusion molding while melting at 260 ° C. using an inflation film-forming machine. Removable adhesive sheet of ABS resin film, Removable adhesive sheet of polycarbonate resin film, Removable adhesive sheet of film made of polycarbonate resin-ABS resin mixed resin, Mixture of polycarbonate resin and polystyrene resin A re-peelable pressure-sensitive adhesive sheet made of a resin was prepared. Thus, five types of pressure-sensitive adhesive sheets having different surface base materials were prepared.
（実施例２）
実施例１の（２）において、エマルション型ロジンエステル系粘着付与剤及びエマルション型テルペンフェノール系粘着付与剤を添加しなかった以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
(Example 2)
In Example 1 (2), five different surface base materials were used in the same manner as in Example 1 except that the emulsion type rosin ester tackifier and the emulsion type terpene phenol tackifier were not added. An adhesive sheet was prepared.
（実施例３）
実施例１の（１）において、水添ロジンエステル系粘着付与剤、テルペンフェノール系粘着付与剤を添加せず、実施例１の（２）において、エマルション型水添ロジンエステル系粘着付与剤及びエマルション型テルペンフェノール系粘着付与剤を添加しなかった以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
(Example 3)
In (1) of Example 1, a hydrogenated rosin ester tackifier and a terpene phenol tackifier were not added. In (2) of Example 1, an emulsion-type hydrogenated rosin ester tackifier and emulsion Five types of pressure-sensitive adhesive sheets having different surface base materials were prepared in the same manner as in Example 1 except that the type terpene phenol-based tackifier was not added.
（実施例４）
実施例１の（１）において、テルペンフェノール系粘着付与剤を添加せず、実施例１の（２）において、エマルション型ロジンエステル系粘着付与剤及びエマルション型テルペンフェノール系粘着付与剤を添加しなかった以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
Example 4
In Example 1 (1), no terpene phenol tackifier was added, and in Example 1 (2), an emulsion rosin ester tackifier and an emulsion terpene phenol tackifier were not added. Except for the above, five types of pressure-sensitive adhesive sheets having different surface base materials were prepared in the same manner as in Example 1.
（実施例５）
実施例１の（２）において、エマルション型テルペンフェノール系粘着付与剤を添加しなかった以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
(Example 5)
In Example 1 (2), five types of pressure-sensitive adhesive sheets having different surface base materials were prepared in the same manner as in Example 1 except that the emulsion type terpene phenol-based tackifier was not added.
（実施例６）
実施例１の（２）において、エマルション型ロジンエステル系粘着付与剤を添加しなかった以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
(Example 6)
In Example 1 (2), five types of pressure-sensitive adhesive sheets having different surface base materials were prepared in the same manner as in Example 1 except that the emulsion-type rosin ester-based tackifier was not added.
（実施例７）
実施例１において、可塑剤としてのポリオキシエチレンアルキルアミン（ライオン・アクゾ株式会社製、商品名「エソミンＣ／２５」）の配合量を０．４質量部にした以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
(Example 7)
Example 1 is the same as Example 1 except that the amount of polyoxyethylene alkylamine (product name “Esomine C / 25” manufactured by Lion Akzo Co., Ltd.) as a plasticizer is 0.4 parts by mass. Thus, five types of pressure-sensitive adhesive sheets having different surface base materials were prepared.
（実施例８）
実施例１において、可塑剤としてのポリオキシエチレンアルキルアミン（ライオン・アクゾ株式会社製、商品名「エソミンＣ／２５」）の配合量を０．２質量部にした以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
(Example 8)
Example 1 is the same as Example 1 except that the amount of polyoxyethylene alkylamine (product name “Esomine C / 25” manufactured by Lion Akzo Co., Ltd.) as a plasticizer is 0.2 parts by mass. Thus, five types of pressure-sensitive adhesive sheets having different surface base materials were prepared.
（実施例９）
実施例１において、可塑剤としてポリオキシエチレンアルキルアミン（ライオン・アクゾ株式会社製、商品名「エソミンＯ／２０」、式（１）におけるＲがオレイル基であり、ｘ＋ｙが１０である。ＨＬＢ値１２．５）を０．６質量部配合した以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
Example 9
In Example 1, as a plasticizer, polyoxyethylene alkylamine (manufactured by Lion Akzo Co., Ltd., trade name “Esomine O / 20”, R in Formula (1) is an oleyl group, and x + y is 10. HLB value 5 types of pressure-sensitive adhesive sheets having different surface base materials were prepared in the same manner as in Example 1 except that 0.6 part by mass of 12.5) was blended.
（実施例１０）
実施例１において、可塑剤としてポリオキシエチレンアルキルアミン（ライオン・アクゾ株式会社製、商品名「エソミンＣ／２５」）と、ポリオキシエチレンアルキルアミン（ライオン・アクゾ株式会社製、商品名「エソミンＯ／２０」）をそれぞれ０．３質量部ずつ、合計０．６質量部配合した以外は、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
(Example 10)
In Example 1, polyoxyethylene alkylamine (manufactured by Lion Akzo Co., Ltd., trade name “Esomin C / 25”) as a plasticizer and polyoxyethylene alkylamine (manufactured by Lion Akzo Co., Ltd., trade name “Esomin O”) / 20 ") was prepared in the same manner as in Example 1 except that 0.3 parts by mass of each and 0.3 parts by mass in total were blended to prepare five types of pressure-sensitive adhesive sheets having different surface base materials.
（比較例１）
実施例１の（１）において、オキシエチレンアルキルエーテル硫酸ナトリウム（界面活性剤、花王株式会社製、商品名「ラテムルＥ−１１８Ｂ」）０．９質量部、ポリプロピレングリコールクレゾールエーテル（界面活性剤、日本乳化剤社製、商品名「ニューコールＣＦ−６」）０．５質量部、ポリオキシエチレンアルキルエーテル（界面活性剤、花王株式会社製、商品名「エマルゲン１０３」）０．５質量部を配合して、水添ロジン系粘着付与剤の配合量を２．５質量部にして、テルペンフェノール系粘着付与剤を添加せず、実施例１の（２）において、可塑剤としてポリオキシエチレンアルキルアミンを配合せず、ジグリセリン（東京化成工業（株）製、商品名「ジグリセロール」）を２．０質量部及びトリエタノールアミン（日本触媒（株））製）を２．５質量部配合した以外は、実施例１と同様な方法で、実施例１と同様な方法で、表面基材が異なる５種類の粘着シートを作成した。
実施例及び比較例の粘着シートの粘着剤層に使用した水分散型粘着剤の組成、及び粘着シートの剥離試験結果を表１及び表２に示した。なお、表１及び表２において、水分散型粘着剤の配合成分の配合量を示す数値の単位は、質量部である。
(Comparative Example 1)
In Example 1 (1), 0.9 part by mass of sodium oxyethylene alkyl ether sulfate (surfactant, manufactured by Kao Corporation, trade name “Latemul E-118B”), polypropylene glycol cresol ether (surfactant, Japan) Emulsifier Co., Ltd., trade name “New Coal CF-6”) 0.5 part by mass, polyoxyethylene alkyl ether (surfactant, Kao Corporation, trade name “Emulgen 103”) 0.5 part by mass Then, the blending amount of the hydrogenated rosin tackifier was 2.5 parts by mass, and no terpene phenol tackifier was added. In Example 1 (2), polyoxyethylene alkylamine was used as a plasticizer. Without blending, 2.0 parts by mass of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd., trade name “diglycerol”) and triethanolamine (Nippon Shokubai) Ltd.)) Ltd.) except that the 2.5 parts by mass is in the same manner as in Example 1. In the same manner as in Example 1, surface substrate creates the five different adhesive sheet.
Tables 1 and 2 show the composition of the water-dispersed pressure-sensitive adhesive used in the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples and Comparative Examples, and the results of the peel test of the pressure-sensitive adhesive sheet. In Tables 1 and 2, the unit of the numerical value indicating the blending amount of the blending component of the water-dispersed pressure-sensitive adhesive is part by mass.
粘着シートの剥離試験は、以下に示す方法で行い、評価した。
（１）剥離試験
被着体として、ポリスチレン樹脂フィルム（オージー株式会社製、商品名「ハイスチレンＰＳ６５」、厚み６５μｍ）、ＡＢＳ樹脂フィルム（信越ポリマー社製、商品名「ＰＳＺ９８０」、厚み８０μｍ）、ポリカーボネート樹脂フィルム（帝人社製、商品名「ピュアエースＣ−１１０−１００」、厚み１００μｍ）、ポリカーボネート樹脂−ＡＢＳ樹脂の混合樹脂（ＰＣ−ＡＢＳ樹脂）からなるフィルム（帝人化成社製のポリカーボネート樹脂−ＡＢＳ樹脂系ポリマーアロイ「マルチロンＴ２７１１」をインフレーション製膜機を用いて、２４０℃で溶融させながら押出成形して得られた厚さ１００μｍのフィルム）、ポリカーボネート樹脂−ポリスチレン樹脂の混合樹脂（ＰＣ−ＰＳ樹脂）からなるフィルム（ポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製の「ノバレックス７０２７Ｒ」）とポリスチレン樹脂（日本ポリスチレン社製の「Ｇ６９０Ｎ」）を等量ずつ混合し、インフレーション製膜機を用いて、２６０℃で溶融させながら押出成形して得られた厚さ１００μｍのフィルム）の５種類のフィルムを用意した。このフィルムを、板に固定して被着体とした。
The peel test of the pressure-sensitive adhesive sheet was performed and evaluated by the following method.
(1) Peel test As an adherend, a polystyrene resin film (manufactured by OG Co., Ltd., trade name “High Styrene PS65”, thickness 65 μm), an ABS resin film (manufactured by Shin-Etsu Polymer Co., Ltd., trade name “PSZ980”, thickness 80 μm), Polycarbonate resin film (manufactured by Teijin Ltd., trade name “Pure Ace C-110-100”, thickness 100 μm), polycarbonate resin-ABS resin mixed resin (PC-ABS resin) (polycarbonate resin produced by Teijin Chemicals Ltd.) ABS resin-based polymer alloy “Multilon T2711” is extruded at 100 ° C. while being melted at 240 ° C. using an inflation film forming machine, and a polycarbonate resin-polystyrene resin mixed resin (PC-PS). Resin film (polycarbonate) To resin (“Novalex 7027R” manufactured by Mitsubishi Engineering Plastics) and polystyrene resin (“G690N” manufactured by Nippon Polystyrene Co., Ltd.) are mixed in equal amounts and melted at 260 ° C. using an inflation film forming machine. Five types of films having a thickness of 100 μm obtained by extrusion molding were prepared. This film was fixed to a plate to form an adherend.
粘着シートの表面基材の樹脂と、被着体を構成する樹脂が同じである組み合わせの粘着シートと被着体を室温で貼り合わせ、次に、６０℃、９５％ＲＨの環境下に７日間放置し、その後室温に戻して、室温で粘着シートを被着体から剥がした。粘着シートが剥がれた被着体の表面に糊残りがあるか否かを目視で観察し、下記の基準で評価した。
◎：被着体の表面に糊残りがなかった。
×：被着体の表面に糊残りがあった。
The adhesive sheet of the surface base material of the adhesive sheet and the adhesive sheet and the adherend in which the resin constituting the adherend is the same are bonded together at room temperature, and then 7 days in an environment of 60 ° C. and 95% RH. It was left to stand and then returned to room temperature, and the adhesive sheet was peeled off from the adherend at room temperature. Whether or not there was any adhesive residue on the surface of the adherend from which the pressure-sensitive adhesive sheet was peeled was visually observed and evaluated according to the following criteria.
A: No adhesive residue on the surface of the adherend.
X: There was adhesive residue on the surface of the adherend.
本発明の粘着シートの製造方法により得られる粘着シートは、家電製品や電子機器の樹脂製筺体などの種々の被着体に貼付することが出来る。
The pressure-sensitive adhesive sheet obtained by the method for manufacturing a pressure-sensitive adhesive sheet of the present invention can be attached to various adherends such as a resin casing for home appliances and electronic devices.
Claims (7)
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| JP2010081410 | 2010-03-31 | ||
| JP2010081410 | 2010-03-31 | ||
| PCT/JP2011/058372 WO2011125918A1 (en) | 2010-03-31 | 2011-03-25 | Adhesive sheet |
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| JPWO2011125918A1 JPWO2011125918A1 (en) | 2013-07-11 |
| JP5925676B2 true JP5925676B2 (en) | 2016-05-25 |
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| JP6172502B2 (en) * | 2013-03-15 | 2017-08-02 | Dic株式会社 | Adhesive tape |
| JP6133109B2 (en) * | 2013-04-09 | 2017-05-24 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| JP6343364B2 (en) * | 2017-04-19 | 2018-06-13 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| CN112004878A (en) * | 2018-04-20 | 2020-11-27 | 巴斯夫欧洲公司 | Adhesive composition having a gel content based on crosslinking by ketone or aldehyde groups |
| JP7318408B2 (en) * | 2019-08-09 | 2023-08-01 | 三菱瓦斯化学株式会社 | Adhesive sheet for lamination, multi-layer body, and method for producing multi-layer body |
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| JP2002221906A (en) * | 2001-01-24 | 2002-08-09 | Lintec Corp | Adhesive label |
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| WO2011125918A1 (en) | 2011-10-13 |
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