JP2020012017A - Aqueous re-releasable adhesive and adhesive sheet - Google Patents
Aqueous re-releasable adhesive and adhesive sheet Download PDFInfo
- Publication number
- JP2020012017A JP2020012017A JP2018132906A JP2018132906A JP2020012017A JP 2020012017 A JP2020012017 A JP 2020012017A JP 2018132906 A JP2018132906 A JP 2018132906A JP 2018132906 A JP2018132906 A JP 2018132906A JP 2020012017 A JP2020012017 A JP 2020012017A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- aqueous
- acrylic polymer
- polymer particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 57
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 23
- 239000004908 Emulsion polymer Substances 0.000 claims abstract description 11
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 82
- 125000003277 amino group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 31
- 125000000217 alkyl group Chemical group 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 7
- -1 alkyl methacrylate Chemical compound 0.000 description 41
- 239000003995 emulsifying agent Substances 0.000 description 21
- 238000007720 emulsion polymerization reaction Methods 0.000 description 20
- 239000000839 emulsion Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 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 11
- 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 11
- 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 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 206010040844 Skin exfoliation Diseases 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 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 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- AURYLBASVGNSON-UHFFFAOYSA-N (2,5-dioxopyrrolidin-3-ylidene)methyl prop-2-enoate Chemical compound C=CC(=O)OC=C1CC(=O)NC1=O AURYLBASVGNSON-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
- XTKZBPGQKMDFMC-UHFFFAOYSA-N 1-butyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CCCCN1C(=O)CC(=C)C1=O XTKZBPGQKMDFMC-UHFFFAOYSA-N 0.000 description 1
- BGKQCHAKBLWCDU-UHFFFAOYSA-N 1-cyclohexyl-3-methylidenepyrrolidine-2,5-dione Chemical compound O=C1C(=C)CC(=O)N1C1CCCCC1 BGKQCHAKBLWCDU-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- GXDLZONOWLZMTG-UHFFFAOYSA-N 1-dodecyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)CC(=C)C1=O GXDLZONOWLZMTG-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- PBDXUGSZYRYWMI-UHFFFAOYSA-N 1-ethyl-3-heptylidenepyrrolidine-2,5-dione Chemical compound CCCCCCC=C1CC(=O)N(CC)C1=O PBDXUGSZYRYWMI-UHFFFAOYSA-N 0.000 description 1
- BMZZOWWYEBTMBX-UHFFFAOYSA-N 1-ethyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CCN1C(=O)CC(=C)C1=O BMZZOWWYEBTMBX-UHFFFAOYSA-N 0.000 description 1
- QSWFISOPXPJUCT-UHFFFAOYSA-N 1-methyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CN1C(=O)CC(=C)C1=O QSWFISOPXPJUCT-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- KRGXWTOLFOPIKV-UHFFFAOYSA-N 3-(methylamino)propan-1-ol Chemical compound CNCCCO KRGXWTOLFOPIKV-UHFFFAOYSA-N 0.000 description 1
- RDRWAAIUFCYJPH-UHFFFAOYSA-N 3-methylidene-1-octylpyrrolidine-2,5-dione Chemical compound CCCCCCCCN1C(=O)CC(=C)C1=O RDRWAAIUFCYJPH-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、水性再剥離粘着剤に関する。 The present invention relates to an aqueous removable pressure-sensitive adhesive.
粘着剤は、マスキングテープ、両面テープ、表面保護フィルム、包装用テープ等、様々な用途で用いられている。そして、環境対策、省資源、安全性などの観点から有機溶剤を使用しない水性粘着剤が盛んに使用されている。このような水性粘着剤は、低コストかつ諸物性を満足し易いアクリル系粘着剤が、主にラベル用途で用いられている。 BACKGROUND ART Adhesives are used in various applications such as masking tapes, double-sided tapes, surface protection films, and packaging tapes. A water-based pressure-sensitive adhesive that does not use an organic solvent is actively used from the viewpoint of environmental measures, resource saving, safety, and the like. As such an aqueous pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive which is low in cost and easily satisfies various physical properties is mainly used for label applications.
このラベル用途の課題は、金属板やプラスチック板等の被着体へ貼り合わせた直後と比較して、貼り合わせ経過後の粘着力が上昇してしまうことで再剥離性が低下することが挙げられる。再剥離性が低下することで、被着体からの引き剥がしが困難となる問題が発生する。 The problem of this label application is that the re-peelability decreases due to an increase in the adhesive force after the lamination, as compared to immediately after lamination to an adherend such as a metal plate or a plastic plate. Can be When the re-peelability is reduced, there is a problem that it is difficult to peel the material from the adherend.
そこで特許文献1では、(メタ)アクリル酸アルキルエステルとカルボキシル基含有モノマー、多官能性モノマーとを含むモノマー混合物を、アニオン型反応性乳化剤の存在下に、乳化重合させて得たエマルジョンと、オキサゾリン系架橋剤とを含む再剥離型水性粘着剤が開示されている。 Thus, Patent Document 1 discloses an emulsion obtained by subjecting a monomer mixture containing an alkyl (meth) acrylate, a carboxyl group-containing monomer, and a polyfunctional monomer to emulsion polymerization in the presence of an anionic reactive emulsifier, and oxazoline. There is disclosed a removable aqueous pressure-sensitive adhesive containing a system crosslinking agent.
また、特許文献2では、アクリル酸アルキルエステルとカルボキシル基含有モノマーとのモノマー混合物を反応性乳化剤および連鎖移動剤の存在下、乳化重合してなるポリマーエマルションを含む、水性粘着剤が開示されている。 Further, Patent Document 2 discloses an aqueous pressure-sensitive adhesive containing a polymer emulsion obtained by emulsion polymerization of a monomer mixture of an alkyl acrylate and a carboxyl group-containing monomer in the presence of a reactive emulsifier and a chain transfer agent. .
しかし、特許文献1の水性粘着剤は、アクリルエマルジョン自体の凝集力が高いため、基材に対する密着性が十分ではなく、また、特許文献2の水性粘着剤は、乳化重合時に連鎖移動剤を用いていることからポリマーエマルション自体の凝集力が低いため、被着体に貼り合わせた後の粘着力が上昇してしまうという問題があった。 However, the water-based pressure-sensitive adhesive disclosed in Patent Document 1 has a high cohesive force of the acrylic emulsion itself, and thus does not have sufficient adhesion to a substrate. In addition, the water-based pressure-sensitive adhesive disclosed in Patent Document 2 uses a chain transfer agent during emulsion polymerization. Therefore, there is a problem that the cohesive strength of the polymer emulsion itself is low, so that the adhesive strength after bonding to the adherend increases.
そこで本発明は、硬化剤混合後の粘着剤の保存安定性が良好であり、かつ貼り合せ経時後の粘着力上昇を抑制し、再剥離性が良好な粘着シートが得られる水性再剥離粘着剤の提供を目的とする。 Therefore, the present invention provides an aqueous re-peelable pressure-sensitive adhesive which has good storage stability of the pressure-sensitive adhesive after mixing of the curing agent, and suppresses an increase in the adhesive force after lamination with time, thereby obtaining a pressure-sensitive adhesive sheet having good re-peelability. The purpose is to provide.
本発明の水性再剥離粘着剤は、アクリル系ポリマー粒子と、粒子型硬化剤とを含有し、前記アクリル系ポリマー粒子は、モノマー混合物および粘着付与樹脂の乳化重合物であり、前記モノマー混合物は、(メタ)アクリル酸アルキルエステルおよびカルボキシル基含有モノマーを含有し、多官能モノマーを含有しない水性再剥離粘着剤に関する。 The aqueous removable pressure-sensitive adhesive of the present invention contains acrylic polymer particles and a particle-type curing agent, and the acrylic polymer particles are an emulsion polymer of a monomer mixture and a tackifier resin, and the monomer mixture is The present invention relates to an aqueous removable pressure-sensitive adhesive containing a (meth) acrylic acid alkyl ester and a carboxyl group-containing monomer and not containing a polyfunctional monomer.
本発明のアクリル系ポリマー粒子、および粒子型硬化剤を使用した粘着シートは、凝集力が非常に高い。一般に、硬化剤は水に不溶の疎水性原料から構成されているが、水性粘着剤に用いるためには、硬化剤に親水性の原料を添加する必要がある。これにより、親水性の原料の比率が高い場合は水溶化できるため、粘着剤との硬化反応を均一に進行する一方、粘着剤との反応に寄与しない親水性原料の比率が増加してしまい、被着体に貼り合わせた後の粘着力が上昇しやすく、糊残りが発生するなど再剥離性も低下してしまう。一方で、親水性の原料の比率が低い場合は、硬化剤が、粒子型硬化剤となり、粘着剤との硬化反応は均一に進行しにくい。
このように、本発明の再剥離粘着剤は、粘着剤との反応に寄与しない親水性の原料である粒子型硬化剤の含有比率が低いため、貼り合わせ後の粘着力上昇を抑制でき、良好な再剥離性を得ることができた。さらに、硬化剤混合後の粘着剤の粘度変化を抑制でき、一液型でも安定に使用可能な粘着剤を得ることができた。
The pressure-sensitive adhesive sheet using the acrylic polymer particles and the particle-type curing agent of the present invention has an extremely high cohesive force. Generally, the curing agent is composed of a hydrophobic raw material that is insoluble in water. However, in order to use the curing agent in an aqueous pressure-sensitive adhesive, it is necessary to add a hydrophilic raw material to the curing agent. Thereby, when the ratio of the hydrophilic raw material is high, it can be made water-soluble, so that the curing reaction with the adhesive proceeds uniformly, while the ratio of the hydrophilic raw material that does not contribute to the reaction with the adhesive increases. The adhesive strength after bonding to the adherend is likely to increase, and the removability will decrease, such as the occurrence of adhesive residue. On the other hand, when the ratio of the hydrophilic raw material is low, the curing agent becomes a particle-type curing agent, and the curing reaction with the pressure-sensitive adhesive hardly proceeds uniformly.
As described above, the removable pressure-sensitive adhesive of the present invention has a low content ratio of the particle-type curing agent that is a hydrophilic raw material that does not contribute to the reaction with the pressure-sensitive adhesive. High removability was obtained. Furthermore, the change in viscosity of the pressure-sensitive adhesive after mixing the curing agent could be suppressed, and a pressure-sensitive adhesive that could be used stably even with a one-pack type could be obtained.
本発明により、硬化剤混合後の粘着剤の保存安定性が良好でありながら、被着体に貼り合わせ後の粘着力上昇を抑制し、再剥離性が良好な粘着シートが得られる水性再剥離粘着剤を提供できる。 According to the present invention, while the storage stability of the pressure-sensitive adhesive after mixing the curing agent is good, an increase in the adhesive force after bonding to the adherend is suppressed, and the water-based re-peeling can obtain a pressure-sensitive adhesive sheet having good re-peelability. An adhesive can be provided.
本発明を詳細に説明する前に用語を定義する。(メタ)アクリル酸アルキルエステルは、アクリル酸アルキルエステルおよびメタクリル酸アルキルエステルを含む。モノマーは、エチレン性不飽和二重結合含有単量体である。被着体は、粘着シートを貼付する相手方である。密着性は、粘着剤層の基材に対する密着性をいう。 Before describing the present invention in detail, terms will be defined. The alkyl (meth) acrylate includes an alkyl acrylate and an alkyl methacrylate. The monomer is an ethylenically unsaturated double bond containing monomer. The adherend is a partner to which the adhesive sheet is to be attached. Adhesion refers to the adhesion of the pressure-sensitive adhesive layer to the substrate.
《水性再剥離粘着剤》
本発明の水性再剥離粘着剤は、アクリル系ポリマー粒子と、粒子型硬化剤とを含有し、前記アクリル系ポリマー粒子は、モノマー混合物および粘着付与樹脂の乳化重合物であり、前記モノマー混合物は、(メタ)アクリル酸アルキルエステルおよびカルボキシル基含有モノマーを含有し、多官能モノマーを含有しない。
モノマー混合物と粘着付与樹脂を含有する混合物の乳化重合物であるアクリル系ポリマー粒子に、粒子型硬化剤と、必要に応じてアミノ基含有化合物、消泡剤、レベリング剤、防腐剤、増粘剤等のその他添加剤を加えることで、水性再剥離粘着剤を得ることができる。
アクリル系ポリマー粒子と粒子型硬化剤を含む乳化重合物に、必要に応じてアミノ基含有化合物、消泡剤、レベリング剤、防腐剤、増粘剤等のその他添加剤を加えることで、水性再剥離粘着剤を得ることができる。
《Aqueous removable adhesive》
The aqueous removable pressure-sensitive adhesive of the present invention contains acrylic polymer particles and a particle-type curing agent, and the acrylic polymer particles are an emulsion polymer of a monomer mixture and a tackifier resin, and the monomer mixture is It contains an alkyl (meth) acrylate and a carboxyl group-containing monomer and does not contain a polyfunctional monomer.
Acrylic polymer particles that are an emulsion polymer of a mixture containing a monomer mixture and a tackifier resin, a particle-type curing agent and, if necessary, an amino group-containing compound, an antifoaming agent, a leveling agent, a preservative, and a thickening agent By adding other additives such as the above, an aqueous removable pressure-sensitive adhesive can be obtained.
By adding other additives such as an amino group-containing compound, an antifoaming agent, a leveling agent, a preservative, and a thickening agent to the emulsion polymer containing the acrylic polymer particles and the particle-type curing agent, if necessary, A release adhesive can be obtained.
また、本発明の水性再剥離粘着剤は、硬化剤混合後の粘着剤の保存安定性が良好であるため、一液型水性再剥離粘着剤として好適に用いることができる。
水性再剥離粘着剤の40℃で90日間経過後の粘度変化率は、0%以上10%未満であることが好ましく、より好ましくは、0%以上5%未満である。粘度変化率が0%以上10%未満であることで保存安定性が良好となり、二液型粘着剤のように硬化剤混合後の粘着剤をその日に使い切る工程が不要となる。さらに、二液型粘着剤で通常行なっている、粘着剤の塗工前に硬化剤を混合する配合工程が不要となり、塗工時の作業性が良好となる。
粘度変化率(%)=[(40℃90日間後の粘度)/(初期粘度)−1]×100の絶対値
Further, the aqueous removable pressure-sensitive adhesive of the present invention can be suitably used as a one-component aqueous removable pressure-sensitive adhesive because the storage stability of the pressure-sensitive adhesive after mixing the curing agent is good.
The viscosity change rate of the aqueous removable adhesive after 90 days at 40 ° C. is preferably 0% or more and less than 10%, more preferably 0% or more and less than 5%. When the rate of change in viscosity is 0% or more and less than 10%, the storage stability is improved, and the step of using up the pressure-sensitive adhesive after mixing the curing agent, such as a two-pack type pressure-sensitive adhesive, becomes unnecessary. Furthermore, the compounding step of mixing a curing agent before the application of the adhesive, which is usually performed with a two-part adhesive, becomes unnecessary, and the workability during application is improved.
Viscosity change rate (%) = [(viscosity after 90 days at 40 ° C.) / (Initial viscosity) −1] × 100 absolute value
<アクリル系ポリマー粒子>
本発明におけるアクリル系ポリマー粒子は、少なくとも、アクリル系モノマーの混合物および粘着付与樹脂を乳化重合して得ることができる乳化重合物である。アクリル系モノマーは、(メタ)アクリル酸アルキルエステルおよびカルボキシル基含有モノマーを含有し、多官能モノマーを含有しないモノマー混合物を用いる。
このモノマー混合物を、粘着付与樹脂の存在下で乳化重合することで、本発明のアクリル系ポリマー粒子が得られる。
また、アクリル系ポリマー粒子は、乳化重合後に、アミノ基含有化合物を加えることが好ましい。アミノ基含有化合物を加えることで、硬化剤混合後の粘着剤の保存安定性がより良好で、貼り合せ経時後の粘着力上昇抑制、再剥離性がより良好な粘着シートが得られるために好ましい。
乳化重合する際において、その他に消泡剤、レベリング剤、溶剤、ウレタン樹脂やエポキシ樹脂等の各種樹脂を用いてもよい。
<Acrylic polymer particles>
The acrylic polymer particles in the present invention are emulsion polymers obtained by emulsion polymerization of at least a mixture of acrylic monomers and a tackifier resin. As the acrylic monomer, a monomer mixture containing a (meth) acrylic acid alkyl ester and a carboxyl group-containing monomer and not containing a polyfunctional monomer is used.
The acrylic polymer particles of the present invention can be obtained by subjecting this monomer mixture to emulsion polymerization in the presence of a tackifier resin.
Further, it is preferable to add an amino group-containing compound to the acrylic polymer particles after the emulsion polymerization. By adding the amino group-containing compound, the storage stability of the pressure-sensitive adhesive after mixing the curing agent is more favorable, the suppression of the increase in the adhesive force after lamination and the removability are preferable because a pressure-sensitive adhesive sheet with better removability is obtained. .
At the time of emulsion polymerization, other resins such as an antifoaming agent, a leveling agent, a solvent, and a urethane resin or an epoxy resin may be used.
[モノマー混合物]
本発明のモノマー混合物は、(メタ)アクリル酸アルキルエステルとカルボキシル基含有モノマーを含有し、多官能モノマーを含有しない。
多官能モノマーは、重合可能な二重結合を2個以上有しているため重合時に架橋反応を起こす。そのため得られるアクリル系ポリマー粒子の架橋度が高くなり、得られる粘着シートの金属板等の被着体に貼り合わせ後の粘着力上昇を抑制できる一方、基材に対する密着性は低下する。そのため、粘着シートを金属板等の被着体に貼り合わせ後、被着体から引きはがした際に糊残りが発生する問題点が生じるためである。
[Monomer mixture]
The monomer mixture of the present invention contains a (meth) acrylic acid alkyl ester and a carboxyl group-containing monomer and does not contain a polyfunctional monomer.
Since the polyfunctional monomer has two or more polymerizable double bonds, a crosslinking reaction occurs during polymerization. As a result, the degree of crosslinking of the obtained acrylic polymer particles is increased, and the increase in the adhesive force after bonding the obtained pressure-sensitive adhesive sheet to an adherend such as a metal plate can be suppressed, while the adhesion to the base material decreases. For this reason, after sticking the pressure-sensitive adhesive sheet to an adherend such as a metal plate, there is a problem that adhesive residue occurs when the adhesive sheet is peeled off from the adherend.
(メタ)アクリル酸アルキルエステルは、例えばエチル(メタ)アクリレート、プロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、iso−ブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、n−オクチル(メタ)アクリレート、iso−オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート、iso−ノニル(メタ)アクリレート、およびシクロヘキシル(メタ)アクリレート等が挙げられる。これらの中でも、n−ブチルアクリレート、2−エチルヘキシルアクリレートが好ましい。(メタ)アクリル酸アルキルエステルは、単独または2種類以上併用できる Examples of the alkyl (meth) acrylate include ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl ( (Meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, iso-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred. (Meth) acrylic acid alkyl esters can be used alone or in combination of two or more.
(メタ)アクリル酸アルキルエステルは、モノマー混合物100重量%中に、50〜99.5重量%含むことが好ましく、70〜99重量%がより好ましい。50〜99.5重量%含むことで粘着剤層を形成した際の粘着力、タックおよび再剥離性を得やすくなる。 The alkyl (meth) acrylate preferably contains 50 to 99.5% by weight, and more preferably 70 to 99% by weight, based on 100% by weight of the monomer mixture. When the content is 50 to 99.5% by weight, the adhesive strength, tack and removability at the time of forming the pressure-sensitive adhesive layer can be easily obtained.
カルボキシル基含有モノマーは、例えば(メタ)アクリル酸、β−カルボキシエチルアクリレート、イタコン酸、クロトン酸、フマル酸、無水フマル酸、マレイン酸、無水マレイン酸、およびマレイン酸ブチル等が挙げられる。カルボキシル基含有モノマーは、単独または2種類以上併用できる。なお、カルボキシル基含有モノマーは酸無水物基含有モノマーを包含する。 Examples of the carboxyl group-containing monomer include (meth) acrylic acid, β-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, and butyl maleate. The carboxyl group-containing monomers can be used alone or in combination of two or more. The carboxyl group-containing monomer includes an acid anhydride group-containing monomer.
カルボキシル基含有モノマーは、モノマー混合物中に0.5〜5重量%含むことが好ましく、0.8〜2重量%がより好ましい。0.5〜5重量%含むことで粘着力および再剥離性がより向上する。 The carboxyl group-containing monomer is preferably contained in the monomer mixture in an amount of 0.5 to 5% by weight, more preferably 0.8 to 2% by weight. By containing 0.5 to 5% by weight, the adhesive strength and removability are further improved.
モノマー混合物は、(メタ)アクリル酸アルキルエステルおよびカルボキシル基含有モノマー以外の「その他モノマー」を使用できる。例えばアミノメチル(メタ)アクリレート、ジメチルアミノメチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、(メタ)アクリルアミド、アセトアセトキシエチルメタクリレート、ダイアセトン(メタ)アクリルアミド、(メタ)アクリロニトリル、N−シクロヘキシルマレイミド、N−イソプロピルマレイミド、N−ラウリルマレイミド、N−フェニルマレイミド、N−メチルイタコンイミド、N−エチルイタコンイミド、N−ブチルイタコンイミド、N−オクチルイタコンイミド、N−2−エチルヘキシルイタコンイミド、N−シクロヘキシルイタコンイミド、N−ラウリルイタコンイミド、N−(メタ)アクリロイルオキシメチレンスクシンイミド、N−(メタ)アクリロイル−6−オキシヘキサメチレンスクシンイミド、N−(メタ)アクリロイル−8−オキシオクタメチレンスクシンイミド、グリシジル(メタ)アクリレート、酢酸ビニル、スチレン、メチルスチレン、ビニルトルエン、2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、およびメトキシポリエチレングリコール(メタ)アクリレート等が挙げられる。また、ポリエチレングリコールジ(メタ)アクリレート、およびネオペンチルグリコールアジペートジ(メタ)アクリレートなどの公知の多官能(メタ)アクリレート化合物等が挙げられる。その他モノマーは、単独または2種類以上併用できる。 As the monomer mixture, “other monomers” other than the alkyl (meth) acrylate and the carboxyl group-containing monomer can be used. For example, aminomethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acrylamide, acetoacetoxyethyl methacrylate, diacetone (meth) acrylamide, (Meth) acrylonitrile, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N- 2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide, N- (meth) acryloyloxymethylene succinimide, N- (meth ) Acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, glycidyl (meth) acrylate, vinyl acetate, styrene, methylstyrene, vinyl toluene, 2-methoxyethyl (meth) acrylate, Examples include 2-ethoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. In addition, known polyfunctional (meth) acrylate compounds such as polyethylene glycol di (meth) acrylate and neopentyl glycol adipate di (meth) acrylate may be used. Other monomers can be used alone or in combination of two or more.
本発明のアクリル系ポリマー粒子の平均粒子径は、100〜500nmが好ましく、150〜450nmがより好ましい。平均粒子径は100〜500nmにすることで、アクリル系ポリマー粒子の安定性を向上できる。
ここで平均粒子径とは、動的光散乱型装置「Nanоtrack Wave(マイクロトラック・ベル(株)社製)」で測定した際の、累積50%粒子径の体積平均径である。
The average particle size of the acrylic polymer particles of the present invention is preferably from 100 to 500 nm, more preferably from 150 to 450 nm. By setting the average particle diameter to 100 to 500 nm, the stability of the acrylic polymer particles can be improved.
Here, the average particle diameter is a volume average diameter of a cumulative 50% particle diameter measured by a dynamic light scattering type apparatus “Nanotrack Wave” (manufactured by Microtrack Bell Co., Ltd.).
[粘着付与樹脂]
粘着付与樹脂は、アクリル樹脂に添加することで粘着性を発現させたり、粘着力性能を向上できる樹脂である。さらに、(メタ)アクリル酸アルキルエステルとカルボキシル基含有モノマーを含有するモノマー混合物に添加して乳化重合を行なうと連鎖移動反応を引き起こすことができる。
[Tackifying resin]
The tackifier resin is a resin that can exhibit tackiness or improve adhesive strength by being added to an acrylic resin. Further, when the emulsion polymerization is carried out by adding to a monomer mixture containing an alkyl (meth) acrylate and a carboxyl group-containing monomer, a chain transfer reaction can be caused.
本発明では、所望の溶剤不溶分、および重量平均分子量を得るために、乳化重合の際、粘着付与樹脂を用いる。一般に、乳化重合で得られるアクリル系ポリマー粒子は分子量が非常に大きく、テトラヒドロフランのような溶解力のある溶剤を用いても難溶であるが、粘着付与樹脂を用いることで、溶剤に可溶な成分を、増加させることができる。 In the present invention, a tackifier resin is used at the time of emulsion polymerization in order to obtain a desired solvent-insoluble content and a weight average molecular weight. In general, acrylic polymer particles obtained by emulsion polymerization have a very large molecular weight and are hardly soluble even with a solvent having a dissolving power such as tetrahydrofuran, but are soluble in a solvent by using a tackifier resin. Ingredients can be increased.
このように、粘着付与樹脂は、連鎖移動効果が大きく、アクリル系ポリマー粒子の分子量調節が容易になるだけでなく、粘着剤層を形成した際の密着性を向上できる。
分子量を調節するために、チオール基や水酸基を有する化合物のような連鎖移動剤を用いる場合では、アクリル系ポリマー粒子の凝集力が低くなり、被着体に貼り合わせた後の粘着力が上昇してしまう場合があるが、粘着付与樹脂を用いた場合には、連鎖移動効果が穏やかに進行するため、アクリル系ポリマー粒子の凝集力を低下させることなく、再剥離性に優れた粘着剤とすることができる。
As described above, the tackifier resin has a large chain transfer effect, not only facilitates the adjustment of the molecular weight of the acrylic polymer particles, but also improves the adhesion when the pressure-sensitive adhesive layer is formed.
In the case where a chain transfer agent such as a compound having a thiol group or a hydroxyl group is used to adjust the molecular weight, the cohesive force of the acrylic polymer particles decreases, and the adhesive force after bonding to the adherend increases. However, when a tackifier resin is used, the chain transfer effect proceeds gently, without reducing the cohesive force of the acrylic polymer particles, and the adhesive is excellent in removability. be able to.
粘着付与樹脂は、例えばロジン系樹脂、テルペン系樹脂、芳香族系石油樹脂、および脂肪族系石油樹脂等からなる群より選択される1種以上を使用することが好ましい。さらに、基材への密着性の観点から、粘着付与樹脂の軟化点は80℃以下が好ましい。ロジン系樹脂は、例えば天然ロジン、ロジンエステル、水添ロジン、水添ロジンエステル、重合ロジン、重合ロジンエステル、不均化ロジン、および不均化ロジンエステル等が挙げられる。テルペン系樹脂は、例えばα−ピネン樹脂、β−ピネン樹脂、テルペンフェノール樹脂、および水添テルペンフェノール樹脂等が挙げられる。芳香族系石油樹脂は、例えばスチレンオリゴマー、およびα−メチルスチレン・スチレン共重合体等が挙げられる。
粘着付与樹脂は、単独または2種類以上併用できる
As the tackifying resin, it is preferable to use one or more selected from the group consisting of, for example, a rosin resin, a terpene resin, an aromatic petroleum resin, and an aliphatic petroleum resin. Furthermore, the softening point of the tackifier resin is preferably 80 ° C. or less from the viewpoint of adhesion to the substrate. Examples of the rosin resin include natural rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, disproportionated rosin, and disproportionated rosin ester. Examples of the terpene resin include an α-pinene resin, a β-pinene resin, a terpene phenol resin, and a hydrogenated terpene phenol resin. Examples of the aromatic petroleum resin include a styrene oligomer and an α-methylstyrene / styrene copolymer.
Tackifying resins can be used alone or in combination of two or more
粘着付与樹脂は、モノマー混合物100重量部に対して、0.1〜10重量部が好ましく、0.2〜8重量部がより好ましい。0.1重量部以上用いることで、粘着剤層を形成した際の密着性が良好になる。10重量部以下用いることで、アクリル系ポリマー粒子を高分子量に設計でき、粘着剤層を形成した際の凝集力がより増大する。 The tackifier resin is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, based on 100 parts by weight of the monomer mixture. By using 0.1 parts by weight or more, the adhesiveness when the pressure-sensitive adhesive layer is formed is improved. By using 10 parts by weight or less, the acrylic polymer particles can be designed to have a high molecular weight, and the cohesive force when the pressure-sensitive adhesive layer is formed is further increased.
本発明でアクリル系ポリマー粒子は、上記モノマー混合物と粘着付与樹脂を乳化重合して得る。乳化重合で使用する乳化剤は、アニオン性乳化剤およびノニオン性乳化剤から適宜選択して使用する。また乳化剤は、ラジカル重合性の官能基を有する反応性乳化剤であってもよいし、ラジカル重合性の官能基を有さない非反応性乳化剤であってもよく、両者を併用することもできる。耐水白化性の観点から、反応性乳化剤を使用するのがより好ましい。 In the present invention, the acrylic polymer particles are obtained by emulsion polymerization of the above monomer mixture and a tackifier resin. The emulsifier used in the emulsion polymerization is appropriately selected from an anionic emulsifier and a nonionic emulsifier. The emulsifier may be a reactive emulsifier having a radically polymerizable functional group, a non-reactive emulsifier having no radically polymerizable functional group, or both may be used in combination. From the viewpoint of water whitening resistance, it is more preferable to use a reactive emulsifier.
本発明において乳化剤の中で、反応性乳化剤は、分子内にラジカル重合可能な不飽和二重結合を1個以上有するアニオン性の乳化剤である。例えば、スルホコハク酸エステル系乳化剤、アルキルフェノールエーテル系乳化剤等が挙げられる。 In the present invention, among the emulsifiers, the reactive emulsifier is an anionic emulsifier having one or more radically polymerizable unsaturated double bonds in the molecule. For example, a sulfosuccinate-based emulsifier, an alkylphenol ether-based emulsifier, and the like can be given.
非反応性アニオン性乳化剤は、ポリオキシエチレン多環フェニルエーテル硫酸塩、ステアリン酸ナトリウム等の高級脂肪酸塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルアリールスルホン酸塩、ラウリル硫酸ナトリウム等のアルキル硫酸エステル塩、ポリオキシエチレンラウリルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルアリールエーテル硫酸エステル塩等が挙げられる。 Non-reactive anionic emulsifiers include polyoxyethylene polycyclic phenyl ether sulfate, higher fatty acid salts such as sodium stearate, alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate salts such as sodium lauryl sulfate, And polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl aryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate.
非反応性ノニオン性乳化剤はポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類;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オレイルエーテル等のポリオキシエチレンアルキルエーテル類;ポリオキシエチレンジスチレン化フェニルエーテル等のポリオキシ多環フェニルエーテル類;ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。
乳化剤は、単独または2種類以上使用できる。
Non-reactive nonionic emulsifiers include polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octyl phenyl ether; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether such as polyoxyethylene oleyl ether. Oxyethylene alkyl ethers; polyoxy polycyclic phenyl ethers such as polyoxyethylene distyrenated phenyl ether; polyoxyethylene sorbitan fatty acid esters;
Emulsifiers can be used alone or in combination of two or more.
前記乳化剤のなかでも、良好な重合安定性が得られるため反応性または非反応性のアニオン性乳化剤を使用するのが好ましく、特に反応性のポリオキシエチレンアルキルエーテル硫酸エステル塩類がより好ましく、炭素数が9〜14のアルキル基を有するポリオキシエチレンアルキルエーテル硫酸エステルアンモニウム塩がさらに好ましい。乳化剤はモノマー混合物100重量部に対して0.5〜3重量部使用するのが好ましい。 Among the emulsifiers, it is preferable to use a reactive or non-reactive anionic emulsifier because good polymerization stability is obtained, and particularly preferable are reactive polyoxyethylene alkyl ether sulfate salts, Is more preferably an ammonium salt of a polyoxyethylene alkyl ether sulfate having an alkyl group of 9 to 14. The emulsifier is preferably used in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the monomer mixture.
乳化重合に使用する重合開始剤は、水溶性重合開始剤を使用することが好ましい。
水溶性重合開始剤は、例えば過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、4,4’−アゾビス−4−シアノバレリックアシッドのアンモニウム(アミン)塩、2,2’−アゾビス(2−メチルアミドオキシム)ジヒドロクロライド、2,2’−アゾビス(2−メチルブタンアミドオキシム)ジヒドロクロライドテトラヒドレート、2,2’−アゾビス{2−メチル−N−〔1,1−ビス(ヒドロキシメチル)−2−ヒドロキシエチル〕−プロピオンアミド}、2,2’−アゾビス〔2−メチル−N−(2−ヒドロキシエチル)−プロピオンアミド〕等が挙げられる。これらの中でも過硫酸カリウムおよび過硫酸ナトリウムが好ましい。
As the polymerization initiator used for the emulsion polymerization, it is preferable to use a water-soluble polymerization initiator.
Examples of the water-soluble polymerization initiator include potassium persulfate, sodium persulfate, ammonium persulfate, ammonium (amine) salt of 4,4′-azobis-4-cyanovaleric acid, and 2,2′-azobis (2-methylamide Oxime) dihydrochloride, 2,2'-azobis (2-methylbutanamidooxime) dihydrochloride tetrahydrate, 2,2'-azobis @ 2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] -propionamide} and 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide]. Of these, potassium persulfate and sodium persulfate are preferred.
また重合開始剤は、レドックス系重合開始剤(酸化剤と還元剤を併用する)として使用できる。酸化剤は、例えば過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム、過酸化水素、t−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、キュメンハイドロパーオキサイド、p−メタンハイドロパーオキサイド等が挙げられる。また、還元剤は、例えば亜硫酸ナトリウム、酸性亜硫酸ナトリウム、ロンガリット、アスコルビン酸等が挙げられる。これらの中でも重合反応性に優れるため、酸化剤:過硫酸カリウムまたは過硫酸ナトリウムと、還元剤:亜硫酸ナトリウムまたは酸性亜硫酸ナトリウムとを組み合わせて使用することが好ましい。 Further, the polymerization initiator can be used as a redox-based polymerization initiator (using both an oxidizing agent and a reducing agent). Examples of the oxidizing agent include ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-methane hydroperoxide and the like. Examples of the reducing agent include sodium sulfite, sodium acid sulfite, Rongalit, ascorbic acid, and the like. Among them, it is preferable to use a combination of an oxidizing agent: potassium persulfate or sodium persulfate and a reducing agent: sodium sulfite or sodium acid sulfite because of excellent polymerization reactivity.
重合開始剤は、モノマー混合物100重量部に対して、0.01〜0.5重量部を使用することが好ましく、0.02〜0.3重量部がより好ましい。0.01〜0.5重量部であることで重合反応性および水性再剥離粘着剤の機械安定性をより向上できる。 The polymerization initiator is preferably used in an amount of 0.01 to 0.5 part by weight, more preferably 0.02 to 0.3 part by weight, based on 100 parts by weight of the monomer mixture. When the amount is 0.01 to 0.5 part by weight, the polymerization reactivity and the mechanical stability of the aqueous removable pressure-sensitive adhesive can be further improved.
本発明で乳化重合は、例えばモノマーを乳化して乳化物を形成してから合成することが好ましい(プレ乳化法)。乳化重合の方法は、前記乳化物の全量を予め反応容器中に仕込んでから反応する方法、または前記乳化物の一部を反応容器中に仕込んで、前記乳化物の残分を数回に分けて添加または連続滴下する方法等公知の方法を使用できる。 In the present invention, the emulsion polymerization is preferably carried out, for example, after emulsifying a monomer to form an emulsion, followed by synthesis (pre-emulsification method). The method of emulsion polymerization is a method in which the whole amount of the emulsion is previously charged in a reaction vessel and then reacts, or a part of the emulsion is charged in a reaction vessel and the residue of the emulsion is divided into several times. A known method such as a method of adding or continuously dropping can be used.
また、アクリル系ポリマー粒子は、そのゲル分率を30〜70%に調整することが好ましい。ゲル分率を前記範囲にすることで密着性、粘着力および再剥離性を高いレベルで得ることができる The acrylic polymer particles preferably have a gel fraction of 30 to 70%. By setting the gel fraction within the above range, it is possible to obtain a high level of adhesion, adhesive strength and removability.
なお、ゲル分率の算出は以下の方法で行なうことができる。アクリル系共ポリマー粒子をポリエチレンテレフタレートフィルム(以下、PETフィルムという)上に塗工し、乾燥後の厚さが約20g/m2になるように乾燥被膜を形成する(塗工物という)。得られた塗工物を200メッシュのステンレス網で包み込み、次いでそれを酢酸エチルに投入し23℃で72時間浸漬した後、乾燥して酢酸エチルを除去する。そして浸漬前の乾燥被膜の重量に対する、浸漬後の乾燥被膜の重量の割合(重量%)を求めたものを酢酸エチルに対するゲル分率という。ゲル分率は下記数式に従い求める。
数式1 ゲル分率(%)=(浸漬前の乾燥被膜重量−PETフィルムの重量)/(浸漬後の乾燥被膜重量−PETフィルムの重量)×100
The calculation of the gel fraction can be performed by the following method. The acrylic copolymer particles are applied on a polyethylene terephthalate film (hereinafter referred to as a PET film), and a dried film is formed so that the thickness after drying becomes about 20 g / m 2 (referred to as a coated material). The obtained coated product is wrapped in a stainless steel mesh of 200 mesh, then put into ethyl acetate, immersed at 23 ° C. for 72 hours, and dried to remove ethyl acetate. The ratio of the weight of the dried film after immersion to the weight of the dried film before immersion (% by weight) is referred to as a gel fraction with respect to ethyl acetate. The gel fraction is determined according to the following equation.
Formula 1 Gel fraction (%) = (weight of dry film before immersion−weight of PET film) / (weight of dry film after immersion−weight of PET film) × 100
<粒子型硬化剤>
本発明の水性再剥離粘着剤は、粒子型硬化剤を含む。粒子型硬化剤とは、形態が水分散型のエマルションであり、硬化剤の外観が不透明で硬化剤が平均粒子径を有するものである。
粒子型硬化剤を用いることにより、粒子型硬化剤の親水基部分が疎水性の硬化剤を保護することで乳化重合物中での粒子型硬化剤とアクリル系ポリマーのカルボキシル基の反応を抑制することができる。そのため、本発明の粘着剤は、エマルションを塗工、乾燥することで、粒子型硬化剤の粒子構造が崩壊して速やかに反応が進行する。粒子型硬化剤は架橋反応に関与しない親水性成分が少ないため架橋密度が高くなり、得られる粘着シートの経時後の粘着力上昇が低い、優れた再剥離粘着剤が得られる。
<Particle type curing agent>
The aqueous removable pressure-sensitive adhesive of the present invention contains a particle-type curing agent. The particle-type curing agent is a water-dispersed emulsion in which the appearance of the curing agent is opaque and the curing agent has an average particle diameter.
By using the particle type curing agent, the hydrophilic group part of the particle type curing agent protects the hydrophobic curing agent, thereby suppressing the reaction between the particle type curing agent and the carboxyl group of the acrylic polymer in the emulsion polymer. be able to. Therefore, by applying and drying the emulsion of the pressure-sensitive adhesive of the present invention, the particle structure of the particle-type curing agent collapses and the reaction proceeds promptly. Since the particle-type curing agent has a small amount of a hydrophilic component that does not participate in the crosslinking reaction, the crosslinking density is increased, and an excellent re-peelable pressure-sensitive adhesive is obtained in which the pressure-sensitive adhesive strength of the obtained pressure-sensitive adhesive sheet after aging is low.
粒子型硬化剤の平均粒子径は、1〜100nmが好ましく、1〜50nmがより好ましい。粒子型硬化剤の平均粒子径を100nm以下にすることで、粒子型硬化剤とアクリル系ポリマーのカルボキシル基の硬化反応がより進行しやすく、再剥離性が向上する。粒子型硬化剤の平均粒子径の測定方法は、アクリル系ポリマーと同じである。 The average particle diameter of the particle-type curing agent is preferably from 1 to 100 nm, more preferably from 1 to 50 nm. By setting the average particle diameter of the particle-type curing agent to 100 nm or less, the curing reaction between the particle-type curing agent and the carboxyl group of the acrylic polymer more easily proceeds, and the removability is improved. The method for measuring the average particle diameter of the particle-type curing agent is the same as that for the acrylic polymer.
粒子型硬化剤は、例えばアジリジン系化合物、カルボジイミド系化合物、オキサゾリン型等が挙げられる。これらの中でもポットライフが長く、基材との密着性が向上する面からカルボジイミド系化合物が好ましい。粒子型硬化剤は、単独または2種類以上併用できる。 Examples of the particle-type curing agent include an aziridine compound, a carbodiimide compound, and an oxazoline compound. Of these, carbodiimide compounds are preferred from the viewpoint of long pot life and improved adhesion to the substrate. The particle-type curing agents can be used alone or in combination of two or more.
硬化剤は、アクリル系ポリマー100重量部に対して0.01〜8重量部が好ましく、0.01〜5重量部配合することが好ましく、0.03〜2.5重量部がより好ましい。0.01〜5重量部の配合により、基材との密着性および凝集力がより向上する。 The curing agent is preferably used in an amount of 0.01 to 8 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.03 to 2.5 parts by weight, based on 100 parts by weight of the acrylic polymer. By adding 0.01 to 5 parts by weight, the adhesion to the substrate and the cohesive force are further improved.
<アミノ基含有化合物>
本発明の水性再剥離粘着剤は、さらにアミノ基含有化合物を含むことができる。アミノ基含有化合物を用いることで、得られた粘着シートの平滑性が向上するため、貼り合わせ経過後の粘着力を抑制でき、再剥離性に優れたものとすることができる。さらに、水性再剥離粘着剤を配合する際、粒子型硬化剤と、アクリル系ポリマー粒子のカルボキシル基との硬化反応を抑制でき、水性再剥離粘着剤の粘度上昇を抑制し、粘度の変化を抑えることができるために好ましい。
<Amino group-containing compound>
The aqueous removable pressure-sensitive adhesive of the present invention may further contain an amino group-containing compound. The use of the amino group-containing compound improves the smoothness of the obtained pressure-sensitive adhesive sheet, so that the pressure-sensitive adhesive force after the pasting can be suppressed, and the removability can be excellent. Furthermore, when compounding the aqueous removable adhesive, the curing reaction between the particle type curing agent and the carboxyl group of the acrylic polymer particles can be suppressed, the increase in the viscosity of the aqueous removable adhesive is suppressed, and the change in viscosity is suppressed. It is preferred because it can be.
アミノ基含有化合物としては、モノメチルアミン、モノエチルアミン、モノプロピルアミン、モノブチルアミン及びモノエタノールアミン等の1級アミン、ジメチルアミン、ジエチルアミン、ジブチルアミン、ジエタノールアミン及びジイソプロパノールアミン、メチルプロパノールアミン等の2級アミン並びにトリメチルアミン、トリエチルアミン、ジメチルエチルアミン、ジメチルモノエタノールアミン及びトリエタノールアミン等の3級アミンが挙げられる。
これらの中でも、2級アミン、または3級アミンが、立体的な傘高い構造のため、アクリル系ポリマー粒子のカルボキシル基との硬化反応の抑制効果がより大きいことから好ましい。
Examples of the amino group-containing compound include primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine and monoethanolamine, and secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine and diisopropanolamine, and methylpropanolamine. Amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.
Among these, secondary amines and tertiary amines are preferred because they have a three-dimensionally umbrella structure and have a greater effect of suppressing the curing reaction with the carboxyl group of the acrylic polymer particles.
アミノ基含有化合物の添加量は、アミノ基含有化合物のアミノ基と、アクリル系ポリマー粒子とのカルボキシル基のモル比が0.1/1〜5/1であることが好ましく、0.25/1〜2.5/1がより好ましい。添加量をアクリル系ポリマー粒子とのカルボキシル基のモル比が0.1/1〜5/1にすることで、水性再剥離粘着剤の安定性を向上できる。 The amount of the amino group-containing compound to be added is preferably such that the molar ratio of the amino group of the amino group-containing compound to the carboxyl group of the acrylic polymer particles is 0.1 / 1 to 5/1, and 0.25 / 1. ~ 2.5 / 1 is more preferred. The stability of the aqueous removable pressure-sensitive adhesive can be improved by adjusting the amount of the carboxyl group to the acrylic polymer particles in a molar ratio of 0.1 / 1 to 5/1.
本発明の水性再剥離粘着剤は、乳化重合後に粘着付与樹脂を配合できる。粘着付与樹脂の配合により粘着力の調整が容易になる。 The aqueous removable pressure-sensitive adhesive of the present invention can contain a tackifier resin after emulsion polymerization. Adjustment of the adhesive force is facilitated by the addition of the tackifier resin.
<水性再剥離粘着剤の製造方法>
本発明のアクリル系ポリマー粒子は、(メタ)アクリル酸アルキルエステルとカルボキシル基含有モノマーを含有するモノマー混合物、粘着付与樹脂、水、乳化剤からなる乳化物の存在下に開始剤を用いて乳化重合させ、アクリル系ポリマー粒子とすることができる。ここでの乳化物は、乳化重合前のモノマー混合物、粘着付与樹脂、水、乳化剤のことであり、乳化物を乳化重合することで、乳化重合物が得られる。
粘着付与樹脂はモノマー混合物に溶解させて使用するため、乳化重合後、粘着付与樹脂からなる粒子とアクリル系ポリマー粒子が分離して存在せずに、粘着付与樹脂がアクリル系ポリマー粒子内に一体となって組み込むことができる。
得られたアクリル系ポリマー粒子にアミノ基含有化合物、粒子型硬化剤、消泡剤、レベリング剤、防腐剤、増粘剤等のその他添加剤を加えることで、水性再剥離粘着剤を得ることができる。
本発明の再剥離粘着剤は、硬化剤混合後の保存安定性が良好であるため、一液型で用いられる水性再剥離粘着剤として、好適に使用することができる。
<Production method of aqueous removable adhesive>
The acrylic polymer particles of the present invention are emulsion polymerized using an initiator in the presence of a monomer mixture containing an alkyl (meth) acrylate and a carboxyl group-containing monomer, a tackifier resin, water, and an emulsifier. And acrylic polymer particles. The emulsion here means a monomer mixture, a tackifier resin, water, and an emulsifier before emulsion polymerization, and an emulsion polymer is obtained by emulsion polymerization of the emulsion.
Since the tackifier resin is used by dissolving it in the monomer mixture, the particles of the tackifier resin and the acrylic polymer particles do not exist separately after the emulsion polymerization, and the tackifier resin is integrated into the acrylic polymer particles. Can be incorporated.
By adding other additives such as an amino group-containing compound, a particle-type curing agent, an antifoaming agent, a leveling agent, a preservative, and a thickener to the obtained acrylic polymer particles, an aqueous removable pressure-sensitive adhesive can be obtained. it can.
Since the removable adhesive of the present invention has good storage stability after mixing the curing agent, it can be suitably used as an aqueous removable adhesive used in a one-pack type.
《粘着シート》
本発明の粘着シートは、基材と、水性再剥離粘着剤の硬化物である粘着剤層とを備える。
製造方法を例示すると(1)剥離性シートに水性再剥離粘着剤を塗工、乾燥することで粘着剤層を形成し、次いで基材上に粘着剤層を転写する方法。および(2)基材に水性再剥離粘着剤を塗工、乾燥することで粘着剤層を形成し、次いで剥離性シートを貼り合わせる方法。等が挙げられる。
《Adhesive sheet》
The pressure-sensitive adhesive sheet of the present invention includes a substrate and a pressure-sensitive adhesive layer that is a cured product of an aqueous removable pressure-sensitive adhesive.
Examples of the production method include (1) a method of applying an aqueous re-peelable pressure-sensitive adhesive to a release sheet, drying the pressure-sensitive adhesive layer, and then transferring the pressure-sensitive adhesive layer onto a substrate. And (2) a method in which an aqueous re-peelable pressure-sensitive adhesive is applied to a substrate, dried to form a pressure-sensitive adhesive layer, and then a release sheet is laminated. And the like.
塗工方法は、例えばマイヤーバー、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、スピンコーター等公知の方法が挙げられる。塗工に際し、乾燥を行うことが通常である。乾燥は、特に制限はなく、熱風乾燥、赤外線ヒーターおよび減圧法等公知の方法を適宜選択して使用できる。乾燥温度は通常60〜180℃程度である。 Examples of the coating method include known methods such as a Meyer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a lip coater, a comma coater, a knife coater, a reverse coater, and a spin coater. Drying is usually performed during coating. Drying is not particularly limited, and a known method such as hot air drying, an infrared heater, and a reduced pressure method can be appropriately selected and used. The drying temperature is usually about 60 to 180 ° C.
粘着剤層の厚さは、一般的に5〜100μm程度であり、10〜50μmがより好ましい。 The thickness of the pressure-sensitive adhesive layer is generally about 5 to 100 μm, and more preferably 10 to 50 μm.
基材は、例えば紙、セロハン、プラスチックシート、ゴム、発泡体、布帛、ゴムびき布、樹脂含浸布、ガラス板、金属板、木材、偏光板などの光学フィルム等の板材またはシートが挙げられる。前記基材は、単独または複数の積層体であっても良い。また、前記基材は、裏面(粘着剤層と接しない面)に剥離処理、または帯電防止処理をすることができる。また基材は、公知の易接着処理を行うことで粘着剤層との密着性を向上できる。 Examples of the substrate include plate materials or sheets such as paper, cellophane, plastic sheet, rubber, foam, cloth, rubber cloth, resin impregnated cloth, glass plate, metal plate, wood, and optical film such as polarizing plate. The substrate may be a single or a plurality of laminates. Further, the base material may be subjected to a peeling treatment or an antistatic treatment on the back surface (the surface not in contact with the pressure-sensitive adhesive layer). In addition, the substrate can be improved in adhesion to the pressure-sensitive adhesive layer by performing a known easy adhesion treatment.
基材の厚さは、一般的に10〜100μm程度であり、30〜80μmがより好ましい。 The thickness of the substrate is generally about 10 to 100 μm, and more preferably 30 to 80 μm.
本発明の粘着シートの被着体は、素材として例えば、金属、ガラス、プラスチックフィルム、ゴム、木材、ダンボール、紙および塗料コート面など幅広い素材に使用できる。 The adherend of the pressure-sensitive adhesive sheet of the present invention can be used as a material for a wide range of materials such as metal, glass, plastic film, rubber, wood, cardboard, paper and paint-coated surfaces.
本発明の粘着シートの用途は、特に限定されないが、例えば各種ラベル用、マスキングテープ用途やプロテクトフィルム用途等の再剥離が必要な用途に好適に使用できる。 The application of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but it can be suitably used for applications requiring re-peeling, such as various labels, masking tapes, and protective films.
次に、実施例を示して本発明を更に具体的に説明するが、本発明はこれらによって限定されるものではない。尚、以下の説明において、部は重量部、%は重量%を意味する。 Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the following description, “part” means “part by weight” and “%” means “% by weight”.
(実施例1)
(メタ)アクリル酸アルキルエステルとして2−エチルヘキシルアクリレート98.5部、カルボキシ基含有モノマーとしてアクリル酸1.5部に、粘着付与樹脂としてピコラスチックA−5(スチレン系樹脂、イーストマンケミカル社製)1.0部を添加し溶解した。さらにアニオン系反応性乳化剤として「アクアロンKH−10」(ポリオキシエチレン−1−(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム塩 第一工業製薬社製)1.0部、および脱イオン水25.1部を加えて攪拌し乳化物を得た。得られた乳化物を滴下ロートに入れた。
別途、撹拌機、冷却管、温度計および上記滴下ロートを取り付けた4つ口フラスコに、脱イオン水を45.6部、上記乳化物のうちの1.0部を仕込み、フラスコ内部を窒素ガスで置換し、撹拌しながら内温を70℃まで加熱した。その後濃度10%過硫酸アンモニウムを添加して、反応を開始した。内温を70℃に保持したまま、上記乳化物を180分かけて滴下した後に、さらに撹拌しながら内温を70℃に保持したまま1時間反応を継続した。その後内温を65℃に冷却し、酸化剤の「パーブチルH−69」(日本油脂社製)の濃度10%水溶液1.0部、還元剤の「エルビットN」(扶桑化学工業社製)の濃度10%水溶液1.0部をそれぞれ10分おきに3回添加し、さらに1時間反応を継続した。
その後、冷却し、不揮発分濃度50%、平均粒子径300nmのアクリル系ポリマー粒子である乳化重合物を得た。尚、このアクリル系ポリマー粒子のゲル分率は40%であった。
(Example 1)
98.5 parts of 2-ethylhexyl acrylate as an alkyl (meth) acrylate, 1.5 parts of acrylic acid as a carboxy group-containing monomer, and picolastic A-5 as a tackifying resin (styrene-based resin, manufactured by Eastman Chemical Company) 1.0 part was added and dissolved. Further, 1.0 part of "AQUALON KH-10" (polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt, Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic reactive emulsifier, and 25.1 deionized water. The mixture was added and stirred to obtain an emulsion. The obtained emulsion was put into a dropping funnel.
Separately, 45.6 parts of deionized water and 1.0 part of the above emulsion were charged into a four-necked flask equipped with a stirrer, a condenser, a thermometer and the above-mentioned dropping funnel. And the internal temperature was heated to 70 ° C. while stirring. Thereafter, 10% ammonium persulfate was added to start the reaction. After the above emulsion was added dropwise over 180 minutes while maintaining the internal temperature at 70 ° C, the reaction was continued for 1 hour while maintaining the internal temperature at 70 ° C with further stirring. Thereafter, the internal temperature was cooled to 65 ° C., and 1.0 part of a 10% aqueous solution of oxidizing agent “Perbutyl H-69” (manufactured by NOF Corporation) and a reducing agent “Erbit N” (manufactured by Fuso Chemical Industry Co., Ltd.) were used. 1.0 part of a 10% strength aqueous solution was added three times every 10 minutes, and the reaction was further continued for 1 hour.
Thereafter, the mixture was cooled to obtain an emulsion polymer as acrylic polymer particles having a nonvolatile content of 50% and an average particle size of 300 nm. The gel fraction of the acrylic polymer particles was 40%.
次に、アクリル系ポリマー粒子を含有する乳化重合物100部に対し、中和剤としてトリエチルアミンを2部、消泡剤としてSNデフォーマー364(サンノプコ社製)を0.3部、防腐剤としてユニケムフレックスBN−202(ユニオンケミカル社製)を0.05部、レベリング剤として「ペレックスOT−P」(花王社製)0.2部を加え、架橋剤としてカルボジイミド系粒子型硬化剤のカルボジライトE−05(粒子径45nm、不揮発分40%、日清紡ケミカル社製)を1.25部加え、さらにアルカリ増粘剤で増粘し、水性再剥離粘着剤を得た。
得られた水性再剥離粘着剤を乾燥後の厚さが20μmになるようにコンマコーターを使用して剥離性シート上に塗工し、100℃の乾燥オーブンで75秒間乾燥した後、市販のPETフィルムを貼り合わせて粘着シートを得た。
後述する試験方法で性能を評価し、その結果を表1に示した。
Next, with respect to 100 parts of the emulsion polymer containing the acrylic polymer particles, 2 parts of triethylamine as a neutralizing agent, 0.3 parts of SN Deformer 364 (manufactured by San Nopco) as a defoaming agent, and Unichem as a preservative 0.05 parts of Flex BN-202 (manufactured by Union Chemical Co.), 0.2 parts of "Perex OT-P" (manufactured by Kao Corporation) as a leveling agent, and a carbodiimide-based particle-type curing agent, carbodilite E-, as a crosslinking agent Addition of 1.25 parts of Nitrogen 05 (particle size: 45 nm, non-volatile content: 40%, manufactured by Nisshinbo Chemical Co., Ltd.) and further thickening with an alkali thickener gave an aqueous removable adhesive.
The obtained aqueous re-peelable pressure-sensitive adhesive was applied on a release sheet using a comma coater so that the thickness after drying was 20 μm, dried in a drying oven at 100 ° C. for 75 seconds, and then commercially available PET The films were laminated to obtain an adhesive sheet.
The performance was evaluated by the test method described later, and the results are shown in Table 1.
(実施例2〜20、比較例1〜7)
実施例1の配合を表1の原料および配合量(重量部)に変更した以外は、実施例1と同様にして、水性再剥離粘着剤および粘着シートを得た。
また、乳化重合時の内温、滴下速度、反応時間等を適宜調整することにより、それぞれ表に示す平均粒子径のアクリル系粒子ポリマー粒子を得た。
(Examples 2 to 20, Comparative Examples 1 to 7)
An aqueous removable pressure-sensitive adhesive and pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1, except that the composition of Example 1 was changed to the raw materials and the amounts (parts by weight) shown in Table 1.
In addition, by appropriately adjusting the internal temperature, the dropping rate, the reaction time, and the like during the emulsion polymerization, acrylic-based polymer particles having an average particle diameter shown in the table were obtained.
表1の略称は下記の通りである。
・EHA:2−エチルヘキシルアクリレート
・BA:アクリル酸ブチル
・MMA:メタクリル酸メチル
・AA:アクリル酸
・MAA:メタクリル酸
・TPGDA:トリプロピレングリコールジアクリレート
・A−5:「ピコラスチックA−5」(スチレン系樹脂、イーストマンケミカル社製)
・KE364C:「KE364C」(ロジン系樹脂、荒川化学社製)
・OTG:チオグリコール酸オクチル
・KH−10:「アクアロンKH−10」(アニオン系反応性乳化剤、ポリオキシエチレン−1−(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム塩 不揮発分100%、第一工業製薬社製)
・RA9612:「ニューコールRA9612」(アニオン系非反応性乳化剤、ポリオキシエチレンアルキルエーテル硫酸エステルアンモニウム塩 不揮発分25% 日本乳化剤社製)
・E−05:「カルボジライトE−05(カルボジイミド系粒子型硬化剤、粒子径45nm、不揮発分40%、日清紡ケミカル社製)」
・K−2010E:「エポクロスK−2010E」(オキサゾリン系粒子型硬化剤、粒子径208nm、不揮発分100%、日本触媒社製)
・DZ−22E:「ケミタイトDZ−22E」(アジリジン系粒子型硬化剤、粒子径700nm、揮発分100%、日本触媒社製)
・SV−02:「カルボジライトSV−02(カルボジイミド系溶液型硬化剤、不揮発分40%、日清紡ケミカル社製)」
・EX−313:「デナコールEX−313」(エポキシ系溶液型硬化剤、不揮発分100%、ナガセケムテックス社製)
・PZ−33:「ケミタイトPZ−33」(アジリジン系溶液型硬化剤、揮発分100%、日本触媒社製)
・TEN:トリエチルアミン
・TEA:トリエタノールアミン
・DEA:ジエチルアミン
・PA:モノプロピルアミン
The abbreviations in Table 1 are as follows.
-EHA: 2-ethylhexyl acrylate-BA: butyl acrylate-MMA: methyl methacrylate-AA: acrylic acid-MAA: methacrylic acid-TPGDA: tripropylene glycol diacrylate-A-5: "picolastic A-5" ( Styrene resin, manufactured by Eastman Chemical Company)
・ KE364C: “KE364C” (rosin resin, Arakawa Chemical Co., Ltd.)
-OTG: octyl thioglycolate-KH-10: "AQUALON KH-10" (anionic reactive emulsifier, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt, 100% non-volatile content, Daiichi Kogyo) Pharmaceutical company)
RA9612: "Newcol RA9612" (anionic non-reactive emulsifier, polyoxyethylene alkyl ether sulfate ammonium salt, nonvolatile content 25%, manufactured by Nippon Emulsifier Co.)
E-05: "Carbodilite E-05 (carbodiimide-based particle-type curing agent, particle diameter 45 nm, nonvolatile content 40%, manufactured by Nisshinbo Chemical Inc.)"
-K-2010E: "Epocross K-2010E" (oxazoline-based particle-type curing agent, particle diameter 208 nm, nonvolatile content 100%, manufactured by Nippon Shokubai Co., Ltd.)
DZ-22E: “Chemiteite DZ-22E” (aziridine-based particle-type curing agent, particle diameter 700 nm, volatile content 100%, manufactured by Nippon Shokubai Co., Ltd.)
SV-02: "Carbodilite SV-02 (carbodiimide-based solution-type curing agent, nonvolatile content 40%, manufactured by Nisshinbo Chemical Inc.)"
EX-313: "Denacol EX-313" (Epoxy-based solution-type curing agent, nonvolatile content 100%, manufactured by Nagase ChemteX Corporation)
-PZ-33: "Chemiteit PZ-33" (aziridine-based solution-type curing agent, volatile matter 100%, manufactured by Nippon Shokubai Co., Ltd.)
・ TEN: triethylamine ・ TEA: triethanolamine ・ DEA: diethylamine ・ PA: monopropylamine
[試験方法]
(1)常温粘着力
得られた粘着シートを23℃50%RH環境下にて長さ100mm×幅25mmの大きさに準備し試料とした。次いで、JIS Z 0237に準拠して、試料から剥離性シートを剥がし、露出した粘着剤層を表面を研磨したステンレス鋼板(以下、SUSという)に貼付け、2kgロールを1往復して、24時間直後の粘着力を測定した。なお粘着力の測定は引張試験機を用いて、剥離速度:300mm/分、剥離角180゜で行った。
[Test method]
(1) Room temperature adhesive strength
The obtained pressure-sensitive adhesive sheet was prepared as a sample in a size of 100 mm long × 25 mm wide under an environment of 23 ° C. and 50% RH. Next, in accordance with JIS Z 0237, the peelable sheet was peeled off from the sample, the exposed pressure-sensitive adhesive layer was stuck to a stainless steel plate (hereinafter referred to as SUS) whose surface was polished, and a 2 kg roll was reciprocated once, immediately after 24 hours. Was measured for adhesion. The adhesion was measured using a tensile tester at a peeling speed of 300 mm / min and a peeling angle of 180 °.
(2)高温粘着力
得られた粘着シートを23℃50%RH環境下にて長さ100mm×幅25mmの大きさに準備し試料とした。次いで、試料から剥離性シートを剥がし、露出した粘着剤層を表面を研磨したステンレス鋼板(以下、SUSという)に貼付け、2kgロールを1往復して、圧着後に試料を40℃雰囲気下のオーブンで7日間放置後、オーブンから取り出して2時間後、23℃50%RH雰囲気下で粘着力を測定した。なお粘着力の測定は引張試験機を用いて、剥離速度:300mm/分、剥離角180゜で行った。また、下記の式より粘着力の上昇率を算出した。
粘着力維持率(%)=[(高温粘着力)/(常温粘着力)−1]×100
粘着力維持率の判定は、下記の基準で評価した。
◎:粘着力維持率50%以下。非常に良好。
○:粘着力維持率50%以上100%未満。良好。
△:粘着力維持率100%以上、200%未満。実用可。
×:粘着力維持率200%%以上。実用不可。
(2) High-Temperature Adhesive Force The obtained adhesive sheet was prepared as a sample in a size of 100 mm long × 25 mm wide under an environment of 23 ° C. and 50% RH. Next, the peelable sheet was peeled off from the sample, the exposed pressure-sensitive adhesive layer was pasted on a stainless steel plate (hereinafter referred to as SUS) whose surface was polished, and a 2 kg roll was reciprocated once. After standing for 7 days, 2 hours after removing from the oven, the adhesive strength was measured in an atmosphere of 23 ° C. and 50% RH. The adhesion was measured using a tensile tester at a peeling speed of 300 mm / min and a peeling angle of 180 °. The rate of increase in adhesive strength was calculated from the following equation.
Adhesive strength maintenance rate (%) = [(high temperature adhesive strength) / (normal temperature adhesive strength) −1] × 100
The determination of the adhesive strength maintenance rate was evaluated according to the following criteria.
:: Adhesive strength maintenance rate of 50% or less. Very good.
:: Adhesive strength maintenance rate of 50% or more and less than 100%. Good.
Δ: Adhesive strength maintenance rate of 100% or more and less than 200%. Practical.
×: Adhesion strength retention rate of 200 %% or more. Not practical.
(3)再剥離性
得られた粘着シートを23℃50%RH環境下にて長さ100mm×幅25mmの大きさに準備し試料とした。次いで、試料の剥離性シートを剥がし、露出した粘着剤層をSUSに貼付け、2kgロールで1往復して圧着した。圧着後の試料を40℃雰囲気下のオーブンで7日間放置後、オーブンから取り出して2時間後、23℃50%RH雰囲気下で、引張試験機を用いて、試料をSUSから300mm/分の速さで180゜方向に剥離して、SUS表面に粘着剤層に由来する汚染が付着しているか否かを目視により下記の基準で評価した。
◎:SUS表面がきれいだった。非常に良好。
○:SUS表面にわずかに汚染が付着していたが、良好。
△:SUS表面に汚染の付着がやや多かったが、実用上問題ない。
×:SUS表面に汚染の付着が非常に多かった。実用不可。
(3) Removability The obtained pressure-sensitive adhesive sheet was prepared as a sample having a size of 100 mm long × 25 mm wide under an environment of 23 ° C. and 50% RH. Next, the peelable sheet of the sample was peeled off, the exposed pressure-sensitive adhesive layer was adhered to SUS, and pressure-bonded by reciprocating once with a 2 kg roll. The sample after crimping was allowed to stand in an oven at 40 ° C. for 7 days, taken out of the oven, two hours later, and then sampled at a speed of 300 mm / min from SUS using a tensile tester in an atmosphere of 23 ° C. and 50% RH. Then, the film was peeled in the 180 ° direction, and whether or not contamination derived from the pressure-sensitive adhesive layer adhered to the SUS surface was visually evaluated according to the following criteria.
A: The SUS surface was clean. Very good.
:: Stain was slightly adhered to the SUS surface, but good.
Δ: Slight contamination was observed on the SUS surface, but there was no practical problem.
X: Very large amount of contamination adhered to the SUS surface. Not practical.
(4)耐水白化性
得られた粘着シートから剥離性シートを剥がし、PETフィルムを貼り合せ、40℃のイオン交換水に24時間浸漬した。浸漬前後の濁度をヘイズメーター(NDH5000W、日本電色工業社製)で測定した。
◎:浸漬前後の濁度変化が0.5未満。非常に良好。
○:浸漬前後の濁度変化が0.5以上1.0未満。良好。
△:浸漬前後の濁度変化が1.0以上1.5未満。実用上問題ない。
×:浸漬前後の濁度変化が1.5以上。実用不可。
(4) Water Whitening Resistance The peelable sheet was peeled off from the obtained pressure-sensitive adhesive sheet, a PET film was bonded, and the sheet was immersed in ion-exchanged water at 40 ° C. for 24 hours. The turbidity before and after the immersion was measured with a haze meter (NDH5000W, manufactured by Nippon Denshoku Industries Co., Ltd.).
A: Turbidity change before and after immersion is less than 0.5. Very good.
:: Change in turbidity before and after immersion is 0.5 or more and less than 1.0. Good.
Δ: Change in turbidity before and after immersion is 1.0 or more and less than 1.5. No problem in practical use.
X: The turbidity change before and after immersion is 1.5 or more. Not practical.
(5)粘度変化率
得られた水性再剥離粘着剤を40℃で90日間放置させ、放置前後の粘度をB型粘度計で測定した。また、下記の式より粘度変化率を算出した。
粘度変化率(%)=[(40℃90日間後の粘度)/(初期粘度)−1]×100の絶対値
粘度変化率の判定は、下記の基準で評価した。
◎:粘度上昇率0%以上5%未満。非常に良好。
○:粘度上昇率5%以上10%未満。良好。
△:粘度上昇率10%以上20%未満。実用可。
×:粘度上昇率20%以上。実用不可。
(5) Change in Viscosity The obtained aqueous removable pressure-sensitive adhesive was allowed to stand at 40 ° C. for 90 days, and the viscosity before and after the standing was measured with a B-type viscometer. The rate of change in viscosity was calculated from the following equation.
Viscosity change rate (%) = [(viscosity after 90 days at 40 ° C.) / (Initial viscosity) −1] × 100 The determination of the absolute value viscosity change rate was evaluated based on the following criteria.
A: Viscosity increase rate is 0% or more and less than 5%. Very good.
:: The rate of increase in viscosity is 5% or more and less than 10%. Good.
Δ: Viscosity increase rate of 10% or more and less than 20%. Practical.
X: Viscosity increase rate 20% or more. Not practical.
Claims (9)
前記アクリル系ポリマー粒子は、モノマー混合物および粘着付与樹脂の乳化重合物であり、
前記モノマー混合物は、(メタ)アクリル酸アルキルエステルおよびカルボキシル基含有モノマーを含有し、多官能モノマーを含有しない、水性再剥離粘着剤。 Acrylic polymer particles, an aqueous removable adhesive containing a particle-type curing agent,
The acrylic polymer particles are an emulsion polymer of a monomer mixture and a tackifier resin,
An aqueous removable pressure-sensitive adhesive, wherein the monomer mixture contains a (meth) acrylic acid alkyl ester and a carboxyl group-containing monomer and does not contain a polyfunctional monomer.
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JP2004107545A (en) * | 2002-09-20 | 2004-04-08 | Saiden Chemical Industry Co Ltd | Water-based adhesive composition for film base material |
JP2008163127A (en) * | 2006-12-27 | 2008-07-17 | Lintec Corp | Adhesive composition, manufacturing method for adhesive sheet using it, adhesive sheet and manufacturing method for adhesive composition |
JP2014214219A (en) * | 2013-04-25 | 2014-11-17 | 東洋インキScホールディングス株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet obtained using the same |
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JP2004107545A (en) * | 2002-09-20 | 2004-04-08 | Saiden Chemical Industry Co Ltd | Water-based adhesive composition for film base material |
JP2008163127A (en) * | 2006-12-27 | 2008-07-17 | Lintec Corp | Adhesive composition, manufacturing method for adhesive sheet using it, adhesive sheet and manufacturing method for adhesive composition |
JP2014214219A (en) * | 2013-04-25 | 2014-11-17 | 東洋インキScホールディングス株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet obtained using the same |
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JP6981517B1 (en) * | 2020-10-30 | 2021-12-15 | 東洋インキScホールディングス株式会社 | Method for Producing Acrylic Polymer Particles, Acrylic Polymer Particles, and Acrylic Polymer Particle-Containing Composition |
JP2022073088A (en) * | 2020-10-30 | 2022-05-17 | 東洋インキScホールディングス株式会社 | Process for producing acrylic polymer particle, acrylic polymer particle, and acrylic polymer particle-containing composition |
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