JP4547145B2 - Re-peelable water-based adhesive composition - Google Patents
Re-peelable water-based adhesive composition Download PDFInfo
- Publication number
- JP4547145B2 JP4547145B2 JP2003412673A JP2003412673A JP4547145B2 JP 4547145 B2 JP4547145 B2 JP 4547145B2 JP 2003412673 A JP2003412673 A JP 2003412673A JP 2003412673 A JP2003412673 A JP 2003412673A JP 4547145 B2 JP4547145 B2 JP 4547145B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- meth
- sensitive adhesive
- pressure
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 65
- 239000000853 adhesive Substances 0.000 title claims description 36
- 230000001070 adhesive effect Effects 0.000 title claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 32
- 239000000178 monomer Substances 0.000 claims description 88
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 52
- -1 oxazoline compound Chemical class 0.000 claims description 43
- 239000000839 emulsion Substances 0.000 claims description 37
- 239000003995 emulsifying agent Substances 0.000 claims description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 125000000129 anionic group Chemical group 0.000 claims description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 230000000873 masking effect Effects 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 57
- 239000000344 soap Substances 0.000 description 19
- 238000011109 contamination Methods 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 11
- 239000000758 substrate Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 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 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- CCQJKEYNLSZZNO-UHFFFAOYSA-N 10-trimethoxysilyldecyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCCCOC(=O)C=C CCQJKEYNLSZZNO-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- 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 2
- 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 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-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
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- CLBKIFXWWJFHGC-UHFFFAOYSA-N 18-trimethoxysilyloctadecyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCCCCCCCCCCCOC(=O)C=C CLBKIFXWWJFHGC-UHFFFAOYSA-N 0.000 description 1
- UFUXVJFOILLERS-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(C)(C)CO UFUXVJFOILLERS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- NWIIFBPIDORBCY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O.OCC(O)CO NWIIFBPIDORBCY-UHFFFAOYSA-N 0.000 description 1
- ZAYGISOXMIXWHX-UHFFFAOYSA-N 2-methylpropoxycarbonyloxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(=O)OCC(C)C ZAYGISOXMIXWHX-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- LFIVUPGZYYBPKC-UHFFFAOYSA-N 3,4-dihydro-2h-chromene;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2CCCOC2=C1 LFIVUPGZYYBPKC-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- CSBJCQMIXISILC-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl prop-2-enoate Chemical compound C[Si](C)(Cl)CCCOC(=O)C=C CSBJCQMIXISILC-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- DGBFOBNYTYHFPN-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C=C DGBFOBNYTYHFPN-UHFFFAOYSA-N 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
- MYEFGHBUFAPKJO-UHFFFAOYSA-N 3-[methyl(dipropoxy)silyl]propyl prop-2-enoate Chemical compound CCCO[Si](C)(OCCC)CCCOC(=O)C=C MYEFGHBUFAPKJO-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
- YFISHOAHNLGUEL-UHFFFAOYSA-N 3-tributoxysilylpropyl prop-2-enoate Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCOC(=O)C=C YFISHOAHNLGUEL-UHFFFAOYSA-N 0.000 description 1
- LEPRPXBFZRAOGU-UHFFFAOYSA-N 3-trichlorosilylpropyl prop-2-enoate Chemical compound Cl[Si](Cl)(Cl)CCCOC(=O)C=C LEPRPXBFZRAOGU-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- TUUKLRVBYCHYOG-UHFFFAOYSA-N 4-trimethoxysilylbutyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCOC(=O)C=C TUUKLRVBYCHYOG-UHFFFAOYSA-N 0.000 description 1
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- INVAIHOVGZNBFS-UHFFFAOYSA-N 6-triethoxysilylhexyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCCCCOC(=O)C=C INVAIHOVGZNBFS-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- 239000002480 mineral oil Substances 0.000 description 1
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- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
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- HNXZJRFPLKGGHC-UHFFFAOYSA-N n-butoxy-n-(hydroxymethyl)prop-2-enamide Chemical compound CCCCON(CO)C(=O)C=C HNXZJRFPLKGGHC-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- WVSZBAHKLHXQFN-UHFFFAOYSA-N tetrahydrate;dihydrochloride Chemical compound O.O.O.O.Cl.Cl WVSZBAHKLHXQFN-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、金属板、ガラス板、プラスチック板等の運搬、加工、切断等の際の傷防止や汚染防止等のための一時的な表面保護用或いは仮接着用の粘着テープ又はシートの粘着剤として有用な再剥離型の水性粘着剤組成物に関し、更に詳しくは、経時での接着力上昇が少なく、かつ、再剥離時における被着体への糊残りや貼り跡などの汚染が少ないといった耐汚染性に優れ、更に水性粘着剤組成物としての機械的安定性にも優れた再剥離型水性粘着剤組成物に関するものである。 The present invention relates to a pressure-sensitive adhesive tape or sheet for temporary surface protection or temporary adhesion for preventing scratches or preventing contamination during transportation, processing, cutting, etc. of metal plates, glass plates, plastic plates, etc. In particular, the re-peelable water-based pressure-sensitive adhesive composition useful as the above is more resistant to an increase in adhesive strength over time and less contamination such as adhesive residue and sticking marks on the adherend during re-peeling. The present invention relates to a re-peelable water-based pressure-sensitive adhesive composition that is excellent in contamination and further excellent in mechanical stability as a water-based pressure-sensitive adhesive composition.
従来より、再剥離型粘着剤組成物は、表面保護フイルム、塗料用マスキングテープ、粘着シール等に広く用いられている。例えば、表面保護フイルムは、金属製品やプラスチック製品、ガラス製品等の運搬、加工、切断、貯蔵等の際に、傷付きや汚染、腐食等を防止するために、これらの製品の表面を一時的に保護するもので、目的が達した後は製品表面から剥離される。
このような表面保護フイルムは、金属製品やプラスチック製品、ガラス製品等の運搬、加工、切断、貯蔵時等には被着体に接着して充分な接着力を持ち剥離されることがなく、目的が達した後は被着体から容易に剥離できるといった再剥離性が要求される。
Conventionally, re-peelable pressure-sensitive adhesive compositions have been widely used for surface protective films, masking tapes for paints, adhesive seals and the like. For example, surface protection films temporarily protect the surface of these products to prevent scratches, contamination, corrosion, etc. during transportation, processing, cutting, storage, etc. of metal products, plastic products, glass products, etc. After the purpose is reached, it is peeled off from the product surface.
Such surface protective film adheres to the adherend during transportation, processing, cutting, storage, etc. of metal products, plastic products, glass products, etc. Therefore, re-peelability is required so that it can be easily peeled off from the adherend.
しかし、粘着テープ又はシートは、貼り付け後の経時変化により接着力の上昇が起こりやすく、その結果、表面保護フイルムを被着体から再剥離する際に剥離し難く、剥離作業に時間がかかったり、粘着剤の糊残りや貼り跡等の汚染を生じる等、剥離時の粘着性や剥離後の耐汚染性等の再剥離性が問題となることがある。 However, the adhesive tape or sheet is likely to have an increase in adhesive force due to a change with time after being applied, and as a result, it is difficult to peel off when the surface protective film is peeled off again from the adherend, and the peeling work takes time. In addition, there may be a problem of re-peelability such as adhesiveness at the time of peeling and stain resistance after peeling, such as contamination of adhesive residue and sticking marks of the adhesive.
一方、再剥離型粘着剤組成物においても、近年の環境衛生上の観点より、溶剤を用いない水分散型粘着剤の検討が種々行われており、中でも上記の問題点を解決するものとして、例えば、ａ）炭素数２〜１４のアルキル基を有するアクリレート系単量体５０〜９９．９重量％、ｂ）カルボキシル基含有単量体０．１〜５重量％、ｃ）上記ａ，ｂ成分と共重合可能な単量体０〜４９．９重量％からなる単量体混合物の水分散系共重合体に、オキサゾリン基を含有する水溶性架橋剤を、上記共重合体に含まれるカルボキシル基１当量あたり、オキサゾリン基が０．１〜５当量となるように配合してなり、かつ溶剤可溶分が４０重量％以下、弾性率が２〜５０ｋｇ／ｃｍ２で、再剥離力が５００ｇ／２０ｍｍ幅以下である再剥離型感圧接着剤が提案されている（例えば、特許文献１参照。）。 On the other hand, in the re-peelable pressure-sensitive adhesive composition, from the viewpoint of environmental hygiene in recent years, various studies of water-dispersed pressure-sensitive adhesives that do not use a solvent have been conducted, and among them, as a solution to the above problems, For example, a) 50 to 99.9% by weight of an acrylate monomer having an alkyl group having 2 to 14 carbon atoms, b) 0.1 to 5% by weight of a carboxyl group-containing monomer, c) components a and b above A water-soluble cross-linking agent containing an oxazoline group is added to a water-dispersed copolymer of a monomer mixture consisting of 0 to 49.9% by weight of a monomer copolymerizable with a carboxyl group contained in the copolymer. It is blended so that the oxazoline group is 0.1 to 5 equivalents per equivalent, the solvent-soluble component is 40% by weight or less, the elastic modulus is 2 to 50 kg / cm 2 , and the re-peeling force is 500 g / Proposed re-peelable pressure-sensitive adhesive with a width of 20 mm or less (For example, refer to Patent Document 1).
又、ａ）炭素数２〜１４のアルキル基を有するアクリレート系単量体５０〜９９．９重量％と、ｂ）カルボキシル基含有単量体０．１〜５重量％と、ｃ）上記ａ，ｂ成分と共重合可能な単量体０〜４９．９重量％からなる単量体混合物の水分散型アクリレート系共重合体に、カルボジイミド基を含有する架橋剤を、上記共重合体のカルボキシル基に対するカルボジイミド基の比率（カルボジイミド基／カルボキシル基）が０．１〜５．０となるように配合してなり、再剥離性が５００ｇ／２０ｍｍ幅以下である水分散型再剥離用感圧接着剤も提案されている（例えば、特許文献２参照。）。
しかしながら、上記特許文献１及び２の開示技術では、再剥離性については、特許文献１では２３℃で２０分間の経時程度、特許文献２でも２３℃、６５％ＲＨで２４時間の経時程度での再剥離性であり、近年の要求性能に対してまだまだ満足するものではなく更なる長時間の経時における再剥離性が求められている。又、耐汚染性についても上記技術ではまだまだ不充分であり更なる改良が求められるうえ、更に水性粘着剤組成物としての機械的安定性も不充分であり、塗工時にブツが発生し均一な塗工ができなくなるという問題も生じるものであった。 However, in the disclosed technologies of Patent Documents 1 and 2, the removability is about 20 minutes at 23 ° C. in Patent Document 1 and about 24 hours at 23 ° C. and 65% RH in Patent Document 2. It is re-peeling property, and it is not yet satisfied with the performance required in recent years, and further re-peeling property with time is required. In addition, the above technique is still insufficient with respect to the stain resistance, and further improvement is required. Further, the mechanical stability as an aqueous pressure-sensitive adhesive composition is also insufficient, resulting in unevenness during coating. There was also a problem that coating could not be performed.
そこで、本発明ではこのような背景下において、経時での接着力上昇が少なく、かつ、再剥離時における被着体への糊残りや貼り跡などの汚染が少ないといった耐汚染性に優れ、更に水性粘着剤組成物としての機械的安定性にも優れた再剥離型水性粘着剤組成物を提供することを目的とするものである。 Therefore, in the present invention, under such a background, there is little increase in adhesive strength over time, and excellent anti-contamination properties such as less adhesive residue and sticking marks on the adherend during re-peeling, An object of the present invention is to provide a re-peelable water-based pressure-sensitive adhesive composition having excellent mechanical stability as a water-based pressure-sensitive adhesive composition.
しかるに、本発明者等はかかる課題を解決すべく鋭意研究を重ねた結果、炭素数４〜１２のアルキル基を含有する（メタ）アクリル酸アルキルエステル（ａ１）５０〜９９．８重量％、カルボキシル基含有不飽和単量体（ａ２）０．１〜２０重量％、多官能性不飽和単量体（ａ３）０．１〜２０重量％、その他の不飽和単量体（ａ４）０〜４９．８重量％を含む単量体混合物を、アニオン型反応性乳化剤の存在下に、乳化重合させて得られるエマルジョン［Ａ］と、架橋剤［Ｂ］とを含有してなり、架橋剤［Ｂ］がエマルジョン型オキサゾリン系化合物である再剥離型水性粘着剤組成物が、上記目的に合致することを見出し、本発明を完成した。
However, as a result of intensive studies to solve such problems, the present inventors have found that a (meth) acrylic acid alkyl ester (a1) containing an alkyl group having 4 to 12 carbon atoms is 50 to 99.8% by weight, carboxyl Group-containing unsaturated monomer (a2) 0.1-20% by weight, multifunctional unsaturated monomer (a3) 0.1-20% by weight, other unsaturated monomer (a4) 0-49 the monomer mixture containing .8% by weight, in the presence of anionic reactive emulsifier, an emulsion [a] obtained by emulsion polymerization, Ri name contains a crosslinking agent [B], the crosslinking agent [ B] is releasable aqueous pressure-sensitive adhesive composition Ru emulsion type oxazoline compound der is found that matches the above-mentioned object, the present invention has been completed.
本発明の再剥離型水性粘着剤組成物は、炭素数４〜１２のアルキル基を含有する（メタ）アクリル酸アルキルエステル（ａ１）５０〜９９．８重量％、カルボキシル基含有不飽和単量体（ａ２）０．１〜２０重量％、多官能性不飽和単量体（ａ３）０．１〜２０重量％、その他の不飽和単量体（ａ４）０〜４９．８重量％を含む単量体混合物を、アニオン型反応性乳化剤の存在下に、乳化重合させて得られるエマルジョン［Ａ］と、架橋剤［Ｂ］とを含有してなり、架橋剤［Ｂ］がエマルジョン型オキサゾリン系化合物であるため、経時での接着力上昇が少なく、かつ、再剥離時における被着体への糊残りや貼り跡などの汚染が少ないといった耐汚染性に優れ、更に水性粘着剤組成物としての機械安定性にも優れた効果を示すものである。
The re-peelable water-based pressure-sensitive adhesive composition of the present invention comprises (meth) acrylic acid alkyl ester (a1) 50 to 99.8% by weight, carboxyl group-containing unsaturated monomer containing an alkyl group having 4 to 12 carbon atoms. (A2) 0.1 to 20% by weight, polyfunctional unsaturated monomer (a3) 0.1 to 20% by weight, other unsaturated monomer (a4) 0 to 49.8% by weight the mer mixture, in the presence of anionic reactive emulsifier, an emulsion [a] obtained by emulsion polymerization, the crosslinking agent [B] Ri and name contained, crosslinking agent [B] is an emulsion type oxazoline compound der because, less adhesion force increase with time, and is excellent in stain resistance, such contamination is small, such as adhesive residue and paste traces to the adherend upon re-peeling, as further aqueous pressure-sensitive adhesive composition This also has an excellent effect on the mechanical stability.
以下、本発明について具体的に説明する。
本発明のエマルジョン［Ａ］は、炭素数４〜１２のアルキル基を含有する（メタ）アクリル酸アルキルエステル（ａ１）、カルボキシル基含有不飽和単量体（ａ２）、多官能性不飽和単量体（ａ３）、その他の不飽和単量体（ａ４）を含む単量体混合物を乳化重合させてなるものである。
Hereinafter, the present invention will be specifically described.
The emulsion [A] of the present invention is a (meth) acrylic acid alkyl ester (a1) containing a C 4-12 alkyl group, a carboxyl group-containing unsaturated monomer (a2), a polyfunctional unsaturated monomer. It is obtained by emulsion polymerization of a monomer mixture containing the body (a3) and other unsaturated monomers (a4).
炭素数４〜１２のアルキル基を含有する（メタ）アクリル酸アルキルエステル（ａ１）としては、特に限定されず、例えばｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、イソウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、イソドデシル（メタ）アクリレート等が挙げられ、中でもｎ−ブチル（メタ）アクリレート、２−エチルヘキシルアクリレート等が好ましく用いられる。又、これらは１種又は２種以上併用して用いられる。 The (meth) acrylic acid alkyl ester (a1) containing an alkyl group having 4 to 12 carbon atoms is not particularly limited. For example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl ( (Meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, isoundecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate, and the like. ) Acrylate, 2-ethylhexyl acrylate are preferably used. These may be used alone or in combination of two or more.
カルボキシル基含有不飽和単量体（ａ２）としては、特に限定されず、例えばアクリル酸、アクリル酸ダイマー、メタクリル酸、クロトン酸、イタコン酸、マレイン酸等が挙げられ、中でもアクリル酸、メタクリル酸等が好ましく用いられる。又、これらは１種又は２種以上併用して用いられる。 The carboxyl group-containing unsaturated monomer (a2) is not particularly limited, and examples thereof include acrylic acid, acrylic acid dimer, methacrylic acid, crotonic acid, itaconic acid, maleic acid and the like, among which acrylic acid, methacrylic acid and the like. Is preferably used. These may be used alone or in combination of two or more.
多官能性不飽和単量体（ａ３）としては、特に限定されず、例えばエチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、グリセリンメタクリレートアクリレート、トリス（メタ）アクリロイルオキシフォスフェート、グリセリンジ（メタ）アクリレート、ジアリルテレフタレート、テトラアリルオキシエタン、ジビニルベンゼン、トリ（メタ）アリルイソシアヌレート等が挙げられ、中でもトリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等が好適である。又、これらは１種又は２種以上併用して用いられる。 The polyfunctional unsaturated monomer (a3) is not particularly limited. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trime Roll propane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, glycerin methacrylate acrylate, tris (meth) acryloyloxyphosphate, glycerin di (meth) acrylate, diallyl terephthalate, tetra Examples include allyloxyethane, divinylbenzene, tri (meth) allyl isocyanurate, and tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1 , 4-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate Neopentyl glycol di (meth) acrylate and the like. These may be used alone or in combination of two or more.
更に、その他の不飽和単量体（ａ４）としては、特に限定されず、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート等の炭素数１〜３のアルキル基を有する（メタ）アクリル酸アルキルエステルや、トリデシル（メタ）アクリレート、イソトリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート等の炭素数１３以上のアルキル基を有する（メタ）アクリル酸アルキルエステル、ジメチルアミノエチル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、アクリロニトリル、メタクリロニトリル、スチレン、α−メチルスチレン、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、アルキルビニルエーテル等が挙げられる。 Furthermore, it does not specifically limit as another unsaturated monomer (a4), For example, carbon number, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, etc. (Meth) acrylic acid alkyl ester having 1 to 3 alkyl groups, (meth) acrylic acid having 13 or more alkyl groups such as tridecyl (meth) acrylate, isotridecyl (meth) acrylate, tetradecyl (meth) acrylate, etc. Alkyl ester, dimethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, acrylonitrile, methacrylonitrile, styrene, α-methyls Ren, vinyl acetate, vinyl propionate, vinyl chloride, alkyl vinyl ether.
更に、不飽和単量体（ａ４）として、上記の他に、カルボキシル基含有不飽和単量体（ａ２）と反応する単量体、互いに反応し得る単量体や自己架橋可能な官能基をもつ単量体等、例えば水酸基含有単量体、エポキシ基含有単量体、アルコキシシリル基含有単量体、アミド基やメチロール基、カルボニル基を含有する単量体等を用いてもよい。 Furthermore, as the unsaturated monomer (a4), in addition to the above, a monomer that reacts with the carboxyl group-containing unsaturated monomer (a2), a monomer that can react with each other, and a self-crosslinkable functional group. For example, a monomer containing a hydroxyl group, a monomer containing an epoxy group, a monomer containing an alkoxysilyl group, a monomer containing an amide group, a methylol group, or a carbonyl group may be used.
水酸基含有単量体としては、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等が挙げられる。
エポキシ基含有単量体としては、グリシジル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
アルコキシシリル基含有単量体としては、例えばβ−（メタ）アクリロキシエチルトリメトキシシラン、β−（メタ）アクリロキシエチルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルジメチルメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルジメチルエトキシシラン、γ−（メタ）アクリロキシプロピルトリクロロシラン、γ−（メタ）アクリロキシプロピルメチルジクロロシラン、γ−（メタ）アクリロキシプロピルジメチルクロロシラン、γ−（メタ）アクリロキシプロピルトリプロピオキシシラン、γ−（メタ）アクリロキシプロピルメチルジプロピオキシシラン、γ−（メタ）アクリロキシプロピルトリブトキシシラン、（メタ）アクリロキシブチルトリメトキシシラン、（メタ）アクリロキシペンチルトリメトキシシラン、（メタ）アクリロキシヘキシルトリメトキシシラン、（メタ）アクリロキシヘキシルトリエトキシシラン、（メタ）アクリロキシオクチルトリメトキシシラン、（メタ）アクリロキシデシルトリメトキシシラン、（メタ）アクリロキシドデシルトリメトキシシラン、（メタ）アクリロキシオクタデシルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリポロポキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、ビニルメチルジプロポキシシラン等が挙げられる。 Examples of the alkoxysilyl group-containing monomer include β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- ( (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) ) Acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyldimethylchlorosilane, γ- (meth) acryloxypropyl Tripropio Sisilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxypropyltributoxysilane, (meth) acryloxybutyltrimethoxysilane, (meth) acryloxypentyltrimethoxysilane, (meta ) Acryloxyhexyltrimethoxysilane, (meth) acryloxyhexyltriethoxysilane, (meth) acryloxyoctyltrimethoxysilane, (meth) acryloxydecyltrimethoxysilane, (meth) acryloxydecyltrimethoxysilane, (meth) ) Acryloxyoctadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripolopoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropo Shishiran, and the like.
アミド基やメチロール基、カルボニル基を含有する単量体としては、例えばアクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、ブトキシＮ−メチロールアクリルアミド、ダイアセトンアクリルアミド、２−（アセトアセトキシ）エチル（メタ）アクリレート、アリルアセトアセテート等が挙げられる。 Examples of monomers containing an amide group, a methylol group, or a carbonyl group include acrylamide, methacrylamide, N-methylol acrylamide, butoxy N-methylol acrylamide, diacetone acrylamide, 2- (acetoacetoxy) ethyl (meth) acrylate, Examples include allyl acetoacetate.
本発明において、上記（メタ）アクリル酸アルキルエステル（ａ１）、カルボキシル基含有不飽和単量体（ａ２）、多官能性不飽和単量体（ａ３）、その他の不飽和単量体（ａ４）の含有割合としては、（メタ）アクリル酸アルキルエステル（ａ１）が５０〜９９．８重量％、カルボキシル基含有不飽和単量体（ａ２）が０．１〜２０重量％、多官能性不飽和単量体（ａ３）が０．１〜２０重量％、その他の不飽和単量体（ａ４）が０〜４９．８重量％であり、好ましくは（メタ）アクリル酸アルキルエステル（ａ１）が５５〜９９重量％、カルボキシル基含有不飽和単量体（ａ２）が０．５〜１５重量％、多官能性不飽和単量体（ａ３）が０．５〜１５重量％、その他の不飽和単量体（ａ４）が０〜４４重量％であり、更に好ましくは（メタ）アクリル酸アルキルエステル（ａ１）が６０〜９８重量％、カルボキシル基含有不飽和単量体（ａ２）が１〜１０重量％、多官能性不飽和単量体（ａ３）が１〜１０重量％、その他の不飽和単量体（ａ４）が０〜３８重量％である。 In the present invention, the above (meth) acrylic acid alkyl ester (a1), carboxyl group-containing unsaturated monomer (a2), polyfunctional unsaturated monomer (a3), other unsaturated monomer (a4) The content ratio of (meth) acrylic acid alkyl ester (a1) is 50 to 99.8% by weight, carboxyl group-containing unsaturated monomer (a2) is 0.1 to 20% by weight, and polyfunctional unsaturated. The monomer (a3) is 0.1 to 20% by weight, the other unsaturated monomer (a4) is 0 to 49.8% by weight, and preferably the (meth) acrylic acid alkyl ester (a1) is 55%. ~ 99 wt%, carboxyl group-containing unsaturated monomer (a2) 0.5 to 15 wt%, polyfunctional unsaturated monomer (a3) 0.5 to 15 wt%, other unsaturated monomers The monomer (a4) is 0 to 44% by weight, more preferably (medium ) 60-98 wt% of acrylic acid alkyl ester (a1), 1-10 wt% of carboxyl group-containing unsaturated monomer (a2), 1-10 wt% of polyfunctional unsaturated monomer (a3) The other unsaturated monomer (a4) is 0 to 38% by weight.
（メタ）アクリル酸アルキルエステル（ａ１）が５０重量％未満では充分な接着力、タックが得られず、９９．８重量％を越えるとカルボキシル基含有不飽和単量体（ａ２）や多官能性不飽和単量体（ａ３）が少量となり充分な再剥離性が得られない。カルボキシル基含有不飽和単量体（ａ２）が０．１重量％未満では重合安定性や機械安定性が低下するとともに再剥離性が不充分となり、２０重量％を越えるとエマルジョンの粘度が上昇し取り扱いが悪くなり、又接着力、タックも低下することとなる。多官能性不飽和単量体（ａ３）が０．１重量％未満では接着力の経時上昇が大きくなり、耐剥離性も低下することとなり、２０重量％を越えると糊残りが大きくなったり、重合時の安定性が低下することとなる。その他の不飽和単量体（ａ４）が４９．８重量％を越えると接着力、タックが低下し好ましくない。 When the (meth) acrylic acid alkyl ester (a1) is less than 50% by weight, sufficient adhesive strength and tack cannot be obtained, and when it exceeds 99.8% by weight, the carboxyl group-containing unsaturated monomer (a2) and polyfunctionality are obtained. The amount of the unsaturated monomer (a3) becomes small and sufficient removability cannot be obtained. When the carboxyl group-containing unsaturated monomer (a2) is less than 0.1% by weight, the polymerization stability and mechanical stability are lowered and the removability is insufficient, and when it exceeds 20% by weight, the viscosity of the emulsion is increased. The handling becomes worse and the adhesive strength and tack are also lowered. If the polyfunctional unsaturated monomer (a3) is less than 0.1% by weight, the increase in adhesive strength with time will increase, and the peel resistance will also decrease. If it exceeds 20% by weight, the adhesive residue will increase, Stability at the time of polymerization will decrease. If the other unsaturated monomer (a4) exceeds 49.8% by weight, the adhesive strength and tack are lowered, which is not preferable.
本発明では、上記（メタ）アクリル酸アルキルエステル（ａ１）、カルボキシル基含有不飽和単量体（ａ２）、多官能性不飽和単量体（ａ３）、その他の不飽和単量体（ａ４）の単量体混合物を用いて、乳化重合させてエマルジョン［Ａ］を得るわけであるが、かかる乳化重合においてはアニオン型反応性乳化剤の存在下に行うことが必要であり、かかるアニオン型反応性乳化剤を用いることにより、重合を安定に行うことができ、かつ基材密着性や再剥離性が良好となり、本発明の効果を顕著に発揮する。 In the present invention, the above (meth) acrylic acid alkyl ester (a1), carboxyl group-containing unsaturated monomer (a2), polyfunctional unsaturated monomer (a3), other unsaturated monomer (a4) In this emulsion polymerization, it is necessary to carry out in the presence of an anionic reactive emulsifier, and such an anionic reactivity is obtained. By using an emulsifier, the polymerization can be performed stably, the substrate adhesion and removability are improved, and the effects of the present invention are remarkably exhibited.
かかるアニオン型反応性乳化剤としては、アニオン型であって、かつ反応性を有する乳化剤であれば特に限定されないが、例えば、下記一般式（１）〜（１１）のような構造をもつものが挙げられる。 Such an anionic reactive emulsifier is not particularly limited as long as it is an anionic emulsifier and has a reactivity, and examples thereof include those having the structures of the following general formulas (1) to (11). It is done.
〔ここで、一般式（１）〜（１１）において、Ｒ１はアルキル基、Ｒ２は水素又はメチル基、Ｒ３はアルキレン基、ｎは１以上の整数、ｍ、ｌは１以上の整数（ｍ＋ｌ＝３）、ＸはＳＯ３ＮＨ４、ＳＯ３Ｎａのいずれかである。〕 [In the general formulas (1) to (11), R 1 is an alkyl group, R 2 is hydrogen or a methyl group, R 3 is an alkylene group, n is an integer of 1 or more, and m and l are integers of 1 or more. (M + 1 = 3), X is either SO 3 NH 4 or SO 3 Na. ]
上記乳化剤として具体的には、「アデカリアソープＳＥ−２０Ｎ」、「アデカリアソープＳＥ−１０Ｎ」、「アデカリアソープＰＰ−７０」、「アデカリアソープＰＰ−７１０」、「アデカリアソープＳＲ−１０」、「アデカリアソープＳＲ−２０」〔以上、旭電化工業社製〕、「エレミノールＪＳ−２」、「エレミノールＲＳ−３０」〔以上、三洋化成工業社製〕、「ラテムルＳ−１８０Ａ」、「ラテムルＳ−１８０」、「ラテムルＰＤ−１０４」〔以上、花王社製〕、「アクアロンＢＣ−０５」、「アクアロンＢＣ−１０」、「アクアロンＢＣ−２０」、「アクアロンＨＳ−０５」、「アクアロンＨＳ−１０」、「アクアロンＨＳ−２０」、「ニューフロンティアＳ−５１０」、「アクアロンＫＨ−０５」、「アクアロンＫＨ−１０」〔以上、第一工業製薬社製〕、「フォスフィノ−ルＴＸ」〔東邦化学工業社製〕）等の市販品が挙げられる。 Specific examples of the emulsifier include “ADEKA rear soap SE-20N”, “ADEKA rear soap SE-10N”, “ADEKA rear soap PP-70”, “ADEKA rear soap PP-710”, and “ADEKA rear soap SR-”. "10", "Adekaria soap SR-20" (manufactured by Asahi Denka Kogyo Co., Ltd.), "Eleminol JS-2", "Eleminol RS-30" (manufactured by Sanyo Kasei Kogyo Co., Ltd.), "Latemul S-180A" “Latemul S-180”, “Latemul PD-104” (manufactured by Kao Corporation), “Aqualon BC-05”, “Aqualon BC-10”, “Aqualon BC-20”, “Aqualon HS-05”, “Aqualon HS-10”, “Aquaron HS-20”, “New Frontier S-510”, “Aquaron KH-05”, “Aquaron KH-10” [ On, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], "phosphino - Le TX" [manufactured by Toho Chemical Industry Co., Ltd.]) commercially available products, and the like.
上記乳化剤の中でも特に、アクリルとの反応が良好であり、エマルジョンの安定性がよく、再剥離性にも優れる点で、上記一般式（３）、（５）、（４）、（９）、（１０）で示される構造の乳化剤、即ちアルキルフェノール構造を有さないアニオン型反応性乳化剤、具体的には、「アデカリアソープＳＲ−１０」、「アデカリアソープＳＲ−２０」、「エレミノールＪＳ−２」、「エレミノールＲＳ−３０」、「ラテムルＳ−１８０Ａ」、「ラテムルＳ−１８０」、「ラテムルＰＤ−１０４」、「アクアロンＫＨ−０５」、「アクアロンＫＨ−１０」等が好適である。 Among the emulsifiers, in particular, the reaction with acrylic is good, the stability of the emulsion is good, and the removability is excellent, so that the general formulas (3), (5), (4), (9), The emulsifier having the structure represented by (10), that is, an anionic reactive emulsifier having no alkylphenol structure, specifically, “ADEKA rear soap SR-10”, “ADEKA rear soap SR-20”, “ELEMINOL JS-” 2 ”,“ Eleminol RS-30 ”,“ Latemul S-180A ”,“ Latemul S-180 ”,“ Latemul PD-104 ”,“ Aqualon KH-05 ”,“ Aqualon KH-10 ”and the like are suitable.
かかるアニオン型反応性乳化剤の使用量は、（ａ１）〜（ａ４）の単量体混合物１００重量部に対して、０．５〜１０重量部であることが好ましく、より好ましくは０．８〜７重量部、特に好ましくは１〜５重量部である。該乳化剤が０．５重量部未満では乳化重合が不安定となり、１０重量部を越えると未反応の乳化剤が多くなり基材密着性や被着体汚染の原因となり好ましくない。
尚、乳化剤は単量体混合物からなる乳化モノマー液に添加したり、予め重合缶に添加しておいたりしてもよく、又両者を併用してもよい。
The amount of the anionic reactive emulsifier used is preferably 0.5 to 10 parts by weight, more preferably 0.8 to 100 parts by weight with respect to 100 parts by weight of the monomer mixture (a1) to (a4). 7 parts by weight, particularly preferably 1 to 5 parts by weight. If the emulsifier is less than 0.5 parts by weight, the emulsion polymerization becomes unstable, and if it exceeds 10 parts by weight, the amount of unreacted emulsifier increases, which is not preferable because it causes substrate adhesion and adherend contamination.
In addition, an emulsifier may be added to the emulsion monomer liquid which consists of a monomer mixture, may be previously added to the superposition | polymerization can, and may use both together.
又、必要に応じて、反応性を有しないアニオン型乳化剤や、反応性を有しないノニオン型乳化剤或いはノニオン型反応性乳化剤を併用することもできる。
反応性を有しないアニオン型乳化剤としては、例えばアルキル硫酸エステル、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルホン酸塩、ポリオキシエチレンアルキル硫酸塩、ポリオキシエチレンアルキルリン酸エステル等が挙げられる。
If necessary, an anionic emulsifier having no reactivity, a nonionic emulsifier having no reactivity, or a nonionic reactive emulsifier can be used in combination.
Examples of the anionic emulsifier having no reactivity include alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl phosphates, and the like. .
反応性を有しないノニオン型乳化剤としては、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フェニルエーテル、オキシエチレン−オキシプロピレンブロックポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸等が挙げられる。 Examples of the nonionic emulsifier having no reactivity include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, oxyethylene-oxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene fatty acid and the like.
ノニオン型反応性乳化剤としては、例えば上記一般式（１）〜（１１）において、Ｘが水素に変更されたものが挙げられ、具体的には、「アデカリアソープＮＥ−１０」、「アデカリアソープＮＥ−２０」、「アデカリアソープＮＥ−３０」、「アデカリアソープＮＥ−４０」、「アデカリアソープＥＲ−１０」、「アデカリアソープＥＲ−２０」、「アデカリアソープＥＲ−３０」、「アデカリアソープＥＲ−４０」、〔以上、旭電化工業社製〕、「アクアロンＲＮ−１０」、「アクアロンＲＮ−２０」、「アクアロンＲＮ−３０」、「アクアロンＲＮ−５０」〔以上、第一工業製薬社製〕等の市販品が挙げられる。 Nonionic reactive emulsifiers include, for example, those in the above general formulas (1) to (11) in which X is changed to hydrogen. Specifically, “Adekalia soap NE-10”, “Adekalia” "SOPE NE-20", "ADEKA rear soap NE-30", "ADEKA rear soap NE-40", "ADEKA rear soap ER-10", "ADEKA rear soap ER-20", "ADEKA rear soap ER-30" , "Adekaria soap ER-40" [manufactured by Asahi Denka Kogyo Co., Ltd.], "AQUALON RN-10", "AQUALON RN-20", "AQUALON RN-30", "AQUALON RN-50" [above, Commercial products such as “Daiichi Kogyo Seiyaku Co., Ltd.”.
乳化重合を行うに当たっては重合開始剤を用いるが、かかる重合開始剤としては、特に制限されず、水溶性、油溶性のいずれのものも用いることが可能で、具体的には、アルキルパーオキサイド、ｔ−ブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、ｐ−メタンヒドロパーオキサイド、ラウロイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、ジクロルベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、３，３，５−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド、ジ−イソブチルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ｔ−ブチルパーオキシイソブチレート等の有機過酸化物、２，２’−アゾビスイソブチロニトリル、ジメチル−２，２’−アゾビスイソブチレート、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、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〕、各種レドックス系触媒（この場合酸化剤としては、過硫酸アンモニウム、過硫酸カリウム、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−メンタンハイドロパーオキサイド等が、還元剤としては亜硫酸ナトリウム、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用いられる。）等が挙げられ、これらの中でも過硫酸カリウム、過硫酸アンモニウム、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、ジメチル−２，２’−アゾビスイソブチレート、各種レドックス系触媒等が好適である。 In performing the emulsion polymerization, a polymerization initiator is used. However, the polymerization initiator is not particularly limited, and any of water-soluble and oil-soluble can be used. Specifically, an alkyl peroxide, t-Butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide , Dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone Peroxide, methylcyclohexa Organic peroxides such as N-peroxide, di-isobutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, t-butylperoxyisobutyrate, 2,2′-azobisisobutyronitrile, dimethyl- 2,2′-azobisisobutyrate, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, Ammonium persulfate, hydrogen peroxide, ammonium (amine) salt of 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (2-methylamidooxime) dihydrochloride, 2,2′-azobis ( 2-methylbutanamidooxime) dihydrochloride tetrahydrate, 2,2′-azobis {2-mes Ru-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] -propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], various Redox catalyst (in this case, as the oxidizing agent, ammonium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, etc. are used as reducing agents. And sodium sulfite, acidic sodium sulfite, Rongalite, ascorbic acid, etc. are used. Among them, potassium persulfate, ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′- Azobis (2-methylbutyronitrile), 2,2′-azobis ( 2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, various redox catalysts and the like are suitable.
重合開始剤の使用量は、（ａ１）〜（ａ４）の単量体混合物１００重量部に対して、０．０３〜５重量部、更には０．０５〜３重量部であることが好ましく、０．０３重量部未満では重合速度が遅くなり、５重量部を越えると耐剥離性が低下し好ましくない。 The amount of the polymerization initiator used is preferably 0.03 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, with respect to 100 parts by weight of the monomer mixture (a1) to (a4). If it is less than 0.03 parts by weight, the polymerization rate is slow, and if it exceeds 5 parts by weight, the peel resistance is lowered, which is not preferable.
尚、該重合開始剤は重合缶内に予め加えておいてもよいし、重合開始直前に加えてもよいし、必要に応じて重合途中に追加添加してもよい。又、（ａ１）〜（ａ４）の単量体混合物に予め添加したり、該単量体混合物からなる乳化液に添加してもよい。添加に当たっては重合開始剤を別途溶媒や上記単量体に溶解して添加したり、溶解した重合開始剤を更に乳化状にして添加してもよい。 The polymerization initiator may be added in advance to the polymerization can, may be added immediately before the start of polymerization, or may be added during the polymerization as necessary. Moreover, you may add to the monomer mixture of (a1)-(a4) previously, or may add to the emulsion liquid which consists of this monomer mixture. In addition, the polymerization initiator may be separately dissolved in a solvent or the above monomer and added, or the dissolved polymerization initiator may be further added in an emulsified form.
又、必要に応じて、重合時に、重合時のｐＨ調整のため、ｐＨ緩衝剤を併用してもよく、該ｐＨ緩衝剤の使用量は、（ａ１）〜（ａ４）の単量体混合物１００重量部に対して０．０１〜１０重量部、特には０．１〜３重量部であることが好ましい。
かかるｐＨ緩衝剤としては、ｐＨ緩衝作用を有するものであれば特に制限されないが、具体的には、炭酸水素ナトリウム、炭酸水素カリウム、リン酸一ナトリウム、リン酸一カリウム、リン酸二ナトリウム、リン酸三ナトリウム、酢酸ナトリウム、酢酸アンモニウム、蟻酸ナトリウム、ギ酸アンモニウム等が挙げられる。
Further, if necessary, a pH buffer may be used at the time of polymerization to adjust the pH at the time of polymerization. The amount of the pH buffer used is the monomer mixture 100 of (a1) to (a4). It is preferable that it is 0.01-10 weight part with respect to a weight part, especially 0.1-3 weight part.
The pH buffering agent is not particularly limited as long as it has a pH buffering action. Specifically, sodium bicarbonate, potassium bicarbonate, monosodium phosphate, monopotassium phosphate, disodium phosphate, phosphorus Examples thereof include trisodium acid, sodium acetate, ammonium acetate, sodium formate, and ammonium formate.
水の使用量は、（ａ１）〜（ａ４）の単量体混合物１００重量部に対して、２０〜４００重量部であることが好ましく、より好ましくは２５〜２００重量部、特に好ましくは３０〜１５０重量部である。水の使用量が２０重量部未満では得られる樹脂組成物が高粘度となり、又、重合安定性も低下することとなり、４００重量部を越えると得られる樹脂組成物の濃度が低くなり、被膜化する際の乾燥性が低下し好ましくない。 The amount of water used is preferably 20 to 400 parts by weight, more preferably 25 to 200 parts by weight, particularly preferably 30 to 100 parts by weight based on 100 parts by weight of the monomer mixture (a1) to (a4). 150 parts by weight. If the amount of water used is less than 20 parts by weight, the resulting resin composition will have a high viscosity and the polymerization stability will be reduced. If the amount exceeds 400 parts by weight, the resulting resin composition will have a low concentration and become a coating. This is not preferable because the drying property is reduced.
上記（ａ１）〜（ａ４）の単量体混合物をアニオン型反応性乳化剤の存在下に、上記開始剤により重合を行うのであるが、その方法としては、
（１）単量体混合物、乳化剤、水等の全量を仕込み、昇温し重合する。
（２）反応缶に水、乳化剤、単量体混合物の一部を仕込み、昇温し重合した後、残りの単量体混合物を滴下又は分割添加して重合を継続する。
（３）反応缶に水、乳化剤等を仕込んでおき昇温した後、単量体混合物を全量滴下又は分割添加して重合する。
等が挙げられるが、重合温度の制御が容易である点で、（２）、（３）の方法が好ましい。
The monomer mixture of (a1) to (a4) is polymerized with the initiator in the presence of an anionic reactive emulsifier.
(1) Charge the entire amount of monomer mixture, emulsifier, water, etc., and polymerize by heating.
(2) Water, an emulsifier, and a part of the monomer mixture are charged into a reaction can, polymerized by heating, and then the remaining monomer mixture is added dropwise or dividedly to continue the polymerization.
(3) Water, an emulsifier, etc. are charged into a reaction can and the temperature is raised, and then the entire monomer mixture is added dropwise or dividedly and polymerized.
However, the methods (2) and (3) are preferable in that the polymerization temperature can be easily controlled.
上記重合方法における重合条件としては、特に限定されないが、例えば、
（１）の方法では、通常４０〜１００℃程度の温度範囲が適当であり、昇温開始後１〜８時間程度反応を行う。
（２）の方法では、単量体混合物の１〜５０重量％を４０〜９０℃で０．１〜４時間重合した後、残りの単量体混合物を１〜５時間程度かけて滴下又は分割添加して、その後同温度で１〜３時間程度熟成する。
（３）の方法では、重合缶に水を仕込み、４０〜９０℃に昇温し、単量体混合物を２〜５時間程度かけて滴下又は分割添加し、その後同温度で１〜３時間程度熟成する。
The polymerization conditions in the polymerization method are not particularly limited.
In the method (1), a temperature range of about 40 to 100 ° C. is appropriate, and the reaction is carried out for about 1 to 8 hours after the start of temperature increase.
In the method (2), 1 to 50% by weight of the monomer mixture is polymerized at 40 to 90 ° C. for 0.1 to 4 hours, and then the remaining monomer mixture is dropped or divided over about 1 to 5 hours. After that, it is aged for about 1 to 3 hours at the same temperature.
In the method (3), water is charged into a polymerization can, heated to 40 to 90 ° C., and the monomer mixture is dropped or added over about 2 to 5 hours, and then at the same temperature for about 1 to 3 hours. Mature.
上記重合方法において、単量体混合物は、乳化剤（又は乳化剤の一部）を単量体混合物に溶解しておくか、又は、予めＯ／Ｗ型の乳化液の状態としておいたほうが重合安定性の点で好ましい。
乳化液の調整方法としては、特に限定されないが、水に乳化剤を溶解した後上記（ａ１）〜（ａ４）を仕込み、この混合液を撹拌乳化する方法、或いは水に乳化剤を溶解した後撹拌しながら上記（ａ１）〜（ａ４）を仕込む方法等が挙げられる。
In the above polymerization method, the monomer mixture is preferably polymerized by dissolving the emulsifier (or part of the emulsifier) in the monomer mixture or by preliminarily setting it as an O / W type emulsion. This is preferable.
The method for adjusting the emulsified liquid is not particularly limited, but the above-described (a1) to (a4) are prepared after dissolving the emulsifier in water, and the mixed liquid is stirred and emulsified, or the emulsifier is dissolved in water and then stirred. However, the method etc. which prepare said (a1)-(a4) are mentioned.
上記乳化液の乳化の際の撹拌は、各成分を混合し、ホモディスパー、パドル翼等の撹拌翼を取り付けた撹拌装置を用いて行うことができる。
乳化時の温度は、乳化中に混合物が反応しない程度の温度であれば問題なく、通常５〜６０℃程度が適当である。
Agitation at the time of emulsification of the emulsion can be carried out using a stirring device in which the components are mixed and a stirring blade such as a homodisper or paddle blade is attached.
There is no problem as long as the temperature during emulsification is such that the mixture does not react during emulsification.
かくしてエマルジョン［Ａ］が得られるが、本発明においては、かかるエマルジョン［Ａ］のゲル分率が７０重量％以上であることが好ましく、更に７５重量％以上、特には８０重量％以上が好ましい。かかるゲル分率が７０重量％未満では糊残りが多く耐汚染性が不良となり、又経時での接着力上昇が大きくなり好ましくない。 Thus, an emulsion [A] is obtained. In the present invention, the gel fraction of the emulsion [A] is preferably 70% by weight or more, more preferably 75% by weight or more, and particularly preferably 80% by weight or more. If the gel fraction is less than 70% by weight, the amount of adhesive residue is large and the stain resistance is poor, and the increase in adhesive strength with time is unfavorable.
かかるエマルジョン［Ａ］のゲル分率を７０％以上に調整する方法としては、特に限定されないが、多官能性不飽和単量体や自己架橋性官能基を有する不飽和単量体（加水分解性シリル基含有単量体やメチロール基含有単量体等）を共重合する方法や、互いに反応しうる官能基をもつ不飽和単量体を共重合する方法等が挙げられる。 The method for adjusting the gel fraction of the emulsion [A] to 70% or more is not particularly limited, but is a polyfunctional unsaturated monomer or an unsaturated monomer having a self-crosslinkable functional group (hydrolyzable). And a method of copolymerizing unsaturated monomers having functional groups capable of reacting with each other.
尚、エマルジョン［Ａ］のゲル分率とは、樹脂組成物の溶剤不溶解分の割合のことであり、エマルジョン［Ａ］の、４０℃で２４時間乾燥した１０μｍの塗膜において、トルエンに２０℃で２４時間浸漬し乾燥したときの、浸漬前の塗膜重量に対する浸漬後の残存塗膜重量の割合（％）として求められる。 The gel fraction of the emulsion [A] is the ratio of the solvent-insoluble component of the resin composition. In the 10 μm coating film of the emulsion [A] dried at 40 ° C. for 24 hours, It is calculated | required as a ratio (%) of the remaining coating-film weight after immersion with respect to the coating-film weight before immersion when immersed for 24 hours and drying.
又、得られたエマルジョン［Ａ］の粒子径については０．５μｍ以下、特には０．３μｍ以下の微粒子であることが基材密着性や接着力の経時安定性の点で好ましい。
更に、エマルジョン［Ａ］の樹脂分濃度は１０〜６５重量％、特には２０〜５５重量％であることが乾燥性、塗工性の点で好ましい。
In addition, the particle size of the obtained emulsion [A] is preferably 0.5 μm or less, particularly 0.3 μm or less in terms of adhesion to the substrate and stability over time of the adhesive force.
Furthermore, the resin concentration of the emulsion [A] is preferably 10 to 65% by weight, particularly 20 to 55% by weight from the viewpoint of drying property and coating property.
次に、本発明で用いられる架橋剤［Ｂ］としては、エマルジョン型オキサゾリン系化合物であることが必要であり、より長期的な耐汚染性が付与される点で最も好ましい。 Next, as a cross-linking agent used in the present invention [B] it is required to be an error Marujon type oxazoline compounds, most preferable because longer-term stain resistance is imparted.
オキサゾリン系化合物としては、例えば、エマルジョン型の「エポクロスＫ−２０１０Ｅ」、「エポクロスＫ−２０２０Ｅ」、「エポクロスＫ−２０３０」等が耐汚染性及び経時での接着力上昇の抑制効果が優れる点で好適である。
Is an oxazoline-based compound, for example, the d Marujon type "EPOCROS K-2010E", "EPOCROS K-2020E", "EPOCROS K-2030", etc. effect of suppressing adhesion increase in stain resistance and time Is preferable in that it is excellent .
上記架橋剤［Ｂ］の含有量は、上記エマルジョン［Ａ］の固形分１００重量部に対して、有効成分として０．０１〜３０重量部であることが好ましく、更には０．１〜２０重量部、特には０．５〜１０重量部であることが好ましい。かかる含有量が０．０１重量部未満では粒子間の架橋が不充分となり糊残りが大きく耐汚染性が不良となり、３０重量部を越えると未反応の架橋剤により被着体汚染の原因となり好ましくない。 The content of the cross-linking agent [B] is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight as an active ingredient with respect to 100 parts by weight of the solid content of the emulsion [A]. Parts, particularly 0.5 to 10 parts by weight. If the content is less than 0.01 parts by weight, the crosslinking between the particles is insufficient and the adhesive residue is large, resulting in poor stain resistance. If the content exceeds 30 parts by weight, the unreacted crosslinking agent causes contamination of the adherend. Absent.
又、必要に応じて更に、粘着付与剤（例えばロジン系、ロジンエステル系、ポリテルペン樹脂、クロマン−インデン樹脂、石油系樹脂及びテルペンフェノール系樹脂等）、可塑剤（例えば液状ポリブテン、鉱油、ラノリン、液状ポリイソプレン及び液状ポリアクリレート等）、防腐・防黴剤、防錆剤、凍結融解安定剤、可塑剤、高沸点溶剤、顔料、着色剤、充填剤（亜鉛華、チタン白、炭酸カルシウム、クレー等）、金属粉末、消泡剤、増粘剤、接着力コントロール剤等を適宜添加したり、又、上記の乳化重合の重合前や重合途中に添加したりすることもできる。 Further, if necessary, a tackifier (for example, rosin, rosin ester, polyterpene resin, chroman-indene resin, petroleum resin and terpene phenol resin), plasticizer (for example, liquid polybutene, mineral oil, lanolin, Liquid polyisoprene and liquid polyacrylate, etc.), antiseptic / antifungal agent, rust preventive agent, freeze-thaw stabilizer, plasticizer, high boiling point solvent, pigment, colorant, filler (zinc white, titanium white, calcium carbonate, clay) Etc.), a metal powder, an antifoaming agent, a thickener, an adhesive strength control agent, etc. can be added as appropriate, or can be added before or during the polymerization of the emulsion polymerization.
かくして本発明の再剥離型水性粘着剤組成物が得られるが、かかる再剥離型水性粘着剤組成物は、通常、基材シート等に塗布されて粘着シートや粘着テープ等として実用に供されることが多く、かかる粘着シートや粘着テープ等を製造するには、まず本発明の再剥離型水性粘着剤組成物をそのまま又は適当な濃度に調整し、シリコン処理等が施された基材の処理面に塗工したり、あるいは直接基材に塗工して、例えば８０〜１０５℃、５秒〜１０分間加熱処理等により乾燥させて粘着層を形成させることができる。
又、再剥離型水性粘着剤組成物を離型フイルムに塗布し乾燥した後、基材上に転写することもできる。
Thus, the re-peelable water-based pressure-sensitive adhesive composition of the present invention can be obtained, and such a re-peelable water-based pressure-sensitive adhesive composition is usually applied to a base sheet or the like and is practically used as a pressure-sensitive adhesive sheet or a pressure-sensitive adhesive tape. In many cases, such a pressure-sensitive adhesive sheet or pressure-sensitive adhesive tape is produced by first adjusting the re-peelable water-based pressure-sensitive adhesive composition of the present invention as it is or at an appropriate concentration, and treating the substrate subjected to silicon treatment or the like. The pressure-sensitive adhesive layer can be formed by coating on the surface or directly on the substrate and drying by, for example, heat treatment at 80 to 105 ° C. for 5 seconds to 10 minutes.
Alternatively, the re-peelable aqueous pressure-sensitive adhesive composition can be applied to a release film and dried, and then transferred onto a substrate.
かかる基材としては、特に限定されず、例えば、ポリ塩化ビニル、ポリブテン、ポリブタジエン、ポリウレタン、エチレン−酢酸ビニル共重合体、ポリエチレンテレフタレート、ポリエチレン、ポリピロピレン、エチレン−プロピレン共重合体、ポリメチルペンテン、ポリブチレンテレフタレート等のフイルムや金属箔、紙や不織布等の多孔性材料等が挙げられる。
基材の厚さは通常、１０〜３００μｍ、特には２０〜１００μｍが好ましく、かかる基材の片面又は両面に、上記の再剥離型水性粘着剤組成物からなる層を１〜１００μｍ、更には３〜５０μｍ、特には５〜３０μｍの厚さに設けて、シート状やテープ状等の形態とする。
Such a substrate is not particularly limited, and for example, polyvinyl chloride, polybutene, polybutadiene, polyurethane, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, poly Examples thereof include films such as butylene terephthalate, metal foils, and porous materials such as paper and nonwoven fabric.
The thickness of the substrate is usually preferably 10 to 300 μm, particularly preferably 20 to 100 μm. On one side or both sides of the substrate, a layer made of the above-described re-peelable aqueous pressure-sensitive adhesive composition is 1 to 100 μm, and further 3 It is provided in a thickness of ˜50 μm, particularly 5-30 μm, and forms such as a sheet shape or a tape shape.
本発明の再剥離型水性粘着剤組成物は、金属板、ガラス板、プラスチック板等の運搬、加工、切断等の際の傷防止や汚染防止等のための一時的な表面保護用或いは仮接着用の粘着テープ又はシートの粘着剤として用いられるものである。
例えば、被着体の表面を保護する時には充分な粘着力を有しており、運搬、加工、切断等の処理が行われた後には、粘着シート又は粘着テープ等を被着体から容易に剥離することができる。
The re-peelable water-based pressure-sensitive adhesive composition of the present invention is used for temporary surface protection or temporary adhesion to prevent scratches or contamination during transport, processing, cutting, etc. of metal plates, glass plates, plastic plates, etc. It is used as a pressure-sensitive adhesive tape or sheet pressure-sensitive adhesive.
For example, it has sufficient adhesive strength to protect the surface of the adherend, and after carrying out processing such as transportation, processing, cutting, etc., the adhesive sheet or adhesive tape can be easily peeled off from the adherend. can do.
かくして本発明の再剥離型粘着剤組成物は、炭素数４〜１２のアルキル基を含有する（メタ）アクリル酸アルキルエステル（ａ１）５０〜９９．８重量％、カルボキシル基含有不飽和単量体（ａ２）０．１〜２０重量％、多官能性不飽和単量体（ａ３）０．１〜２０重量％、その他の不飽和単量体（ａ４）０〜４９．８重量％を含む単量体混合物を、アニオン型反応性乳化剤の存在下に、乳化重合させて得られるエマルジョン［Ａ］と、架橋剤［Ｂ］とを含有してなり、架橋剤［Ｂ］がエマルジョン型オキサゾリン系化合物であるため、経時での接着力上昇が少なく、かつ、再剥離時における被着体への糊残りや貼り跡などの汚染が少ないといった耐汚染性に優れ、更に水性粘着剤組成物としての機械的安定性にも優れた効果を示すものである。
Thus, the re-peelable pressure-sensitive adhesive composition of the present invention comprises (meth) acrylic acid alkyl ester (a1) 50 to 99.8% by weight, carboxyl group-containing unsaturated monomer containing an alkyl group having 4 to 12 carbon atoms. (A2) 0.1 to 20% by weight, polyfunctional unsaturated monomer (a3) 0.1 to 20% by weight, other unsaturated monomer (a4) 0 to 49.8% by weight the dimer mixtures, in the presence of anionic reactive emulsifier, an emulsion [a] obtained by emulsion polymerization, the crosslinking agent [B] Ri and name contained, crosslinking agent [B] is an emulsion type oxazoline compound der because, less adhesion force increase with time, and is excellent in stain resistance, such contamination is small, such as adhesive residue and paste traces to the adherend upon re-peeling, as further aqueous pressure-sensitive adhesive composition It has an excellent effect on the mechanical stability of .
以下、実施例を挙げて本発明を具体的に説明する。
尚、実施例中「％」、「部」とあるのは、断りのない限り重量基準を意味する。
Hereinafter, the present invention will be specifically described with reference to examples.
In the examples, “%” and “part” mean weight basis unless otherwise specified.
参考例１
ｎ−ブチルアクリレート（ａ１）６７．５部、アクリル酸（ａ２）１．５部、トリプロピレングリコールジアクリレート（ａ３）１．０部、メチルメタクリレート（ａ４）３０．０部、アニオン型反応性乳化剤（旭電化社製、「アデカリアソープＳＲ−１０」）２．０部、水４８．０部を混合撹拌し、単量体混合物からなる乳化液を得た。
次に、冷却管、撹拌翼を備えたフラスコに、アニオン型反応性乳化剤（旭電化社製、「アデカリアソープＳＲ−１０」）０．１５部とｐＨ緩衝剤としての第二リン酸ナトリウム０．３部及び水６７．５部を加え撹拌して溶解して、７５℃に昇温した後、上記乳化液の７．５部を添加した。更に、８０℃に昇温した後、３％過硫酸カリウム水溶液を１．３３部添加し、乳化重合を行い、その後１５分後に、乳化液の残り１４２．５部と３％過硫酸カリウム水溶液５．３３部を混合した混合液を３．５時間かけて滴下した。滴下終了後、８０℃に保持したまま２時間撹拌を続けた後、６０℃まで冷却し、１０％アンモニア水溶液２部を添加し、酸基を中和した。その後、５５℃まで冷却し、ターシャリーブチルハイドロパーオキサイド（日本油脂社製、「パーブチルＨ−６９」）の１０％水溶液０．５部と１０％亜硫酸水素ナトリウム水溶液０．５部をそれぞれ添加し、１５分間反応させた後、再度、ターシャリーブチルハイドロパーオキサイド（日本油脂社製、「パーブチルＨ−６９」）の１０％水溶液０．５部と１０％亜硫酸水素ナトリウム水溶液０．５部をそれぞれ添加し、１５分間反応させた。その後、３０℃まで冷却し、２００メッシュのナイロンメッシュでろ過し、１０％アンモニア水でｐＨを８に調整して、エマルジョン［Ａ］を得た（ゲル分率８１％、固形分４５％、粘度５０ｍＰａ・ｓ、粒子径０．１６μｍ）。
Reference example 1
n-butyl acrylate (a1) 67.5 parts, acrylic acid (a2) 1.5 parts, tripropylene glycol diacrylate (a3) 1.0 part, methyl methacrylate (a4) 30.0 parts, anionic reactive emulsifier (Asahi Denka Co., Ltd., “ADEKA rear soap SR-10”) 2.0 parts and 48.0 parts of water were mixed and stirred to obtain an emulsion composed of a monomer mixture.
Next, in a flask equipped with a cooling tube and a stirring blade, 0.15 part of an anionic reactive emulsifier (Adeka Soap SR-10 manufactured by Asahi Denka Co., Ltd.) and dibasic sodium phosphate 0 as a pH buffering agent were added. .3 parts and 67.5 parts of water were added and dissolved by stirring. After the temperature was raised to 75 ° C., 7.5 parts of the emulsion was added. Further, after the temperature was raised to 80 ° C., 1.33 parts of 3% potassium persulfate aqueous solution was added to carry out emulsion polymerization, and then 15 minutes later, the remaining 142.5 parts of the emulsion and 3% potassium persulfate aqueous solution 5 The mixed liquid in which 33 parts were mixed was dropped over 3.5 hours. After completion of the dropwise addition, stirring was continued for 2 hours while maintaining at 80 ° C., and then the mixture was cooled to 60 ° C. and 2 parts of 10% aqueous ammonia solution was added to neutralize the acid groups. Then, it cools to 55 degreeC and adds 0.5 part of 10% aqueous solution of tertiary butyl hydroperoxide (Nippon Yushi Co., Ltd. "Perbutyl H-69") and 0.5 part of 10% sodium hydrogensulfite aqueous solution, respectively. After reacting for 15 minutes, 0.5 parts of 10% aqueous solution of tertiary butyl hydroperoxide (manufactured by NOF Corporation, “Perbutyl H-69”) and 0.5 part of 10% aqueous sodium hydrogen sulfite solution are again added. Added and allowed to react for 15 minutes. Thereafter, it was cooled to 30 ° C., filtered through a 200 mesh nylon mesh, and adjusted to pH 8 with 10% aqueous ammonia to obtain an emulsion [A] (gel fraction 81%, solid content 45%, viscosity) 50 mPa · s, particle size 0.16 μm).
得られたエマルジョン［Ａ］について以下の評価を行った。
（粗粒子量）
上記の如くエマルジョン［Ａ］を得る際の、２００ｍｅｓｈのナイロンメッシュで濾過したものの濾過残分を１０５℃で１時間乾燥して得られた粗粒子について、その重量をエマルジョン１００ｇに対する重量（ｍｇ）で評価した。
The following evaluation was performed about the obtained emulsion [A].
(Rough particle amount)
As described above, when the emulsion [A] is obtained by filtering the residue with 200 mesh nylon mesh dried at 105 ° C. for 1 hour, the weight is expressed in terms of weight (mg) with respect to 100 g of the emulsion. evaluated.
更に、得られたエマルジョン［Ａ］に、架橋剤として日本触媒社製の「エポクロスＷＳ−５００」をエマルジョンの固形分１００部に対して４．７８部（有効成分として１．９１部）を添加し、本発明の再剥離型水性粘着剤組成物を得た。
得られた再剥離型水性粘着剤組成物について、以下の評価を行った。
Furthermore, 4.78 parts (1.91 parts as an active ingredient) of “Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd. as a crosslinking agent with respect to 100 parts of the solid content of the emulsion was added to the obtained emulsion [A]. Then, the re-peelable water-based pressure-sensitive adhesive composition of the present invention was obtained.
The following evaluation was performed about the obtained re-peelable water-based pressure-sensitive adhesive composition.
（機械的安定性）
得られた再剥離型水性粘着剤組成物を５０ｇ採取し、マーロン試験機（日立工機社製、「Ｂ１３ＳＨ」）にて、２０ｋｇ×１０００ｒｐｍの条件で２０分間撹拌したものを、２００ｍｅｓｈのナイロンメッシュでろ過し、その残留粗粒子量より、機械安定性を以下の通り評価した。
○・・・水性粘着剤組成物５０ｇ中の粗粒子量が５ｍｇ未満
△・・・水性粘着剤組成物５０ｇ中の粗粒子量が５ｍｇ以上１５ｍｇ未満
×・・・水性粘着剤組成物５０ｇ中の粗粒子量が１５ｍｇ以上
(Mechanical stability)
50 g of the obtained re-peelable water-based pressure-sensitive adhesive composition was sampled and stirred for 20 minutes under the condition of 20 kg × 1000 rpm with a Marlon tester (manufactured by Hitachi Koki Co., Ltd., “B13SH”). A 200 mesh nylon mesh The mechanical stability was evaluated as follows from the amount of residual coarse particles.
○ ... The amount of coarse particles in 50 g of the aqueous pressure-sensitive adhesive composition is less than 5 mg. Δ ... The amount of coarse particles in 50 g of the water-based pressure-sensitive adhesive composition is 5 mg or more and less than 15 mg. Coarse particle amount is 15mg or more
（初期接着力）
得られた再剥離型水性粘着剤組成物を表面コロナ処理された６０μｍのポリエチレンフイルム上に乾燥後の厚みが１０μｍになるように塗布し、室温で１０分間、８０℃で１分間乾燥させた後、未処理のポリエチレンフイルムを貼り合わせて粘着シートを作製した。該粘着シートを、４０℃で３日間エージング処理した後、ＳＵＳ３０４ＢＡ板に２０℃、６５％ＲＨにて、２ｋｇローラーを２往復させて接着させてから３０分後に、ＪＩＳ Ｚ ０２３７の接着力の測定法に準じて１８０度剥離強度（ｇｆ／２５ｍｍ）を測定した。
(Initial adhesive strength)
The obtained re-peelable water-based pressure-sensitive adhesive composition was applied onto a 60 μm polyethylene film subjected to surface corona treatment so that the thickness after drying was 10 μm, and dried at room temperature for 10 minutes and at 80 ° C. for 1 minute. Then, an untreated polyethylene film was bonded to prepare an adhesive sheet. After the adhesive sheet was aged at 40 ° C. for 3 days, the adhesive strength of JIS Z 0237 was measured 30 minutes after the 2 kg roller was reciprocated twice at 20 ° C. and 65% RH on the SUS304BA plate. 180 degree peel strength (gf / 25 mm) was measured according to the method.
（再剥離性）
（１）経時後の接着力
得られた再剥離型水性粘着剤組成物を表面コロナ処理された６０μｍのポリエチレンフイルム上に乾燥後の厚みが１０μｍになるように塗布し、室温で１０分間、８０℃で１分間乾燥させた後、未処理のポリエチレンフイルムを貼り合わせて粘着シートを作製した。該粘着シートを、４０℃で３日間エージング処理した後、ＳＵＳ３０４ＢＡ板に２０℃、６５％ＲＨにて２ｋｇローラーを２往復させて接着させ、その後（ｉ）７０℃、７日間放置した後と、（ｉｉ）４０℃、９０％ＲＨ、７日間放置した後について、ＪＩＳ Ｚ ０２３７の接着力の測定法に準じて１８０度剥離強度（ｇｆ／２５ｍｍ）を測定した。
(Removability)
(1) Adhesive strength after time The obtained re-peelable water-based pressure-sensitive adhesive composition was applied on a 60 μm polyethylene film having been subjected to surface corona treatment so that the thickness after drying was 10 μm, and 80 minutes at room temperature for 80 minutes. After drying at a temperature of 1 ° C. for 1 minute, an untreated polyethylene film was bonded to prepare an adhesive sheet. After the aging treatment of the pressure-sensitive adhesive sheet at 40 ° C. for 3 days, the 2 kg roller was reciprocated twice at 20 ° C. and 65% RH on the SUS304BA plate, and then (i) left at 70 ° C. for 7 days; (Ii) After leaving at 40 ° C. and 90% RH for 7 days, 180 degree peel strength (gf / 25 mm) was measured according to the measurement method of adhesive strength of JIS Z 0237.
（２）経時後の耐汚染性
上記の（ｉ）７０℃、７日間放置した後と、（ｉｉ）４０℃、９０％ＲＨ、７日間放置した後の接着力を測定した後に、被着体表面の汚染度合いを目視観察し、耐汚染性を以下の通り評価した。
◎・・・汚染もなく、表面の艶変化も認められなかった
○・・・汚染は認められなかったが、わずかに貼り跡（表面の艶変化）が認められた
△・・・貼り跡が認められた
×・・・糊残りが認められた
(2) Contamination resistance after elapse of time After the above (i) standing at 70 ° C. for 7 days and (ii) measuring the adhesive strength after standing at 40 ° C., 90% RH for 7 days, the adherend The degree of contamination on the surface was visually observed, and the contamination resistance was evaluated as follows.
◎ ・ ・ ・ No contamination and no change in surface gloss ○ No contamination was observed, but slight marks (surface gloss change) were observed △ ・ ・ ・X: Adhesive residue was observed
参考例２〜１５、実施例１，２、比較例１〜４
表１〜５に示す如き配合に変更した以外は参考例１と同様に行い、エマルジョン［Ａ］を得、参考例１と同様に評価した。
更に、得られたエマルジョン［Ａ］に、表１〜５に示す通り架橋剤を添加し、再剥離型水性粘着剤組成物を得、得られた再剥離型水性粘着剤組成物について参考例１と同様の評価を行った。
参考例、実施例と比較例の評価結果を表６に示す。
Reference Examples 2 to 15 , Examples 1 and 2 and Comparative Examples 1 to 4
Except having changed to the mixing | blending as shown in Tables 1-5, it carried out like Reference Example 1 and obtained emulsion [A], and evaluated similarly to Reference Example 1.
Furthermore, the resulting emulsion [A], was added as a crosslinking agent shown in Table 1-5, to obtain a releasable aqueous pressure-sensitive adhesive composition, the releasable aqueous pressure-sensitive adhesive composition obtained in Reference Example 1 The same evaluation was performed.
Table 6 shows the evaluation results of the reference examples, examples, and comparative examples.
乳化剤：ＳＲ−１０（旭電化工業社製の「アデカリアソ−プＳＲ−１０」）
ＫＨ−１０（第一工業製薬社製の「アクアロンＫＨ−１０」）
ＥＲ−１０（旭電化工業社製の「アデカリアソープＥＲ−１０」）
架橋剤：ＷＳ−５００（日本触媒社製の「エポクロスＷＳ−５００」：有効成分４０％） Ｖ−０４（日清紡社製の「カルボジライトＶ−０４」：有効成分４０％） ＥＸ−３１３（ナガセケムテックス社製の「デナコールＥＸ−３１３」：有効成 分１００％）
ＰＺ−３３（日本触媒社製の「ケミタイトＰＺ−３３」：有効成分９９％以上） Ｋ−２０１０Ｅ（日本触媒社製の「エポクロスＫ−２０１０Ｅ」：有効成分 ４０％、テトラヒドロフラン不溶分８８％、テトラヒドロフラン可溶分の重量平 均分子量８２０００）
Emulsifier: SR-10 ("Adekaria soap SR-10" manufactured by Asahi Denka Kogyo Co., Ltd.)
KH-10 (“AQUALON KH-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
ER-10 (Adeka Soap ER-10 manufactured by Asahi Denka Kogyo Co., Ltd.)
Cross-linking agent: WS-500 (“Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd .: 40% active ingredient) V-04 (“Carbodilite V-04” manufactured by Nisshinbo Co., Ltd .: 40% active ingredient) EX-313 (Nagase Chem) "Denacol EX-313" manufactured by Tex Corporation: 100% effective component)
PZ-33 (“Chemite PZ-33” manufactured by Nippon Shokubai Co., Ltd .: effective component 99% or more) K-2010E (“Epocross K-2010E” manufactured by Nippon Shokubai Co., Ltd .: active component 40%, tetrahydrofuran insoluble content 88%, tetrahydrofuran Soluble weight average molecular weight 82000)
経時後の接着力の( )内の数値は初期接着力に対する割合（％）である。
The numerical value in () of the adhesive strength after time is the ratio (%) to the initial adhesive strength.
本発明の再剥離型水性粘着剤組成物は、炭素数４〜１２のアルキル基を含有する（メタ）アクリル酸アルキルエステル（ａ１）５０〜９９．８重量％、カルボキシル基含有不飽和単量体（ａ２）０．１〜２０重量％、多官能性不飽和単量体（ａ３）０．１〜２０重量％、その他の不飽和単量体（ａ４）０〜４９．８重量％を含む単量体混合物を、アニオン型反応性乳化剤の存在下に、乳化重合させて得られるエマルジョン［Ａ］と、架橋剤［Ｂ］とを含有してなり、架橋剤［Ｂ］がエマルジョン型オキサゾリン系化合物であるため、経時での接着力上昇が少なく、かつ、再剥離時における被着体への糊残りや貼り跡などの汚染が少ないといった耐汚染性に優れ、更に水性粘着剤組成物としての機械安定性にも優れた効果を示すものであり、金属板、ガラス板、プラスチック板等の運搬、加工、切断等の際の傷防止や汚染防止等のための一時的な表面保護用或いは仮接着用の粘着テープ又はシートの粘着剤として有用な再剥離型の水性粘着剤組成物として非常に有用である。
The re-peelable water-based pressure-sensitive adhesive composition of the present invention comprises (meth) acrylic acid alkyl ester (a1) 50 to 99.8% by weight, carboxyl group-containing unsaturated monomer containing an alkyl group having 4 to 12 carbon atoms. (A2) 0.1 to 20% by weight, polyfunctional unsaturated monomer (a3) 0.1 to 20% by weight, other unsaturated monomer (a4) 0 to 49.8% by weight the mer mixture, in the presence of anionic reactive emulsifier, an emulsion [a] obtained by emulsion polymerization, the crosslinking agent [B] Ri and name contained, crosslinking agent [B] is an emulsion type oxazoline compound der because, less adhesion force increase with time, and is excellent in stain resistance, such contamination is small, such as adhesive residue and paste traces to the adherend upon re-peeling, as further aqueous pressure-sensitive adhesive composition It has an excellent effect on the mechanical stability of Re-peeling useful as a pressure-sensitive adhesive tape or sheet for temporary surface protection or temporary adhesion to prevent scratches or contamination during transport, processing, cutting, etc. of plates, glass plates, plastic plates, etc. It is very useful as a water-based pressure-sensitive adhesive composition.
Claims (5)
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| DE602006018906D1 (en) | 2005-05-20 | 2011-01-27 | Nitto Denko Corp | ADHESIVE ADHESIVE, ADHESIVE ADHESIVE AND SURFACE PROTECTION FILM |
| JP5242020B2 (en) * | 2005-05-20 | 2013-07-24 | 日東電工株式会社 | Adhesive composition, adhesive sheet and surface protective film |
| JP5235273B2 (en) * | 2005-12-27 | 2013-07-10 | 日東電工株式会社 | Water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling and pressure-sensitive adhesive sheet |
| JP5497258B2 (en) * | 2007-07-23 | 2014-05-21 | リンテック株式会社 | Removable adhesive sheet |
| JP5349031B2 (en) * | 2008-12-17 | 2013-11-20 | 日本合成化学工業株式会社 | Peelable aqueous pressure-sensitive adhesive composition, peelable aqueous pressure-sensitive adhesive, and peelable pressure-sensitive adhesive member using the same |
| JP6023538B2 (en) * | 2011-10-19 | 2016-11-09 | 日東電工株式会社 | Water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling and pressure-sensitive adhesive sheet |
| JP6017217B2 (en) * | 2012-07-27 | 2016-10-26 | 日東電工株式会社 | Re-peeling water-dispersed acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and optical member |
| JP6484880B1 (en) * | 2018-09-27 | 2019-03-20 | サイデン化学株式会社 | Aqueous pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| EP4059967A4 (en) * | 2019-11-12 | 2023-01-25 | Nippon Shokubai Co., Ltd. | Emulsion composition and production method therefor |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171117A (en) * | 1991-12-24 | 1993-07-09 | Mitsui Toatsu Chem Inc | Tape for processing wafer |
| JPH09208910A (en) * | 1996-02-02 | 1997-08-12 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive and surface-protecting film formed by coating the same |
| JPH10114887A (en) * | 1996-10-14 | 1998-05-06 | Nitto Denko Corp | Re-releasable pressure-sensitive adhesive and adhesive sheet or the like coated therewith |
| JP2001040313A (en) * | 1999-07-28 | 2001-02-13 | Chuo Rika Kogyo Corp | Acrylic emulsion type pressure-sensitive adhesive and pressuere-sensitfive adhesive article |
| JP2001131512A (en) * | 1999-11-02 | 2001-05-15 | Nitto Denko Corp | Water dispersion type removable pressure-sensitive adhesive and adhesive sheets thereof |
| JP2002363521A (en) * | 2001-06-08 | 2002-12-18 | Nitto Denko Corp | Water-dispersion-type pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| JP2004107545A (en) * | 2002-09-20 | 2004-04-08 | Saiden Chemical Industry Co Ltd | Water-based adhesive composition for film base material |
| JP2004277601A (en) * | 2003-03-17 | 2004-10-07 | Nippon Synthetic Chem Ind Co Ltd:The | Re-releasable aqueous adhesive composition |
-
2003
- 2003-12-11 JP JP2003412673A patent/JP4547145B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171117A (en) * | 1991-12-24 | 1993-07-09 | Mitsui Toatsu Chem Inc | Tape for processing wafer |
| JPH09208910A (en) * | 1996-02-02 | 1997-08-12 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive and surface-protecting film formed by coating the same |
| JPH10114887A (en) * | 1996-10-14 | 1998-05-06 | Nitto Denko Corp | Re-releasable pressure-sensitive adhesive and adhesive sheet or the like coated therewith |
| JP2001040313A (en) * | 1999-07-28 | 2001-02-13 | Chuo Rika Kogyo Corp | Acrylic emulsion type pressure-sensitive adhesive and pressuere-sensitfive adhesive article |
| JP2001131512A (en) * | 1999-11-02 | 2001-05-15 | Nitto Denko Corp | Water dispersion type removable pressure-sensitive adhesive and adhesive sheets thereof |
| JP2002363521A (en) * | 2001-06-08 | 2002-12-18 | Nitto Denko Corp | Water-dispersion-type pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
| JP2004107545A (en) * | 2002-09-20 | 2004-04-08 | Saiden Chemical Industry Co Ltd | Water-based adhesive composition for film base material |
| JP2004277601A (en) * | 2003-03-17 | 2004-10-07 | Nippon Synthetic Chem Ind Co Ltd:The | Re-releasable aqueous adhesive composition |
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| JP2004256789A (en) | 2004-09-16 |
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