JP2004300366A - Aqueous pressure-sensitive adhesive composition and method for producing the same - Google Patents
Aqueous pressure-sensitive adhesive composition and method for producing the same Download PDFInfo
- Publication number
- JP2004300366A JP2004300366A JP2003097736A JP2003097736A JP2004300366A JP 2004300366 A JP2004300366 A JP 2004300366A JP 2003097736 A JP2003097736 A JP 2003097736A JP 2003097736 A JP2003097736 A JP 2003097736A JP 2004300366 A JP2004300366 A JP 2004300366A
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- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- adhesive composition
- meth
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 23
- 238000003860 storage Methods 0.000 claims abstract description 15
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000839 emulsion Substances 0.000 claims description 42
- -1 polyethylene Polymers 0.000 claims description 41
- 239000003995 emulsifying agent Substances 0.000 claims description 32
- 239000010410 layer Substances 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920006255 plastic film Polymers 0.000 claims description 6
- 239000002985 plastic film Substances 0.000 claims description 6
- 229920002799 BoPET Polymers 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 2
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 abstract description 16
- 238000004873 anchoring Methods 0.000 abstract description 14
- 238000002845 discoloration Methods 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 11
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 56
- 238000000034 method Methods 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 17
- 125000000129 anionic group Chemical group 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000344 soap Substances 0.000 description 10
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 9
- 241001566735 Archon Species 0.000 description 8
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 8
- 235000011613 Pinus brutia Nutrition 0.000 description 8
- 241000018646 Pinus brutia Species 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 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 7
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 150000003505 terpenes Chemical class 0.000 description 7
- 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 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 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
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000002087 whitening effect Effects 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
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-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
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- CCQJKEYNLSZZNO-UHFFFAOYSA-N 10-trimethoxysilyldecyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCCCOC(=O)C=C CCQJKEYNLSZZNO-UHFFFAOYSA-N 0.000 description 1
- PQSUQHLHEZHGPZ-UHFFFAOYSA-N 12-trimethoxysilyldodecyl prop-2-enoate Chemical compound CO[Si](CCCCCCCCCCCCOC(=O)C=C)(OC)OC PQSUQHLHEZHGPZ-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
- 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
- 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
- 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
- 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 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
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-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
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 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
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- WWSNKXVETXETTP-UHFFFAOYSA-N 3,3-dihydroxyprop-2-enoic acid Chemical compound OC(O)=CC(O)=O WWSNKXVETXETTP-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
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-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
- RRBONVXWAGQXDJ-UHFFFAOYSA-N 4-methoxybutyl 2-sulfanylacetate Chemical compound COCCCCOC(=O)CS RRBONVXWAGQXDJ-UHFFFAOYSA-N 0.000 description 1
- VIQGKXOVPDLASV-UHFFFAOYSA-N 4-methoxybutyl 2-sulfanylpropanoate Chemical compound COCCCCOC(=O)C(C)S VIQGKXOVPDLASV-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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Abstract
Description
【０００１】
【発明の属する技術分野】
ポリオレフィン等の低表面エネルギー被着体に対する接着力に優れ、かつ良好な耐変色性、耐水性、基材への投錨性、加工性を併せ持つ１液型の水性感圧性接着剤組成物とその製造方法に関する。
【０００２】
【従来の技術】
感圧性接着剤の使用分野は多岐にわたるが、特にポリオレフィン等への強粘着性、透明性、耐水性、裁断および打ち抜き加工性、耐変色性、基材への投錨性を要求されるプラスチックフィルムを表面基材とする用途には、たとえばアクリル樹脂溶液と架橋剤からなる２液架橋型溶剤系感圧性接着剤が広く使用されている。しかし、全世界的な環境保護の流れから、上記要求物性を求められる用途にも水系の感圧性接着剤が求められる様になっている。通常、水系感圧性接着剤は乳化重合により得られた水系アクリル樹脂に各種添加剤を加えて製造され、その製造工程から最終製品形態になるまで溶剤をほとんど使用することがないため環境保護、安全衛生面で優位性がある。しかし、上記要求物性に対して以下の問題があるため普及が進んでいないのが実状である。まず、水系感圧性接着剤でも水系アクリル樹脂と架橋剤の２液型のフィルム用に好適な粘着シートが開示されているが（特許文献１参照）、２液を使用するという煩雑性、２液混合後の可使時間の問題、架橋反応のための熟成時間、加熱エネルギーの問題があり、水系の大きな利点を無くしてしまうため１液型が好ましい。
【０００３】
また、１液型でも従来の水系感圧性接着剤の問題は以下になる。水系感圧性接着剤は親水性の界面活性剤（Ｅ）を使用するためポリオレフィンなどの低表面エネルギー被着体に対する接着力が溶剤系に較べ低いという欠点を有している。この接着力をあげるために粘着付与樹脂が使用されるが、この粘着付与樹脂は水に溶けないものが多いため、あらかじめ水性分散体としたものを水系アクリル樹脂に配合する方法が一般に用いられる。この方法で少しの効果は得られるが、アクリル樹脂と粘着付与樹脂が下し感圧性接着層中で均一に存在しないためポリエチレン被着体に対して１０Ｎ／２５ｍｍ以上の接着力を出すことは他の物性を犠牲にしないと難しかった。
【０００４】
かかる欠点を克服するために、水系アクリル樹脂を製造する際に粘着付与樹脂で変性し、アクリル樹脂中に均一に存在させる方法もある。例えば、エチレン性不飽和単量体に粘着付与樹脂を溶解させて乳化重合を行う方法が開示されている（特許文献２、３参照）。しかし、この方法では重合中に粘着付与樹脂を高濃度に含む２μｍ以上の粗大粒子が多量に発生したり、それが保存中に沈降したりする場合がある。この問題は、シードポリマーの存在下に粘着付与樹脂を溶解させたエチレン性不飽和単量体を乳化重合させる方法（特許文献４参照）、粘着付与樹脂を溶解させたエチレン性不飽和単量体を界面活性剤（Ｅ）の存在下１μｍ以下に微細乳化させてから重合する方法（特許文献５参照）で解決できるとする開示がある。
【０００５】
しかし、一方で開示された文献で使用される粘着付与樹脂は連鎖移動剤としても強く働くので、重合時に粘着付与樹脂を共存させるとアクリル樹脂の分子量が低下し、凝集力が低下し感圧性接着シートとしたあとの裁断または打ち抜き加工性が非常に悪くなるため、極性基含有単量体や架橋性単量体を多量に使用して凝集力の低下を防いでいる。しかし、特にプラスチックフィルム基材を用いた場合、エチレン性不飽和単量体１００重量部中に極性基含有単量体を３重量部を超えて用いると耐水性が悪くなり、また架橋性単量体を１重量部を超えて用いると、裁断または打ち抜き時、加工歯に感圧性接着層が引っ張られ感圧性接着層と基材層の界面での剥離が起こり（以下、投錨性が悪いと表記する）、トラブルの原因となる。
【０００６】
また、一方で開示された文献で使用される粘着付与樹脂はアクリル樹脂や界面活性剤（Ｅ）の共存下、熱時に変色するものが多く、特に透明のプラスチックフィルム基材を用いた場合に外観を損ねる。
【０００７】
【特許文献１】特開２００１−１７２５７８号公報
【特許文献２】特開昭５４−２３６４１号公報
【特許文献３】特開昭５８−１８５６６８号公報
【特許文献４】特公平０７−５７８６４号公報
【特許文献５】特開２００１−３４８５５１号公報
【０００８】
【発明が解決しようとする課題】
本発明の目的は、ポリオレフィン等の低表面エネルギー被着体に対する接着力に優れ、かつ良好な耐変色性、耐水性、基材への投錨性、加工性を併せ持つ１液型の水性感圧性接着剤組成物とその製造方法を提供することである。
【０００９】
【課題を解決するための手段】
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、ガードナーカラーが３以下の淡色固形樹脂（Ｔ）及びエチレン性不飽和単量体混合物（Ｍ）を含んでなる混合物（Ｙ）を、水中で界面活性剤（Ｅ）の存在下重合させた樹脂を含む水性感圧性接着剤組成物の不揮発分の１００℃〜１５０℃での貯蔵弾性率が常に１．５×１０４〜６×１０４の範囲であることを特徴とする水性感圧性接着剤組成物が、上記目的に合致することを見出し、本発明を完成した。
【００１０】
すなわち、本発明は、ガードナーカラーが３以下の淡色固形樹脂（Ｔ）、およびエチレン性不飽和単量体混合物（Ｍ）を含む混合物（Ｙ）を界面活性剤（Ｅ）の存在下に水中で重合してなる樹脂を含む水性感圧性接着剤組成物であって、前記組成物の不揮発分の１００℃〜１５０℃での貯蔵弾性率が常に１．５×１０４〜６×１０４ Ｐａの範囲であることを特徴とする水性感圧性接着剤組成物に関する。
【００１１】
また、本発明は、水性感圧性接着剤組成物（乾燥重量２０ｇ／ｍ２）を厚さ５０μｍのＰＥＴフィルム上に感圧性接着層として積層し、２ｍｍ厚のポリエチレン板に２３℃湿度５０％にて２ｋｇのロールを一往復させて接着させて、２４時間２３℃湿度５０％の環境下に放置後、２３℃湿度５０％の条件下で３００ｍｍ／分の速度、角度１８０度でポリエチレン板から剥離した時の力が１０Ｎ／２５ｍｍ以上であり、かつ剥離時に感圧性接着層が凝集破壊、またはポリエチレン板への転着を示さないものである上記水性感圧性接着剤組成物に関する。
【００１２】
また、本発明は、少なくともエチレン性不飽和単量体混合物（Ｍ）、及び淡色固形樹脂（Ｔ）を混合して混合物（Ｙ）を得る工程［１］、
前記混合物（Ｙ）と界面活性剤（Ｅ）と水とを混合し、強制乳化して０．４〜３．０μｍのメディアン径を有する乳化物（Ｚ）を得る工程［２］、
前記乳化物（Ｚ）をラジカル重合開始剤の存在下重合する工程［３］を含む上記水性感圧性接着剤組成物の製造方法に関する。
【００１３】
また、本発明は、工程［２］は、回転型連続乳化機で強制乳化する工程であって、回転型連続乳化機は、
円盤状の基盤部にスリットを有する環状の突起を備えた固定子と、円盤状の基盤部にスリットを有する環状の突起を備えた回転子とを備え、
前記固定子の環状の突起と前記回転子の突起とは、回転子の回転軸に対して同心円状に咬み合みあわされている上記水性感圧性接着剤組成物の製造方法に関する。
【００１４】
また、本発明は、基材上に、上記水性感圧性接着剤組成物を積層してなる感圧性接着シートに関する。
【００１５】
また、本発明は、基材がプラスチックフィルムであることを特徴とする上記感圧性接着シートに関する。
【００１６】
【発明の実施の形態】
以下、本発明について具体的に説明する。本発明で用いられるエチレン性不飽和単量体混合物（Ｍ）の成分には、アルキル基の炭素数が１〜１８の（メタ）アクリル酸エステルを主成分とするものであり、かかる（メタ）アクリル酸エステルとしては、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、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）アクリレート等、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、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、トリデシル（メタ）アクリレート、イソトリデシル（メタ）アクリレートが挙げられ、中でもメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレートが好適に用いられる。
【００１７】
又、エチレン性不飽和単量体混合物（Ｍ）の成分として、極性基含有単量体を含有することが好ましく、その極性基としてはカルボキシル基、水酸基、アミド基等が挙げられる。カルボキシル基含有単量体としては、アクリル酸、メタクリル酸、アクリル酸ダイマー、クロトン酸、イタコン酸、マレイン酸等が挙げられる。水酸基含有単量体としてはヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ジヒドロキシアクリレート、グリセロール（メタ）アクリレート等が挙げられる。アミド基含有単量体としては、（メタ）アクリルアミド、Ｎ−アルキル（メタ）アクリルアミド、Ｎ、Ｎ−ジアルキル（メタ）アクリルアミドが挙げられる。
【００１８】
このうちカルボキシル基含有単量体がエチレン性不飽和単量体混合物（Ｍ）１００重量部中０．１〜３重量部の範囲で用いられるのが耐水性と重合安定性を両立する点で好ましい。
【００１９】
又、エチレン性不飽和単量体混合物（Ｍ）の成分として、架橋性基を有する単量体を含有させることもできる。架橋性基としてはエポキシ基、アルコキシシリル基、メチロール基、アセトアセチル基等が挙げられる。その他に架橋性基を有する単量体として、エチレン性不飽和二重結合を２つ以上有する多官能性エチレン性不飽和単量体も挙げられる。
【００２０】
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。
【００２１】
アルコキシシリル基含有単量体としては、γ−（メタ）アクリロキシエチルトリメトキシシラン、γ−（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、γ−（メタ）アクリロキシブチルトリメトキシシラン、γ−（メタ）アクリロキシペンチルトリメトキシシラン、γ−（メタ）アクリロキシヘキシルトリメトキシシラン、γ−（メタ）アクリロキシヘキシルトリエトキシシラン、γ−（メタ）アクリロキシオクチルトリメトキシシラン、γ−（メタ）アクリロキシデシルトリメトキシシラン、γ−（メタ）アクリロキシドデシルトリメトキシシラン、γ−（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、ビニルトリピロポキシシラン、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。
【００２２】
メチロール基含有単量体としては、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が挙げられる。
【００２３】
アセトアセチル基含有単量体としては、ダイアセトン（メタ）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。
【００２４】
多官能性エチレン性不飽和単量体としては、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、アリル（メタ）アクリレートジアリルフタレート、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る。
【００２５】
上記架橋性基を有する単量体は必ずしも用いなくて構わないが、エチレン性不飽和単量体混合物（Ｍ）１００重量部中０〜１重量部の範囲で用いられるのが、ポリオレフィンへの接着力、プラスチックフィルム基材に対する投錨性の点で好ましい。
【００２６】
又、本発明では、必要に応じて上記架橋性基を有する単量体の官能基を架橋する目的で、架橋剤を併用してもよい。かかる架橋剤としては、例えば、イソシアネート系化合物、メラミン系化合物、アジリジン系化合物、ヒドラジン系化合物、エポキシ系化合物、オキサゾリン系化合物、カルボジイミド系化合物、金属錯体等の金属系化合物、アミノ基含有化合物等が挙げられる。これらのうち、２官能以上であり、かつ１液型で使用できるように、本発明の水性感圧性接着剤組成物に混合して４０℃で１ヶ月放置しても、粘度変化やゲル化などないものが好ましい。
【００２７】
又、本発明では、その他共重合可能な単量体を用いることも可能で、かかる共重合可能な単量体として、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、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）アクリレート等が挙げられる。
【００２８】
ここで、上記記載の（メタ）アクリレートとはメタクリレートまたはアクリレートのことを、（メタ）アクリルアミドとはメタクリルアミドまたはアクリルアミドのことを示す。
【００２９】
又、本発明では、公知の連鎖移動剤を必要に応じて重合中に使用することもできる。具体的には、ラウリルメルカプタン、ステアリルメルカプタン等の炭素数１２以上のアルキルメルカプタン、２−メルカプトオクタン酸エステル等のメルカプトエタノールとアルキル酸のエステル化物、チオグリコール酸オクチル、チオグリコール酸メトキシブチル等のチオグリコール酸誘導体、メルカプトプロピオン酸オクチル、メルカプトプロピオン酸メトキシブチル、メルカプトプロピオン酸トリデシルなどのメルカプトプロピオン酸誘導体などが用いられる。
【００３０】
上記エチレン性不飽和単量体混合物（Ｍ）において、（メタ）アクリル酸エステル、極性基含有単量体、架橋性基を有する単量体、及び共重合可能な単量体の含有割合は、（メタ）アクリル酸エステルが５０〜９９．９重量％、極性基含有単量体が０．１〜３重量％、架橋性基を有する単量体が０〜１重量％、共重合可能な単量体が０〜４９．９重量％であることが好ましい。
【００３１】
本発明に用いられるガードナーカラーが３以下の淡色固形樹脂（Ｔ）としては、エチレン性不飽和単量体混合物（Ｍ）に溶解又は分散するものであればよく、例えばアルコンＰ−７０、アルコンＰ−９０、アルコンＰ−１００、アルコンＰ−１１５、アルコンＰ−１２０、アルコンＰ−１４０、アルコンＭ−９０、アルコンＭ−１００、アルコンＭ−１１５、アルコンＭ−１３５等の水添石油樹脂、ＫＲ−１８４０、ＫＲ−１８４２等の水酸基含有水添石油樹脂、パインクリスタルＫＲ−８５、パインクリスタルＫＲ−６１２、パインクリスタルＫＲ−６１４、パインクリスタルＫＥ−６０４等の水添ロジン、パインクリスタルＫＥ−１００、パインクリスタルＫＥ−３１１、パインクリスタルＫＥ−３５９等の水添ロジンエステル、パインクリスタルＤ−６０１０等の水添ロジン含有ジオール、パインクリスタルＭ−１５００、パインクリスタルＭ−１５５０等の水添ロジン金属塩、パインクリスタルＫＥ−６０４等の高酸価水添ロジン、パインクリスタルＫＥ−６０４Ｂ等の高酸価水添ロジン酸（以上、荒川化学工業（株）製）、ＹＳレジンＰＸ１２５０、ＹＳレジンＰＸ１１５０、ＹＳレジンＰＸ１０００、ＹＳレジンＰＸ８００、ＹＳレジンＤ１０５、ＹＳレジンＤ１１５、ＹＳレジンＰＸ１１５０Ｎ、ＹＳレジンＡ８００等のテルペン樹脂、ＹＳレジンＴＯ１２５、ＹＳレジンＴＯ１１５、ＹＳレジンＴＯ１０５、ＹＳレジンＴＯ８５、ＹＳレジンＴＲ１０５等の芳香族変性テルペン樹脂、クリアロンＰ１２５、クリアロンＰ１１５、クリアロンＰ１０５、クリアロンＰ８５等の水添テルペン樹脂、クリアロンＭ１１５、クリアロンＭ１０５、クリアロンＫ１１０、クリアロンＫ１００、クリアロンＫ４０９０等の芳香族変性水添テルペン樹脂、ＹＳポリスターＴＨ１３０等の水添テルペンフェノール樹脂（以上、ヤスハラケミカル（株）製）、ＦＴＲ０１００、ＦＴＲ０１２０、ＦＴＲ０１４０等のα−メチルスチレン樹脂、ＦＴＲ２１２０、ＦＴＲ２１４０等のα−メチルスチレン／スチレン共重合系樹脂、ＦＴＲ６１００、ＦＴＲ６１１０、ＦＴＲ６１２５等のスチレン系モノマー／脂肪族系モノマー共重合系樹脂、ＦＴＲ７０８０、ＦＴＲ７１００、ＦＴＲ７１２５等のスチレン系モノマー／脂肪族系モノマー／α−メチルスチレン共重合系樹脂、ＦＴＲ８０８０、ＦＴＲ８１００、ＦＴＲ８１２０等のスチレン樹脂、ＦＭＲ０１５０等のスチレン系モノマー／芳香族系モノマー共重合系樹脂（以上、三井化学（株）製）、クイントンＰ１９５Ｎ等の脂肪族系炭化水素樹脂、クイントン１３２５、クイントン１３４５等の脂環族系炭化水素樹脂（以上、日本ゼオン（株）製）などが挙げられる。
【００３２】
このうち特に好ましくはガードナーカラーが１以下のものであり、さらに好ましくは、ロジン骨格またはテルペン骨格を有するものである。ここで、水添とは一部または全部の炭素炭素二重結合に水素を反応させ、炭素炭素一重結合に変性させることを示す。
【００３３】
ガードナーカラーが３を超えるものは、連鎖移動剤、重合遅延剤として強く働くものが多く、分子量の低下を招き、保持力や加工性の低下をもたらすものが多い。その問題解決のために極性基含有単量体、架橋性基を有する単量体を増やす方法が従来とられているが、ポリオレフィンへの接着力や基材への投錨性が悪くなるため好ましくない。同時に、ガードナーカラーが３を超えるものは感圧性接着シートとしたのちの熱時の変色が著しいという公知の問題点を併せ持つため好ましくない。つまり、ガードナーカラーが３以下の淡色固形樹脂（Ｔ）を使用することで、耐変色性、加工性、保持力、ポリオレフィンへの接着力を同時に満たす感圧性接着組成物を得ることが可能になる。また、淡色であっても常温で液状の樹脂は、保持力や加工性の低下をもたらすためそれのみで用いるのは好ましくないが、上記の淡色固形樹脂と併用されるならば使用しても構わない。
【００３４】
本発明では、上記エチレン性不飽和単量体混合物（Ｍ）と淡色固形樹脂（Ｔ）を配合し、混合物（Ｙ）を形成するが、かかる配合割合は、エチレン性不飽和単量体混合物（Ｍ）１００重量部に対して、淡色固形樹脂（Ｔ）が１〜５０重量部であることが好ましく、より好ましくは５．５〜４０重量部、特に好ましくは７〜３０重量部である。淡色固形樹脂（Ｔ）が１重量部未満では充分な接着性、特にポリオレフィンに対する接着性が得られず、５０重量部を越えると重合が不安定になり好ましくない。
【００３５】
エチレン性不飽和単量体混合物（Ｍ）と淡色固形樹脂（Ｔ）を含んでなる混合物（Ｙ）を、水媒体中で界面活性剤（Ｅ）を用いて乳化させるに当たり、用いられる界面活性剤（Ｅ）としては、各成分を水媒体中に乳化させ得る機能を持つものであれば特には限定されず公知のものが限定無く使用できる。例えば、エチレン性不飽和二重結合を有するイオン性又は非イオン性の反応性界面活性剤、エチレン性不飽和二重結合を有さないイオン性又は非イオン性の非反応性界面活性剤等が単独又は併用して用いられる。中でも、耐水性を考慮すれば、反応性界面活性剤を用いるほうが好ましい。
【００３６】
該反応性界面活性剤（Ｅ）として具体的には、アデカリアソープＳＥ−２０Ｎ（アニオン性）、アデカリアソープＳＥ−１０Ｎ（アニオン性）、アデカリアソープＮＥ−１０（ノニオン性）、アデカリアソープＮＥ−２０（ノニオン性）、アデカリアソープＮＥ−３０（ノニオン性）、アデカリアソープＮＥ−４０（ノニオン性）、アデカリアソープＳＤＸ−７３０（アニオン性）、アデカリアソープＳＤＸ−７３１（アニオン性）〔以上、旭電化（株）製〕、エレミノールＪＳ−２（アニオン性）、エレミノールＲＳ−３０（アニオン性）〔以上、三洋化成（株）製〕、ラテムルＳ−１８０Ａ（アニオン性）、ラテムルＳ−１８０（アニオン性）、ラテムルＰＤ−１０４（アニオン性）〔以上、花王（株）製〕、アクアロンＢＣ−０５（アニオン性）、アクアロンＢＣ−１０（アニオン性）、アクアロンＢＣ−２０（アニオン性）、アクアロンＫＨ−１０（アニオン性）、アクアロンＫＨ−２０（アニオン性）、アクアロンＨＳ−０５（アニオン性）、アクアロンＨＳ−１０（アニオン性）、アクアロンＨＳ−２０（アニオン性）、アクアロンＲＮ−１０（ノニオン性）、アクアロンＲＮ−２０（ノニオン性）、アクアロンＲＮ−３０（ノニオン性）、アクアロンＲＮ−５０（ノニオン性）、ニューフロンティアＳ−５１０（アニオン）〔以上、第一工業製薬（株）製〕、フォスフィノ−ルＴＸ（アニオン性）〔東邦化学工業（株）製〕）等の市販品が挙げられる。
【００３７】
界面活性剤（Ｅ）の配合量は、エチレン性不飽和単量体混合物（Ｍ）１００重量部に対して、０．５〜５重量部であることが好ましく、より好ましくは０．８〜４重量部、特に好ましくは１〜３重量部である。界面活性剤（Ｅ）が０．５重量部未満では重合時に凝集物などが発生しやすく、５重量部を越えると塗膜の耐水性が低下し好ましくない。尚、界面活性剤（Ｅ）は乳化液に添加する以外に、一部を予め反応缶に添加しておいてもよい。
【００３８】
水の使用量は、エチレン性不飽和単量体混合物（Ｍ）、淡色固形樹脂（Ｔ）、界面活性剤（Ｅ）及び水の合計量１００重量部に対して、２５〜５０重量部であることが好ましく、より好ましくは２５〜４５重量部である。水の使用量が２５重量部未満ではＯ／Ｗ型の乳化物ができない場合があり、またできても高粘度となり作業性が悪くなる。５０重量部を越えると乳化物の濃度が低くなり、後の水性感圧性接着剤組成物の濃度が下がり、感圧性接着シートとするときの乾燥エネルギーが多く必要になり好ましくない。
【００３９】
本発明の水性感圧性接着剤組成物はエチレン性不飽和単量体混合物（Ｍ）と淡色固形樹脂（Ｔ）を含んでなる混合物（Ｙ）を、水中で界面活性剤（Ｅ）を用いて、あらかじめＯ／Ｗ型に乳化させた乳化物（Ｚ）を重合して得られる。このとき乳化物（Ｚ）のメディアン径は、合成時に凝集物が出ない、もしくは水性感圧性接着剤組成物としたときに放置安定性が良ければどのような大きさでも構わないが、特にこの様な問題を生じない重合物を得るには、該乳化物（Ｚ）のメディアン径が０．４〜３．０μｍであることが好ましい。また、さらに好ましくは０．５〜２．０μｍ、特に好ましくは０．５５〜１．５μｍである。ここで、０．４μｍ未満の場合は、乳化物（Ｚ）の粘度が高くなりすぎることや、強制乳化に必要なエネルギーや時間が多くなり生産性が低下するので好ましくない。
【００４０】
ここで、本発明でいうメディアン径とは、水中での油滴径を動的光散乱法で測定した場合の、累積体積平均径で、例えば、日機装（株）製マイクロトラックＵＰＡ粒度分布計で測定された値のことを示す。
【００４１】
メディアン径が３．０μｍ以下である乳化物（Ｚ）を得る方法としては、通常市販されている乳化機が使用でき、回転型連続乳化機、コロイドミル型乳化機、高圧ホモジナイザー型乳化機、超音波処理型乳化機等の強制乳化機を使用することができるが、この中で回転型連続乳化機である回転子／固定子型高速回転連続型乳化機が、本発明範囲のメディアン径を有する乳化物（Ｚ）を得るのに適合し、またメンテナンス、単位時間あたりの処理量が多く好ましい。
【００４２】
中でも、円盤状の基盤部にスリットを有する環状の突起を備えた固定子と、円盤状の基盤部にスリットを有する環状の突起を備えた回転子とを備え、前記固定子の環状の突起と前記回転子の突起とは、回転子の回転軸に対して同心円状に咬み合みあわされて、固定子と回転子との間隔を保って設けられた構造を有する回転型連続乳化機を用い、該乳化機への供給物を回転子を回転させながら該スリットと該間隔とを通して中心部分から外周の方向に流動させることにより乳化物（Ｚ）を得る方法が好ましい。この様な機構を有する乳化機としては、具体的にキャビトロン（太平洋機工（株）製）、エバラマイルダー（太平洋機工（株）製）、ウルトラターラックス（ＩＫＡ製）、マルチシアー（ＳＩＬＶＥＲＳＯＮ製）が挙げられ、このうち特にキャビトロンが好ましい。
【００４３】
スリットは、該乳化機への供給物を中心部分から外周方向へ流動させるためのものであるから、突起を貫通するものであれば、その形状や数も、特に限定されるものではない。
【００４４】
また、固定子および回転子が有する環状の突起の個数は、特に限定なく、それぞれ１環以上であればよい。
【００４５】
以下、図面により上記のような回転子／固定子型高速回転連続型乳化機を用いた本発明の製造方法について詳しく説明する。
【００４６】
図１は本発明の製造方法に用いられる回転子／固定子型高速回転連続型乳化機の固定子の一例を示す斜視図、図２は本発明の製造方法に用いられる回転子／固定子型高速回転連続型乳化機の回転子の一例を示す斜視図、図３は本発明に用いる回転子／固定子型高速回転連続型乳化機の要部の一例を表した断面図、図４は図３のＡ−Ａ’断面を側面から見たときの固定子突起と回転子突起の組み合わせ状態を表した図である。
【００４７】
図１〜図４に示すように、回転子／固定子型高速回転連続型乳化機の固定子１は、中心に設置され、その中心に液入口２を備えている。固定子１の円盤状の基盤部には、固定子１と同心円で環状に並べられた突起３が１段又は２段以上の多段状に備えられており、従って、突起３同士の間隙には、円周溝４が形成されている。そして、突起３同士の間には複数のスリット５が形成されている。
【００４８】
この乳化機内の固定子１に対向する内壁の中心には駆動軸６が設置され、駆動装置に接続されて回転される。回転子７は、固定子１と平行で、かつ中心が揃うように駆動軸６の先端に固定されている。固定子１に対向する回転子７の円盤状の基盤部には、回転子７と同心円で環状に並べられた突起８が一段または２段以上の多段状に備わっている。従って、突起８同士の間隙には、固定子１と同様に、環状の溝９が形成されている。そして、突起８同士の間には複数のスリット１０が形成されている。
【００４９】
この固定子１と回転子７とは、固定子１の突起３と回転子７の突起８が僅かな間隙を保つように、咬み合わされた状態で使用に供される。
【００５０】
この乳化機の液入口部２に、少なくともエチレン性不飽和単量体混合物（Ｍ）、及び固形樹脂（Ｔ）を混合した混合物（Ｙ）と、界面活性剤（Ｅ）と水が同時に加えられるか、もしくはあらかじめ該混合物（Ｙ）と、界面活性剤（Ｅ）と水とを混合し予備乳化したものが供給され、これらからなる供給物は回転子７が回転すると、最も内側に位置する回転子７の突起８のスリット１０に入り、遠心力により該回転子７の突起８の外側から環状の溝９に吐出され、次いで最も内側に位置する固定子１の突起３のスリット５に入る。さらに、このスリット５に流入した混合物は、固定子１の環状の溝４に押し出される。
【００５１】
このようにして該供給物は、回転子７の回転により遠心力を受け、スリット内を液入口から吐出
口へと流動する。一方、回転子７と固定子１のスリットのずれにより混合物の遠心流れの封じ込めと開放が繰り返されて差圧が発生する。さらに、回転子７と固定子１の微少隙間で混合液に対し剪断力が働く。この中心から外周方向への流れと円周方向流れが直角に衝突し、それによって、強力な撹拌・破砕効果が発生し、これによりメディアン径が０．４〜３．０μｍとなった乳化物（Ｚ）が得られる。
【００５２】
この乳化機の回転子７の回転数は駆動軸に接続された駆動モーターで制御される。回転数が大きく周速度が大きいほど大きい遠心力と剪断力を受けて、該メディアン径が小さくなる。本発明のメディアン径にするには、回転子の再外周の周速度が３０ｍ／秒以上、更には３５ｍ／秒以上となる回転数にするのが好ましい。
【００５３】
上記回転子および固定子の対は、同一装置上に二対以上設置されていても構わない。
【００５４】
このような回転子／固定子型高速回転連続型乳化機を使用する場合、乳化物（Ｚ）の良好な流動性を維持するために、当該乳化機または該乳化機に接続する配管には加温および冷却のためのジャケットを設置することが好ましい。そして、乳化機内の温度は、供給物の温度、および、ジャケットによる温度調節効果と装置内での剪断により発生する熱量のバランスを取ることにより、一定温度に制御される。
【００５５】
かかる乳化機内の圧力は、乳化物（Ｚ）の装置内における蒸気圧と高速回転する回転子による吐出圧で決まる。また、得られた乳化物（Ｚ）は、取り出し口に自動圧力制御弁を設けて、内部圧を一定に保ちつつ、分散液を大気圧下に連続的に取り出すのが好ましい。
【００５６】
乳化時の温度は、乳化中に供給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。又、乳化液の通過（Ｐａｓｓ）回数は１〜３回程度が好ましい。３回を超えても良いが生産性が落ちる。
【００５７】
上記の乳化物（Ｚ）を調製後、乳化物（Ｚ）を重合開始剤の存在下で重合を行うのであるが、その方法としては、１．）乳化物（Ｚ）全量をそのまま昇温して重合する、２．）乳化物（Ｚ）の一部を昇温して重合を開始し、残りの乳化物（Ｚ）を滴下又は分割添加して重合を継続する、３．）反応缶に水、必要に応じて界面活性剤（Ｅ）を仕込んで昇温した後、乳化物（Ｚ）を全量滴下又は分割添加して重合する等が挙げられ、重合開始剤は反応缶、または滴下缶の両方もしくはどちらか一方に任意の割合で仕込んでも良く、また、別に開始剤のみを滴下または分割添加しても良い。この中で、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。
【００５８】
重合開始剤の使用量は、エチレン性不飽和単量体混合物（Ｍ）１００重量部に対して、０．０５〜５重量部であることが好ましく、更に好ましくは０．１〜３重量部である。重合開始剤が０．０５重量部未満では重合速度が遅くなり、５重量部を越えると樹脂の分子量が低くなり、保持力、加工性が低下し好ましくない。
【００５９】
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、イソブチルパーオキサイド、ラウロリルパーオキサイド、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、アゾビスイソブチロニトリル、ジメチルアゾジイソブチレート、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。）等が挙げられる。このうち水溶性のものが好適に用いられる。
【００６０】
尚、該重合開始剤は反応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、又、乳化の前のエチレン性不飽和単量体混合物（Ｍ）及び淡色固形樹脂（Ｔ）を含む混合物（Ｙ）に予め添加したり、該乳化後の微細乳化物（Ｚ）に添加したりしてもよい。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いし、カルボキシル基含有単量体を使用する場合は、この一部または全部をアンモニア、有機アミン、水酸化カリウム、水酸化ナトリウムなどの塩基性化合物で中和してもよい。
【００６１】
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、微細乳化物（Ｚ）の１〜５０重量％を４０〜９０℃で０．１〜４時間重合した後、残りの微細乳化物（Ｚ）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、水を微細乳化物（Ｚ）の５〜１００重量％となるように仕込み、４０〜９０℃に昇温し、微細乳化物（Ｚ）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。
【００６２】
上記のようにして得られた樹脂分散体は、そのメディアン径が、乳化物（Ｚ）のメディアン径の０．１倍〜０．５倍であることがポリオレフィン接着力、加工性の点で好ましい。
【００６３】
又、必要に応じて、消泡剤、粘度調製剤、ｐＨ調製剤、防腐・防黴剤、防錆剤、凍結融解安定剤、可塑剤、顔料、充填剤等を得られたエマルジョンに適宜添加したり、重合前や重合途中に添加したりすることができる。
【００６４】
本発明の水性感圧性接着剤組成物は、その不揮発分を８ｍｍ×８ｍｍ×１．５ｍｍの試験片をズリモードで、角振動数１Ｈｚで測定したときの１００℃〜１５０℃での貯蔵弾性率が常に１．５×１０４〜６×１０４Ｐａの範囲であることを特徴とする。貯蔵弾性率は、例えば、レオメトリック・サイエンティフィック・エフ・イー社製動的粘弾性測定装置ＲＤＡ−ＩＩＩで測定できる。
【００６５】
このうち特に好ましくは、常に１．７５×１０４〜５．５×１０４Ｐａの範囲の場合であり、さらには２×１０４〜５×１０４Ｐａの範囲の場合が特に好ましい。１．５×１０４Ｐａ未満であると加工性が悪くなり、感圧性接着シートとしたのち裁断する際に、裁断する歯に感圧性接着剤の一部が付着し易く、裁断機のメンテナンス回数が増える。これは同時に打ち抜き加工を受ける用途においては、感圧性接着層の切れが悪く、打ち抜いたラベルがカス上げの際にカスと一緒に持っていかれるといった問題が生じることとなる。６×１０４Ｐａを超えるとポリオレフィンへの接着力やプラスチックフィルム基材への投錨性が悪くなる。
【００６６】
また、本発明の水性感圧性接着剤組成物は、乾燥重量で２０ｇ／ｍ２を厚さ５０μｍのＰＥＴフィルム上に感圧性接着層として積層し、２ｍｍ厚のポリエチレン板に２３℃湿度５０％にて２ｋｇのロールを一往復させて接着させて、２４時間２３℃湿度５０％の環境下に放置後、２４時間経過後に２３℃湿度５０％の条件下で３００ｍｍ／分の速度、角度１８０度でポリエチレン板から剥離した時の力が１０Ｎ／２５ｍｍ以上であり、かつ剥離時に感圧性接着層が凝集破壊、またはポリエチレン板への転着を示さないものであることが好ましい。
【００６７】
感圧性接着シートの形態は、基材の片面または両面に、感圧性接着層を設けた、感圧性接着シートや感圧性接着テープなどの形態としたものであってもよいし、表面を離型処理した剥難ライナー上に、架橋構造物層を設けて、上記同様の形態とし、基材レスで使用されるものであってもよい。
【００６８】
基材としては、フィルム基材、紙基材、不織布基材等が使用できる。フィルム基材としては、ポリ塩化ビニルフィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリウレタンフィルム、ナイロンフィルム、トリアセチルセルロースフィルム、処理ポリオレフィンフィルム、未処理ポリオレフィンフィルム、ポリカーボネートフィルム等が挙げられる。紙基材としては、普通紙、コート紙、アート紙等が挙げられる。本発明の水性感圧性接着剤組成物は水性でありながらフィルム基材でも使用できることを特徴とし、特にフィルム基材でも水浸漬時の耐白化や熱時の耐変色性に優れ、外観を損ねない点で優れる特徴を有する。基材の厚みは１５〜１００μｍであるものが好ましい。また基材への粘着剤の塗工量は５〜１００μｍが好ましい。なお、本発明の感圧性接着剤を基材上に塗布するには、公知の塗工法で適宜塗工できる。
【００６９】
水性感圧性接着剤組成物の乾燥は、通常、８０〜１５０℃程度で、１〜２分間程度行う。２分以上でも構わないが、生産性が落ちる。
【００７０】
【実施例】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。また、実施例および比較例中に記載されたメディアン径は日機装（株）製マイクロトラックＵＰＡ粒度分布計で測定された累積体積平均径のことを示す。
【００７１】
実施例１：２−エチルヘキシルアクリレート７０部、エチルアクリレート１０部、メチルメタクリレート１２部、メチルアクリレート６部、アクリル酸２部、Ｎ−メチロールアクリルアミド０．１部のエチレン性不飽和単量体混合物（Ｍ）に淡色固形樹脂（Ｔ）としてパインクリスタルＫＥ−１００（水添ロジンエステル樹脂：荒川化学社製、ガードナーカラー１以下）１５部をあらかじめ溶解し混合物（Ｙ）を得た。該混合物（Ｙ）を、水４９．３部に界面活性剤アデカリアソ―プＳＥ−１０Ｎ（旭電化（株）製）２．５部を溶解した水溶液に加え、撹拌翼を用いて撹拌混合し予備乳化を行った。
【００７２】
次いで、回転子／固定子にスリット式ユニットを使用したキャビトロンＣＤ１０１０型（株式会社ユーロテック製）を用いて、回転数１１２００ｒｐｍ、回転子の最外周の周速度が４０ｍ／秒、圧力が０．１２ＭＰａ、処理量１０ｋｇ／分 の運転条件で２Ｐａｓｓ処理し乳化させて、油溶成分のメディアン径が０．７５μｍの乳化物（Ｚ）１５１．９部を得た。
【００７３】
又、別容器にて重合開始剤として過硫酸アンモニウム０．５部を水４．５部に溶解し、開始剤液を調製した。
【００７４】
次に、窒素導入管、コンデンサー、攪拌翼、温度計を備え付けた反応缶に水６９．０部、界面活性剤（Ｅ）としてアデカリアソ―プＳＥ−１０Ｎを０．２部仕込み、窒素を導入しながら昇温して内温が８０℃となったところで、上記開始剤液の２０％を反応缶に添加し、乳化物（Ｚ）及び残りの開始剤液をそれぞれ３．５時間かけて８０℃で滴下しながら重合を行い、更に６５℃で２時間重合を行って、不揮発分５０．０％、粘度１００ｍＰａ・ｓ、メディアン径０．１８μｍの樹脂分散体を得た。２５％アンモニア水でｐＨを７．５に調製した該樹脂分散体１００重量部に対しレベリング剤としてペレックスＯＴＰ（花王（株）製）を０．２５部、粘度調製剤のアデカノールＵＨ−４２０（旭電化（株）製）を０．５部添加し、良く攪拌して粘度３０００ｍＰａ・ｓの水性感圧性接着剤組成物を得た。
【００７５】
得られた水性感圧性接着剤組成物を用い下記の如く評価した。
【００７６】
該水性感圧性接着剤組成物を離型紙上に乾燥重量で２０ｇ／ｍ２塗工し１０５℃で１．５分間乾燥させた後、厚さ５０μｍのＰＥＴフィルムに貼り合わせ、２３℃湿度５０％の環境下で１０時間以上放置し水性感圧性接着剤組成物の不揮発分がＰＥＴフィルムと離型紙で挟まれた感圧性接着シートを得た。該感圧性接着シートを、縦１００ｍｍ×横２５ｍｍの短冊状にカッターで切断し接着力、保持力、熱時変色性、耐水白化性、投錨性試験の試験片とした。
【００７７】
（ポリオレフィンに対する接着力）上記試験片から離型紙を取り除き、２ｍｍ厚のポリエチレン板に２３℃湿度５０％にて２ｋｇのロールを一往復させて接着させて、２４時間２３℃湿度５０％の環境下に放置後、同環境でＪＩＳ Ｚ ０２３７の粘着力の測定法に準じて１８０度剥離強度を測定した。
【００７８】
（保持力）上記試験片から離型紙を取り除き、ステンレス板（ＳＵＳ３０４）の試験板に面積が２５ｍｍ×２５ｍｍになるように貼付け、４０℃湿度５０％の条件下にて１ｋｇの荷重をかけて、ＪＩＳ Ｚ ０２３７の保持力の測定法に準じて、７２０００秒後の該フィルムのズレ（ｍｍ）又はフィルムの落下時間（秒）を測定した。
【００７９】
（耐水性）上記試験片から離型紙を剥がし取り、２５℃のイオン交換水中に２４時間浸漬したあと、目視により透明性を評価した。
【００８０】
○：透明性が良好である
△：若干透明性が悪くなる
×：透明性が悪く実用上問題となるレベルである。
【００８１】
（熱時変色性）上記試験片から離型紙を取り除き、厚さ２ｍｍのガラス板に気泡が入らないように張り付け、１４０℃のオーブンで４８時間加熱した後の変色度合いを日本電色工業（株）製色差計ＳＺ−Σ８０を用い、ガラス板のみに対するΔＹＩ値を測定し判断した。
【００８２】
○：３未満
△：３以上５未満
×：５以上
（投錨性）上記試験片から離型紙を取り除き、感圧性接着面を親指で強くしごきＰＥＴ基材からの取れ具合を目視で確認し、判断した。
【００８３】
○：ＰＥＴ基材が露出しない
×：ＰＥＴ基材が一部露出する
（加工性）上記感圧性接着シートを縦１５０ｍｍ×横５０ｍｍに切り、５０枚重ねて断裁試験機（（株）ホリゾン 電動断裁機 ＰＣ−３９）で横方向に１０回連続して断裁した後の断裁試験機の刃および断裁面に付着する粘着剤の重量を秤量し判断した。
【００８４】
○：５０ｍｇ未満
×：５０ｍｇ以上
（貯蔵弾性率） 該水性感圧性接着剤組成物を離型紙上に乾燥重量で２０ｇ／ｍ２塗工し１０５℃で１．５分間乾燥させたものを２枚用意し、その感圧性接着面同士を貼付け、これを半分に切断し、切断されたそれぞれの片面の離型紙を剥がして、再度感圧性接着面同士を貼付けるという操作を繰り返して感圧性接着層を積層することで離型紙に挟まれた厚さ１．５ｍｍの貯蔵弾性率試験片を得た。これを８ｍｍ×８ｍｍにカットし、両面の離型紙を取り除いてレオメトリック・サイエンティフィック・エフ・イー社製動的粘弾性測定装置ＲＤＡ−ＩＩＩを使用して、ズリモードで、角振動数１Ｈｚで測定した。測定は−６０℃から２００℃まで１０℃／分の昇温速度で行い、そのうちの１００℃〜１５０℃の貯蔵弾性率を確認した。代表値として表１に１００℃と１５０℃の値を載せるが、１００℃と１５０℃の間に極大値や極小値はなく、全てのサンプルで１００℃から１５０℃へ向け値が下がる傾向にあった。従って、１００℃と１５０℃の値からその間の値は判断できる。
【００８５】
実施例２：実施例１において、パインクリスタルＫＥ−１００の代わりに、ＫＲ−１８４２（水酸基含有水添石油樹脂：荒川化学工業（株）製、ガードナーカラー１以下）を用いた以外は同様に行った。乳化物（Ｚ）のメディアン径は０．８０μｍとなり、そこから得られた樹脂分散体は不揮発分５０．０％、粘度９０ｍＰａ・ｓ、メディアン径０．１８μｍであった。得られた水性感圧性接着剤組成物について、実施例１と同様の評価を行った。
【００８６】
実施例３：実施例１において、パインクリスタルＫＥ−１００の代わりに、ＹＳレジンＤ１０５（テルペン樹脂：ヤスハラケミカル（株）製、ガードナーカラー１以下）を用い、キャビトロンでの処理を１ｐａｓｓとした以外は同様に行った。乳化物（Ｚ）のメディアン径は１．１２μｍとなり、そこから得られた樹脂分散体は不揮発分５０．０％、粘度８０ｍＰａ・ｓ、メディアン径０．１７μｍであった。得られた水性感圧性接着剤組成物について、実施例１と同様の評価を行った。
【００８７】
実施例４：実施例１においてパインクリスタルＫＥ−１００の代わりに、クリアロンＫ４０９０（芳香族変性水添テルペン樹脂：ヤスハラケミカル（株）製、ガードナーカラー１以下）を用い、エチレン性不飽和単量体混合物（Ｍ）にアセトアセトキシエチルメタクリレート（イーストマンケミカルジャパン（株）製）０．４部を追加した以外は同様に行った。乳化物（Ｚ）のメディアン径は０．７１μｍとなり、そこから得られた樹脂分散体は不揮発分５０．２％、粘度１２０ｍＰａ・ｓ、メディアン径０．１７μｍであった。得られた水性感圧性接着剤組成物について、実施例１と同様の評価を行った。
【００８８】
比較例１：実施例１において、パインクリスタルＫＥ−１００の代わりに、スーパーエステルＡ−１００（ロジンエステル系樹脂：ガードナーカラー７：荒川化学工業（株）製）を用いた以外は同様に行った。乳化物（Ｚ）のメディアン径は０．７５μｍとなり、そこから得られた樹脂分散体は不揮発分５０．０％、粘度１００ｍＰａ・ｓ、メディアン径０．１９μｍであった。得られた水性感圧性接着剤組成物について、実施例１と同様の評価を行った。
【００８９】
比較例２：実施例１において、パインクリスタルＫＥ−１００の代わりに、ペンセルＡＤ（ロジンエステル系樹脂：ガードナーカラー６〜７：荒川化学工業（株）製）を用いた以外は同様に行った。乳化物（Ｚ）のメディアン径は０．８１μｍとなり、そこから得られた樹脂分散体は不揮発分５０．０％、粘度９０ｍＰａ・ｓ、メディアン径０．１７μｍであった。得られた水性感圧性接着剤組成物について、実施例１と同様の評価を行った。
【００９０】
比較例３：比較例１において、エチレン性不飽和単量体混合物（Ｍ）に架橋性基を有する単量体としてジビニルベンゼン３．０部を追加した以外は同様に行った。乳化物（Ｚ）のメディアン径は０．８０μｍとなり、そこから得られた樹脂分散体は不揮発分５１．０％、粘度１３０ｍＰａ・ｓ、メディアン径０．１９μｍであった。得られた樹脂分散体について、実施例１と同様の評価を行った。
【００９１】
比較例４：実施例１において、エチレン性不飽和単量体混合物（Ｍ）に架橋性基を有する単量体としてジビニルベンゼン２．０部を追加した以外は同様に行った。乳化物（Ｚ）のメディアン径は０．７６μｍとなり、そこから得られた樹脂分散体は不揮発分５０．８％、粘度１００ｍＰａ・ｓ、メディアン径０．１７μｍであった。得られた樹脂分散体について、実施例１と同様の評価を行った。
【００９２】
比較例５：実施例１において、混合物（Ｙ）に連鎖移動剤としてオクチルチオグリコレート０．１部を加えた以外は同様に行った。乳化物（Ｚ）のメディアン径は０．７８μｍとなり、そこから得られた樹脂分散体は不揮発分５０．８％、粘度１００ｍＰａ・ｓ、メディアン径０．１７μｍであった。得られた樹脂分散体について、実施例１と同様の評価を行った。
表１
【００９３】
【表１】
実施例１〜５は、ガードナーカラーが３以下の淡色固形樹脂（Ｔ）、エチレン性不飽和単量体混合物（Ｍ）を含む混合物（Ｙ）を界面活性剤（Ｅ）の存在下に水中で重合してなる樹脂を含む水性感圧性接着剤組成物であって、１００℃〜１５０℃での貯蔵弾性率が常に１．５×１０４〜６×１０４Ｐａであるため、ポリオレフィン接着力が１０Ｎ／２５ｍｍ以上であり、かつ保持力もあり、かつ耐水性、熱時変色性、投錨性、加工性を全てにおいて良好である。比較例１、２は、ガードナーカラーが３を超える固形樹脂を使用しており、かつ貯蔵弾性率が低く、そのため各物性が悪くなっている。比較例３はガードナーカラーが３を超える固形樹脂を使用しているが、架橋性基を有する単量体を多く使用して貯蔵弾性率を本発明の範囲にしたものである。しかし、熱時変色性だけでなく投錨性も悪い。比較例４は淡色固形樹脂（Ｔ）を使用してはいるが、貯蔵弾性率が本発明の範囲より高くなっているため、ポリオレフィン接着力が低く、また基材に対する投錨性が悪い。一方、比較例５は淡色固形樹脂（Ｔ）を使用してはいるが、貯蔵弾性率が本発明の範囲より低くなっているため、加工性が悪くなっている。
【００９５】
【発明の効果】
本発明者らは、従来溶剤２液型感圧性接着剤が好適に使用されていた、透明フィルムを基材とする感圧性接着シートに使用しても、ポリオレフィン等の低表面エネルギー被着体に対する接着力に優れ、かつ良好な耐変色性、耐水性、基材への投錨性、加工性を併せ持つ１液型の水性感圧性接着剤組成物を提供することができた。また、その好適な製造方法を提供することができた。
【図面の簡単な説明】
【図１】本発明に用いる回転子／固定子型高速回転連続型乳化機の固定子の一例を示す斜視図である。
【図２】本発明に用いる回転子／固定子型高速回転連続型乳化機の回転子の一例を示す斜視図である。
【図３】本発明に用いる回転子／固定子型高速回転連続型乳化機の要部の一例を表した断面図である。
【図４】図３のＡ−Ａ′部を側面から見たときの固定子突起と回転子突起の組み合わせ状態を表した図である。
【符号の説明】
１ 固定子
２ 液入口
３ 固定子の突起
４ 固定子の円周溝
５ 固定子突起のスリット
６ 回転子の駆動軸
７ 回転子
８ 回転子の突起
９ 回転子の円周溝
１０ 回転子突起のスリット[0001]
TECHNICAL FIELD OF THE INVENTION
One-part type water-based pressure-sensitive adhesive composition having excellent adhesion to low surface energy adherends such as polyolefins and having good discoloration resistance, water resistance, anchoring property to a substrate, and processability, and production thereof About the method.
[0002]
[Prior art]
The field of application of pressure-sensitive adhesives is wide-ranging, especially for plastic films that require strong adhesion to polyolefins, transparency, water resistance, cutting and punching workability, discoloration resistance, anchoring to substrates. For use as a surface substrate, for example, a two-component cross-linkable solvent-based pressure-sensitive adhesive composed of an acrylic resin solution and a cross-linking agent is widely used. However, from the worldwide trend of environmental protection, a water-based pressure-sensitive adhesive has been required for applications requiring the above-mentioned required physical properties. Normally, water-based pressure-sensitive adhesives are manufactured by adding various additives to water-based acrylic resin obtained by emulsion polymerization, and almost no solvent is used from the manufacturing process to the final product form, so environmental protection and safety Superior in hygiene. However, in reality, the above physical properties have not been widely used due to the following problems. First, a pressure-sensitive adhesive sheet suitable for a two-component film of a water-based pressure-sensitive adhesive and a water-based acrylic resin and a cross-linking agent has been disclosed (see Patent Literature 1). The one-pack type is preferable because there are problems of the pot life after mixing, the aging time for the crosslinking reaction, and the problems of heating energy, and the great advantage of the aqueous system is lost.
[0003]
In addition, the problems of the conventional water-based pressure-sensitive adhesive even with the one-pack type are as follows. The water-based pressure-sensitive adhesive has a disadvantage that the adhesive force to a low surface energy adherend such as polyolefin is lower than that of a solvent-based pressure-sensitive adhesive because a hydrophilic surfactant (E) is used. A tackifier resin is used to increase the adhesive strength. However, since many of the tackifier resins are insoluble in water, a method in which an aqueous dispersion is previously mixed with an aqueous acrylic resin is generally used. Although a little effect can be obtained by this method, since the acrylic resin and the tackifying resin are not present uniformly in the pressure-sensitive adhesive layer, it is impossible to give an adhesive force of 10 N / 25 mm or more to the polyethylene adherend. It was difficult without sacrificing the physical properties of
[0004]
In order to overcome such a drawback, there is a method in which a water-based acrylic resin is modified with a tackifier resin in the production thereof and is uniformly present in the acrylic resin. For example, a method is disclosed in which a tackifier resin is dissolved in an ethylenically unsaturated monomer to carry out emulsion polymerization (see Patent Documents 2 and 3). However, in this method, a large amount of coarse particles of 2 μm or more containing a high concentration of a tackifier resin may be generated during polymerization, or the particles may settle during storage. This problem is solved by a method of emulsion-polymerizing an ethylenically unsaturated monomer in which a tackifier resin is dissolved in the presence of a seed polymer (see Patent Document 4), an ethylenically unsaturated monomer in which a tackifier resin is dissolved, There is a disclosure that the method can be solved by a method of finely emulsifying to less than 1 μm in the presence of a surfactant (E) and then polymerizing (see Patent Document 5).
[0005]
However, on the other hand, the tackifying resin used in the disclosed literature also acts strongly as a chain transfer agent, so that the coexistence of the tackifying resin during polymerization lowers the molecular weight of the acrylic resin, lowers the cohesive force, and reduces pressure-sensitive adhesion. Since the cutting or punching processability after forming the sheet becomes extremely poor, a large amount of a polar group-containing monomer or a crosslinkable monomer is used to prevent a decrease in cohesive force. However, particularly when a plastic film substrate is used, if the polar group-containing monomer is used in an amount of more than 3 parts by weight in 100 parts by weight of the ethylenically unsaturated monomer, the water resistance becomes poor, and a crosslinkable monomer is used. When the body is used in an amount exceeding 1 part by weight, the pressure-sensitive adhesive layer is pulled by the processed teeth at the time of cutting or punching, and peeling occurs at the interface between the pressure-sensitive adhesive layer and the base material layer (hereinafter referred to as poor anchoring property). Yes), causing trouble.
[0006]
On the other hand, most of the tackifier resins used in the disclosed documents discolor when heated in the presence of an acrylic resin or a surfactant (E). Impair.
[0007]
[Patent Document 1] JP-A-2001-172578
[Patent Document 2] JP-A-54-23641
[Patent Document 3] JP-A-58-185668
[Patent Document 4] Japanese Patent Publication No. 07-57864
[Patent Document 5] JP-A-2001-348551
[0008]
[Problems to be solved by the invention]
It is an object of the present invention to provide a one-part aqueous pressure-sensitive adhesive having excellent adhesion to a low surface energy adherend such as a polyolefin and having good discoloration resistance, water resistance, anchoring property to a substrate, and workability. And a method for producing the same.
[0009]
[Means for Solving the Problems]
However, the present inventors have conducted intensive studies in order to solve such problems, and as a result, a mixture comprising a light-colored solid resin (T) having a Gardner color of 3 or less and an ethylenically unsaturated monomer mixture (M) ( The storage elastic modulus at 100 ° C. to 150 ° C. of the non-volatile content of the aqueous pressure-sensitive adhesive composition containing a resin obtained by polymerizing Y) in water in the presence of a surfactant (E) is always 1.5 × 10 5 4 ~ 6 × 10 4 It has been found that a water-based pressure-sensitive adhesive composition characterized by the above range meets the above-mentioned object, and the present invention has been completed.
[0010]
That is, the present invention provides a light-colored solid resin (T) having a Gardner color of 3 or less and a mixture (Y) containing an ethylenically unsaturated monomer mixture (M) in water in the presence of a surfactant (E). An aqueous pressure-sensitive adhesive composition containing a polymerized resin, wherein the non-volatile content of the composition at 100 ° C. to 150 ° C. is always 1.5 × 10 5. 4 ~ 6 × 10 4 The present invention relates to an aqueous pressure-sensitive adhesive composition characterized by being in the range of Pa.
[0011]
Further, the present invention relates to an aqueous pressure-sensitive adhesive composition (dry weight 20 g / m2). 2 ) Was laminated as a pressure-sensitive adhesive layer on a PET film having a thickness of 50 μm, and was adhered to a 2 mm-thick polyethylene plate by reciprocating a 2 kg roll at 23 ° C. and 50% humidity for 50 hours at 23 ° C. for 24 hours. After leaving in an environment of 23 ° C., the force when peeled from the polyethylene plate at a speed of 300 mm / min and an angle of 180 ° under a condition of 23 ° C. and 50% humidity is 10 N / 25 mm or more, and the pressure-sensitive adhesive layer is The present invention relates to the above-mentioned aqueous pressure-sensitive adhesive composition which does not show cohesive failure or transfer to a polyethylene plate.
[0012]
Further, the present invention provides a step [1] of mixing at least an ethylenically unsaturated monomer mixture (M) and a light-colored solid resin (T) to obtain a mixture (Y),
Mixing the mixture (Y), the surfactant (E) and water, and forcibly emulsifying to obtain an emulsion (Z) having a median diameter of 0.4 to 3.0 μm [2],
The present invention relates to a method for producing the aqueous pressure-sensitive adhesive composition, comprising a step [3] of polymerizing the emulsion (Z) in the presence of a radical polymerization initiator.
[0013]
Further, in the present invention, the step [2] is a step of forcibly emulsifying with a rotary continuous emulsifier, and the rotary continuous emulsifier comprises:
A stator having an annular projection having a slit on a disk-shaped base portion, and a rotor having an annular projection having a slit on the disk-shaped base portion,
The present invention relates to a method for producing the aqueous pressure-sensitive adhesive composition, wherein the annular projection of the stator and the projection of the rotor are engaged with each other concentrically with respect to the rotation axis of the rotor.
[0014]
The present invention also relates to a pressure-sensitive adhesive sheet obtained by laminating the above-mentioned aqueous pressure-sensitive adhesive composition on a substrate.
[0015]
The present invention also relates to the pressure-sensitive adhesive sheet, wherein the substrate is a plastic film.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically. The component of the ethylenically unsaturated monomer mixture (M) used in the present invention is mainly composed of (meth) acrylic ester having 1 to 18 carbon atoms in the alkyl group. Examples of the acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n- Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, etc., nonyl (meth) acrylate, isononyl (meth) ) Acrylate, decyl (meta Acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate, tridecyl (meth) acrylate, and isotridecyl (meth) acrylate, among which methyl (meth) acrylate, ethyl (meth) acrylate, n- Butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferably used.
[0017]
The ethylenically unsaturated monomer mixture (M) preferably contains a polar group-containing monomer, and examples of the polar group include a carboxyl group, a hydroxyl group, and an amide group. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, itaconic acid, and maleic acid. Examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxyacrylate, and glycerol (meth) acrylate. Examples of the amide group-containing monomer include (meth) acrylamide, N-alkyl (meth) acrylamide, and N, N-dialkyl (meth) acrylamide.
[0018]
Of these, it is preferable that the carboxyl group-containing monomer is used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer mixture (M), since both water resistance and polymerization stability are compatible. .
[0019]
Further, a monomer having a crosslinkable group may be contained as a component of the ethylenically unsaturated monomer mixture (M). Examples of the crosslinkable group include an epoxy group, an alkoxysilyl group, a methylol group, and an acetoacetyl group. Other examples of the monomer having a crosslinkable group include a polyfunctional ethylenically unsaturated monomer having two or more ethylenically unsaturated double bonds.
[0020]
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
[0021]
Examples of the alkoxysilyl group-containing monomer include γ- (meth) acryloxyethyltrimethoxysilane, γ- (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) acryloxypropyltri Propioxysi Γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxypropyltributoxysilane, γ- (meth) acryloxybutyltrimethoxysilane, γ- (meth) acryloxypentyltrimethoxy Silane, γ- (meth) acryloxyhexyltrimethoxysilane, γ- (meth) acryloxyhexyltriethoxysilane, γ- (meth) acryloxyoctyltrimethoxysilane, γ- (meth) acryloxydecyltrimethoxysilane, γ- (meth) acryloxydodecyltrimethoxysilane, γ- (meth) acryloxyoctadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripyropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane , And vinylmethyldipropoxysilane.
[0022]
Examples of the methylol group-containing monomer include N-methylolacrylamide and butoxy N-methylolacrylamide.
[0023]
Examples of the acetoacetyl group-containing monomer include diacetone (meth) acrylamide, 2- (acetoacetoxy) ethyl (meth) acrylate, and allyl acetoacetate.
[0024]
Examples of the polyfunctional ethylenically unsaturated monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. ) 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, trimethylolpropanetri (Meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, glycerin methacrylate acrylate, tris (meth) acryloyloxyphosphate, glycerin di (meth) acrylate, allyl (meth) acrylate diallyl phthalate, Examples include tetraallyloxyethane, divinylbenzene, and tri (meth) allyl isocyanurate.
[0025]
The monomer having a crosslinkable group may not necessarily be used, but it is used in the range of 0 to 1 part by weight based on 100 parts by weight of the ethylenically unsaturated monomer mixture (M). It is preferable in terms of force and anchoring property to the plastic film substrate.
[0026]
Further, in the present invention, a crosslinking agent may be used in combination for the purpose of crosslinking the functional group of the monomer having a crosslinking group as required. Examples of such a crosslinking agent include isocyanate compounds, melamine compounds, aziridine compounds, hydrazine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, metal compounds such as metal complexes, and amino group-containing compounds. No. Among them, even if they are mixed with the aqueous pressure-sensitive adhesive composition of the present invention and left at 40 ° C. for one month so that they are bifunctional or more and can be used in a one-pack type, viscosity changes, gelation, etc. None is preferred.
[0027]
In the present invention, it is also possible to use other copolymerizable monomers, such as acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate , Vinyl chloride, alkyl vinyl ether, dimethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and the like.
[0028]
Here, the (meth) acrylate described above refers to methacrylate or acrylate, and the (meth) acrylamide refers to methacrylamide or acrylamide.
[0029]
In the present invention, a known chain transfer agent can be used during the polymerization, if necessary. Specifically, alkyl mercaptans having 12 or more carbon atoms such as lauryl mercaptan and stearyl mercaptan; esterified products of mercaptoethanol and alkyl acid such as 2-mercaptooctanoic acid ester; thiol such as octyl thioglycolate and methoxybutyl thioglycolate. Glycolic acid derivatives, mercaptopropionic acid derivatives such as octyl mercaptopropionate, methoxybutyl mercaptopropionate, and tridecyl mercaptopropionate are used.
[0030]
In the ethylenically unsaturated monomer mixture (M), the content ratio of the (meth) acrylic acid ester, the polar group-containing monomer, the monomer having a crosslinkable group, and the copolymerizable monomer is as follows: (Meth) acrylic acid ester is 50 to 99.9% by weight, polar group-containing monomer is 0.1 to 3% by weight, crosslinkable group-containing monomer is 0 to 1% by weight, copolymerizable monomer It is preferable that the amount of the monomer be 0 to 49.9% by weight.
[0031]
The light-colored solid resin (T) having a Gardner color of 3 or less used in the present invention may be any resin that dissolves or disperses in the ethylenically unsaturated monomer mixture (M). For example, Alcon P-70, Alcon P -90, Archon P-100, Archon P-115, Archon P-120, Archon P-140, Archon M-90, Archon M-100, Archon M-115, Archon M-135 and other hydrogenated petroleum resins, KR Hydrogenated petroleum resins having a hydroxyl group such as -1840 and KR-1842, hydrogenated rosins such as pine crystal KR-85, pine crystal KR-612, pine crystal KR-614 and pine crystal KE-604, and pine crystal KE-100; Hydrogenated rosin esters such as pine crystal KE-311 and pine crystal KE-359, pine Hydrogenated rosin-containing diols such as Listal D-6010, hydrogenated rosin metal salts such as Pine Crystal M-1500 and Pine Crystal M-1550, high acid value hydrogenated rosins such as Pine Crystal KE-604, and Pine Crystal KE-604B YS Resin PX1250, YS Resin PX1150, YS Resin PX1000, YS Resin PX800, YS Resin D105, YS Resin D115, YS Resin PX1150N, YS Terpene resins such as Resin A800, aromatic modified terpene resins such as YS Resin TO125, YS Resin TO115, YS Resin TO105, YS Resin TO85, YS Resin TR105, Clearon P125, Clearon P115, Clearon P105, Clearon P Hydrogenated terpene resins such as Clearon M115, Clearon M105, Clearon K110, Clearon K100, Clearon K4090, etc .; hydrogenated terpene phenolic resins such as YS Polystar TH130 (all manufactured by Yashara Chemical Co., Ltd.) ), Α-methylstyrene resins such as FTR0100, FTR0120 and FTR0140, α-methylstyrene / styrene copolymer resins such as FTR2120 and FTR2140, and styrene monomer / aliphatic monomer copolymer resins such as FTR6100, FTR6110 and FTR6125 Styrene monomer / aliphatic monomer / α-methylstyrene copolymer resin such as FTR7080, FTR7100, FTR7125, and the like such as FTR8080, FTR8100, and FTR8120. Tylene resin, styrene-based monomer / aromatic-based monomer copolymer resin such as FMR0150 (hereinafter, manufactured by Mitsui Chemicals, Inc.), aliphatic hydrocarbon resin such as Quinton P195N, and alicyclic group such as Quinton 1325 and Quinton 1345 Based hydrocarbon resins (all manufactured by Nippon Zeon Co., Ltd.).
[0032]
Among them, those having a Gardner color of 1 or less are particularly preferable, and those having a rosin skeleton or terpene skeleton are more preferable. Here, hydrogenation indicates that a part or all of a carbon-carbon double bond is reacted with hydrogen to modify it into a carbon-carbon single bond.
[0033]
Those having a Gardner color of more than 3 often act strongly as chain transfer agents and polymerization retarders, leading to a decrease in molecular weight and a decrease in holding power and processability. In order to solve the problem, a method of increasing the number of monomers having a polar group and a monomer having a crosslinkable group has been conventionally used, but it is not preferable because adhesion to a polyolefin or anchoring property to a substrate is deteriorated. . At the same time, those having a Gardner color of more than 3 are not preferable because they also have a known problem that discoloration upon heating after forming a pressure-sensitive adhesive sheet is remarkable. That is, by using a light-colored solid resin (T) having a Gardner color of 3 or less, it becomes possible to obtain a pressure-sensitive adhesive composition that simultaneously satisfies discoloration resistance, processability, holding power, and adhesive power to polyolefin. . Further, even if it is a light-colored resin that is liquid at room temperature, it is not preferable to use the resin alone because it causes a reduction in holding power and workability, but it may be used if it is used in combination with the light-colored solid resin described above. Absent.
[0034]
In the present invention, the above ethylenically unsaturated monomer mixture (M) and the light-colored solid resin (T) are blended to form a mixture (Y). M) The light-colored solid resin (T) is preferably 1 to 50 parts by weight, more preferably 5.5 to 40 parts by weight, particularly preferably 7 to 30 parts by weight with respect to 100 parts by weight. If the amount of the light-colored solid resin (T) is less than 1 part by weight, sufficient adhesiveness, particularly to polyolefin, cannot be obtained. If the amount exceeds 50 parts by weight, polymerization becomes unstable, which is not preferable.
[0035]
When emulsifying the mixture (Y) comprising the ethylenically unsaturated monomer mixture (M) and the light-colored solid resin (T) with the surfactant (E) in an aqueous medium, a surfactant used (E) is not particularly limited as long as it has a function of emulsifying each component in an aqueous medium, and known ones can be used without limitation. For example, an ionic or non-ionic reactive surfactant having an ethylenically unsaturated double bond, an ionic or non-ionic non-reactive surfactant having no ethylenically unsaturated double bond, etc. Used alone or in combination. Above all, it is preferable to use a reactive surfactant in consideration of water resistance.
[0036]
Specific examples of the reactive surfactant (E) include Adecaria Soap SE-20N (anionic), Adecaria Soap SE-10N (anionic), Adecaria Soap NE-10 (nonionic), and Adecaria Soap NE-20 (nonionic), Adecaria Soap NE-30 (nonionic), Adecaria Soap NE-40 (nonionic), Adecaria Soap SDX-730 (anionic), Adecaria Soap SDX-731 (anion Properties) [above, manufactured by Asahi Denka Co., Ltd.], Eleminol JS-2 (anionic), Eleminol RS-30 (anionic) [above, manufactured by Sanyo Chemical Co., Ltd.], Latemul S-180A (anionic), Latemul S-180 (anionic), latemul PD-104 (anionic) (all manufactured by Kao Corporation), Aqualon BC-05 (A Aqualon BC-10 (anionic), Aqualon BC-20 (anionic), Aqualon KH-10 (anionic), Aqualon KH-20 (anionic), Aqualon HS-05 (anionic), Aqualon HS-10 (anionic), Aqualon HS-20 (anionic), Aqualon RN-10 (nonionic), Aqualon RN-20 (nonionic), Aqualon RN-30 (nonionic), Aqualon RN-50 (nonionic) And commercial products such as New Frontier S-510 (anion) (above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and Phosphinol TX (anionic) (manufactured by Toho Chemical Industry Co., Ltd.).
[0037]
The amount of the surfactant (E) is preferably 0.5 to 5 parts by weight, more preferably 0.8 to 4 parts by weight, per 100 parts by weight of the ethylenically unsaturated monomer mixture (M). Parts by weight, particularly preferably 1 to 3 parts by weight. When the amount of the surfactant (E) is less than 0.5 part by weight, agglomerates and the like are easily generated during polymerization, and when the amount exceeds 5 parts by weight, the water resistance of the coating film is undesirably reduced. The surfactant (E) may be partially added to the reaction vessel in addition to the emulsion.
[0038]
The amount of water used is 25 to 50 parts by weight based on 100 parts by weight of the total amount of the ethylenically unsaturated monomer mixture (M), the light-colored solid resin (T), the surfactant (E) and water. And more preferably 25 to 45 parts by weight. If the amount of water used is less than 25 parts by weight, an O / W emulsion may not be formed, and even if it is formed, the viscosity becomes high and the workability deteriorates. If the amount exceeds 50 parts by weight, the concentration of the emulsion becomes low, and the concentration of the aqueous pressure-sensitive adhesive composition becomes low.
[0039]
The aqueous pressure-sensitive adhesive composition of the present invention is obtained by mixing a mixture (Y) containing an ethylenically unsaturated monomer mixture (M) and a light-colored solid resin (T) with a surfactant (E) in water. It is obtained by polymerizing an emulsion (Z) previously emulsified into an O / W type. At this time, the median diameter of the emulsion (Z) may be any size as long as no agglomerate is produced during the synthesis, or the aqueous pressure-sensitive adhesive composition has good storage stability. In order to obtain a polymer which does not cause such problems, it is preferable that the median diameter of the emulsion (Z) is 0.4 to 3.0 μm. Further, the thickness is more preferably 0.5 to 2.0 μm, and particularly preferably 0.55 to 1.5 μm. Here, when the thickness is less than 0.4 μm, the viscosity of the emulsion (Z) becomes too high, and the energy and time required for forced emulsification increase, which is not preferable because the productivity is reduced.
[0040]
Here, the median diameter as referred to in the present invention is a cumulative volume average diameter when an oil droplet diameter in water is measured by a dynamic light scattering method, for example, using a Nikkiso Co., Ltd. Microtrac UPA particle size distribution meter. Indicates the measured value.
[0041]
As a method for obtaining an emulsion (Z) having a median diameter of 3.0 μm or less, a commercially available emulsifier can be used, and a rotary continuous emulsifier, a colloid mill-type emulsifier, a high-pressure homogenizer-type emulsifier, A forced emulsifier such as a sonication emulsifier can be used. Among them, a rotor / stator high-speed rotation continuous emulsifier, which is a rotary continuous emulsifier, has a median diameter within the range of the present invention. It is suitable for obtaining the emulsion (Z), and has a large maintenance amount and a large amount of processing per unit time.
[0042]
Among them, a stator provided with an annular protrusion having a slit in a disk-shaped base portion, and a rotor provided with an annular protrusion having a slit in the disk-shaped base portion, the annular protrusion of the stator, The protrusions of the rotor are concentrically engaged with the rotation axis of the rotor, using a rotary continuous emulsifier having a structure provided with a space between the stator and the rotor, It is preferable to obtain the emulsion (Z) by causing the feed to the emulsifier to flow from the center to the outer periphery through the slit and the gap while rotating the rotor. Specific examples of the emulsifier having such a mechanism include Cavitron (manufactured by Taiheiyo Kiko Co., Ltd.), Ebara Milder (manufactured by Taiheiyo Kiko Co., Ltd.), Ultra Turrax (manufactured by IKA), and Multi Shear (manufactured by SILVERSON). Among them, Cavitron is particularly preferred.
[0043]
The shape and number of the slits are not particularly limited as long as the slits penetrate the projections, since the slits are for allowing the supply to the emulsifier to flow from the central portion to the outer peripheral direction.
[0044]
In addition, the number of annular protrusions of the stator and the rotor is not particularly limited, and may be one or more rings.
[0045]
Hereinafter, the production method of the present invention using the above-described rotor / stator type high-speed rotation continuous emulsifier will be described in detail with reference to the drawings.
[0046]
FIG. 1 is a perspective view showing an example of a stator of a rotor / stator type high-speed rotary continuous emulsifier used in the production method of the present invention, and FIG. 2 is a rotor / stator type used in the production method of the present invention. FIG. 3 is a perspective view showing an example of a rotor of a high-speed rotation type continuous emulsifier, FIG. 3 is a sectional view showing an example of a main part of a rotor / stator type high-speed rotation type continuous emulsifier used in the present invention, and FIG. FIG. 3 is a diagram illustrating a combined state of a stator protrusion and a rotor protrusion when the AA ′ section of No. 3 is viewed from the side.
[0047]
As shown in FIGS. 1 to 4, the stator 1 of the rotor / stator type high-speed rotation continuous emulsifier is installed at the center and has a liquid inlet 2 at the center. The disk-shaped base portion of the stator 1 is provided with one or two or more stages of
[0048]
A drive shaft 6 is provided at the center of the inner wall facing the stator 1 in this emulsifier, and is connected to a drive device and rotated. The
[0049]
The stator 1 and the
[0050]
A mixture (Y) obtained by mixing at least an ethylenically unsaturated monomer mixture (M) and a solid resin (T), a surfactant (E) and water are simultaneously added to a liquid inlet 2 of the emulsifier. Alternatively, a pre-emulsified mixture of the mixture (Y), the surfactant (E) and water is supplied in advance, and when the
[0051]
In this way, the supply receives centrifugal force due to the rotation of the
Flows to mouth. On the other hand, due to the displacement of the slit between the
[0052]
The rotation speed of the
[0053]
Two or more pairs of the rotor and the stator may be installed on the same device.
[0054]
When such a rotor / stator type high-speed continuous emulsifier is used, in order to maintain good fluidity of the emulsion (Z), an emulsifier or a pipe connected to the emulsifier is added to the emulsifier. It is preferable to provide jackets for warming and cooling. The temperature in the emulsifier is controlled to a constant temperature by balancing the temperature of the feed, the temperature control effect of the jacket, and the amount of heat generated by shearing in the device.
[0055]
The pressure in the emulsifier is determined by the vapor pressure of the emulsion (Z) in the device and the discharge pressure of the high-speed rotating rotor. The obtained emulsion (Z) is preferably provided with an automatic pressure control valve at a take-out port, and the dispersion is continuously taken out at atmospheric pressure while keeping the internal pressure constant.
[0056]
The temperature at the time of emulsification is not problematic as long as the feed does not react during the emulsification, and usually about 5 to 60 ° C is appropriate. The number of times the emulsion is passed (Pass) is preferably about 1 to 3 times. It may be more than three times, but productivity will decrease.
[0057]
After preparing the above-mentioned emulsion (Z), the emulsion (Z) is polymerized in the presence of a polymerization initiator. 1.) The whole amount of the emulsion (Z) is directly heated to polymerize. 2.) A part of the emulsion (Z) is heated to start the polymerization, and the remaining emulsion (Z) is added dropwise or dividedly to continue the polymerization. ) Water and, if necessary, a surfactant (E) are charged into a reaction vessel, and the temperature is raised. Then, the emulsion (Z) is added dropwise or dividedly and polymerized. Alternatively, both or either one of the dropping cans may be charged at an arbitrary ratio, and only the initiator may be dropped or added separately. Among them, in that the control of the polymerization temperature is easy, ), 3. Is preferred.
[0058]
The amount of the polymerization initiator to be used is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer mixture (M). is there. If the amount of the polymerization initiator is less than 0.05 part by weight, the polymerization rate becomes slow, and if it exceeds 5 parts by weight, the molecular weight of the resin becomes low, and the holding power and the processability are undesirably reduced.
[0059]
The polymerization initiator is not particularly limited, and any of water-soluble and oil-soluble polymerization initiators can be used. Specifically, alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p- Methane hydroperoxide, isobutyl peroxide, lauryl 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, methylcyclohexanone peroxide, -Iso Organic peroxides such as tilperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, t-butylperoxyisobutyrate, azobisisobutyronitrile, dimethylazodiisobutyrate, 2,2-azobis ( 2,4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, 4,4'-azobis-4-cyanovaleric Ammonium (amine) salt of acid, 2,2′-azobis (2-methylamidooxime) dihydrochloride, 2,2′-azobis (2-methylbutanamidooxime) dihydrochloride tetrahydrate, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxye ] -Propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], various redox catalysts (in this case, oxidizing agents include ammonium persulfate, potassium persulfate, Hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, etc., and sodium sulfite, sodium acid sulfite, Rongalit, ascorbic acid, etc. are used as reducing agents.) And the like. Among them, water-soluble ones are preferably used.
[0060]
The polymerization initiator may be added to the reaction vessel in advance, may be added immediately before the start of the polymerization, or may be added to the ethylenically unsaturated monomer mixture (M) before emulsification and the light-colored solid. It may be added in advance to the mixture (Y) containing the resin (T) or may be added to the fine emulsion (Z) after the emulsification. If necessary, a pH buffer may be used in combination for the pH adjustment at the time of the polymerization, or when a carboxyl group-containing monomer is used, a part or all of the monomer may be ammonia or organic. It may be neutralized with a basic compound such as amine, potassium hydroxide, sodium hydroxide and the like.
[0061]
The polymerization conditions in the above polymerization method are not particularly limited. In the method (2), a temperature range of usually about 40 to 100 ° C. is appropriate, and the reaction is performed for about 1 to 8 hours after the start of the temperature rise. 2. In the method of (1), after 1 to 50% by weight of the fine emulsion (Z) is polymerized at 40 to 90 ° C. for 0.1 to 4 hours, the remaining fine emulsion (Z) is dropped over about 1 to 5 hours. Alternatively, they are added in portions and then aged at the same temperature for about 1 to 3 hours. 3. In the method of (1), water is charged so as to be 5 to 100% by weight of the fine emulsion (Z), the temperature is raised to 40 to 90 ° C., and the fine emulsion (Z) is added dropwise over about 2 to 5 hours or The mixture is added in portions, and then aged at the same temperature for about 1 to 3 hours.
[0062]
The resin dispersion obtained as described above preferably has a median diameter of 0.1 to 0.5 times the median diameter of the emulsion (Z) in terms of polyolefin adhesion and workability. .
[0063]
Also, if necessary, an antifoaming agent, a viscosity adjusting agent, a pH adjusting agent, an antiseptic / antifungal agent, a rust inhibitor, a freeze-thaw stabilizer, a plasticizer, a pigment, a filler, etc. are appropriately added to the obtained emulsion. Or it can be added before or during the polymerization.
[0064]
The aqueous pressure-sensitive adhesive composition of the present invention has a storage modulus at 100 ° C. to 150 ° C. when the nonvolatile content of a test piece of 8 mm × 8 mm × 1.5 mm is measured in shear mode at an angular frequency of 1 Hz. Always 1.5 × 10 4 ~ 6 × 10 4 It is a range of Pa. The storage elastic modulus can be measured by, for example, a dynamic viscoelasticity measuring device RDA-III manufactured by Rheometric Scientific F.E.
[0065]
Of these, particularly preferred is always 1.75 × 10 4 ~ 5.5 × 10 4 Pa range, and 2 × 10 4 ~ 5 × 10 4 The range of Pa is particularly preferred. 1.5 × 10 4 If it is less than Pa, workability deteriorates, and when a pressure-sensitive adhesive sheet is cut after cutting, a part of the pressure-sensitive adhesive easily adheres to teeth to be cut, and the number of maintenance operations of the cutting machine increases. This causes a problem in that the pressure-sensitive adhesive layer is poorly cut in applications where the stamping process is performed at the same time, and the stamped label is carried together with the waste when the waste is lifted. 6 × 10 4 If it exceeds Pa, the adhesive strength to polyolefin and the anchoring property to a plastic film substrate will be poor.
[0066]
The aqueous pressure-sensitive adhesive composition of the present invention has a dry weight of 20 g / m2. 2 Was laminated as a pressure-sensitive adhesive layer on a PET film having a thickness of 50 μm, and was adhered to a 2 mm-thick polyethylene plate by reciprocating a 2 kg roll at 23 ° C. and 50% humidity for 24 hours. After leaving for 24 hours in the environment, the force when peeled from the polyethylene plate at a speed of 300 mm / min and an angle of 180 degrees under the condition of 23 ° C. and 50% humidity after 24 hours is 10 N / 25 mm or more, and the pressure sensitivity at the time of peeling It is preferable that the adhesive layer does not show cohesive failure or transfer to a polyethylene plate.
[0067]
The pressure-sensitive adhesive sheet may be in the form of a pressure-sensitive adhesive sheet or a pressure-sensitive adhesive tape provided with a pressure-sensitive adhesive layer on one or both sides of the substrate, or the surface may be released. A crosslinked structure layer may be provided on the treated peelable liner to form the same form as described above and used without a substrate.
[0068]
As the substrate, a film substrate, a paper substrate, a nonwoven fabric substrate, or the like can be used. Examples of the film substrate include a polyvinyl chloride film, a polyethylene terephthalate (PET) film, a polyurethane film, a nylon film, a triacetyl cellulose film, a treated polyolefin film, an untreated polyolefin film, and a polycarbonate film. Examples of the paper base include plain paper, coated paper, art paper, and the like. The aqueous pressure-sensitive adhesive composition of the present invention is characterized in that it can be used even on a film substrate while being aqueous, and is particularly excellent in whitening resistance when immersed in water or discoloration resistance when heated, even when the film substrate is used, and does not impair the appearance. It has excellent characteristics. The substrate preferably has a thickness of 15 to 100 μm. The coating amount of the pressure-sensitive adhesive on the base material is preferably 5 to 100 μm. In order to apply the pressure-sensitive adhesive of the present invention on a substrate, it can be appropriately applied by a known application method.
[0069]
Drying of the aqueous pressure-sensitive adhesive composition is usually performed at about 80 to 150 ° C. for about 1 to 2 minutes. It may be more than 2 minutes, but productivity will decrease.
[0070]
The present invention will be specifically described below with reference to examples. In the examples, “%” and “parts” mean by weight unless otherwise specified. The median diameter described in Examples and Comparative Examples indicates the cumulative volume average diameter measured with a Microtrac UPA particle size distribution analyzer manufactured by Nikkiso Co., Ltd.
[0071]
Example 1: 70 parts of 2-ethylhexyl acrylate, 10 parts of ethyl acrylate, 12 parts of methyl methacrylate, 6 parts of methyl acrylate, 2 parts of acrylic acid, and 0.1 part of N-methylolacrylamide in an ethylenically unsaturated monomer mixture (M 15) Pine Crystal KE-100 (hydrogenated rosin ester resin: Arakawa Chemical Co., Gardner Color 1 or less) was previously dissolved as a light-colored solid resin (T) to obtain a mixture (Y). The mixture (Y) was added to an aqueous solution in which 2.5 parts of a surfactant Adecaria Soap SE-10N (manufactured by Asahi Denka Co., Ltd.) was dissolved in 49.3 parts of water, and the mixture was stirred and mixed using a stirring blade to prepare a preliminary mixture. Emulsification was performed.
[0072]
Next, using a Cavitron CD1010 type (manufactured by Eurotech Co., Ltd.) using a slit type unit for the rotor / stator, the number of revolutions was 11,200 rpm, the peripheral speed of the outermost periphery of the rotor was 40 m / sec, and the pressure was 0.12 MPa. The mixture was emulsified by performing 2 Pass treatment under an operating condition of a treatment amount of 10 kg / min to obtain 151.9 parts of an emulsion (Z) having a median diameter of 0.75 μm of an oil-soluble component.
[0073]
In a separate container, 0.5 part of ammonium persulfate was dissolved as a polymerization initiator in 4.5 parts of water to prepare an initiator solution.
[0074]
Next, 69.0 parts of water and 0.2 parts of Adekaria Soap SE-10N as a surfactant (E) were charged into a reaction vessel equipped with a nitrogen inlet tube, a condenser, a stirring blade, and a thermometer, and nitrogen was introduced. When the internal temperature reached 80 ° C. while adding, 20% of the above-mentioned initiator solution was added to the reaction vessel, and the emulsion (Z) and the remaining initiator solution were each heated to 80 ° C. for 3.5 hours. The polymerization was further performed at 65 ° C. for 2 hours to obtain a resin dispersion having a nonvolatile content of 50.0%, a viscosity of 100 mPa · s, and a median diameter of 0.18 μm. 0.25 parts of Perex OTP (manufactured by Kao Corporation) as a leveling agent and ADECANOL UH-420 (Asahi) as a leveling agent were added to 100 parts by weight of the resin dispersion adjusted to pH 7.5 with 25% aqueous ammonia. 0.5 parts of Electrification Co., Ltd.) was added and stirred well to obtain an aqueous pressure-sensitive adhesive composition having a viscosity of 3000 mPa · s.
[0075]
The obtained water-based pressure-sensitive adhesive composition was evaluated as follows.
[0076]
20 g / m2 of dry weight of the aqueous pressure-sensitive adhesive composition on release paper 2 After coating and drying at 105 ° C. for 1.5 minutes, it is bonded to a PET film having a thickness of 50 μm and left in an environment of 23 ° C. and 50% humidity for 10 hours or more to remove the non-volatile content of the aqueous pressure-sensitive adhesive composition. A pressure-sensitive adhesive sheet sandwiched between a PET film and release paper was obtained. The pressure-sensitive adhesive sheet was cut into a strip having a length of 100 mm x a width of 25 mm with a cutter to obtain a test piece for an adhesive strength, a holding power, a heat discoloration property, a water whitening resistance, and an anchoring property test.
[0077]
(Adhesive force to polyolefin) The release paper was removed from the test piece, and a 2 kg roll was reciprocated one time at 23 ° C. and 50% humidity on a 2 mm thick polyethylene plate for 24 hours in an environment of 23 ° C. and 50% humidity. Then, in the same environment, a 180-degree peel strength was measured in accordance with the measuring method of the adhesive strength of JIS Z 0237.
[0078]
(Holding force) The release paper was removed from the test piece, and the test piece was affixed to a stainless steel (SUS304) test plate so that the area was 25 mm × 25 mm, and a 1 kg load was applied under conditions of 40 ° C. and 50% humidity. According to the measuring method of the holding power of JIS Z 0237, the displacement (mm) of the film after 72,000 seconds or the falling time (second) of the film was measured.
[0079]
(Water resistance) The release paper was peeled off from the test piece, immersed in ion-exchanged water at 25 ° C. for 24 hours, and the transparency was visually evaluated.
[0080]
：: good transparency
Δ: Transparency slightly deteriorated
C: Transparency is at a level that poses a practical problem.
[0081]
(Heat discoloration property) The release paper was removed from the above test piece, attached to a glass plate having a thickness of 2 mm so that air bubbles did not enter, and the degree of discoloration after heating in a 140 ° C. oven for 48 hours was measured by Nippon Denshoku Industries Co., Ltd. ) Using a color difference meter SZ-Σ80, the ΔYI value of only the glass plate was measured and judged.
[0082]
○: less than 3
Δ: 3 or more and less than 5
×: 5 or more
(Anchoring property) The release paper was removed from the test piece, the pressure-sensitive adhesive surface was strongly squeezed with a thumb, and the degree of removal from the PET base material was visually confirmed and judged.
[0083]
：: PET substrate is not exposed
×: PET substrate is partially exposed
(Workability) The above pressure-sensitive adhesive sheet was cut into 150 mm long × 50 mm wide, and 50 sheets were piled up and cut continuously 10 times in the horizontal direction by a cutting tester (Horizon Electric Cutting Machine PC-39). The weight of the pressure-sensitive adhesive adhered to the blade and the cutting surface of the cutting test machine was weighed and judged.
[0084]
：: less than 50 mg
×: 50 mg or more
(Storage modulus) The aqueous pressure-sensitive adhesive composition was dried on release paper at a dry weight of 20 g / m 2. 2 Two pieces of coated and dried at 105 ° C. for 1.5 minutes were prepared, the pressure-sensitive adhesive surfaces were adhered to each other, cut in half, peeled off one side of the cut release paper, and again The operation of sticking the pressure-sensitive adhesive surfaces to each other was repeated to laminate the pressure-sensitive adhesive layer, thereby obtaining a 1.5-mm-thick storage modulus test piece sandwiched between release papers. This was cut into 8 mm x 8 mm, the release paper on both sides was removed, and using a dynamic viscoelasticity measuring device RDA-III manufactured by Rheometric Scientific F.E., in shear mode at an angular frequency of 1 Hz. It was measured. The measurement was performed from -60 ° C to 200 ° C at a heating rate of 10 ° C / min, and the storage elastic modulus at 100 ° C to 150 ° C was confirmed. The values of 100 ° C and 150 ° C are listed in Table 1 as representative values, but there is no maximum or minimum between 100 ° C and 150 ° C, and the values tend to decrease from 100 ° C to 150 ° C for all samples. Was. Therefore, a value between 100 ° C. and 150 ° C. can be determined.
[0085]
Example 2 Example 2 was repeated, except that KR-1842 (hydroxylated hydrogenated petroleum resin: Arakawa Chemical Industry Co., Ltd., Gardner Color 1 or less) was used in place of Pine Crystal KE-100. Was. The median diameter of the emulsion (Z) was 0.80 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 50.0%, a viscosity of 90 mPa · s, and a median diameter of 0.18 μm. The same evaluation as in Example 1 was performed for the obtained aqueous pressure-sensitive adhesive composition.
[0086]
Example 3 Example 1 is the same as Example 1, except that YS Resin D105 (terpene resin: manufactured by Yashara Chemical Co., Ltd., Gardner Color 1 or less) was used instead of Pine Crystal KE-100, and the treatment with Cavitron was 1 pass. I went to. The median diameter of the emulsion (Z) was 1.12 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 50.0%, a viscosity of 80 mPa · s, and a median diameter of 0.17 μm. The same evaluation as in Example 1 was performed for the obtained aqueous pressure-sensitive adhesive composition.
[0087]
Example 4: An ethylenically unsaturated monomer mixture was obtained by using Clearon K4090 (aromatically modified hydrogenated terpene resin: Gardner Color 1 or less, manufactured by Yashara Chemical Co., Ltd.) in place of Pine Crystal KE-100 in Example 1. (M) was performed in the same manner except that 0.4 parts of acetoacetoxyethyl methacrylate (manufactured by Eastman Chemical Japan Co., Ltd.) was added to (M). The median diameter of the emulsion (Z) was 0.71 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 50.2%, a viscosity of 120 mPa · s, and a median diameter of 0.17 μm. The same evaluation as in Example 1 was performed for the obtained aqueous pressure-sensitive adhesive composition.
[0088]
Comparative Example 1: The same procedure was performed as in Example 1 except that Super Ester A-100 (rosin ester resin: Gardner Color 7: manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of Pine Crystal KE-100. . The median diameter of the emulsion (Z) was 0.75 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 50.0%, a viscosity of 100 mPa · s, and a median diameter of 0.19 μm. The same evaluation as in Example 1 was performed for the obtained aqueous pressure-sensitive adhesive composition.
[0089]
Comparative Example 2: The procedure was performed in the same manner as in Example 1 except that Pensel AD (rosin ester resin: Gardner Color 6-7: manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of Pine Crystal KE-100. The median diameter of the emulsion (Z) was 0.81 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 50.0%, a viscosity of 90 mPa · s, and a median diameter of 0.17 μm. The same evaluation as in Example 1 was performed for the obtained aqueous pressure-sensitive adhesive composition.
[0090]
Comparative Example 3: The same procedure was performed as in Comparative Example 1, except that 3.0 parts of divinylbenzene was added as a monomer having a crosslinkable group to the ethylenically unsaturated monomer mixture (M). The median diameter of the emulsion (Z) was 0.80 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 51.0%, a viscosity of 130 mPa · s, and a median diameter of 0.19 μm. The same evaluation as in Example 1 was performed on the obtained resin dispersion.
[0091]
Comparative Example 4: The procedure was performed in the same manner as in Example 1, except that 2.0 parts of divinylbenzene was added as a monomer having a crosslinkable group to the ethylenically unsaturated monomer mixture (M). The median diameter of the emulsion (Z) was 0.76 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 50.8%, a viscosity of 100 mPa · s, and a median diameter of 0.17 μm. The same evaluation as in Example 1 was performed on the obtained resin dispersion.
[0092]
Comparative Example 5 The same procedure was performed as in Example 1, except that 0.1 part of octylthioglycolate was added as a chain transfer agent to the mixture (Y). The median diameter of the emulsion (Z) was 0.78 μm, and the resin dispersion obtained therefrom had a nonvolatile content of 50.8%, a viscosity of 100 mPa · s, and a median diameter of 0.17 μm. The same evaluation as in Example 1 was performed on the obtained resin dispersion.
Table 1
[0093]
[Table 1]
In Examples 1 to 5, a mixture (Y) containing a light-colored solid resin (T) having a Gardner color of 3 or less and an ethylenically unsaturated monomer mixture (M) was prepared in water in the presence of a surfactant (E). An aqueous pressure-sensitive adhesive composition containing a polymerized resin, wherein the storage elastic modulus at 100 ° C. to 150 ° C. is always 1.5 × 10 5 4 ~ 6 × 10 4 Since it is Pa, the polyolefin adhesive strength is 10 N / 25 mm or more, it also has a holding power, and is excellent in all of water resistance, hot discoloration property, anchoring property and workability. In Comparative Examples 1 and 2, a solid resin having a Gardner color of more than 3 was used, and the storage elastic modulus was low, so that each physical property was poor. Comparative Example 3 uses a solid resin having a Gardner color of more than 3, but uses a large amount of a monomer having a crosslinkable group to make the storage elastic modulus fall within the range of the present invention. However, not only the hot discoloration property but also the anchoring property are poor. In Comparative Example 4, although the light-colored solid resin (T) was used, since the storage elastic modulus was higher than the range of the present invention, the polyolefin adhesion was low and the anchoring property to the substrate was poor. On the other hand, in Comparative Example 5, although the light-colored solid resin (T) was used, the workability was poor because the storage elastic modulus was lower than the range of the present invention.
[0095]
【The invention's effect】
The present inventors have found that a solvent-based two-part pressure-sensitive adhesive has been conventionally used favorably. Even when used for a pressure-sensitive adhesive sheet having a transparent film as a base, it can be applied to a low surface energy adherend such as polyolefin. It was possible to provide a one-pack type water-based pressure-sensitive adhesive composition having excellent adhesive strength and having good resistance to discoloration, water resistance, anchoring to a substrate, and workability. In addition, a suitable production method could be provided.
[Brief description of the drawings]
FIG. 1 is a perspective view showing an example of a stator of a rotor / stator type high-speed rotation continuous emulsifier used in the present invention.
FIG. 2 is a perspective view showing an example of a rotor of a rotor / stator type high-speed rotation continuous emulsifier used in the present invention.
FIG. 3 is a cross-sectional view illustrating an example of a main part of a rotor / stator type high-speed rotation continuous emulsifier used in the present invention.
FIG. 4 is a diagram showing a combined state of a stator projection and a rotor projection when the AA ′ part of FIG. 3 is viewed from the side.
[Explanation of symbols]
1 Stator
2 liquid inlet
3 Stator protrusion
4 Circumferential groove of stator
5 Stator projection slits
6. Rotor drive shaft
7 Rotor
8. Rotor protrusion
9 Rotor circumferential groove
10. Slit of rotor projection
Claims (6)
前記混合物（Ｙ）と界面活性剤（Ｅ）と水とを混合し、強制乳化して０．４〜３．０μｍのメディアン径を有する乳化物（Ｚ）を得る工程［２］、
前記乳化物（Ｚ）をラジカル重合開始剤の存在下重合する工程［３］を含む請求項１または２記載の水性感圧性接着剤組成物の製造方法。A step [1] of mixing at least the ethylenically unsaturated monomer mixture (M) and the light-colored solid resin (T) to obtain a mixture (Y);
Mixing the mixture (Y), the surfactant (E) and water, and forcibly emulsifying to obtain an emulsion (Z) having a median diameter of 0.4 to 3.0 μm [2],
The method for producing an aqueous pressure-sensitive adhesive composition according to claim 1 or 2, comprising a step [3] of polymerizing the emulsion (Z) in the presence of a radical polymerization initiator.
円盤状の基盤部にスリットを有する環状の突起を備えた固定子と、円盤状の基盤部にスリットを有する環状の突起を備えた回転子とを備え、
前記固定子の環状の突起と前記回転子の突起とは、回転子の回転軸に対して同心円状に咬み合みあわされている請求項３記載の水性感圧性接着剤組成物の製造方法。Step [2] is a step of forcibly emulsifying with a rotary continuous emulsifier.
A stator having an annular projection having a slit on a disk-shaped base portion, and a rotor having an annular projection having a slit on the disk-shaped base portion,
The method for producing a water-based pressure-sensitive adhesive composition according to claim 3, wherein the annular projection of the stator and the projection of the rotor are engaged concentrically with the rotation axis of the rotor.
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| JP2007002147A (en) * | 2005-06-27 | 2007-01-11 | Toyo Ink Mfg Co Ltd | Aqueous adhesive composition and method for producing the same |
| JP2008063469A (en) * | 2006-09-08 | 2008-03-21 | Daio Paper Corp | Self-adhesive sheet |
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| JP2006509890A (en) * | 2002-12-13 | 2006-03-23 | イーストマン ケミカル カンパニー | Method for producing aqueous composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006169348A (en) * | 2004-12-15 | 2006-06-29 | Konishi Co Ltd | Curable resin composition |
| JP4636867B2 (en) * | 2004-12-15 | 2011-02-23 | コニシ株式会社 | Moisture curable resin composition |
| JP2007002147A (en) * | 2005-06-27 | 2007-01-11 | Toyo Ink Mfg Co Ltd | Aqueous adhesive composition and method for producing the same |
| JP2008063469A (en) * | 2006-09-08 | 2008-03-21 | Daio Paper Corp | Self-adhesive sheet |
| JP4625436B2 (en) * | 2006-09-08 | 2011-02-02 | 大王製紙株式会社 | Adhesive sheet |
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