JP5348932B2 - Label adhesive - Google Patents
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- Publication number
- JP5348932B2 JP5348932B2 JP2008112649A JP2008112649A JP5348932B2 JP 5348932 B2 JP5348932 B2 JP 5348932B2 JP 2008112649 A JP2008112649 A JP 2008112649A JP 2008112649 A JP2008112649 A JP 2008112649A JP 5348932 B2 JP5348932 B2 JP 5348932B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- adhesive
- water
- manufactured
- meth
- 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.)
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- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 78
- 239000005018 casein Substances 0.000 claims abstract description 45
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 235000021240 caseins Nutrition 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 24
- 229920002472 Starch Polymers 0.000 claims description 19
- 239000008107 starch Substances 0.000 claims description 18
- 235000019698 starch Nutrition 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 9
- 239000002195 soluble material Substances 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 93
- 239000003513 alkali Substances 0.000 abstract description 16
- 239000011521 glass Substances 0.000 abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 150000007942 carboxylates Chemical group 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- -1 ethylene, propylene Chemical group 0.000 description 58
- 239000012153 distilled water Substances 0.000 description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 46
- 239000007864 aqueous solution Substances 0.000 description 37
- 239000000126 substance Substances 0.000 description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 29
- 239000000839 emulsion Substances 0.000 description 28
- 229920001577 copolymer Polymers 0.000 description 27
- 239000002518 antifoaming agent Substances 0.000 description 25
- 239000003995 emulsifying agent Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 239000000178 monomer Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 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 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 239000003999 initiator Substances 0.000 description 16
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 16
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 230000002421 anti-septic effect Effects 0.000 description 8
- 238000007664 blowing Methods 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 7
- 239000012736 aqueous medium Substances 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 230000002335 preservative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004034 viscosity adjusting agent Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- RORNXMCYQBXAFF-UHFFFAOYSA-N 1-(4-octadecanoylpiperidin-4-yl)octadecan-1-one Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)C1(CCNCC1)C(CCCCCCCCCCCCCCCCC)=O RORNXMCYQBXAFF-UHFFFAOYSA-N 0.000 description 1
- LTNTWHDUCTWIPO-UHFFFAOYSA-N 2,3-dioctadecylbutanedioic acid Chemical compound CCCCCCCCCCCCCCCCCCC(C(O)=O)C(C(O)=O)CCCCCCCCCCCCCCCCCC LTNTWHDUCTWIPO-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-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
- BKKIOUJCJQIQQT-UHFFFAOYSA-N 2-(3-methylbutyl)octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)CCC(C)C BKKIOUJCJQIQQT-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JZYAVTAENNQGJB-UHFFFAOYSA-N 3-tripropoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C(C)=C JZYAVTAENNQGJB-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- NONNTIQBZWNPAA-UHFFFAOYSA-N 6-phenoxydodecan-6-ol Chemical compound CCCCCCC(O)(CCCCC)OC1=CC=CC=C1 NONNTIQBZWNPAA-UHFFFAOYSA-N 0.000 description 1
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 1
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- 229940082004 sodium laurate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- XCPXWEJIDZSUMF-UHFFFAOYSA-M sodium;dioctyl phosphate Chemical compound [Na+].CCCCCCCCOP([O-])(=O)OCCCCCCCC XCPXWEJIDZSUMF-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、ラベル用接着剤に関する。より詳しくは、ガラス瓶等の容器に貼り付けるラベルに塗工されるものであって、耐水性、アルカリ洗瓶性、初期接着性、感温性、経時粘度安定性及びラベラー洗浄性に優れるラベル用接着剤に関する。 The present invention relates to an adhesive for labels. More specifically, it is applied to a label to be attached to a container such as a glass bottle, and is used for a label having excellent water resistance, alkaline washing properties, initial adhesiveness, temperature sensitivity, viscosity stability with time, and labeler washing properties. It relates to adhesives.
ビール及び日本酒等の瓶は、冷却するために水に浸漬され、また、冷蔵庫で保管後、室温中に取り出されて、瓶表面に結露が生ずる。このような場合でも、瓶に貼り付けられたラベルは瓶から剥離してはならない。従って、瓶にラベルを貼り付けるために用いられる接着剤は一般的に耐水性を有する。また、瓶は再利用されるため、工場に回収された後、加温されたアルカリ水中に浸漬され、ラベルが除去される。そのため、アルカリ水によりラベルが瓶から短時間で剥離する性質（アルカリ洗瓶性）を有する必要がある。従来、このような耐水性とアルカリ洗瓶性の両性能を有する接着剤として、カゼインをベースとする接着剤が使用されてきた。 Bottles such as beer and sake are immersed in water to cool them, and after being stored in a refrigerator, they are taken out to room temperature, causing condensation on the bottle surface. Even in such a case, the label affixed to the bottle must not peel from the bottle. Accordingly, the adhesive used to attach the label to the bottle is generally water resistant. Further, since the bottle is reused, after being collected in the factory, it is immersed in warmed alkaline water to remove the label. Therefore, it is necessary to have a property (alkali washing bottle property) that the label is peeled from the bottle in a short time by alkaline water. Conventionally, an adhesive based on casein has been used as an adhesive having both water resistance and alkaline washing performance.
例えば、特許文献１は、カゼインにジルコニウム化合物、ビニルポリマー溶液又は分散液を含有して成る接着剤を開示し、特許文献２は、カゼイン、水不溶性でかつアルカリ可溶性又はアルカリ膨潤性の物質を含む接着剤を開示する。
また、特許文献３は、カゼインに、約１０〜１９０℃の軟化点と３００〜１０，０００の重量平均分子量（Ｍｗ）を有する樹脂を含む接着剤を開示する。
更に、特許文献４は、エチレン酢酸ビニルエマルジョンを粘度調節剤として含むカゼイン系接着剤を開示する。
For example, Patent Document 1 discloses an adhesive containing a zirconium compound, a vinyl polymer solution or a dispersion in casein, and Patent Document 2 includes casein, a water-insoluble and alkali-soluble or alkali-swellable substance. An adhesive is disclosed.
Patent Document 3 discloses an adhesive containing a resin having a softening point of about 10 to 190 ° C. and a weight average molecular weight (Mw) of 300 to 10,000 in casein.
Further, Patent Document 4 discloses a casein adhesive containing an ethylene vinyl acetate emulsion as a viscosity modifier.
しかし、これらのカゼイン系接着剤は、その初期接着性が不充分であるため、ラベルを瓶に貼付けた後、瓶と瓶との接触により、貼り付けたラベルが瓶に対して傾斜したり、ラベルに皺が発生する等の外観状の問題が発生することがある。更に、冬場になると、カゼイン系接着剤の粘度が極端に上昇するため、ラベラーの立ち上げ時に時間がかかり、生産効率が低下することもある。またカゼインは牛乳を原料とする天然物であるため、経時での粘度安定性が非常に悪く、高温での保管では粘度が著しく低下してしまう。 However, these casein adhesives have insufficient initial adhesiveness, so after the label is attached to the bottle, the attached label is inclined with respect to the bottle due to the contact between the bottle and the bottle, Appearance problems such as wrinkles on the label may occur. Furthermore, in winter, the viscosity of the casein-based adhesive extremely increases, so it takes time to start up the labeler, and the production efficiency may decrease. In addition, since casein is a natural product that uses milk as a raw material, its viscosity stability over time is very poor, and when stored at high temperatures, the viscosity is significantly reduced.
カゼインの含有量を低くし、他の成分を多く含むカゼイン系接着剤又はカゼインを含まない接着剤も検討されているが、これらの接着剤は、カゼインを主成分とする接着剤と比較して、耐水性及びアルカリ洗瓶性が劣り、初期接着性も不充分となる。また、接着剤使用後にラベラーを水で洗浄する際に、接着剤の除去が困難なため、洗浄に非常に時間がかかるという問題もある。 Casein adhesives that contain a low amount of casein and contain many other components, or adhesives that do not contain casein, are also being investigated, but these adhesives are compared to adhesives based on casein. In addition, the water resistance and alkali washing ability are poor, and the initial adhesiveness is insufficient. In addition, when the labeler is washed with water after using the adhesive, it is difficult to remove the adhesive, which causes a problem that the cleaning takes a very long time.
本発明は、上記現状に鑑みてなされたものであり、初期接着性に優れ、冬場の粘度上昇が少なく、経時での粘度が安定で、ラベラー洗浄性に優れ、カゼインを多く含む接着剤と同等の耐水性及びアルカリ洗瓶性を有するラベル用接着剤を提供することを目的とする。 The present invention has been made in view of the above situation, and has excellent initial adhesiveness, little viscosity increase in winter, stable viscosity over time, excellent labeler detergency, and equivalent to an adhesive containing a large amount of casein It aims at providing the adhesive agent for labels which has the water resistance of this, and an alkali washability.
本発明者等は、鋭意研究を重ねた結果、特定の重量平均分子量と特定の酸価を有し、特定の官能基を含む水溶性樹脂とカゼインを配合することによって、カゼイン系接着剤の有する耐水性とアルカリ洗瓶性を損なうことなく、初期接着性と冬場の粘度上昇及び経時粘度安定性を改善でき、更に、これまでの、カゼイン量を少なくし、他の成分を添加したカゼイン系接着剤（又はカゼインベース接着剤）又はカゼインを含まない接着剤（又はカゼインフリー接着剤）と比較して、良好な、耐水性、アルカリ洗瓶性、初期接着性、ラベラー洗浄性を得られる事を見出し、本発明を完成させるに至ったものである。 As a result of intensive research, the inventors have a casein adhesive by blending a water-soluble resin having a specific weight average molecular weight and a specific acid value and containing a specific functional group with casein. It can improve initial adhesiveness, viscosity increase in winter and viscosity stability over time without impairing water resistance and alkali washability, and can reduce the amount of casein and add other ingredients. Compared with adhesives (or casein-based adhesives) or adhesives that do not contain casein (or casein-free adhesives), good water resistance, alkaline washing properties, initial adhesiveness, and labeler cleaning properties can be obtained. The headline and the present invention have been completed.
即ち、本発明は一の要旨において、
（Ａ）４，０００〜１７０，０００の重量平均分子量（Ｍｗ）及び３０〜２６０の酸価を有し、カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種を含む水溶性樹脂（以下、「（Ａ）水溶性樹脂」又は「（Ａ）成分」ともいう）、及び
（Ｂ）カゼイン（以下、「（Ｂ）成分」ともいう）
を含んで成ることを特徴とするラベル用接着剤を提供する。
That is, the present invention in one aspect,
(A) A water-soluble material having a weight average molecular weight (Mw) of 4,000 to 170,000 and an acid value of 30 to 260 and containing at least one selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group. Resin (hereinafter also referred to as “(A) water-soluble resin” or “(A) component”), and (B) casein (hereinafter also referred to as “(B) component”).
A label adhesive is provided.
本発明の好ましい態様では、成分（Ａ）は、−７０℃〜１６０℃のガラス転移温度（以下、「Ｔｇ」ともいう）を有する。
本発明の更に好ましい態様では、（Ａ）成分は、１５０００〜１１００００の重量平均分子量（以下、「Ｍｗ」又は単に「分子量」ともいう）を有する。
In a preferred embodiment of the present invention, the component (A) has a glass transition temperature (hereinafter also referred to as “Tg”) of −70 ° C. to 160 ° C.
In a further preferred embodiment of the present invention, the component (A) has a weight average molecular weight (hereinafter also referred to as “Mw” or simply “molecular weight”) of 15,000 to 110,000.
本発明の態様では、（Ａ）成分は、（メタ）アクリル酸と（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンと（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンとα−メチルスチレンの共重合体、又はスチレンと無水マレイン酸の共重合体から選択される少なくとも一種である。 In the embodiment of the present invention, the component (A) is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester, a copolymer of (meth) acrylic acid, styrene and (meth) acrylic acid ester, ) At least one selected from a copolymer of acrylic acid, styrene and α-methylstyrene, or a copolymer of styrene and maleic anhydride.
本発明の別の要旨では、上記ラベル用接着剤を塗布することで得られるラベルが提供される。
本発明の好ましい態様では、ガラス瓶に貼り付けられるラベルを例示できる。
In another aspect of the present invention, a label obtained by applying the label adhesive is provided.
In the preferable aspect of this invention, the label affixed on a glass bottle can be illustrated.
本発明に係るラベル用接着剤は、
（Ａ）４，０００〜１７０，０００の重量平均分子量（Ｍｗ）及び３０〜２６０の酸価を有し、カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種を含む水溶性樹脂、及び
（Ｂ）カゼイン
を含んで成るので、
初期接着性に優れ、冬場の粘度上昇が少なく、経時での粘度が安定で、ラベラー洗浄性に優れ、カゼイン接着剤と同等の耐水性、アルカリ洗瓶性を有する。
The adhesive for labels according to the present invention is
(A) A water-soluble material having a weight average molecular weight (Mw) of 4,000 to 170,000 and an acid value of 30 to 260 and containing at least one selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group. A resin, and (B) because it comprises casein,
Excellent initial adhesiveness, little increase in winter viscosity, stable viscosity over time, excellent labeler washability, water resistance and alkaline rinsing performance equivalent to casein adhesive.
本発明のラベル用接着剤は、（Ａ）成分のＴｇが−７０〜１６０℃である場合、より耐水性に優れる。
本発明のラベル用接着剤は、（Ａ）成分の重量平均分子量（Ｍｗ）が１５０００〜１１００００である場合、より耐水性とアルカリ洗瓶性に優れる。
When the Tg of the component (A) is −70 to 160 ° C., the label adhesive of the present invention is more excellent in water resistance.
When the weight average molecular weight (Mw) of the component (A) is 15000 to 110000, the label adhesive of the present invention is more excellent in water resistance and alkaline rinsing properties.
本発明のラベル用接着剤は、（Ａ）成分が、（メタ）アクリル酸と（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンと（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンとα−メチルスチレンの共重合体、又はスチレンと無水マレイン酸の共重合体から選択される少なくとも一種である場合、より耐水性、アルカリ洗瓶性に優れる。 In the label adhesive of the present invention, the component (A) is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester, and a copolymer of (meth) acrylic acid, styrene and (meth) acrylic acid ester. When it is at least one selected from a copolymer of (meth) acrylic acid, styrene and α-methylstyrene, or a copolymer of styrene and maleic anhydride, it is more excellent in water resistance and alkaline rinsing properties.
本発明のラベルは、上記接着剤を塗布することで得られるので、ガラス、金属、プラスチック等の容器に貼り付けられても、結露等で容器から容易に剥がれることがない。
本発明のラベルは、ガラス瓶に貼り付けることができるので、瓶をアルカリで洗浄することで容易に剥離する。従って、容器のリサイクルを促進することが可能である。
Since the label of the present invention is obtained by applying the above-mentioned adhesive, even if it is affixed to a container made of glass, metal, plastic or the like, it is not easily peeled off from the container by condensation or the like.
Since the label of this invention can be affixed on a glass bottle, it peels easily by wash | cleaning a bottle with an alkali. Therefore, it is possible to promote recycling of the container.
本発明に係る「（Ｂ）カゼイン」とは、一般的にカゼインとされているものであって、本発明に係るラベル用接着剤を得ることができる限り、特に限定されるものではない。本発明に係る（Ｂ）カゼインとして、市販されているカゼインを使用することができる。カゼインとして具体的には、塩酸カゼイン、硫酸カゼイン、レンネットカゼイン、ラクチックカゼイン又はこれらの変性化合物を例示できる。 The “(B) casein” according to the present invention is generally casein and is not particularly limited as long as the label adhesive according to the present invention can be obtained. As (B) casein according to the present invention, commercially available casein can be used. Specific examples of casein include casein hydrochloride, casein sulfate, rennet casein, lactic casein, and modified compounds thereof.
本発明に係る「（Ａ）水溶性樹脂」とは、水性媒体に溶解可能な高分子をいう。
ここで、「水性媒体」とは、水道水、蒸留水又はイオン交換水等の一般的な水をいうが、水性媒体に溶解可能な有機溶剤であって、単量体等の本発明に関する樹脂の原料と反応性の乏しい有機溶剤、例えば、アセトン及び酢酸エチル等を含んでもよく、更に水性媒体に溶解可能な単量体、オリゴマー、プレポリマー及び／又は樹脂等を含んでもよく、また後述するように水系の樹脂又は水溶性樹脂を製造する際に通常使用される、乳化剤、重合性乳化剤、重合反応開始剤、鎖延長剤及び／又は各種添加剤等を含んでもよい。
The “(A) water-soluble resin” according to the present invention refers to a polymer that can be dissolved in an aqueous medium.
Here, the “aqueous medium” refers to general water such as tap water, distilled water, or ion exchange water, but is an organic solvent that can be dissolved in an aqueous medium, and is a resin related to the present invention such as a monomer. May contain organic solvents that are poorly reactive with the raw materials, such as acetone and ethyl acetate, and may further contain monomers, oligomers, prepolymers and / or resins that can be dissolved in an aqueous medium, and will be described later. Thus, it may contain an emulsifier, a polymerizable emulsifier, a polymerization initiator, a chain extender and / or various additives, which are usually used when producing a water-based resin or a water-soluble resin.
本発明に係る「（Ａ）水溶性樹脂」は、特定の重量平均分子量（Ｍｗ）と酸価を有する。Ｍｗは４０００〜１７００００であり、特に、１５０００〜１１００００であることが好ましい。Ｍｗが４，０００より低い場合、耐水性が著しく劣るだけでなく、接着剤が分離する傾向が見られ、品質が劣悪なものとなる。また、Ｍｗが低いと接着剤の粘着性が低下するため、充分な初期接着性が得られない。Ｍｗが１７００００より高い場合、樹脂の流動性が低くなるため、アルカリ洗瓶性が著しく劣り、ラベラーの洗浄性も悪くなる。Ｍｗが１５０００〜１１００００の場合、ラベラーでの接着剤の飛び散りが少なく、結露瓶への札貼性がより向上する。 The “(A) water-soluble resin” according to the present invention has a specific weight average molecular weight (Mw) and an acid value. Mw is 4000 to 170000, and particularly preferably 15000 to 110000. When Mw is lower than 4,000, not only the water resistance is remarkably inferior, but also the tendency of the adhesive to separate is seen, resulting in poor quality. Further, when Mw is low, the tackiness of the adhesive is lowered, so that sufficient initial adhesiveness cannot be obtained. When Mw is higher than 170000, the fluidity of the resin is lowered, so that the alkaline bottle washing property is remarkably inferior and the labeler washing property is also deteriorated. When Mw is 15000 to 110000, the adhesive is less scattered by the labeler, and the sticking property to the condensation bottle is further improved.
酸価は３０〜２６０であり、１００〜２００であることが好ましく、１７０までが特に好ましい。酸価が３０より低い場合、アルカリに対する溶解性が低下するため、アルカリ洗瓶性が著しく劣る。また、水への溶解性も低下するためラベラー洗浄性が悪くなる。酸価が２６０より高い場合、水への溶解性が高くなるため、耐水性が著しく劣るだけでなく、接着剤の粘度が経時で上昇する傾向が見られ、品質が劣悪なものとなる。 The acid value is 30 to 260, preferably 100 to 200, and particularly preferably up to 170. When the acid value is lower than 30, the alkali-washing performance is remarkably inferior because the solubility in alkali decreases. Moreover, since the solubility to water also falls, labeler washability worsens. When the acid value is higher than 260, the solubility in water becomes high, so that not only the water resistance is remarkably inferior, but also the viscosity of the adhesive tends to increase with time, resulting in poor quality.
本発明に係る重量平均分子量とは、ゲルパーミュレーションクロマトグラフィー（ＧＰＣ）装置で測定され、単分散分子量ポリスチレンで換算された重量平均分子量をいう。より具体的には、ＨＬＣ−８２２０ＧＰＣ（東ソー社製）を用い、ＲＩ及びＵＶのクロマトグラムを検出した。ＧＰＣカラムとして、ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ ＨＺ−Ｍ（東ソー社製）、ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２０００（東ソー社製） 各２本を用いた。試料をテトラヒドロフランに溶解して、流速を０．３５ｍｌ／ｍｉｎ、カラム温度を４０℃にて流し、標準物質としての単分散分子量のポリスチレンを使用した検量線を用いて分子量の換算を行い、重量平均分子量を求めた。 The weight average molecular weight according to the present invention refers to a weight average molecular weight measured with a gel permeation chromatography (GPC) apparatus and converted to monodisperse molecular weight polystyrene. More specifically, RI and UV chromatograms were detected using HLC-8220GPC (manufactured by Tosoh Corporation). Two GSK columns, TSKgel SuperMultipore HZ-M (manufactured by Tosoh Corp.) and TSKgel SuperHZ2000 (manufactured by Tosoh Corp.), were used. Dissolve the sample in tetrahydrofuran, flow at a flow rate of 0.35 ml / min and a column temperature of 40 ° C., convert the molecular weight using a calibration curve using polystyrene with a monodispersed molecular weight as a standard substance, and calculate the weight average The molecular weight was determined.
本発明に係る酸価とは、樹脂の固形分あたりの酸価を指し、樹脂又は重合体の固形分１ｇを中和するのに必要な水酸化カリウムのミリグラム数と定義される。酸価は通常、試料をアルコールエーテルに溶かし、これにフェノールフタレインを指示薬として加え、０．５Ｎ水酸化カリウムで滴定することによって決定できる。 The acid value according to the present invention refers to the acid value per solid content of the resin and is defined as the number of milligrams of potassium hydroxide required to neutralize 1 g of the solid content of the resin or polymer. The acid value can usually be determined by dissolving a sample in alcohol ether, adding phenolphthalein as an indicator thereto, and titrating with 0.5N potassium hydroxide.
尚、本明細書においては、アクリル酸とメタクリル酸を総称して「（メタ）アクリル酸」ともいい、アクリル酸エステルとメタクリル酸エステルを総称して「（メタ）アクリル酸エステル」又は「（メタ）アクリレート」ともいう。その他も同様である。 In this specification, acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”, and acrylic acid ester and methacrylic acid ester are collectively referred to as “(meth) acrylic acid ester” or “(meta ) Acrylate ". Others are the same.
本発明に係る（Ａ）水溶性樹脂は、カルボン酸基（又はカルボキシル基：−ＣＯＯＨ）、カルボン酸塩基（−ＣＯＯ−）及び無水カルボン酸基（−ＣＯ−Ｏ−ＣＯ−）から選択される少なくとも一種の官能基を含む。ここで、カルボン酸塩基の対カチオンは、本発明が目的とするラベル用接着剤を得ることができる限り、特に限定されるものではない。そのような対カチオンとして、例えば、アンモニウムイオンを例示することができる。 The water-soluble resin (A) according to the present invention is selected from a carboxylic acid group (or carboxyl group: —COOH), a carboxylic acid group (—COO − ), and a carboxylic anhydride group (—CO—O—CO—). Contains at least one functional group. Here, the counter cation of the carboxylate group is not particularly limited as long as the label adhesive targeted by the present invention can be obtained. As such a counter cation, an ammonium ion can be illustrated, for example.
上述の特定の官能基を含む（Ａ）水溶性樹脂として、カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種の官能基を含むオレフィン性単量体の共重合体を例示することができる。
そのようなオレフィン性単量体の共重合体として、例えば（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、無水マレイン酸等のカルボキシル基又は酸無水物を含有するオレフィン性単量体とα−オレフィン、ビニルエステル、ビニルエーテル、（メタ）アクリル酸エステル、塩化ビニル、アクリロニトリル等のオレフィン性単量体との共重合体を例示できる。
Examples of the water-soluble resin (A) containing the specific functional group described above include a copolymer of an olefin monomer containing at least one functional group selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group. can do.
As a copolymer of such olefinic monomers, for example, a carboxyl group or acid anhydride such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, etc. is contained. Examples include copolymers of olefinic monomers and olefinic monomers such as α-olefins, vinyl esters, vinyl ethers, (meth) acrylic acid esters, vinyl chloride, acrylonitrile and the like.
α−オレフィンとして、例えばエチレン、プロピレン、ブテン−１、ブテン−２、イソブテン、２−メチル−ブテン−１、３−メチル−ブテン−１、ペンテン−１、４−メチル−ペンテン−１、オクテン−１、ジイソブチレン、スチレン、α−メチルスチレン等を例示できる。
ビニルエステルとして、例えば酢酸ビニル、プロピオン酸ビニル、ｔ−ブチルビニルエステル、バーサチック酸ビニル等が例示できる。
Examples of the α-olefin include ethylene, propylene, butene-1, butene-2, isobutene, 2-methyl-butene-1, 3-methyl-butene-1, pentene-1, 4-methyl-pentene-1, and octene- 1, diisobutylene, styrene, α-methylstyrene and the like.
Examples of vinyl esters include vinyl acetate, vinyl propionate, t-butyl vinyl ester, and vinyl versatate.
（メタ）アクリル酸エステルとして、メタクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ−ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸セチル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、ポリエチレングリコールモノ（メタ）アクリレート、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、ポリプロピレングリコールモノ（メタ）アクリレート、（メタ）アクリル酸アミド、Ｎ−メチロールアクリルアミド、ジアセトンアクリルイアミド、アセトアセトキシエチル（メタ）アクリレート、メクリル酸グリシジル、３，４−エポキシシクロヘキシル（メタ）アクリレート等を例示できる。 As (meth) acrylic acid ester, methyl methacrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, ( Isononyl methacrylate, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxypropyl, polyethylene glycol mono (meth) acrylate Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic acid amide, N-methylolacrylamide, diacetone acrylic amide, acetoacetoxyethyl (meth) acrylate, methacryl Examples thereof include glycidyl acid and 3,4-epoxycyclohexyl (meth) acrylate.
また、カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種の官能基を含むオレフィン性単量体の共重合体は、アルコキシシラン単量体やラジカル重合可能な二重結合を有する「反応性界面活性剤」を含有しても良い。 In addition, a copolymer of an olefin monomer containing at least one functional group selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group has an alkoxysilane monomer or a radically polymerizable double bond. You may contain the "reactive surfactant" which has.
アルコキシシラン単量体としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、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、ビニルトリス（β-メトキシエトキシ）シラン、ビニルトリアセトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリエトキシシラン、γ-メタクリロキシプロピルトリプロポキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-メタクリロキシプロピルトリス（イソプロポキシ）シラン等が例示できる。 Examples of the alkoxysilane monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, and vinyltris (β-methoxyethoxy). Silane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltripropoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltris ( Examples include isopropoxy) silane.
反応性界面活性剤として、例えば、ポリオキシエチレンアリルグリシジルノニルフェニルエーテルの硫酸エステル塩（アデカリアソープＳＥシリーズ（商品名）、旭電化工業社製）、α−スルホ−ω−（１−（アルコキシ）メチル−２−（２−プロペニルオキシ）エトキシ）−ポリ（オキシ−１，２−エタンジイル）のアンモニウム塩（アデカリアソープＳＲシリーズ（商品名）、旭電化工業社製）、ポリオキシエチレン（又はアルキレン）アルキル（又はアルケニル）エーテル硫酸アンモニウム塩（ＰＤシリーズ（商品名）、花王社製）、スルホコハク酸型反応性活性剤（ラテムル１８０シリーズ（商品名）、花王社製）、アルキルアリルスルホコハク酸ナトリウム塩（エレミノールＪＳ−２（商品名）、三洋化成工業社製）、ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸エステルアンモニウム塩（アクアロンＨＳシリーズ（商品名）、第一工業製薬社製）、ポリオキシエチレン−１−（アリルオキシメチル）アルキルエーテル硫酸エステルアンモニウム塩（アクアロンＫＨシリーズ（商品名）、第一工業製薬社製）、ポリオキシエチレンアリルグリシジルノニルフェニルエーテル（アデカリアソープＮＥシリーズ（商品名）、旭電化工業社製）、ポリオキシエチレンノニルプロペニルエーテル（アクアロンＲＮシリーズ（商品名）、第一工業製薬社製）、α−ヒドロ−ω−（１−（アルコキシ）メチル−２−（プロペニルオキシ）エトキシ）−ポリ（オキシ−１，２−エタンジイル）（アデカリアソープＥＲシリーズ（商品名）、旭電化工業社製）等を例示できる。 Examples of reactive surfactants include polyoxyethylene allyl glycidyl nonyl phenyl ether sulfate (Adekaria soap SE series (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.), α-sulfo-ω- (1- (alkoxy ) Ammonium salt of methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (Adekaria soap SR series (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene (or Alkylene) alkyl (or alkenyl) ether sulfate ammonium salt (PD series (trade name), manufactured by Kao), sulfosuccinic acid type reactive activator (Latemul 180 series (trade name), manufactured by Kao), alkylallylsulfosuccinic acid sodium salt (Eleminol JS-2 (trade name), manufactured by Sanyo Chemical Industries), polyoxye Tylene-nonylpropenyl phenyl ether sulfate ammonium salt (Aqualon HS series (trade name), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt (Aqualon KH series (trade name) ), Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene allyl glycidyl nonyl phenyl ether (Adekaria soap NE series (trade name), manufactured by Asahi Denka Kogyo), polyoxyethylene nonyl propenyl ether (Aqualon RN series (trade name)) , Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), α-hydro-ω- (1- (alkoxy) methyl-2- (propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (Adekalia soap ER series (product) Name), manufactured by Asahi Denka Kogyo Co., Ltd.).
本発明に係る（Ａ）水溶性樹脂は、公知のラジカル重合を用いて得ることができる。そのようなラジカル重合方法として、例えば、塊状重合、溶液重合、懸濁重合及び乳化重合を例示できる。これらの重合方法のうち、乳化重合が特に好ましい。 The (A) water-soluble resin according to the present invention can be obtained by using known radical polymerization. Examples of such radical polymerization methods include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Of these polymerization methods, emulsion polymerization is particularly preferred.
乳化重合とは、水を媒体とした乳化剤を用いるラジカル重合であり、乳化重合の既知のの手順に従って目的とする本発明に係る（Ａ）水溶性樹脂を得ることができる。必要に応じて、乳化重合後にアルカリを添加することが好ましい。乳化重合の手順として、例えば、（ｉ）オレフィン性単量体と乳化剤を水性媒体中に仕込んで重合させる方法、（ｉｉ）オレフィン性単量体と乳化剤を連続的又は間欠的に水性媒体中に滴下して重合させる方法及び（ｉｉｉ）オレフィン性単量体と乳化剤を水に加えて乳化液を調製し、これを連続的又は間欠的に水性媒体中に滴下して重合させる方法等を例示することができる。また、樹脂の分子量を調整するために連鎖移動剤を用いる事ができる。 Emulsion polymerization is radical polymerization using an emulsifier using water as a medium, and the target (A) water-soluble resin according to the present invention can be obtained according to a known procedure of emulsion polymerization. If necessary, it is preferable to add an alkali after emulsion polymerization. As a procedure of emulsion polymerization, for example, (i) a method in which an olefinic monomer and an emulsifier are charged in an aqueous medium and polymerized, and (ii) an olefinic monomer and an emulsifier are continuously or intermittently contained in the aqueous medium. Examples of a method of dropping and polymerizing and (iii) a method of preparing an emulsion by adding an olefinic monomer and an emulsifier to water, and dropping and polymerizing this into an aqueous medium continuously or intermittently, etc. be able to. A chain transfer agent can be used to adjust the molecular weight of the resin.
乳化重合後に添加するアルカリとして、例えば、ナトリウム、カリウム、リチウム等の水酸化物や炭酸塩；マグネシウム、カルシウム等のアルカリ土類金属の水酸化物や炭酸塩；アンモニア；アルキルアミン、アリルアミン、アルカノールアミン等のアミン類等を例示できる。 Examples of alkalis added after emulsion polymerization include hydroxides and carbonates such as sodium, potassium and lithium; hydroxides and carbonates of alkaline earth metals such as magnesium and calcium; ammonia; alkylamines, allylamines and alkanolamines. And the like.
乳化剤はモノマー乳化力を有し、乳化重合の過程ではミセルを形成してモノマーに重合の場を提供し、重合中又は重合後はポリマー粒子の表面に固定化して粒子の分散安定性を図る。乳化剤としては、例えば、アニオン系界面活性剤、ノニオン系界面活性剤、高分子界面活性剤、乳化剤の一分子内にラジカル重合可能な二重結合を有する「反応性界面活性剤」等が挙げられる。 The emulsifier has a monomer emulsifying power. In the process of emulsion polymerization, micelles are formed to provide a field for polymerization to the monomer, and during or after the polymerization, it is immobilized on the surface of the polymer particles to improve the dispersion stability of the particles. Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, a polymer surfactant, and a “reactive surfactant” having a double bond capable of radical polymerization in one molecule of the emulsifier. .
アニオン系界面活性剤として、例えば、
ナトリウムドデシルサルフェート、カリウムドデシルサルフェート等のアルカリ金属アルキルサルフェート；
ナトリウムドデシルポリグリコールエーテルサルフェート；
アンモニウムドデシルサルフェート等のアンモニウムアルキルサルフェート；
ナトリウムスルホシノエート；
スルホン化パラフィンのアルカリ金属塩、スルホン化パラフィンのアンモニウム塩等のアルキルスルホネート；
ナトリウムラウレート、トリエタールアミンオレエート、トリエタールアミンアビエテート等の脂肪酸塩；
ナトリウムドデシルベンゼンスルホネート、アルカリフェノールヒドロキシエチレンのアルカリ金属サルフェート等のアルキルアリールスルホネート；
高アルキルナフタレンスルホン酸塩；
ナフタレンスルホン酸ホルマリン縮合物；
ジアルキルスルホコハク酸塩；
ポリオキシエチレンアルキルサルフェート塩；
ポリオキシエチレンアルキルアリールサルフェート塩；
等を例示できる。
As an anionic surfactant, for example,
Alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate;
Sodium dodecyl polyglycol ether sulfate;
Ammonium alkyl sulfates such as ammonium dodecyl sulfate;
Sodium sulfosinoate;
Alkyl sulfonates such as alkali metal salts of sulfonated paraffin and ammonium salts of sulfonated paraffin;
Fatty acid salts such as sodium laurate, trietalamine oleate, trietalamine abiate;
Alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate, alkali metal sulfate of alkali phenol hydroxyethylene;
High alkyl naphthalene sulfonate;
Naphthalenesulfonic acid formalin condensate;
Dialkyl sulfosuccinates;
Polyoxyethylene alkyl sulfate salts;
Polyoxyethylene alkylaryl sulfate salts;
Etc. can be illustrated.
ノニオン系界面活性剤として、例えば、
ポリオキシエチレンアルキルエーテル；
ポリオキシエチレンアルキルアリールエーテル；
ソルビタン脂肪酸エステル；
ポリオキシエチレンソルビタン脂肪酸エステル；
グリセロールのモノラウレート等の脂肪酸モノグリセライド；
ポリオキシエチレンオキシプロピレン共重合体；
エチレンオキサイドと脂肪族アミン、アミド又は酸との縮合生成物；
等を例示できる。
As a nonionic surfactant, for example,
Polyoxyethylene alkyl ethers;
Polyoxyethylene alkyl aryl ethers;
Sorbitan fatty acid ester;
Polyoxyethylene sorbitan fatty acid ester;
Fatty acid monoglycerides such as monolaurate of glycerol;
Polyoxyethyleneoxypropylene copolymer;
Condensation products of ethylene oxide and aliphatic amines, amides or acids;
Etc. can be illustrated.
高分子界面活性剤として、例えば、ポリビニルアルコール等を例示できる。
反応性界面活性剤として、例えばオレフィン性単量体の項目で記載したものを例示できる。
Examples of the polymer surfactant include polyvinyl alcohol.
Examples of the reactive surfactant include those described in the item of olefin monomer.
また、近年、環境意識の高まりから、ＰＲＴＲ法に該当する乳化剤は使用しない事が好ましい。ＰＲＴＲ法に該当する乳化剤としては、例えば、ポリオキシエチレンアルキル（Ｃ１２〜Ｃ１５）エーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ソフトアルキル（Ｃ１４〜Ｃ１５）ベンゼンスルホン酸ナトリウム等を例示できる。また、ノニルフェニル基は環境ホルモンであることより、特に、ノニルフェニル基を含まない乳化剤、即ち非ノニルフェニル系乳化剤を使用することが好ましい。
非ノニルフェニル系乳化剤として、特に、ポリオキシエチレンオレイルエーテル硫酸ナトリウム（ラテムルＷＸ、花王社製）が好ましい。ポリオキシエチレンオレイルエーテル硫酸ナトリウムを用いると、環境的に好ましいだけではなく、他の乳化剤を用いるよりも、耐水性、アルカリ洗瓶性が高いレベルのラベル用接着剤を得ることができる。
In recent years, it is preferable not to use an emulsifier corresponding to the PRTR method due to the increase in environmental awareness. Examples of emulsifiers corresponding to the PRTR method include polyoxyethylene alkyl (C12 to C15) ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, soft alkyl (C14 to C15) sodium benzenesulfonate, and the like. it can. Further, since the nonylphenyl group is an environmental hormone, it is particularly preferable to use an emulsifier that does not contain a nonylphenyl group, that is, a non-nonylphenyl emulsifier.
As the non-nonylphenyl emulsifier, sodium polyoxyethylene oleyl ether sulfate (Latemul WX, manufactured by Kao Corporation) is particularly preferable. When polyoxyethylene oleyl ether sodium sulfate is used, it is not only environmentally preferable, but a label adhesive having a higher level of water resistance and alkali rinsing ability than other emulsifiers can be obtained.
連鎖移動剤として、メルカプトエタノール、チオグリセロール、チオグリコール酸、チオグリコール酸オクチル、メルカプトプロピオン酸メチル、ｎ−ドデシルメルカプタン等を例示できる。 Examples of chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, octyl thioglycolate, methyl mercaptopropionate, n-dodecyl mercaptan, and the like.
カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種の官能基を含むオレフィン性単量体の共重合体として、特に、（メタ）アクリル酸と（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンと（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンとα−メチルスチレンの共重合体、及びスチレンと無水マレイン酸の共重合体から選択される少なくとも一種が好ましい。 As a copolymer of an olefin monomer containing at least one functional group selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group, in particular, a copolymer of (meth) acrylic acid and (meth) acrylic ester. From a polymer, a copolymer of (meth) acrylic acid, styrene and (meth) acrylic ester, a copolymer of (meth) acrylic acid, styrene and α-methylstyrene, and a copolymer of styrene and maleic anhydride At least one selected is preferred.
カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種の官能基を含むオレフィン性単量体の共重合体が、（メタ）アクリル酸と（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンと（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンとα−メチルスチレンの共重合体、及びスチレンと無水マレイン酸の共重合体から選択される少なくとも一種であると、耐水性、アルカリ洗瓶性も高いレベルのラベル用接着剤を得ることができる。 A copolymer of an olefin monomer containing at least one functional group selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester , (Meth) acrylic acid / styrene / (meth) acrylic acid ester copolymer, (meth) acrylic acid / styrene / α-methylstyrene copolymer, and styrene / maleic anhydride copolymer. If it is at least one kind, it is possible to obtain a label adhesive having a high level of water resistance and alkaline washing ability.
更に、カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種の官能基を含むオレフィン性単量体の共重合体として、（メタ）アクリル酸と（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンと（メタ）アクリル酸エステルの共重合体及びスチレンと無水マレイン酸の共重合体から選択される少なくとも一種がより好ましい。 Furthermore, as a copolymer of an olefin monomer containing at least one functional group selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is used. More preferred is at least one selected from a polymer, a copolymer of (meth) acrylic acid, styrene and (meth) acrylic acid ester, and a copolymer of styrene and maleic anhydride.
（Ａ）水溶性樹脂のＴｇは−７０〜１６０℃であるが、カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種の官能基を含むオレフィン性単量体の共重合体が、（メタ）アクリル酸と（メタ）アクリル酸エステルの共重合体、及び／又は、（メタ）アクリル酸とスチレンと（メタ）アクリル酸エステルの共重合体の場合、Ｔｇは−７０℃〜５０℃であることが好ましい。カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種の官能基を含むオレフィン性単量体の共重合体が、（メタ）アクリル酸とスチレンとα−メチルスチレンの共重合体、及び／又は、スチレンと無水マレイン酸の共重合体の場合、Ｔｇは０〜１６０℃であることが好ましい。 (A) A copolymer of an olefin monomer having a Tg of -70 to 160 ° C and containing at least one functional group selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group Is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester and / or a copolymer of (meth) acrylic acid, styrene and (meth) acrylic acid ester, Tg is -70 ° C to It is preferable that it is 50 degreeC. A copolymer of an olefin monomer containing at least one functional group selected from a carboxylic acid group, a carboxylic acid group and a carboxylic anhydride group is a copolymer of (meth) acrylic acid, styrene and α-methylstyrene. In the case of a copolymer of styrene and maleic anhydride, Tg is preferably 0 to 160 ° C.
（Ａ）水溶性樹脂のＴｇが−７０℃未満の場合は、乾燥後も接着剤が軟らかい状態となり、耐水性が低下してしまう。
（Ａ）水溶性樹脂のＴｇが、１６０℃を超える場合、ボトルへの接着性が低下し、耐水性が低下してしまう。
本明細書において、Ｔｇとは、示差走査熱量計（ＤＳＣ６２２０、ＳＩＩナノテクノロジー社製）を用いて、１０ｍｇの試料のＤＳＣ曲線を１０℃／分の昇温速度で測定し、得られたＤＳＣ曲線の変極点の温度をいう。
(A) When Tg of water-soluble resin is less than -70 degreeC, an adhesive will be in a soft state after drying, and water resistance will fall.
(A) When Tg of water-soluble resin exceeds 160 degreeC, the adhesiveness to a bottle will fall and water resistance will fall.
In the present specification, Tg is a DSC curve obtained by measuring a DSC curve of a 10 mg sample at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC 6220, manufactured by SII Nanotechnology). The temperature at the inflection point.
（Ａ）水溶性樹脂は市販されているものでも良く、固体のものに関しては、アルカリを添加することで水溶性にする事ができる。市販されているものとして例えば、スクリプセット５５０、スクリプセット８１０、スクリプセット７００、スクリプセット７２０（ハーキュリーズ社製）；ＳＭＡ３０００、ＳＭＡＥＦ−４０、ＳＭＡＥＦ−６０、ＳＭＡＥＦ−８０（アーコ社製）；ジョンクリル６７、ジョンクリル６７８、ジョンクリル５８６、ジョンクリル６１１、ジョンクリル６８０、ジョンクリル６８２、ジョンクリル６８３、ジョンクリル６９０、ＨＰＤ−６７１、ＪＤＸ−Ｃ３０００、ジョンクリル５７、ジョンクリル６０、ジョンクリル６０、ジョンクリル６１Ｊ、ジョンクリル６２、ジョンクリル６３、ジョンクリル７０、ＨＰＤ−７１、ＨＰＤ９６、ジョンクリル５０１、ジョンクリル３５４、ジョンクリル６６１０、ＪＤＸ−６５００、ＰＤＸ−６１０２Ｂ（ジョンソンポリマー社製）；イソバン０４（クラレ社製）等が例示できる。いずれの名称も、商品名で示した。 (A) The water-soluble resin may be a commercially available resin, and the solid resin can be made water-soluble by adding an alkali. As commercially available products, for example, script set 550, script set 810, script set 700, script set 720 (manufactured by Hercules); SMA 3000, SMAEF-40, SMAEF-60, SMAEF-80 (manufactured by ARCO); 67, John Crill 678, John Crill 586, John Crill 611, John Crill 680, John Crill 682, John Crill 683, John Crill 690, HPD-671, JDX-C3000, John Crill 57, John Crill 60, John Crill 60, John Crill 61J, John Crill 62, John Crill 63, John Crill 70, HPD-71, HPD 96, John Crill 501, John Crill 354, John Crill 6610, JDX-6500, PDX-61 2B (manufactured by Johnson Polymer Co.); ISOBAM 04 (manufactured by Kuraray Co., Ltd.) and the like. All names are indicated by product names.
ラベル用接着剤中の（Ｂ）カゼインと（Ａ）水溶性樹脂の配合比率は、（Ａ）水溶性樹脂の種類によっても異なるが、（Ｂ）カゼインと（Ａ）水溶性樹脂の固形分の総和を１００重量部（以下、単に「部」ともいう）として、一般に（Ａ）水溶性樹脂が１０〜８０部であることが好ましい。より良好な初期接着性、感温性を得るためには、３０〜７０部であることが好ましい。（Ａ）水溶性樹脂の配合量が８０部より多くなるとアルカリ洗瓶性を損い得る。（Ａ）水溶性樹脂の配合量が１０部より少なくなると初期接着性、感温性を損い得る。 The blending ratio of (B) casein and (A) water-soluble resin in the label adhesive varies depending on the type of (A) water-soluble resin, but the solid content of (B) casein and (A) water-soluble resin is different. In general, the total amount is preferably 100 parts by weight (hereinafter also simply referred to as “parts”), and it is generally preferred that (A) the water-soluble resin is 10-80 parts. In order to obtain better initial adhesiveness and temperature sensitivity, it is preferably 30 to 70 parts. (A) If the amount of the water-soluble resin is more than 80 parts, the alkali rinsing properties may be impaired. (A) If the blending amount of the water-soluble resin is less than 10 parts, the initial adhesiveness and temperature sensitivity may be impaired.
本発明に係るラベル用接着剤は、（Ａ）成分に該当しない他の高分子（以下、「（Ｃ）高分子」ともいう）を含んでもよい。（Ｃ）高分子として、デンプン、セルロース系化合物、ポリビニルアルコール誘導体、ポリビビルピロリドン、ポリアクリルアミド、ポリエチレンオキサイド、ポリビニルエーテル、酢酸ビニル共重合体、エチレン−酢酸ビニル共重合体、天然又は合成ゴムエマルジョン、合成樹脂エマルジョンを例示できる。 The adhesive for labels according to the present invention may contain another polymer not corresponding to the component (A) (hereinafter also referred to as “(C) polymer”). (C) As a polymer, starch, cellulose compound, polyvinyl alcohol derivative, polybivir pyrrolidone, polyacrylamide, polyethylene oxide, polyvinyl ether, vinyl acetate copolymer, ethylene-vinyl acetate copolymer, natural or synthetic rubber emulsion, A synthetic resin emulsion can be illustrated.
デンプンとして、例えば小麦デンプン；馬鈴薯デンプン；とうもろこしデンプン；タピオカデンプン；酸化デンプン；可溶性デンプン；デキストリン；酢酸デンプン、硝酸デンプン、リン酸デンプン等のエステル化デンプン；ヒドロキシプロピルデンプン、カルボキシメチルデンプン、カチオンデンプン等のエーテル化デンプン；リン酸ジデンプン、グリセロールジデンプン、ヒドロキシプロピル架橋デンプン等の架橋デンプン；グラフト化デンプン；未変性アルファ化デンプン；変性アルファ化デンプン等を例示できる。 Examples of starch include wheat starch; potato starch; corn starch; tapioca starch; oxidized starch; soluble starch; dextrin; esterified starch such as acetate starch, nitrate starch, phosphate starch; Examples thereof include: etherified starch; crosslinked starch such as phosphate distarch, glycerol distarch, hydroxypropyl crosslinked starch; grafted starch; unmodified pregelatinized starch; modified pregelatinized starch.
セルロース系化合物として、例えばメチルセルロース；カルボキシメチルセルロース；ヒドロキシエチルセルロース；ヒドロキシプロピルセルロース；メチルヒドロキシエチルセルロース；メチルヒドロキシプロピルセルロース等を例示できる。 Examples of cellulose compounds include methyl cellulose; carboxymethyl cellulose; hydroxyethyl cellulose; hydroxypropyl cellulose; methyl hydroxyethyl cellulose; methyl hydroxypropyl cellulose.
ポリビニルアルコール誘導体として、ケイ素含有変性ポリビニルアルコール、エポキシ変性ポリビニルアルコール、アセトアセチル化ポリビニルアルコール、カルボキシル基変性ポリビニルアルコール、スルホン酸基変性ポリビニルアルコール、リン酸基変性ポリビニルアルコール、アミノ基変性ポリビニルアルコール、アンモニウム基変性ポリビニルアルコール、アミド基変性ポリビニルアルコール、メチロール基変性ポリビニルアルコール等を例示できる。 As polyvinyl alcohol derivatives, silicon-containing modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, phosphate group-modified polyvinyl alcohol, amino group-modified polyvinyl alcohol, ammonium group Examples thereof include modified polyvinyl alcohol, amide group-modified polyvinyl alcohol, and methylol group-modified polyvinyl alcohol.
デンプン、セルロース系化合物、ポリビニルアルコール誘導体、ポリビニルピロリドン、ポリアクリルアミド、ポリエチレンオキサイド、ポリビニルエーテル、酢酸ビニル共重合体、エチレン−酢酸ビニル共重合体、天然又は合成ゴムエマルジョン、合成樹脂エマルジョンを配合する場合、（Ｂ）カゼインと（Ａ）水溶性樹脂の固形分の総和１００部に対し、これらの配合量は、固形分で０〜１００部が好ましい。これらは単独で又は組み合わせて使用することができ、ラベル用接着剤の糸曳きの発生を抑制することができる。但し、過剰に配合すると、耐水性、アルカリ洗瓶性が低下し得る。 When blending starch, cellulosic compounds, polyvinyl alcohol derivatives, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, polyvinyl ether, vinyl acetate copolymer, ethylene-vinyl acetate copolymer, natural or synthetic rubber emulsion, synthetic resin emulsion, These blending amounts are preferably 0 to 100 parts by solid content with respect to 100 parts of the total solid content of (B) casein and (A) water-soluble resin. These can be used alone or in combination, and the occurrence of stringing of the adhesive for labels can be suppressed. However, when it mix | blends excessively, water resistance and an alkali bottle washing property may fall.
本発明の接着剤には、添加剤として、更に、架橋剤、粘性調整剤、可塑剤、消泡剤、防腐剤、着色剤等を必要に応じて適宜配合することができる。
架橋剤として、例えば、酢酸亜鉛、酸化亜鉛、酢酸ジルコニウム、炭酸ジルコニウムアンモニウム等が例示できる。これらの架橋剤は、単独で又は組み合わせて使用することができ、耐水フィルム強度が向上し、ボトルの水浸漬中にラベルにフクレ、皺が発生することを抑制する。但し、過剰に使用すると、アルカリ洗瓶性が低下し得る。
特に、炭酸ジルコニウムアンモニウムが好ましい。
In the adhesive of the present invention, a crosslinking agent, a viscosity modifier, a plasticizer, an antifoaming agent, a preservative, a coloring agent, and the like can be appropriately added as necessary as additives.
Examples of the crosslinking agent include zinc acetate, zinc oxide, zirconium acetate, and ammonium zirconium carbonate. These cross-linking agents can be used alone or in combination, improve the water-resistant film strength, and suppress the occurrence of swelling and wrinkles on the label during water immersion of the bottle. However, if it is used excessively, the alkali washability can be lowered.
In particular, ammonium zirconium carbonate is preferred.
粘性調整剤として、例えば、尿素、尿素化合物、ジシアンジアミド等の窒素含有物質、水酸化カルシウム、酸化カルシウム、炭酸ナトリウム、リン酸３ナトリウム、リン酸水素２アンモニウム、硼砂、フッ化ナトリウム、水ガラス、アンモニア水等を例示できる。
可塑剤として、例えば、グリセリン；エチレングリコール、プロピレングリコール等の多価アルコール類；ショ糖、ソルビトール等の糖類；セロソルブ類等の有機溶剤類等を例示できる。
Examples of viscosity modifiers include, for example, nitrogen-containing substances such as urea, urea compounds, dicyandiamide, calcium hydroxide, calcium oxide, sodium carbonate, trisodium phosphate, diammonium hydrogen phosphate, borax, sodium fluoride, water glass, ammonia Water etc. can be illustrated.
Examples of the plasticizer include glycerin; polyhydric alcohols such as ethylene glycol and propylene glycol; saccharides such as sucrose and sorbitol; organic solvents such as cellosolves.
消泡剤として、例えば、
ジメチルポリシロキサン、ポリオキシアルキレン変性シリコーン、有機変性ポリシロキサン、フッ素シリコーン等のシリコーン系消泡剤；
ヒマシ油、ゴマ油、アマニ油、動植物油等の油脂系消泡剤；
ステアリン酸、オレイン酸、パルミチン酸等の脂肪酸系消泡剤；
イソアミルステアリン酸、ジグリコールラウリン酸、ジステアリルコハク酸、ジステアリン酸、ソルビタンモノラウリン酸、グリセリン脂肪酸エステル、ポリオキシエチレンソルビタン、モノラウリン酸ブチルステアレート、ショ糖脂肪酸エステル、スルホン化リチノール酸のエチル酢酸アルキルエステル、天然ワックス等の脂肪酸エステル系消泡剤；
ポリオキシアルキレングリコールとその誘導体、ポリオキシアルキレンアルコール水和物、ジアミルフェノキシエタノール、３−ヘプタノール、２−エチルヘキサノール等のアルコール系消泡剤；
３−ヘプチルセルソルブ、ノニルセルソルブ−３−ヘプチルカルビトール等のエーテル系消泡剤；
トリブチルホスフェート、オクチルリン酸ナトリウム、トリス（ブトキシエチル）ホスフェート等のリン酸エステル系消泡剤；
ジアミルアミン等のアミン系消泡剤；
ポリアルキレンアマイド、アシレイトポリアミン、ジオクタデカノイルピペリジン等のアマイド系消泡剤；
ステアリン酸アルミニウム、ステアリン酸カルシウム、オレイン酸カリウム、ウールオレインのカルシウム塩等の金属石鹸系消泡剤；
ラウリルスルホン酸ナトリウム、ドデシルスルホン酸ナトリウム等のスルホン酸エステル系消泡剤等を例示することができる。
As an antifoaming agent, for example,
Silicone-based antifoaming agents such as dimethylpolysiloxane, polyoxyalkylene-modified silicone, organic-modified polysiloxane, and fluorine silicone;
Oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils;
Fatty acid-based antifoaming agents such as stearic acid, oleic acid, palmitic acid;
Isoamyl stearic acid, diglycol lauric acid, distearyl succinic acid, distearic acid, sorbitan monolauric acid, glycerin fatty acid ester, polyoxyethylene sorbitan, butyl stearate monolaurate, sucrose fatty acid ester, ethyl acetate alkyl ester of sulfonated lithinolic acid Fatty acid ester antifoaming agents such as natural wax;
Alcohol-based antifoaming agents such as polyoxyalkylene glycol and derivatives thereof, polyoxyalkylene alcohol hydrate, diamylphenoxyethanol, 3-heptanol, 2-ethylhexanol;
Ether type antifoaming agents such as 3-heptylcellosolve and nonylcellosolve-3-heptylcarbitol;
Phosphate-based antifoaming agents such as tributyl phosphate, sodium octyl phosphate, tris (butoxyethyl) phosphate;
Amine-based antifoaming agents such as diamylamine;
Amide antifoaming agents such as polyalkylene amide, acylate polyamine, dioctadecanoyl piperidine;
Metal soap antifoaming agents such as aluminum stearate, calcium stearate, potassium oleate, calcium salt of wool olein;
Examples thereof include sulfonate ester antifoaming agents such as sodium lauryl sulfonate and sodium dodecyl sulfonate.
本発明に係るラベル用接着剤は、ラベル用途に使用される。本発明において、ラベルとは、紙、加工紙（アルミ蒸着加工、アルミラミネート加工、ニス加工、樹脂加工等を施された紙）合成紙等の紙類、有機化合物や無機化合物のフィルム、金属製のフィルム等によって作られるラベルをいう。ラベルを貼る被着体として、ガラス、金属、プラスチック、ポリプロピレン等のポリオレフィン類、ポリ塩化ビニル、ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステル類等を例示できるが、中でも、飲料用ガラス瓶や飲料用コーティングガラス瓶に好適である。 The label adhesive according to the present invention is used for labeling. In the present invention, the label means paper, processed paper (paper subjected to aluminum vapor deposition processing, aluminum lamination processing, varnish processing, resin processing, etc.) synthetic paper and the like, organic compound or inorganic compound films, metal This is a label made of film. Examples of adherends to be labeled include glass, metals, plastics, polyolefins such as polypropylene, polyvinyl chloride, polyesters such as polyethylene terephthalate and polybutylene terephthalate, etc. Among them, glass bottles for beverages and coated glass bottles for beverages It is suitable for.
本発明に係るラベル用接着剤を、ラベルに塗布し、被着体に貼り付けるために、通常、ラベラー（札貼機又はラベル札貼機）が使用される。ラベラーとして、例えばクロネス等のパレット転写型ラベラー及びロール転写型ラベラー等を例示できる。 In order to apply the label adhesive according to the present invention to a label and attach it to an adherend, a labeler (a tag sticking machine or a label tag sticking machine) is usually used. Examples of the labeler include a pallet transfer type labeler such as Krones and a roll transfer type labeler.
以下に、本発明の主な態様を記載する。
１．
（Ａ）４，０００〜１７０，０００の重量平均分子量（Ｍｗ）及び３０〜２６０の酸価を有し、カルボン酸基、カルボン酸塩基及び無水カルボン酸基から選択される少なくとも一種を含む水溶性樹脂、及び
（Ｂ）カゼイン
を含んで成ることを特徴とするラベル用接着剤。
２．
（Ａ）水溶性樹脂は、−７０℃〜１６０℃のガラス転移温度（Ｔｇ）を有する上記１に記載のラベル用接着剤
３．
（Ａ）水溶性樹脂は、１５０００〜１１００００の重量平均分子量（Ｍｗ）を有する上記１又は２に記載のラベル用接着剤。
４．
（Ａ）水溶性樹脂は、（メタ）アクリル酸と（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンと（メタ）アクリル酸エステルの共重合体、（メタ）アクリル酸とスチレンとα−メチルスチレンの共重合体、及びスチレンと無水マレイン酸の共重合体から選択される少なくとも一種である上記１〜３のいずれかに記載のラベル用接着剤。
５．
上記１〜４のいずれかに記載のラベル用接着剤を塗布することで得られるラベル。
６．
ガラス瓶に貼り付けられる上記５に記載のラベル。
The main aspects of the present invention are described below.
1.
(A) A water-soluble material having a weight average molecular weight (Mw) of 4,000 to 170,000 and an acid value of 30 to 260 and containing at least one selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group. A label adhesive comprising: a resin; and (B) casein.
2.
(A) The adhesive for labels according to 1 above, wherein the water-soluble resin has a glass transition temperature (Tg) of −70 ° C. to 160 ° C.
(A) The adhesive for labels according to 1 or 2 above, wherein the water-soluble resin has a weight average molecular weight (Mw) of 15,000 to 110,000.
4).
(A) The water-soluble resin is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester, a copolymer of (meth) acrylic acid, styrene and (meth) acrylic acid ester, (meth) acrylic acid and 4. The label adhesive according to any one of 1 to 3, which is at least one selected from a copolymer of styrene and α-methylstyrene and a copolymer of styrene and maleic anhydride.
5.
The label obtained by apply | coating the adhesive agent for labels in any one of said 1-4.
6).
6. The label according to 5 above, which is attached to a glass bottle.
以下に本発明を実施例及び比較例を用いて説明するが、これらの例は、本発明を説明するためのものであり、本発明を何ら限定するものではない。
まず、下記に示す各成分を準備した。尚、「部」とは、重量部を意味し、「分子量」とは、重量平均分子量（Ｍｗ）を意味する。
[乳化剤]
ポリオキシエチレンオレイルエーテル硫酸ナトリウム（非ノニルフェニル系乳化剤）
（ラテムルＷＸ（商品名）、花王社製）
The present invention will be described below with reference to examples and comparative examples, but these examples are for explaining the present invention and do not limit the present invention in any way.
First, each component shown below was prepared. “Part” means part by weight, and “molecular weight” means weight average molecular weight (Mw).
[emulsifier]
Sodium polyoxyethylene oleyl ether sulfate (non-nonylphenyl emulsifier)
(Latemuru WX (trade name), manufactured by Kao Corporation)
[スチレンと無水マレイン酸の共重合体]
・スチレン−無水マレイン酸共重合体（スクリプセット５５０（商品名）、ハーキュリーズ社製） （分子量 １０５０００ 、酸価 １７５ 、Ｔｇ １５０℃）
・スチレン−無水マレイン酸共重合体（スクリプセット７００（商品名）、ハーキュリーズ社製） （分子量 １２００００ 、酸価 ９５ 、Ｔｇ １５０℃）
・スチレン−無水マレイン酸共重合体（スクリプセット５４０（商品名）、ハーキュリーズ社製） （分子量 １８００００ 、酸価 １８５ 、Ｔｇ １５０℃）
[Copolymer of styrene and maleic anhydride]
Styrene-maleic anhydride copolymer (script set 550 (trade name), manufactured by Hercules) (molecular weight 105000, acid value 175, Tg 150 ° C.)
Styrene-maleic anhydride copolymer (script set 700 (trade name), manufactured by Hercules) (molecular weight 120,000, acid value 95, Tg 150 ° C.)
・ Styrene-maleic anhydride copolymer (script set 540 (trade name), manufactured by Hercules) (molecular weight 180000, acid value 185, Tg 150 ° C.)
[アクリル酸とスチレンとα−メチルスチレンとの共重合体]
・アクリル酸−スチレン−α−メチルスチレン共重合体
（ジョンクリル５８６（商品名）、ジョンソンポリマー社製）
（分子量 ４６００ 、酸価 １１０ 、Ｔｇ ６０℃）
・アクリル酸−スチレン−α−メチルスチレン共重合体
（ジョンクリル６８２（商品名）、ジョンソンポリマー社製）
（分子量 １７００ 、酸価 ２４０ 、Ｔｇ ５６℃）
[Copolymer of acrylic acid, styrene and α-methylstyrene]
・ Acrylic acid-styrene-α-methylstyrene copolymer (John Crill 586 (trade name), manufactured by Johnson Polymer Co., Ltd.)
(Molecular weight 4600, acid value 110, Tg 60 ° C)
Acrylic acid-styrene-α-methylstyrene copolymer (John Krill 682 (trade name), manufactured by Johnson Polymer Co., Ltd.)
(Molecular weight 1700, acid value 240, Tg 56 ° C)
[イソブテンと無水マレイン酸との共重合体]
・イソブチレン−無水マレイン酸共重合体（イソバン０４（商品名）、クラレ社製）
（分子量 ６００００ 、酸価 ２２０ 、Ｔｇ １６０℃）
[Copolymer of isobutene and maleic anhydride]
・ Isobutylene-maleic anhydride copolymer (Isoban 04 (trade name), manufactured by Kuraray Co., Ltd.)
(Molecular weight 60000, acid value 220, Tg 160 ° C)
[成分（Ａ）−１の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２部を蒸留水４５．４部に溶解し、ブチルアクリレート（和光純薬工業社製）５３．２部、メタクリル酸メチル（和光純薬工業社製）２３部、メタクリル酸（和光純薬工業社製）２３部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３部を蒸留水１．７部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４部を蒸留水１７．８部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価１５０、Ｔｇ２℃の成分（Ａ）−１の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -1]
12 parts of an emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts of distilled water, 53.2 parts of butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methyl methacrylate (Wako Pure Chemical Industries, Ltd.) Product) 23 parts, methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 23 parts, and n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) 0.85 parts were mixed and emulsified to prepare an emulsion. On the other hand, 66 parts of distilled water was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. . In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts of sodium persulfate dissolved in 1.7 parts of distilled water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution (0.44 parts of sodium persulfate dissolved in 17.8 parts of distilled water) were added dropwise over about 3 hours to cause reaction. The completion reaction was carried out at (80 ° C.) for about 1 hour. After cooling the obtained reaction mixture, 0.38 part of an antiseptic (ACTICIDE MBS (trade name), manufactured by So Japan), 0.04 part of an antifoaming agent (Nopco 8034 (trade name), manufactured by San Nopco) is added. Added. Furthermore, ammonia water and distilled water were added to obtain a 10% aqueous solution of component (A) -1 having a molecular weight of 40,000, an acid value of 150, and Tg of 2 ° C.
[成分（Ａ）−２の濃度１０％水溶液]
（Ａ）−１のｎ−ドデシルメルカプタン量を３部に変更し、同様の方法にて分子量 １７，０００、酸価１５０、Ｔｇ２℃の成分（Ａ）−２の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -2]
The amount of n-dodecyl mercaptan of (A) -1 was changed to 3 parts, and a 10% aqueous solution of component (A) -2 having a molecular weight of 17,000, an acid value of 150, and Tg of 2 ° C. was obtained in the same manner.
[成分（Ａ）−３の濃度１０％水溶液]
（Ａ）−１のｎ−ドデシルメルカプタン量を４．５部に変更し、同様の方法にて分子量 １２，０００、酸価１５０、Ｔｇ２℃の成分（Ａ）−３の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -3]
The amount of n-dodecyl mercaptan of (A) -1 was changed to 4.5 parts, and a 10% concentration aqueous solution of component (A) -3 having a molecular weight of 12,000, an acid value of 150 and Tg of 2 ° C. was obtained in the same manner. It was.
[成分（Ａ）−４の濃度１０％水溶液]
（Ａ）−１のｎ−ドデシルメルカプタン量を０．４部に変更し、同様の方法にて分子量 １１，０００、酸価１５０、Ｔｇ２℃の成分（Ａ）−４の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -4]
The amount of n-dodecyl mercaptan of (A) -1 was changed to 0.4 part, and a 10% concentration aqueous solution of component (A) -4 having a molecular weight of 11,000, an acid value of 150 and Tg of 2 ° C. was obtained in the same manner. It was.
[成分（Ａ）−５の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２部を蒸留水４５．４部に溶解し、ブチルアクリレート（和光純薬工業社製）５１．２部、メタクリル酸メチル（和光純薬工業社製）４２部、メタクリル酸（和光純薬工業社製）６部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３部を蒸留水１．７部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４部を蒸留水１７．８部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価４０、Ｔｇ２℃の成分（Ａ）−５の濃度１０％水溶液を得た。
[10% concentration aqueous solution of component (A) -5]
12 parts of emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts of distilled water, 51.2 parts of butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methyl methacrylate (Wako Pure Chemical Industries, Ltd.) 42 parts, 6 parts of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.85 part of n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and emulsified to prepare an emulsion. On the other hand, 66 parts of distilled water was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. . In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts of sodium persulfate dissolved in 1.7 parts of distilled water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution (0.44 parts of sodium persulfate dissolved in 17.8 parts of distilled water) were added dropwise over about 3 hours to cause reaction. The completion reaction was carried out at (80 ° C.) for about 1 hour. After cooling the obtained reaction mixture, 0.38 part of an antiseptic (ACTICIDE MBS (trade name), manufactured by So Japan), 0.04 part of an antifoaming agent (Nopco 8034 (trade name), manufactured by San Nopco) is added. Added. Furthermore, aqueous ammonia and distilled water were added to obtain a 10% aqueous solution of component (A) -5 having a molecular weight of 40,000, an acid value of 40, and a Tg of 2 ° C.
[成分（Ａ）−６の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２部を蒸留水４５．４部に溶解し、ブチルアクリレート（和光純薬工業社製）５４．２部、メタクリル酸メチル（和光純薬工業社製）７部、メタクリル酸（和光純薬工業社製）３８部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３部を蒸留水１．７部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４部を蒸留水１７．８部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価２５０、Ｔｇ２℃の成分（Ａ）−６の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -6]
12 parts of an emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts of distilled water, 54.2 parts of butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methyl methacrylate (Wako Pure Chemical Industries, Ltd.) 7 parts), 38 parts of methacrylic acid (manufactured by Wako Pure Chemical Industries), and 0.85 part of n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries) were mixed and emulsified to prepare an emulsion. On the other hand, 66 parts of distilled water was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. . In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts of sodium persulfate dissolved in 1.7 parts of distilled water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution (0.44 parts of sodium persulfate dissolved in 17.8 parts of distilled water) were added dropwise over about 3 hours to cause reaction. The completion reaction was carried out at (80 ° C.) for about 1 hour. After cooling the obtained reaction mixture, 0.38 part of an antiseptic (ACTICIDE MBS (trade name), manufactured by So Japan), 0.04 part of an antifoaming agent (Nopco 8034 (trade name), manufactured by San Nopco) is added. Added. Furthermore, ammonia water and distilled water were added to obtain a 10% aqueous solution of component (A) -6 having a molecular weight of 40,000, an acid value of 250, and a Tg of 2 ° C.
[成分（Ａ）−７の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２部を蒸留水４５．４部に溶解し、アクリル酸２−エチルヘキシル（和光純薬工業社製）８３．２部、メタクリル酸メチル（和光純薬工業社製）１０部、メタクリル酸（和光純薬工業社製）６部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３部を蒸留水１．７部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４部を蒸留水１７．８部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価４０、Ｔｇ−６８℃の成分（Ａ）−７の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -7]
12 parts of emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts of distilled water, 83.2 parts of 2-ethylhexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methyl methacrylate (Wako Pure) 10 parts of Yakuhin Kogyo Co., Ltd., 6 parts of methacrylic acid (manufactured by Wako Pure Chemical Industries), and 0.85 part of n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries) were mixed and emulsified to prepare an emulsion. On the other hand, 66 parts of distilled water was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. . In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts of sodium persulfate dissolved in 1.7 parts of distilled water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution (0.44 parts of sodium persulfate dissolved in 17.8 parts of distilled water) were added dropwise over about 3 hours to cause reaction. The completion reaction was carried out at (80 ° C.) for about 1 hour. After cooling the obtained reaction mixture, 0.38 part of an antiseptic (ACTICIDE MBS (trade name), manufactured by So Japan), 0.04 part of an antifoaming agent (Nopco 8034 (trade name), manufactured by San Nopco) is added. Added. Further, aqueous ammonia and distilled water were added to obtain a 10% aqueous solution of component (A) -7 having a molecular weight of 40,000, an acid value of 40, and Tg-68 ° C.
[成分（Ａ）−８の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２部を蒸留水４５．４部に溶解し、ブチルアクリレート（和光純薬工業社製）５３．２部、スチレン（和光純薬工業社製）２３部、メタクリル酸（和光純薬工業社製）２３部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３部を蒸留水１．７部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４部を蒸留水１７．８部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価１５０、Ｔｇ２℃の成分（Ａ）−８の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -8]
12 parts of an emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts of distilled water, 53.2 parts of butyl acrylate (manufactured by Wako Pure Chemical Industries), and styrene (manufactured by Wako Pure Chemical Industries). 23 parts, 23 parts of methacrylic acid (manufactured by Wako Pure Chemical Industries) and 0.85 part of n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries) were mixed and emulsified to prepare an emulsion. On the other hand, 66 parts of distilled water was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. . In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts of sodium persulfate dissolved in 1.7 parts of distilled water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution (0.44 parts of sodium persulfate dissolved in 17.8 parts of distilled water) were added dropwise over about 3 hours to cause reaction. The completion reaction was carried out at (80 ° C.) for about 1 hour. After cooling the obtained reaction mixture, 0.38 part of an antiseptic (ACTICIDE MBS (trade name), manufactured by So Japan), 0.04 part of an antifoaming agent (Nopco 8034 (trade name), manufactured by San Nopco) is added. Added. Furthermore, ammonia water and distilled water were added to obtain a 10% aqueous solution of component (A) -8 having a molecular weight of 40,000, an acid value of 150, and Tg of 2 ° C.
[成分（Ａ）−９の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２重量部を蒸留水４５．４重量部に溶解し、ブチルアクリレート（和光純薬工業社製）５３．２重量部、メタクリル酸メチル（和光純薬工業社製）２３重量部、アクリル酸（和光純薬工業社製）１７重量部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５重量部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６重量部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３重量部を蒸留水１．７重量部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４重量部を蒸留水１７．８重量部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８重量部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４重量部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価１５０、Ｔｇ−５℃の成分（Ａ）−９の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -9]
12 parts by weight of an emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts by weight of distilled water, 53.2 parts by weight of butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methyl methacrylate (Wako Pure) 23 parts by weight of Yakuhin Kogyo Co., Ltd., 17 parts by weight of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.85 parts by weight of n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) are emulsified and emulsified. It was adjusted. On the other hand, 66 parts by weight of distilled water was added to a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. did. In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts by weight of sodium persulfate dissolved in 1.7 parts by weight of distilled water) were added. Then, after stirring, the remaining emulsified liquid and an aqueous initiator solution (0.44 parts by weight of sodium persulfate dissolved in 17.8 parts by weight of distilled water) were added dropwise over about 3 hours to react. The completion reaction was performed for about 1 hour at the same temperature (80 ° C.). After cooling the resulting reaction mixture, 0.38 parts by weight of an antiseptic (ACTICIDE MBS (trade name), manufactured by Sor Japan), 0.04 weight of an antifoam (Nopco 8034 (trade name), manufactured by San Nopco) Parts were added. Furthermore, ammonia water and distilled water were added to obtain a 10% aqueous solution of component (A) -9 having a molecular weight of 40,000, an acid value of 150, and Tg-5 ° C.
[成分（Ａ）−１０の濃度１０％水溶液]
スクリプセット５５０（商品名）（ハーキュリーズ社製）にアンモニア水と蒸留水を適宜添加し、分子量１０５，０００、酸価１７５、Ｔｇ１５０℃の成分（Ａ）−１０の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -10]
Ammonia water and distilled water were appropriately added to Script Set 550 (trade name) (manufactured by Hercules Co., Ltd.) to obtain a 10% aqueous solution of component (A) -10 having a molecular weight of 105,000, an acid value of 175, and Tg of 150 ° C.
[成分（Ａ）−１１の濃度１０％水溶液]
スクリプセット７００（商品名）（ハーキュリーズ社製）にアンモニア水と蒸留水を適宜添加し、分子量１２０，０００、酸価９５、Ｔｇ１５０℃の成分（Ａ）−１１の濃度１０％水溶液を得た。
[Component (A) -11 concentration 10% aqueous solution]
Ammonia water and distilled water were appropriately added to a script set 700 (trade name) (manufactured by Hercules Co., Ltd.) to obtain a 10% aqueous solution of component (A) -11 having a molecular weight of 120,000, an acid value of 95, and Tg of 150 ° C.
[成分（Ａ）−１２の濃度１０％水溶液]
ジョンクリル５８６（商品名）（ジョンソンポリマー社製）にアンモニア水と蒸留水を適宜添加し、分子量４，６００、酸価１１０、Ｔｇ６０℃の成分（Ａ）−１２の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (A) -12]
Ammonia water and distilled water were appropriately added to Joncrill 586 (trade name) (manufactured by Johnson Polymer Co., Ltd.) to obtain a 10% aqueous solution of component (A) -12 having a molecular weight of 4,600, an acid value of 110, and Tg of 60 ° C. .
[成分（Ａ）−１３の濃度１０％水溶液]
イソバン０４（商品名）（クラレ社製）にアンモニア水と蒸留水を適宜添加し、分子量６０，０００、酸価２２０、Ｔｇ１６０℃の成分（Ａ）−１３の濃度１０％水溶液を得た。
[10% concentration aqueous solution of component (A) -13]
Ammonia water and distilled water were appropriately added to Isoban 04 (trade name) (manufactured by Kuraray Co., Ltd.) to obtain a 10% aqueous solution of component (A) -13 having a molecular weight of 60,000, an acid value of 220, and Tg of 160 ° C.
[成分（Ｘ）−１の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２部を蒸留水４５．４部に溶解し、ブチルアクリレート（和光純薬工業社製）５１．２部、メタクリル酸メチル（和光純薬工業社製）４５部、メタクリル酸（和光純薬工業社製）３部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３部を蒸留水１．７部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４部を蒸留水１７．８部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価２０、Ｔｇ２℃の成分（Ｘ）−１の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (X) -1]
12 parts of emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts of distilled water, 51.2 parts of butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methyl methacrylate (Wako Pure Chemical Industries, Ltd.) 45 parts), 3 parts of methacrylic acid (manufactured by Wako Pure Chemical Industries), and 0.85 part of n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries) were mixed and emulsified to prepare an emulsion. On the other hand, 66 parts of distilled water was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. . In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts of sodium persulfate dissolved in 1.7 parts of distilled water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution (0.44 parts of sodium persulfate dissolved in 17.8 parts of distilled water) were added dropwise over about 3 hours to cause reaction. The completion reaction was carried out at (80 ° C.) for about 1 hour. After cooling the obtained reaction mixture, 0.38 part of an antiseptic (ACTICIDE MBS (trade name), manufactured by So Japan), 0.04 part of an antifoaming agent (Nopco 8034 (trade name), manufactured by San Nopco) is added. Added. Furthermore, ammonia water and distilled water were added to obtain a 10% aqueous solution of component (X) -1 having a molecular weight of 40,000, an acid value of 20, and a Tg of 2 ° C.
[成分（Ｘ）−２の濃度１０％水溶液]
乳化剤（ラテムルＷＸ（商品名）、花王社製）１２部を蒸留水４５．４部に溶解し、ブチルアクリレート（和光純薬工業社製）５４．２部、メタクリル酸メチル（和光純薬工業社製）４部、メタクリル酸（和光純薬工業社製）４１部、ｎ−ドデシルメルカプタン（和光純薬工業社製）０．８５部を配合して乳化させ、乳化液を調整した。一方、攪拌機、温度計、還流冷却器及び窒素導入管を備えた４つ口フラスコに、蒸留水６６部を添加し、窒素ガスを吹き込みながら攪拌下に加熱して液温を８０℃に調整した。この状態で、まず、先に調整した乳化液の約５体積％と、開始剤水溶液（過硫酸ナトリウム０．０３部を蒸留水１．７部で溶解したもの）を添加した。ついで、攪拌した後、更に残りの乳化液と開始剤水溶液（過硫酸ナトリウム０．４４部を蒸留水１７．８部で溶解したもの）を約３時間かけてそれぞれ滴下して反応させ、同温度（８０℃）にて約１時間の完結反応を行った。得られた反応混合物を冷却した後、防腐剤（ＡＣＴＩＣＩＤＥ ＭＢＳ（商品名）、ソージャパン社製）０．３８部、消泡剤（ノプコ８０３４（商品名）、サンノプコ社製）０．０４部を添加した。更に、アンモニア水と蒸留水を添加し、分子量４０，０００、酸価２７０、Ｔｇ２℃の成分（Ｘ）−２の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (X) -2]
12 parts of an emulsifier (Latemul WX (trade name), manufactured by Kao Corporation) is dissolved in 45.4 parts of distilled water, 54.2 parts of butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methyl methacrylate (Wako Pure Chemical Industries, Ltd.) 4 parts), 41 parts of methacrylic acid (manufactured by Wako Pure Chemical Industries) and 0.85 part of n-dodecyl mercaptan (manufactured by Wako Pure Chemical Industries) were mixed and emulsified to prepare an emulsion. On the other hand, 66 parts of distilled water was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the liquid temperature was adjusted to 80 ° C. by heating with stirring while blowing nitrogen gas. . In this state, first, about 5% by volume of the previously prepared emulsion and an aqueous initiator solution (0.03 parts of sodium persulfate dissolved in 1.7 parts of distilled water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution (0.44 parts of sodium persulfate dissolved in 17.8 parts of distilled water) were added dropwise over about 3 hours to cause reaction. The completion reaction was carried out at (80 ° C.) for about 1 hour. After cooling the obtained reaction mixture, 0.38 part of an antiseptic (ACTICIDE MBS (trade name), manufactured by So Japan), 0.04 part of an antifoaming agent (Nopco 8034 (trade name), manufactured by San Nopco) is added. Added. Further, aqueous ammonia and distilled water were added to obtain a 10% aqueous solution of component (X) -2 having a molecular weight of 40,000, an acid value of 270, and Tg of 2 ° C.
[成分（Ｘ）−３の濃度１０％水溶液]
ジョンクリル６８２（商品名）（ジョンソンポリマー社製）にアンモニア水と蒸留水を適宜添加し、分子量１，７００、酸価２４０、Ｔｇ５６℃の成分（Ｘ）−３の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (X) -3]
Ammonia water and distilled water were appropriately added to Jonkrill 682 (trade name) (manufactured by Johnson Polymer Co., Ltd.) to obtain a 10% aqueous solution of component (X) -3 having a molecular weight of 1,700, an acid value of 240 and Tg of 56 ° C. .
[成分（Ｘ）−４の濃度１０％水溶液]
スクリプセット５４０（商品名）（ハーキュリーズ社製）にアンモニア水と蒸留水を適宜添加し、分子量１８０，０００、酸価１８５、Ｔｇ１５０℃の成分（Ｘ）−４の濃度１０％水溶液を得た。
[Concentration 10% aqueous solution of component (X) -4]
Ammonia water and distilled water were appropriately added to Script Set 540 (trade name) (manufactured by Hercules Co., Ltd.) to obtain a 10% aqueous solution of component (X) -4 having a molecular weight of 180,000, an acid value of 185, and Tg of 150 ° C.
[成分（Ｘ）−５の固形分濃度１０％分散液]
イソバン０４（商品名）（クラレ社製）に蒸留水を適宜添加し、分子量６０，０００、酸価２２０、Ｔｇ１６０℃の成分（Ｘ）−５の固形分濃度１０％水分散液を得た。（Ａ）−１３はイソバン０４（商品名）が水に溶解したものであるが、（Ｘ）−５はイソバン０４（商品名）が水に溶解せず、水に分散したものである。
[Dispersion with 10% solid content of component (X) -5]
Distilled water was appropriately added to Isoban 04 (trade name) (manufactured by Kuraray Co., Ltd.) to obtain a 10% solid content concentration aqueous dispersion of component (X) -5 having a molecular weight of 60,000, an acid value of 220, and Tg of 160 ° C. (A) -13 is a product in which isoban 04 (trade name) is dissolved in water, while (X) -5 is a product in which isoban 04 (trade name) is not dissolved in water but is dispersed in water.
［カゼイン］
カゼイン（ニュージーランド産）
［尿素］
尿素（和光純薬工業社製）
［デンプン］
レオタック（商品名）（日澱化学社製）
［架橋剤］
炭酸ジルコニウムアンモニウム（ベイコート２０（商品名）、日本軽金属社製）
［消泡剤］
ノプコ８０３４（商品名）（サンノプコ社製）
［防腐剤］
レバナックスＢＡ１００（商品名）（昌栄化学社製）
[casein]
Casein (New Zealand)
[urea]
Urea (made by Wako Pure Chemical Industries)
[Starch]
Leotac (trade name) (manufactured by Nissho Chemical Co., Ltd.)
[Crosslinking agent]
Zirconium ammonium carbonate (Baycoat 20 (trade name), manufactured by Nippon Light Metal Co., Ltd.)
[Defoaming agent]
Nopco 8034 (trade name) (manufactured by San Nopco)
[Preservative]
Levanax BA100 (trade name) (manufactured by Changei Chemical Co., Ltd.)
＜実施例１〜１１＞
温度計、攪拌機を備えた４つ口フラスコに、蒸留水４０部、カゼイン５０部、成分（Ａ）の１０％水溶液を５００部、デンプン４０部、尿素２２０部、架橋剤３０部を添加し、８０℃に加熱して３０分攪拌する。その後、冷却し、消泡剤０．８重量部、防腐剤０．８重量部を添加後、３０分攪拌し、ラベル用接着剤を得た。
<Examples 1 to 11>
To a four-necked flask equipped with a thermometer and a stirrer, add 40 parts of distilled water, 50 parts of casein, 500 parts of a 10% aqueous solution of component (A), 40 parts of starch, 220 parts of urea, and 30 parts of a crosslinking agent, Heat to 80 ° C. and stir for 30 minutes. Thereafter, the mixture was cooled, 0.8 parts by weight of antifoaming agent and 0.8 parts by weight of preservative were added, and stirred for 30 minutes to obtain an adhesive for labels.
＜比較例１〜５＞
温度計、攪拌機を備えた４つ口フラスコに、蒸留水４０部、カゼイン５０部、成分（Ｘ）の１０％水溶液を５００部、デンプン４０部、尿素２２０部、架橋剤３０部を添加し、８０℃に加熱して３０分攪拌する。その後、冷却し、消泡剤０．８重量部、防腐剤０．８重量部を添加後、３０分攪拌し、ラベル用接着剤を得た。
<Comparative Examples 1-5>
To a four-necked flask equipped with a thermometer and a stirrer, add 40 parts of distilled water, 50 parts of casein, 500 parts of a 10% aqueous solution of component (X), 40 parts of starch, 220 parts of urea, and 30 parts of a crosslinking agent, Heat to 80 ° C. and stir for 30 minutes. Thereafter, the mixture was cooled, 0.8 parts by weight of antifoaming agent and 0.8 parts by weight of preservative were added, and stirred for 30 minutes to obtain an adhesive for labels.
＜比較例６＞
温度計、攪拌機を備えた４つ口フラスコに、蒸留水４９０部、カゼイン１００部、デンプン４０部、尿素２２０部、架橋剤３０部を添加し、８０℃に加熱して３０分攪拌する。その後、冷却し、消泡剤０．８重量部、防腐剤０．８重量部を添加後、３０分攪拌し、ラベル用接着剤を得た。
<Comparative Example 6>
To a four-necked flask equipped with a thermometer and a stirrer, 490 parts of distilled water, 100 parts of casein, 40 parts of starch, 220 parts of urea and 30 parts of a crosslinking agent are added, heated to 80 ° C. and stirred for 30 minutes. Thereafter, the mixture was cooled, 0.8 parts by weight of antifoaming agent and 0.8 parts by weight of preservative were added, and stirred for 30 minutes to obtain an adhesive for labels.
＜評価方法＞
実施例及び比較例の接着剤の評価は以下の様に行った。
［耐水性］
ラベル紙に接着剤をバーコーターにて約３０ｇ／ｍ２塗布し、直ちにガラス瓶に接着した後にゴムローラーにて軽く圧着した。２３℃にて３日間乾燥後、テスト瓶を得た。３０℃の水にテスト瓶を２０日間浸漬し、ラベルの剥がれ具合を確認した。ラベルがテスト瓶浸漬２０日でも剥がれず、手でラベルを剥がす際に材料破壊するものを◎、浸漬２０日でも剥がれないが、手でラベルを剥がす際に界面剥離するものを○、浸漬１０〜１９日で剥がれるものを△、浸漬９日以内で剥がれるものを×として表示した。
<Evaluation method>
The adhesives of the examples and comparative examples were evaluated as follows.
[water resistant]
About 30 g / m 2 of adhesive was applied to the label paper with a bar coater, immediately adhered to a glass bottle, and then lightly pressed with a rubber roller. After drying at 23 ° C. for 3 days, a test bottle was obtained. The test bottle was immersed in 30 ° C. water for 20 days, and the degree of peeling of the label was confirmed. The label does not peel off even when the test bottle is immersed for 20 days, and the material that breaks the material when the label is peeled off by hand is not peeled off even after the immersion for 20 days. Those that peeled off in 19 days were indicated by Δ, and those that peeled off within 9 days were shown as x.
［アルカリ洗瓶性］
ラベル紙に接着剤をバーコーターにて約３０ｇ／ｍ２塗布し、直ちにガラス瓶に接着した後にゴムローラーにて軽く圧着した。２３℃にて３日間乾燥後、テスト瓶を得た。７５℃の４％ＮａＯＨ水溶液にテスト瓶を浸漬しテスト瓶を揺すり、ラベルが剥がれる時間を測定した。ラベルがテスト瓶浸漬３分以内で剥がれるものを◎、浸漬３〜５分以内で剥がれるものを○、浸漬５分〜８分で剥がれるものを△、浸漬８分以上で剥がれるものを×として表示した。
[Alkaline washability]
About 30 g / m 2 of adhesive was applied to the label paper with a bar coater, immediately adhered to a glass bottle, and then lightly pressed with a rubber roller. After drying at 23 ° C. for 3 days, a test bottle was obtained. The test bottle was immersed in a 4% NaOH aqueous solution at 75 ° C., the test bottle was shaken, and the time for the label to peel was measured. The label peels off within 3 minutes of immersion in the test bottle, ◎, peels off within 3-5 minutes, △ peels off after 5-8 minutes, and x peels off after 8 minutes of immersion. .
［初期接着性］
ラベル紙に接着剤をバーコーターにて約３０ｇ／ｍ２塗布し、直ちにガラス板に接着した後にゴムローラーにて軽く圧着した。直ちに一定時間でラベルを剥がし、ラベルの材破が見られた時間を測定した。ラベルの材破が見られた時間が３分以内のものを◎、３〜４分のものを○、４〜５分のものを△、５分以上のものを×として表示した。
[Initial adhesion]
An adhesive was applied to the label paper with a bar coater at about 30 g / m 2 , and immediately adhered to a glass plate and then lightly pressed with a rubber roller. Immediately after that, the label was peeled off at a certain time, and the time when the material breakage of the label was observed was measured. The case where the material breakage of the label was observed was shown as ◎, the case of 3-4 minutes as ○, the case of 4-5 minutes as Δ, and the case of 5 minutes or more as x.
［粘度］
ＢＨ型粘度計（東京計器社製）２０回転にて測定する。
[viscosity]
BH type viscometer (manufactured by Tokyo Keiki Co., Ltd.) is measured at 20 revolutions.
［感温性］
感温性とは、温度の上昇に伴う粘度の増加を示す指標である。
得られた接着剤を３０℃での粘度が３００００ｍＰａ・ｓとなるように尿素、及び蒸留水を適宜加えて感温性評価用接着剤とした。感温性評価用接着剤を１０℃での粘度を測定し、次の式で感温性を求めた。感温性が３以内のものを◎、３〜５のものを○、５〜８のものを△、８以上のものを×として表示した。
感温性＝１０℃での粘度／３０℃での粘度
[Sensitivity]
The temperature sensitivity is an index indicating an increase in viscosity with an increase in temperature.
Urea and distilled water were appropriately added to the obtained adhesive so that the viscosity at 30 ° C. was 30000 mPa · s to obtain an adhesive for temperature sensitivity evaluation. The viscosity at 10 ° C. of the adhesive for temperature sensitivity evaluation was measured, and the temperature sensitivity was determined by the following formula. Those with a temperature sensitivity of 3 or less were indicated as ◎, those with 3 to 5 as ◯, those with 5 to 8 as Δ, and those with 8 or more as ×.
Temperature sensitivity = viscosity at 10 ° C / viscosity at 30 ° C
［経時粘度安定性］
得られた接着剤を３０℃での粘度が３００００ｍＰａ・ｓとなるように尿素、及び蒸留水を適宜加えて経時粘度安定性評価用接着剤を得た。経時粘度安定性評価用接着剤を４０℃にて１ヶ月保管後、３０℃での粘度を測定し、次の式で経時粘度安定性を求めた。経時粘度安定性が１．２〜０．５のものを○、０．５〜０．３５のものを△、０．３５以下又は１．２以上のもの若しくは分離するものを×として表示した。
経時粘度安定性＝４０℃にて１ヶ月保管後の粘度／４０℃に保管する前の粘度
[Viscosity stability over time]
Urea and distilled water were appropriately added to the obtained adhesive so that the viscosity at 30 ° C. was 30000 mPa · s to obtain an adhesive for evaluating viscosity stability over time. The adhesive for evaluating viscosity stability over time was stored at 40 ° C. for 1 month, then the viscosity at 30 ° C. was measured, and the viscosity stability over time was determined by the following formula. Those having a time-dependent viscosity stability of 1.2 to 0.5 are indicated as ◯, those having 0.5 to 0.35 are indicated as Δ, those having 0.35 or less, 1.2 or more, or separated are indicated as ×.
Viscosity stability over time = viscosity after storage for 1 month at 40 ° C./viscosity before storage at 40 ° C.
［ラベラー洗浄性］
ガラス板に接着剤を０．２ｍｉｌのアプリケーターにて塗布し、テスト板を得た。テスト板を密閉環境にて３時間放置し、その後４０℃温水に浸漬した。テスト板を４０℃温水中で揺すり、接着剤がガラス板よりなくなる時間を測定した。接着剤がガラス板よりなくなる時間が５分以内のものを○、５〜７分のものを△、７分以上のものを×として表示した。
[Labeler washability]
An adhesive was applied to a glass plate with a 0.2 mil applicator to obtain a test plate. The test plate was left in a sealed environment for 3 hours and then immersed in 40 ° C. warm water. The test plate was shaken in warm water at 40 ° C., and the time for the adhesive to disappear from the glass plate was measured. The case where the adhesive disappears from the glass plate is indicated as ◯, the case where it is within 5 minutes, the case where it is 5-7 minutes as Δ, and the case where it is 7 minutes or more as X.
表１に示されるように、実施例１〜１３の接着剤は、カゼイン及び（Ａ）成分の２成分を必須成分とするので、各性能が優れている。比較例１〜６の接着剤は、（Ａ）成分を含まないので、実施例の接着剤と比較して、各性能が著しく劣っている。従って、カゼインと、特定の（Ａ）カルボン酸変性水溶性樹脂との２成分を配合すると、耐水性、アルカリ洗浄性、初期接着性、感温性、経時粘度安定性、ラベラー洗浄性に優れた接着剤が得られることが示された。 As Table 1 shows, since the adhesives of Examples 1 to 13 contain casein and two components (A) as essential components, each performance is excellent. Since the adhesives of Comparative Examples 1 to 6 do not contain the component (A), each performance is significantly inferior to the adhesives of the examples. Therefore, when two components, casein and a specific (A) carboxylic acid-modified water-soluble resin, are blended, the water resistance, alkali washability, initial adhesiveness, temperature sensitivity, viscosity stability with time, and labeler washability are excellent. It was shown that an adhesive was obtained.
Claims (4)
（Ｂ）カゼイン
を含んで成り、
（Ｂ）カゼインと（Ａ）水溶性樹脂の固形分の総和を１００重量部として、（Ａ）水
溶性樹脂が１０〜８０重量部であるラベル用接着剤。
(A) A water-soluble material having a weight average molecular weight (Mw) of 4,000 to 170,000 and an acid value of 30 to 260 and containing at least one selected from a carboxylic acid group, a carboxylic acid group, and a carboxylic anhydride group. An aqueous resin solution, and (B) comprising casein ,
(B) Casein and (A) The total solid content of the water-soluble resin is 100 parts by weight.
The adhesive for labels whose soluble resin is 10-80 weight part .
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| JP2008112649A JP5348932B2 (en) | 2008-04-23 | 2008-04-23 | Label adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2284238B1 (en) * | 2009-08-14 | 2013-07-03 | Henkel AG & Co. KGaA | Waterborne adhesive with improved wet adhesion |
| JP5871452B2 (en) * | 2010-03-30 | 2016-03-01 | ヘンケルジャパン株式会社 | Adhesive for roll paper and roll paper |
| JP2018135401A (en) * | 2015-06-30 | 2018-08-30 | 株式会社クラレ | Adhesive for label |
| EP3541886A1 (en) * | 2016-11-18 | 2019-09-25 | Caddis Adhesives, Inc. | Tunable adhesive compositions and methods |
| CN107779130A (en) * | 2017-11-15 | 2018-03-09 | 惠州市永耐宝新材料有限公司 | A kind of waterproofing and leakage-stopping adhesive of rapid-drying properties and preparation method thereof |
| US20220010179A1 (en) * | 2018-11-21 | 2022-01-13 | Greentech Global Pte. Ltd. | Novel aqueous adhesives using saccharide fatty acid esters |
| CN111592842A (en) * | 2020-06-24 | 2020-08-28 | 江南大学 | Thermosetting artificial board starch adhesive with high starch content and preparation method thereof |
| CN111647112A (en) * | 2020-06-24 | 2020-09-11 | 江南大学 | Viscosity-adjustable thermosetting artificial board starch adhesive and preparation method thereof |
| US20240059941A1 (en) * | 2020-12-18 | 2024-02-22 | Upm Raflatac Oy | Acrylic pressure sensitive adhesive composition for food packaging label application |
| CN113150724A (en) * | 2021-03-31 | 2021-07-23 | 江苏唐彩新材料科技股份有限公司 | Water-based PET composite adhesive for cigarette paperboard and preparation method thereof |
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| JPH05230433A (en) * | 1992-02-19 | 1993-09-07 | Kuraray Co Ltd | Adhesive for label |
| JP2006308651A (en) * | 2005-04-26 | 2006-11-09 | Dainippon Ink & Chem Inc | Back face coating agent for label and label coated with the same |
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