JP2021004352A - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- JP2021004352A JP2021004352A JP2020010677A JP2020010677A JP2021004352A JP 2021004352 A JP2021004352 A JP 2021004352A JP 2020010677 A JP2020010677 A JP 2020010677A JP 2020010677 A JP2020010677 A JP 2020010677A JP 2021004352 A JP2021004352 A JP 2021004352A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sheet
- sensitive adhesive
- adhesive sheet
- adhesive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 90
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000012790 adhesive layer Substances 0.000 claims abstract description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- 229920000856 Amylose Polymers 0.000 claims abstract description 10
- 229920000297 Rayon Polymers 0.000 claims abstract description 10
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 99
- 239000010410 layer Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 26
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 238000010998 test method Methods 0.000 claims description 5
- 239000013535 sea water Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 60
- 239000000123 paper Substances 0.000 description 27
- -1 polyethylene Polymers 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 229920002678 cellulose Polymers 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000012874 anionic emulsifier Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 241000360590 Erythrites Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 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 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000010809 marine debris Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、少なくとも基材の片面に粘着剤層が積層された粘着シートに関し、特に誤って海洋に流出した場合には海水により分解し環境負荷の少ない粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is laminated on at least one side of a base material, and particularly to a pressure-sensitive adhesive sheet that is decomposed by seawater and has a small environmental load when accidentally leaked into the ocean.
粘着シートは、商業用、事務用、切手等の印紙用、配送伝票用、工程管理用、家庭用等非常に広範囲にわたって使用されている。粘着シートの一般的な構成は、基材と剥離シートとの間に粘着剤を挟み込んだ状態にしたものである。
基材には紙、フィルム、あるいは金属フォイル等が用いられる。剥離シートには、一般的にシリコーン化合物やフッ素化合物の如き剥離剤が剥離シート用基材に塗布されたものが用いられる。なお、剥離シート用基材には、グラシン紙のような高密度原紙、クレーコート紙、クラフト紙、上質紙などにポリエチレン等の樹脂フィルムをラミネート加工したラミネート紙、あるいはクラフト紙や上質紙等にポリビニルアルコール、澱粉などの水溶性高分子等と顔料とを主成分とする塗被層を設けた樹脂コーティング紙等が挙げられる。中でも、ポリエチレンをラミネート加工したラミネート紙やグラシン紙が一般的に広く使用されている。
Adhesive sheets are widely used for commercial purposes, office use, stamps such as stamps, delivery slips, process control, household use, and the like. The general structure of the pressure-sensitive adhesive sheet is that the pressure-sensitive adhesive is sandwiched between the base material and the release sheet.
Paper, film, metal foil, or the like is used as the base material. As the release sheet, a release agent such as a silicone compound or a fluorine compound is generally applied to the base material for the release sheet. The base material for the release sheet can be high-density base paper such as glassin paper, clay-coated paper, kraft paper, laminated paper obtained by laminating a resin film such as polyethylene on high-quality paper, or kraft paper or high-quality paper. Examples thereof include resin-coated paper provided with a coating layer containing a water-soluble polymer such as polyvinyl alcohol and starch and a pigment as main components. Among them, laminated paper or glassine paper obtained by laminating polyethylene is generally widely used.
また、粘着剤としては、ゴム系、アクリル系、ビニルエーテル系等のエマルジョン型、溶剤型又は無溶剤型の各種粘着剤が使用される。かかる粘着シートは、商品等に貼付けられ、貼付けされた後は被着体に貼りついたまま永続的に利用される永久接着タイプと、商品等の関係から表示の目的を達成した後は剥離され破棄される再剥離タイプのものもある。
一方、最近では地球規模での資源・廃棄物制約の観点で、プラスチックの排出量の削減や再利用の促進、リサイクル率の向上が喫緊の課題となっており、特に海洋へ流出するプラスチックごみによる環境汚染や海洋生物への影響が世界的に懸念されている。
As the pressure-sensitive adhesive, various emulsion-type, solvent-type or solvent-free type pressure-sensitive adhesives such as rubber-based, acrylic-based and vinyl ether-based adhesives are used. Such an adhesive sheet is attached to a product or the like, and after being attached, it is peeled off after achieving the purpose of labeling due to the relationship between the permanent adhesive type that is permanently used while being attached to the adherend and the product or the like. There is also a re-peelable type that is discarded.
On the other hand, recently, from the viewpoint of global resource and waste constraints, reduction of plastic emissions, promotion of reuse, and improvement of recycling rate have become urgent issues, especially due to plastic waste flowing into the ocean. There are global concerns about environmental pollution and its impact on marine life.
このような問題を解決するために、水に溶けるフィルムやポリ乳酸などの生分解性フィルムを基材に用いた粘着シートも提案されているが、水に対して容易に溶けることから耐水性などの実用性に欠けたり、限定された条件下でないと生分解しないなどの欠点があった。
また、粘着剤として水またはアルカリ水に溶解する粘着剤を使用したタイプのものや天然ゴムを主成分としたタイプも提案されているが、粘着剤が溶解するため耐水性に劣ったり、分子量が低く設計されているため高温・高湿の環境下では品質が著しく劣化したり、経時により変色するなどの欠点があった（例えば、特許文献１を参照）。
In order to solve such a problem, an adhesive sheet using a water-soluble film or a biodegradable film such as polylactic acid as a base material has been proposed, but since it is easily dissolved in water, water resistance, etc. There were drawbacks such as lack of practicality and biodegradation only under limited conditions.
In addition, a type that uses a pressure-sensitive adhesive that dissolves in water or alkaline water as a pressure-sensitive adhesive and a type that uses natural rubber as the main component have been proposed, but the pressure-sensitive adhesive dissolves, resulting in poor water resistance and a low molecular weight. Since it is designed to be low, it has drawbacks such as significant deterioration in quality in a high temperature and high humidity environment and discoloration over time (see, for example, Patent Document 1).
本発明は、日常での水濡れ、水性ペンによる筆記および印刷加工に対して十分な耐水性を有し、且つ、誤って海洋に流出した場合でも海水により分解し、環境負荷の極めて少ない粘着シートを提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention has sufficient water resistance against daily water wetting, writing with a water-based pen, and printing processing, and even if it accidentally flows out into the ocean, it is decomposed by seawater and has an extremely low environmental load. The purpose is to provide.
上記課題を解決するため本発明の粘着シートは、以下の構成を有する。 In order to solve the above problems, the adhesive sheet of the present invention has the following constitution.
（１）基材シートと基材シートの少なくとも一部に粘着層を有する粘着シートであって、前記基材シートがアミロース、ポリビニルアルコールまたはビスコースのいずれかを主原料とするフィルムであり、且つ、ＪＩＳ Ｐ ８１４０に準拠して測定される吸水度が１０ｇ／ｍ２以下であり、前記粘着剤層のゲル分率が５０％以下である粘着シート。
（２）前記粘着層が共重合樹脂を主成分として構成され、
前記共重合樹脂中に親水性モノマー単位を前記共重合樹脂中に有し前記親水性モノマー単位を粘着剤組成中に２０〜３０質量％含有する
（１）に記載の粘着シート。
（３）単位面積あたりの前記粘着シートに対する前記粘着層の質量比率が０．１０〜０．３５である（１）または（２）に記載の粘着シート。
（４）前記基材シートが、Ｊ．ＴＡＰＰＩ紙パルプ試験方法Ｎｏ．６８：２０００に従って測定したはっ水度がＲ７以下である（１）〜（３）の何れかに記載の粘着シート。
(1) A base sheet and a pressure-sensitive adhesive sheet having an pressure-sensitive adhesive layer on at least a part of the base material sheet, wherein the base material sheet is a film containing either amylose, polyvinyl alcohol or viscose as a main raw material. , A pressure-sensitive adhesive sheet having a water absorption rate of 10 g / m 2 or less and a gel fraction of the pressure-sensitive adhesive layer of 50% or less, which is measured in accordance with JIS P 8140.
(2) The adhesive layer is composed mainly of a copolymer resin.
The pressure-sensitive adhesive sheet according to (1), wherein the copolymer resin contains a hydrophilic monomer unit in the copolymer resin, and the hydrophilic monomer unit is contained in the pressure-sensitive adhesive composition in an amount of 20 to 30% by mass.
(3) The pressure-sensitive adhesive sheet according to (1) or (2), wherein the mass ratio of the pressure-sensitive adhesive layer to the pressure-sensitive adhesive sheet per unit area is 0.10 to 0.35.
(4) The base material sheet is J.I. TAPPI Pulp and Paper Test Method No. 68: The adhesive sheet according to any one of (1) to (3), wherein the water repellency measured according to 2000 is R7 or less.
上記構成によって、本発明の粘着シートは、通常使用環境において十分な耐水性を有し、誤って海洋に投機された場合には、海水で分解するため環境への負荷の少ない粘着シートである。 With the above configuration, the adhesive sheet of the present invention has sufficient water resistance in a normal use environment, and if it is accidentally speculated in the ocean, it is decomposed by seawater and therefore has a small impact on the environment.
本発明の粘着シートは、基材シートと基材シートの少なくとも一部に粘着層を有する。
前記粘着層は、基材シートの片面の少なくとも一部に積層されていてもよく、基材シートの両面に積層されていてもよい。
The pressure-sensitive adhesive sheet of the present invention has a base material sheet and a pressure-sensitive adhesive layer on at least a part of the base material sheet.
The adhesive layer may be laminated on at least a part of one side of the base sheet, or may be laminated on both sides of the base sheet.
「基材シート」
本発明の粘着シートで使用する基材シートは、アミロース、ポリビニルアルコールまたはビスコースのいずれかを主原料とするフィルムである。
例えば、溶融状または溶液状のアミロース組成物をダイコーターから加熱ロールやベルト上に吐出し、揮発分を乾燥させることによりアミロースを主原料とするフィルム製造することができる。
"Base sheet"
The base material sheet used in the pressure-sensitive adhesive sheet of the present invention is a film containing either amylose, polyvinyl alcohol or viscose as a main raw material.
For example, a film using amylose as a main raw material can be produced by discharging a molten or solution amylose composition from a die coater onto a heating roll or a belt and drying the volatile matter.
ポリビニルアルコールを主原料とするフィルムは、例えばポリビニルアルコールを主成分とする水分散液から溶液流延法により形成したものである。 A film containing polyvinyl alcohol as a main raw material is formed, for example, from an aqueous dispersion containing polyvinyl alcohol as a main component by a solution casting method.
ビスコースを主原料とするフィルムは、一般にはセルロースフィルムの名称で市販されており、例えば、以下の方法で製造されるものである。セルロース供給源であるパルプを水酸化ナトリウム等のアルカリ溶液に浸漬した後、二硫化炭素を添加して硫化し、さらにアルカリ溶解によりビスコースを調製する。ビスコースを硫酸等の酸溶液中へ膜状に吐出することにより凝固反応が生じ、フィルム状に成形される。 A film containing viscose as a main raw material is generally marketed under the name of cellulose film, and is produced by, for example, the following method. After immersing pulp, which is a source of cellulose, in an alkaline solution such as sodium hydroxide, carbon disulfide is added to sulfurize the pulp, and the viscose is further prepared by alkali dissolution. By discharging viscose into an acid solution such as sulfuric acid in the form of a film, a coagulation reaction occurs and the viscose is formed into a film.
このようなフィルムのうち、ＪＩＳ Ｐ ８１４０に準拠して測定される吸水度（水接触時間３０秒）が１０ｇ／ｍ２以下であるものを使用する。
ここで言う吸水度とは、粘着シートの粘着層が積層されていない側を測定面として測定された値、または、粘着層積層前の基材シートの表面を測定面として測定された値である。
Among such films, those having a water absorption degree (water contact time of 30 seconds) measured in accordance with JIS P 8140 of 10 g / m 2 or less are used.
The water absorption rate referred to here is a value measured with the side of the adhesive sheet on which the adhesive layer is not laminated as a measurement surface, or a value measured with the surface of the base material sheet before the adhesive layer laminated as a measurement surface. ..
基材シートは、アミロース、ポリビニルアルコールまたはビスコースのいずれかを主成分として構成されるものであるが、粘着シートの少なくとも粘着層が積層されていない側の吸水度が１０ｇ／ｍ２を超える場合、使用前或いは使用中における水濡れ、水性ペンによる筆記、印刷加工等により、粘着シートが破損する恐れがある。 The base sheet is composed mainly of amylose, polyvinyl alcohol or viscose, but when the water absorption of at least the side of the adhesive sheet on which the adhesive layer is not laminated exceeds 10 g / m 2. The adhesive sheet may be damaged due to water wetting before or during use, writing with a water-based pen, printing processing, or the like.
本発明の粘着シートにおいては、基材シートとしてＪＩＳ Ｐ ８１４０に準拠して測定される吸水度が１０ｇ／ｍ２以下のものを選択して使用する。より好ましくは吸水度が５ｇ／ｍ２以下のもの、更に好ましくは吸水度が２ｇ／ｍ２以下のものを使用する。基材シートに用いることができる材料の例としては、クラレ社製アミロースフィルム（製品名Ｐｌａｎｔｉｃ）、アイセロ社製ポリビニルアルコールフィルム（製品名ソルブロン）、フタムラ化学社製セルロースフィルム（製品名ＮａｔｕｒｅＦｌｅｘシリーズ）、等が挙げられる。 In the pressure-sensitive adhesive sheet of the present invention, a base sheet having a water absorption of 10 g / m 2 or less measured in accordance with JIS P 8140 is selected and used. More preferably, one having a water absorption of 5 g / m 2 or less, and further preferably one having a water absorption of 2 g / m 2 or less is used. Examples of materials that can be used for the base sheet include Kuraray's amylose film (product name: Plantic), Aicero's polyvinyl alcohol film (product name: Solbron), Futamura Chemical's cellulose film (product name: NatureFlex series), and so on. And so on.
基材シートは、アミロース、ポリビニルアルコールまたはビスコースのいずれかを使用したフィルムであっても、過度に耐水化処理が施されていると海洋分解性が劣る可能性がある。本発明の基材シートの表面に耐水化処理が施されている場合は、前記耐水化処理層が０．５ｇ／ｍ２以下であることが好ましい。 Even if the base sheet is a film using any of amylose, polyvinyl alcohol or viscose, if it is excessively water resistant, the marine decomposition property may be inferior. When the surface of the base material sheet of the present invention is subjected to a water resistant treatment, the water resistant treatment layer is preferably 0.5 g / m 2 or less.
また、基材シートの粘着剤層が形成されない面の、Ｊ．ＴＡＰＰＩ紙パルプ試験方法Ｎｏ．６８：２０００に従って測定したはっ水度が、Ｒ７以下であることが好ましい。はっ水度がＲ８以上となると、海洋分解性が劣りやすくなる。 Further, on the surface of the base sheet on which the pressure-sensitive adhesive layer is not formed, J.I. TAPPI Pulp and Paper Test Method No. The water repellency measured according to 68: 2000 is preferably R7 or less. When the water repellency is R8 or higher, the marine degradability tends to be inferior.
「粘着剤層」
本発明の粘着シートは、基材シートの少なくとも一部に粘着層を有する。また、基材シートの片面の少なくとも一部に積層されていてもよく、基材シートの両面に積層されていてもよい。
前記粘着シートの単位面積あたりの前記基材シートに対する前記粘着層の質量比率が０．１０〜０．３５であることが好ましい。より好ましくは０．１５〜０．３５である。
前記基材シートに対する前記粘着層の質量比率が０．１０以上であれば被着体への良好な接着力を確保し、粘着層に水が浸入して基材シート表面に皺や膨れが発生し印字物の読取適性が低下することを防ぐことができる。また、前記基材シートに対する前記粘着層の質量比率が０．３５以下であればより良好な海洋分解性を得ることができる。
"Adhesive layer"
The pressure-sensitive adhesive sheet of the present invention has an pressure-sensitive adhesive layer on at least a part of the base material sheet. Further, it may be laminated on at least a part of one side of the base sheet, or may be laminated on both sides of the base sheet.
The mass ratio of the pressure-sensitive adhesive layer to the base material sheet per unit area of the pressure-sensitive adhesive sheet is preferably 0.10 to 0.35. More preferably, it is 0.15 to 0.35.
When the mass ratio of the adhesive layer to the base sheet is 0.10 or more, good adhesive force to the adherend is ensured, and water penetrates into the adhesive layer to cause wrinkles and swelling on the surface of the base sheet. It is possible to prevent the readability of the printed matter from being lowered. Further, when the mass ratio of the adhesive layer to the base material sheet is 0.35 or less, better marine degradability can be obtained.
本発明の粘着シートで使用する粘着層は、ゲル分率が５０％以下である必要がある。ゲル分率を５０％以下とすることにより海洋分解性を高めることができる。また、ゲル分率の下限値を２５％以上とすることにより粘着層に水が浸入して基材シート表面に皺や膨れが発生し印字物の読取適性が低下することを防ぐことができるので好ましい。。好ましいゲル分率は２５％以上４７％以下であり、より好ましいゲル分率は２７％以上、４５％以下である。 The adhesive layer used in the adhesive sheet of the present invention needs to have a gel fraction of 50% or less. Ocean degradability can be enhanced by setting the gel fraction to 50% or less. Further, by setting the lower limit of the gel fraction to 25% or more, it is possible to prevent water from infiltrating the adhesive layer, causing wrinkles and swelling on the surface of the base sheet, and reducing the readability of the printed matter. preferable. .. The preferred gel fraction is 25% or more and 47% or less, and the more preferable gel fraction is 27% or more and 45% or less.
前記粘着剤層のゲル分率を５０％以下に調整する方法としては、粘着剤層を構成する重合体中の親水性基の量を調整する方法、粘着剤層中に親水性の可塑化物質を添加する方法が挙げられる。 Examples of the method for adjusting the gel content of the pressure-sensitive adhesive layer to 50% or less include a method of adjusting the amount of hydrophilic groups in the polymer constituting the pressure-sensitive adhesive layer and a hydrophilic plasticizer in the pressure-sensitive adhesive layer. Can be mentioned as a method of adding.
親水性の可塑化物質としては、例えば、グリセリン、ソルビット、マンニット、ズルシット、イジット、エリトリット、アラビット、アドニット等の糖アルコール類、ポリエチレンオキシドもしくはポリプロピレンオキシドとグリセリン、キシリットトリオキシイソブタン、ソルビットなどの多価アルコールとの共重合体やポリエチレングリコール、ポリプロピレングリコール等のポリエーテルポリオールや、エチレンオキシドとプロピレンオキシドとの共重合体、ポリオキシエチレンアルキルエーテール、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンポリオキシプロピレングリコール等のノニオン性の界面活性剤等が挙げられる。 Examples of the hydrophilic plasticizing substance include sugar alcohols such as glycerin, sorbit, mannit, zulusit, igit, erythrit, arabit, and adnit, polyethylene oxide or polypropylene oxide and glycerin, xylittrioxyisobutane, and sorbit. Copolymers with polyhydric alcohols, polyether polyols such as polyethylene glycol and polypropylene glycol, copolymers of ethylene oxide and propylene oxide, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxy Examples thereof include nonionic surfactants such as propylene glycol.
これら親水性の可塑化物質の添加量は、粘着性と親水性を考慮して、共重合体１００質量％に対して１０質量％以下、より好ましくは０．５〜１０質量％の範囲で使用することが望ましい。
なお、これら親水性の可塑化物質の中でも、特に、ノニオン系の界面活性剤が、親水性、接着性や保存性の良好な粘着剤を仕上げることができるので好ましい。
The amount of these hydrophilic plasticizers added is 10% by mass or less, more preferably 0.5 to 10% by mass, based on 100% by mass of the copolymer, in consideration of adhesiveness and hydrophilicity. It is desirable to do.
Among these hydrophilic plasticizers, a nonionic surfactant is particularly preferable because it can finish a pressure-sensitive adhesive having good hydrophilicity, adhesiveness and storage stability.
また、特に望むならば、粘着剤の性能、特にポリオレフィン系被着体に対する接着力、凝集力等の物性を向上させる目的で、エチレン−酢ビ共重合体、エチレン−酢酸ビニル−アクリル系共重合体を添加することもできる。
これらの添加物は、粘着性能並びにゲル分率を適正な範囲にするために用いることもできる。
Further, if desired, ethylene-vinyl acetate copolymer and ethylene-vinyl acetate-acrylic copolymer weight are used for the purpose of improving the performance of the pressure-sensitive adhesive, particularly the physical properties such as adhesive force and cohesive force to the polyolefin-based adherend. Cohesion can also be added.
These additives can also be used to bring the adhesive performance and gel fraction within the proper range.
前記粘着層が共重合樹脂を主成分として構成され、前記共重合樹脂中に親水性モノマー単位を前記共重合樹脂中に有し前記親水性モノマー単位を粘着剤組成中に２０〜３０質量％含有することが好ましい。
前記親水性モノマー単位を粘着剤組成中に２０質量％以上含有することにより、軽度の水濡れに対して良好な耐水性を示す。また、前記親水性モノマー単位を粘着剤組成中に３０質量％以下含有することにより、良好な接着性を得ることができる。
The pressure-sensitive adhesive layer is composed of a copolymer resin as a main component, has a hydrophilic monomer unit in the copolymer resin, and contains 20 to 30% by mass of the hydrophilic monomer unit in the pressure-sensitive adhesive composition. It is preferable to do so.
By containing 20% by mass or more of the hydrophilic monomer unit in the pressure-sensitive adhesive composition, it exhibits good water resistance against light water wetting. Further, by containing 30% by mass or less of the hydrophilic monomer unit in the pressure-sensitive adhesive composition, good adhesiveness can be obtained.
前記親水性モノマー単位としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、モノアルキルマレイン酸、モノアルキルイタコン酸、モノアルキルフマル酸等のエチレン性不飽和カルボン酸含有モノマー、メトキシエチルアクリレート、エトキシエチルアクリレート等のアルコキシアルキル（メタ）アクリレート、カルボン酸変性ロジンエステル、（メタ）アクリル酸のカプロラクトン付加物、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリルアミド、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル等が挙げられる。 Examples of the hydrophilic monomer unit include ethylenically unsaturated carboxylic acid-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, monoalkyl maleic acid, monoalkylitaconic acid, and monoalkylfumaric acid. Alkoxyalkyl (meth) acrylates such as methoxyethyl acrylate and ethoxyethyl acrylate, carboxylic acid modified rosin ester, caprolactone adduct of (meth) acrylic acid, hydroxyethyl (meth) acrylic acid, hydroxypropyl (meth) acrylic acid, (meth) ) Acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like.
前記粘着層を構成する親水性モノマー単位以外のモノマーとしては、粘着剤の粘着性を付与する成分として、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸ステアリル等が挙げられ、粘着性能を整える成分として、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸グリシジル、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、スチレン、エチレン等が挙げられる。 Examples of the monomer other than the hydrophilic monomer unit constituting the adhesive layer include butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and (meth) as components that impart adhesiveness to the adhesive. )-2-Ethylhexyl acrylate, stearyl (meth) acrylate, etc., and as components for adjusting the adhesive performance, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) Cyclohexyl acrylate, glycidyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl chloride, styrene, ethylene and the like can be mentioned.
前記粘着性を付与する成分は、粘着剤の粘着性能のバランスを考慮して適宣使用できるが、粘着剤の粘着性や凝集力等の点で、（メタ）アクリル酸ブチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸メチル、酢酸ビニルを使用することがより好ましい。
さらに、該粘着剤を得るための共重合体製造時に（ポリ）アルキレングリコールジ（メタ）アクリレート、（ポリ）アルキレングリコールモノ（メタ）アクリレート、（ポリ）エチレングリコール、（ポリ）プロピレングリコールの少なくともいずれか１種の補助成分を添加しても良い。
The component that imparts adhesiveness can be used appropriately in consideration of the balance of the adhesive performance of the adhesive, but in terms of the adhesiveness and cohesiveness of the adhesive, butyl (meth) acrylate and (meth) acrylic It is more preferable to use -2-ethylhexyl acid acid, methyl (meth) acrylate, and vinyl acetate.
Further, at least one of (poly) alkylene glycol di (meth) acrylate, (poly) alkylene glycol mono (meth) acrylate, (poly) ethylene glycol, and (poly) propylene glycol at the time of producing the copolymer for obtaining the pressure-sensitive adhesive. Alternatively, one auxiliary component may be added.
（ポリ）アルキレングリコールジ（メタ）アクリレートとしては、下記一般式（１）に表される化合物で、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等が挙げられる。 The (poly) alkylene glycol di (meth) acrylate is a compound represented by the following general formula (1), for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth). Examples thereof include acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate.
（ポリ）アルキレングリコールジ（メタ）アクリレートを加えての存在下で共重合体を製造すると、粘着剤に親水性を付与できると共に、分子量を上げることができるので、水中に分散した場合でも粘着性を発現し難い。そのため、海中で粘着シートが分解し易く、他の海洋ゴミと再付着する危険を減らすことができる。
前記補助成分は、粘着剤の親水性、粘着性能のバランスを考慮して適宣使用できる。前記補助成分の中でも特にポリエチレングリコールジメタクリレートは、親水性に優れた共重合体が得られるのでより好ましい。
When a copolymer is produced in the presence of (poly) alkylene glycol di (meth) acrylate, hydrophilicity can be imparted to the pressure-sensitive adhesive and the molecular weight can be increased, so that the pressure-sensitive adhesive can be adhered even when dispersed in water. Is difficult to express. Therefore, the adhesive sheet is easily decomposed in the sea, and the risk of reattachment with other marine debris can be reduced.
The auxiliary component can be properly used in consideration of the balance between the hydrophilicity and the adhesive performance of the adhesive. Among the auxiliary components, polyethylene glycol dimethacrylate is more preferable because a copolymer having excellent hydrophilicity can be obtained.
なお、（ポリ）アルキレングリコールジ（メタ）アクリレートは、粘着剤組成混合物１００質量％に対して、０．１〜５質量％の範囲で添加することが望ましい。因みに０．１質量％未満では、粘着剤の親水性が不十分となる。一方、５質量％を超えると、重合時に粘着剤が凝集しやすくなる。 The (poly) alkylene glycol di (meth) acrylate is preferably added in the range of 0.1 to 5% by mass with respect to 100% by mass of the pressure-sensitive adhesive composition mixture. Incidentally, if it is less than 0.1% by mass, the hydrophilicity of the pressure-sensitive adhesive becomes insufficient. On the other hand, if it exceeds 5% by mass, the pressure-sensitive adhesive tends to aggregate during polymerization.
なお、上記の共重合体の製造方法については、特に限定されるものではなく、例えば、水、溶剤、連鎖移動剤、重合開始剤等の存在下で溶液重合する方法や、乳化剤、連鎖移動剤、重合開始剤、分散剤等の存在下の水系でエマルジョン重合する方法などの公知の方法で製造される。 The method for producing the above-mentioned copolymer is not particularly limited, and for example, a method of solution polymerization in the presence of water, a solvent, a chain transfer agent, a polymerization initiator, etc., an emulsifier, a chain transfer agent, etc. It is produced by a known method such as a method of emulsion polymerization in an aqueous system in the presence of a polymerization initiator, a dispersant or the like.
上記の方法で得られた共重合体は、その共重合体中のカルボキシル基の５０〜１２０モル％に相当するアルカノールアミンや水酸化カリウムや水酸化ナトリウム等のアルカリ金属の水酸化物やアンモニア等で中和処理を施すことにより、機械安定性を改良でき、また粘度調整を行うことができる。粘着シートに加工された後の経時での揮散による粘着性能の劣化防止の点から、アルカリ金属の水酸化物を使用することがより好ましい。 The copolymer obtained by the above method has an alkanolamine corresponding to 50 to 120 mol% of the carboxyl groups in the copolymer, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, ammonia or the like. By performing the neutralization treatment with, the mechanical stability can be improved and the viscosity can be adjusted. It is more preferable to use an alkali metal hydroxide from the viewpoint of preventing deterioration of the adhesive performance due to volatilization over time after being processed into the adhesive sheet.
前記粘着剤層のゲル分率は以下の方法によって測定される。
〔ゲル分率測定方法〕
粘着シートと、粘着層積層前の基材シートまたは粘着シートから粘着層を溶剤により取り除いた基材シートを準備する。
１０ｃｍ角に切った基材シートサンプルの質量Ｗ１を測定する。
１０ｃｍ角に切った粘着シートサンプルの質量Ｗ２を測定する。
上記シートサンプルをそれぞれトルエンに２４時間浸漬させ、取り出して、８０°Ｃのオーブンで１時間乾燥させた後、基材シートサンプルの質量Ｗ３、粘着シートサンプルの 質量Ｗ４を測定する。
下記式に従いゲル分率を算出する。
ゲル分率（％） ＝ （Ｗ４−Ｗ３）／（Ｗ２−Ｗ１）×１００
The gel fraction of the pressure-sensitive adhesive layer is measured by the following method.
[Gel fraction measurement method]
A pressure-sensitive adhesive sheet and a base material sheet before laminating the pressure-sensitive adhesive layer or a base material sheet from which the pressure-sensitive adhesive layer has been removed with a solvent are prepared.
The mass W1 of the base sheet sample cut into 10 cm squares is measured.
The mass W2 of the adhesive sheet sample cut into 10 cm squares is measured.
Each of the above sheet samples is immersed in toluene for 24 hours, taken out, dried in an oven at 80 ° C. for 1 hour, and then the mass W3 of the base sheet sample and the mass W4 of the adhesive sheet sample are measured.
Calculate the gel fraction according to the following formula.
Gel fraction (%) = (W4-W3) / (W2-W1) x 100
「剥離シート」
本発明の粘着シートは、粘着層上に更に剥離シートが積層されていてもよい。
剥離シートの基材に使用するものとしては、特に限定するものではないが、例えば、グラシン紙の如き高密度原紙、クレーコート紙、グラシン紙やクラフト紙または上質紙等に、例えばカゼイン、デキストリン、澱粉、カルボキシメチルセルロース、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ポリビニルアルコール、スチレン−ブタジエン共重合体、メチルメタクリレート−ブタジエン共重合体、エチレン−塩化ビニル共重合体、エチレン−酢酸ビニル共重合体、アクリル酸エステル共重合体等の天然または合成樹脂および／または顔料を主成分とした目止め層を設けた紙類、グラシン紙やクラフト紙または上質紙等にポリエチレン等をラミネートしたラミネート紙（ポリラミ紙）類、ポリプロピレン、ポリエステル等のフィルム類を挙げることができる。
"Release sheet"
In the pressure-sensitive adhesive sheet of the present invention, a release sheet may be further laminated on the pressure-sensitive adhesive layer.
The material used as the base material of the release sheet is not particularly limited, but for example, high-density base paper such as glassin paper, clay-coated paper, glassin paper, kraft paper, high-quality paper, etc., for example, casein, dextrin, etc. Starch, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, acrylic acid ester Papers with a sealing layer mainly composed of natural or synthetic resins such as polymers and / or pigments, laminated papers (polylami papers) made by laminating polyethylene or the like on glassin paper, kraft paper, high-quality paper, etc., polypropylene , Polyester and other films can be mentioned.
「粘着シートの製造方法」
本発明の粘着シートを製造する方法としては公知の方法が採用できるが、一旦エマルジョン型の粘着剤を剥離シートに塗布、乾燥してから基材シートと貼り合わせる転写法を用いることが特に好ましい。上記粘着剤層は、水分散性の塗工液として調整することが好ましく、転写法を採用することにより、塗工液中の水分が基材シートへの接触を避けることができる。更に、乾燥の際に基材シートの僅かな収縮をさけることもできる。
"Manufacturing method of adhesive sheet"
A known method can be adopted as a method for producing the pressure-sensitive adhesive sheet of the present invention, but it is particularly preferable to use a transfer method in which an emulsion-type pressure-sensitive adhesive is once applied to a release sheet, dried, and then bonded to a base sheet. The pressure-sensitive adhesive layer is preferably prepared as a water-dispersible coating liquid, and by adopting the transfer method, it is possible to prevent the moisture in the coating liquid from coming into contact with the base sheet. Furthermore, it is possible to avoid slight shrinkage of the base sheet during drying.
「粘着シートの実施態様」
本発明の粘着シートは、粘着ラベルや粘着テープとして使用することができる。
また、基材シートとして透明性の高いものを採用して、オーバーラミ用粘着フィルムとして使用することができる。印刷等された部分に貼付することで、その部分を保護することができる。
また、基材シートに金属層を施した金属光沢性の粘着シートとすることもできる。金属層は金属箔の貼り合せや金属蒸着なども採用できるが、基材シートと粘着剤層の間に印刷等で設けても良く、例えば、アルミニウムなどの金属粉を含むインキで透明性の高い基材シートと粘着剤層の間に印刷すると、耐擦過性に優れ、筆記や印刷したものが鮮明に視認することができる金属光沢性に富んだ粘着シートを得ることができる。
また、基材シート表面には感熱層などの記録層を施すこともできる。
また、基材シートの両面に粘着剤層を形成する両面粘着シートとすることもできる。この場合、粘着剤により海洋分解性の機能が低下する傾向にあるので、粘着剤をドット状、水玉状、ストライプ状、格子状など非連続皮膜の状態で形成することが好ましい。
"Embodiment of Adhesive Sheet"
The adhesive sheet of the present invention can be used as an adhesive label or an adhesive tape.
Further, a highly transparent base sheet can be adopted and used as an adhesive film for overlamination. By attaching it to a printed part, that part can be protected.
Further, it may be a metallic luster adhesive sheet in which a metal layer is applied to a base material sheet. The metal layer can be bonded with a metal foil or metal vapor deposition, but may be provided between the base sheet and the pressure-sensitive adhesive layer by printing or the like. For example, an ink containing a metal powder such as aluminum has high transparency. When printing is performed between the base sheet and the pressure-sensitive adhesive layer, it is possible to obtain a pressure-sensitive adhesive sheet having excellent scratch resistance and having a high metallic luster so that the written or printed material can be clearly seen.
Further, a recording layer such as a heat-sensitive layer can be provided on the surface of the base sheet.
Further, it can be a double-sided pressure-sensitive adhesive sheet in which pressure-sensitive adhesive layers are formed on both sides of the base material sheet. In this case, since the adhesive has a tendency to reduce the marine degradability function, it is preferable to form the adhesive in a discontinuous film state such as a dot shape, a polka dot shape, a stripe shape, or a lattice shape.
以下、実施例をあげて本発明をより具体的に説明するが、もちろん本発明はこれらに限定されるものではない。また例中の部、割合、塗被量等は特に断らない限り、全て固形分または有効成分質量で示すものである。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is, of course, not limited thereto. Unless otherwise specified, the parts, proportions, coating amount, etc. in the examples are all indicated by the solid content or the mass of the active ingredient.
［実施例１］
（粘着剤Ａの製造）
まず乳化モノマー混合液として、
アクリル酸−２−エチルヘキシル：２９２部
アクリル酸：３２部
（メタ）アクリル酸メチル：２０部
アクリル酸メトキシエチル：３８部
酢酸ビニル：１４部
アニオン系乳化剤（商品名：エマール１０Ｇ／花王社製）：３部
イオン交換水：１５０部
を混合し、乳化剤とイオン交換水を除く全モノマー混合物に対してポリエチレングリコールジメタクリレート（商品名：ＮＫエステル９Ｇ／新中村化学社製）を４．５質量％添加して調製した。
粘着剤Ａにおいて粘着剤組成中の親水性モノマー由来成分の含有率は２６質量％であった。
[Example 1]
(Manufacturing of adhesive A)
First, as an emulsified monomer mixture,
-2-ethylhexyl acrylate: 292 parts Acrylic acid: 32 parts (meth) Methyl acrylate: 20 parts methoxyethyl acrylate: 38 parts Vinyl acetate: 14 parts Anionic emulsifier (trade name: Emar 10G / manufactured by Kao): 3 parts ion-exchanged water: 150 parts are mixed, and 4.5% by mass of polyethylene glycol dimethacrylate (trade name: NK ester 9G / manufactured by Shin-Nakamura Chemical Co., Ltd.) is added to the total monomer mixture excluding the emulsifier and ion-exchanged water. And prepared.
In the pressure-sensitive adhesive A, the content of the hydrophilic monomer-derived component in the pressure-sensitive adhesive composition was 26% by mass.
次ぎに撹拌機、クーラー、滴下ロート、窒素吸入管、温度計を付帯したフラスコに、イオン交換水１５０部、過硫酸カリウム３部、オクチルメルカプタン３部を仕込み、窒素置換しながら８０℃に昇温した後、上記乳化モノマー混合液を１／６滴下した。反応率が９０％に達した時点で残りのモノマー混合液を３時間かけて滴下し重合を行った。滴下終了後、８０℃で３時間熟成して反応を完結させた。次にフラスコ内容物を４０℃に冷却し、トリエタノールアミンと１０％ＫＯＨ水溶液をそれぞれ共重合体中のカルボキシル基の５０モル％添加して中和反応を行った。得られた組成物１００部に対してノニオン系界面活性剤（エマルゲン７０７／花王社製）：４部を添加し、強撹拌して粘着剤Ａを製造した。 Next, 150 parts of ion-exchanged water, 3 parts of potassium persulfate, and 3 parts of octyl mercaptan were placed in a flask equipped with a stirrer, cooler, dropping funnel, nitrogen suction tube, and thermometer, and the temperature was raised to 80 ° C while replacing nitrogen. After that, 1/6 of the above emulsion monomer mixed solution was added dropwise. When the reaction rate reached 90%, the remaining monomer mixed solution was added dropwise over 3 hours to carry out polymerization. After completion of the dropping, the reaction was completed by aging at 80 ° C. for 3 hours. Next, the contents of the flask were cooled to 40 ° C., and 50 mol% of the carboxyl groups in the copolymer were added with triethanolamine and a 10% KOH aqueous solution to carry out a neutralization reaction. To 100 parts of the obtained composition, 4 parts of a nonionic surfactant (Emargen 707 / manufactured by Kao Corporation) was added, and the mixture was vigorously stirred to produce a pressure-sensitive adhesive A.
（粘着シートの作製）
市販のポリエチレンラミネート紙にシリコーン系剥離剤が塗布された剥離紙に、粘着剤Ａを乾燥質量で２０ｇ／ｍ２となるように塗被、乾燥させた後、基材シートとして市販のセルロースフィルム（製品名：ＮａｔｕｒｅＦｌｅｘ ＣＬＷ４２、坪量６５ｇ／ｍ２、フタムラ化学社製）を貼り合わせて粘着シートを得た。
(Making an adhesive sheet)
A release paper obtained by applying a silicone-based release agent to a commercially available polyethylene laminated paper is coated with an adhesive A so as to have a dry mass of 20 g / m 2 , dried, and then a commercially available cellulose film (a commercially available cellulose film) is used as a base sheet. Product name: NatureFlex CLW42, basis weight 65 g / m 2 , manufactured by Futamura Chemical Co., Ltd.) was bonded to obtain an adhesive sheet.
［実施例２］
（粘着剤Ｂの製造）
まず乳化モノマー混合液として、
アクリル酸−２−エチルヘキシル：２８０部
アクリル酸：３５部
（メタ）アクリル酸メチル：２０部
アクリル酸メトキシエチル：５０部
酢酸ビニル：５部
アニオン系乳化剤（商品名：エマール１０ＰＴ／花王社製）：６部
イオン交換水：１５０部
を混合し、乳化剤とイオン交換水を除く全モノマー混合物に対してポリエチレングリコールジメタクリレート（商品名：ＮＫエステル９Ｇ／新中村化学社製）を０．９質量％添加して調製した。
粘着剤Ｂにおいて粘着剤組成中の親水性モノマー由来成分の含有率は２８質量％であった。
[Example 2]
(Manufacturing of adhesive B)
First, as an emulsified monomer mixture,
-2-ethylhexyl acrylate: 280 parts Acrylic acid: 35 parts (meth) Methyl acrylate: 20 parts methoxyethyl acrylate: 50 parts Vinyl acetate: 5 parts Anionic emulsifier (trade name: Emar 10PT / manufactured by Kao): 6 parts ion-exchanged water: 150 parts are mixed, and 0.9% by mass of polyethylene glycol dimethacrylate (trade name: NK ester 9G / manufactured by Shin-Nakamura Chemical Co., Ltd.) is added to the total monomer mixture excluding the emulsifier and ion-exchanged water. And prepared.
In the pressure-sensitive adhesive B, the content of the hydrophilic monomer-derived component in the pressure-sensitive adhesive composition was 28% by mass.
次ぎに撹拌機、クーラー、滴下ロート、窒素吸入管、温度計を付帯したフラスコに、イオン交換水１５０部、過硫酸カリウム３部、オクチルメルカプタン３部を仕込み、窒素置換しながら８０℃に昇温した後、上記乳化モノマー混合液を１／６滴下した。反応率が９０％に達した時点で残りのモノマー混合液を３時間かけて滴下し重合を行った。滴下終了後、８０℃で３時間熟成して反応を完結させた。次にフラスコ内容物を４０℃に冷却し、トリエタノールアミンと１０％ＫＯＨ水溶液をそれぞれ共重合体中のカルボキシル基の５０モル％添加して中和反応を行った。得られた組成物１００部に対し、ノニオン系の界面活性剤（商品名：エマルゲン７０９／花王社製）：４部、エチレン−酢ビ−アクリル共重合（商品名：スミカフレックスＳ−４００ＨＱ／住友化学工業社製）：２０部を添加し、強撹拌して本発明に使用する粘着剤を製造した。 Next, 150 parts of ion-exchanged water, 3 parts of potassium persulfate, and 3 parts of octyl mercaptan were placed in a flask equipped with a stirrer, cooler, dropping funnel, nitrogen suction tube, and thermometer, and the temperature was raised to 80 ° C while replacing nitrogen. After that, 1/6 of the above emulsion monomer mixed solution was added dropwise. When the reaction rate reached 90%, the remaining monomer mixed solution was added dropwise over 3 hours to carry out polymerization. After completion of the dropping, the reaction was completed by aging at 80 ° C. for 3 hours. Next, the contents of the flask were cooled to 40 ° C., and 50 mol% of the carboxyl groups in the copolymer were added with triethanolamine and a 10% KOH aqueous solution to carry out a neutralization reaction. For 100 parts of the obtained composition, a nonionic surfactant (trade name: Emargen 709 / manufactured by Kao Corporation): 4 parts, ethylene-vinyl acetate be-acrylic copolymer (trade name: Sumikaflex S-400HQ / Sumitomo) (Manufactured by Kagaku Kogyo Co., Ltd.): 20 parts were added and vigorously stirred to produce the pressure-sensitive adhesive used in the present invention.
市販のポリエチレンラミネート紙にシリコーン系剥離剤が塗布された剥離紙に、粘着剤Ｂを乾燥質量で２０ｇ／ｍ２となるように塗被、乾燥させた後、基材シートとして市販のセルロースフィルム（製品名：ＮａｔｕｒｅＦｌｅｘ ４２ＮＶＳＷ、坪量６５ｇ／ｍ２、フタムラ化学社製）を貼り合わせて粘着シートを得た。 A release paper obtained by applying a silicone-based release agent to a commercially available polyethylene laminated paper is coated with an adhesive B so as to have a dry mass of 20 g / m 2 , dried, and then a commercially available cellulose film (a commercially available cellulose film) is used as a base sheet. Product name: NatureFlex 42 NVSW, basis weight 65 g / m 2 , manufactured by Futamura Chemical Co., Ltd.) was bonded to obtain an adhesive sheet.
［実施例３］
実施例１の粘着シートの作製において市販のセルロースフィルム（製品名：ＮａｔｕｒｅＦｌｅｘ ４２ＮＶＳＷ、坪量６５ｇ／ｍ２、フタムラ化学社製）の代わりに市販のアミロースを主成分とするフィルム（Ｐｌａｎｔｉｃ／クラレ社製）に易接着層を設けたものを基材シートとして用いた以外は、実施例１と同様にして粘着シートを作成した。
[Example 3]
In the production of the pressure-sensitive adhesive sheet of Example 1, a commercially available film containing amylose as a main component (manufactured by Kuraray Co., Ltd.) instead of a commercially available cellulose film (product name: NatureFlex 42 NVSW, basis weight 65 g / m 2 , manufactured by Futamura Chemical Co., Ltd.) ) Was provided with an easy-adhesion layer, and an adhesive sheet was prepared in the same manner as in Example 1 except that the base sheet was used.
［実施例４］
（粘着剤Ｃの製造）
まず乳化モノマー混合液として、
アクリル酸−２−エチルヘキシル：２６０部
アクリル酸：３５部
（メタ）アクリル酸メチル：２０部
アクリル酸メトキシエチル：６０部
酢酸ビニル：２５部
アニオン系乳化剤（商品名：エマール１０ＰＴ／花王社製）：３部
イオン交換水：１５０部
を混合し、乳化剤とイオン交換水を除く全モノマー混合物に対してポリエチレングリコールジメタクリレート（商品名：ＮＫエステル９Ｇ／新中村化学社製）を１．８質量％添加して調製した。
粘着剤Ｃにおいて粘着剤組成中の親水性モノマー由来成分の含有率は３５質量％であった。
[Example 4]
(Manufacturing of adhesive C)
First, as an emulsified monomer mixture,
-2-ethylhexyl acrylate: 260 parts Acrylic acid: 35 parts (meth) Methyl acrylate: 20 parts methoxyethyl acrylate: 60 parts Vinyl acetate: 25 parts Anionic emulsifier (trade name: Emar 10PT / manufactured by Kao): 3 parts ion-exchanged water: 150 parts are mixed, and 1.8% by mass of polyethylene glycol dimethacrylate (trade name: NK ester 9G / manufactured by Shin-Nakamura Chemical Co., Ltd.) is added to the total monomer mixture excluding the emulsifier and ion-exchanged water. And prepared.
In the pressure-sensitive adhesive C, the content of the hydrophilic monomer-derived component in the pressure-sensitive adhesive composition was 35% by mass.
次ぎに撹拌機、クーラー、滴下ロート、窒素吸入管、温度計を付帯したフラスコに、イオン交換水１５０部、過硫酸カリウム３部、オクチルメルカプタン３部を仕込み、窒素置換しながら８０℃に昇温した後、上記乳化モノマー混合液を１／６滴下した。反応率が９０％に達した時点で残りのモノマー混合液を３時間かけて滴下し重合を行った。滴下終了後、８０℃で３時間熟成して反応を完結させた。次にフラスコ内容物を４０℃に冷却し、トリエタノールアミンと１０％ＫＯＨ水溶液をそれぞれ共重合体中のカルボキシル基の５０モル％添加して中和反応を行った。得られた組成物１００部に対し、ノニオン系の界面活性剤（商品名：エマルゲン７０９／花王社製）：４部、エチレン−酢ビ−アクリル共重合（商品名：スミカフレックスＳ−４００ＨＱ／住友化学工業社製）：２７部を添加し、強撹拌して本発明に使用する粘着剤を製造した。 Next, 150 parts of ion-exchanged water, 3 parts of potassium persulfate, and 3 parts of octyl mercaptan were placed in a flask equipped with a stirrer, cooler, dropping funnel, nitrogen suction tube, and thermometer, and the temperature was raised to 80 ° C while replacing nitrogen. After that, 1/6 of the above emulsion monomer mixed solution was added dropwise. When the reaction rate reached 90%, the remaining monomer mixed solution was added dropwise over 3 hours to carry out polymerization. After completion of the dropping, the reaction was completed by aging at 80 ° C. for 3 hours. Next, the contents of the flask were cooled to 40 ° C., and 50 mol% of the carboxyl groups in the copolymer were added with triethanolamine and a 10% KOH aqueous solution to carry out a neutralization reaction. For 100 parts of the obtained composition, a nonionic surfactant (trade name: Emargen 709 / manufactured by Kao Corporation): 4 parts, ethylene-vinyl acetate be-acrylic copolymer (trade name: Sumikaflex S-400HQ / Sumitomo) (Manufactured by Kagaku Kogyo Co., Ltd.): 27 parts were added and vigorously stirred to produce the pressure-sensitive adhesive used in the present invention.
前記粘着剤Ｃを使用した以外は、実施例１と同様にして粘着シートを作製した An adhesive sheet was produced in the same manner as in Example 1 except that the adhesive C was used.
［実施例５］
（粘着剤Ｄの製造）
まず乳化モノマー混合液として、
アクリル酸−２−エチルヘキシル：２８０部
アクリル酸：２０部
（メタ）アクリル酸メチル：１０部
アクリル酸メトキシエチル：１０部
酢酸ビニル：５部
アニオン系乳化剤（商品名：エマール１０Ｇ／花王社製）：３部
イオン交換水：１５０部
を混合し、乳化剤とイオン交換水を除く全モノマー混合物に対してポリエチレングリコールジメタクリレート（商品名：ＮＫエステル９Ｇ／新中村化学社製）を４．５質量％添加して調製した。
粘着剤Ｄにおいて粘着剤組成中の親水性モノマー由来成分の含有率は１４質量％であった。
[Example 5]
(Manufacturing of adhesive D)
First, as an emulsified monomer mixture,
-2-ethylhexyl acrylate: 280 parts Acrylic acid: 20 parts (meth) Methyl acrylate: 10 parts methoxyethyl acrylate: 10 parts Vinyl acetate: 5 parts Anionic emulsifier (trade name: Emar 10G / manufactured by Kao): 3 parts ion-exchanged water: 150 parts are mixed, and 4.5% by mass of polyethylene glycol dimethacrylate (trade name: NK ester 9G / manufactured by Shin-Nakamura Chemical Co., Ltd.) is added to the total monomer mixture excluding the emulsifier and ion-exchanged water. And prepared.
In the pressure-sensitive adhesive D, the content of the hydrophilic monomer-derived component in the pressure-sensitive adhesive composition was 14% by mass.
次ぎに撹拌機、クーラー、滴下ロート、窒素吸入管、温度計を付帯したフラスコに、イオン交換水１５０部、過硫酸カリウム３部、オクチルメルカプタン３部を仕込み、窒素置換しながら８０℃に昇温した後、上記乳化モノマー混合液を１／６滴下した。反応率が９０％に達した時点で残りのモノマー混合液を３時間かけて滴下し重合を行った。滴下終了後、８０℃で３時間熟成して反応を完結させた。次にフラスコ内容物を４０℃に冷却し、トリエタノールアミンと１０％ＫＯＨ水溶液をそれぞれ共重合体中のカルボキシル基の５０モル％添加して中和反応を行った。得られた組成物１００部に対してノニオン系界面活性剤（エマルゲン７０７／花王社製）：４部を添加し、強撹拌して粘着剤Ｄを製造した。 Next, 150 parts of ion-exchanged water, 3 parts of potassium persulfate, and 3 parts of octyl mercaptan were placed in a flask equipped with a stirrer, cooler, dropping funnel, nitrogen suction tube, and thermometer, and the temperature was raised to 80 ° C while replacing nitrogen. After that, 1/6 of the above emulsion monomer mixed solution was added dropwise. When the reaction rate reached 90%, the remaining monomer mixed solution was added dropwise over 3 hours to carry out polymerization. After completion of the dropping, the reaction was completed by aging at 80 ° C. for 3 hours. Next, the contents of the flask were cooled to 40 ° C., and 50 mol% of the carboxyl groups in the copolymer were added with triethanolamine and a 10% KOH aqueous solution to carry out a neutralization reaction. To 100 parts of the obtained composition, 4 parts of a nonionic surfactant (Emargen 707 / manufactured by Kao Corporation) was added, and the mixture was vigorously stirred to produce an adhesive D.
前記粘着剤Ｄを使用した以外は、実施例１と同様にして粘着シートを作製した An adhesive sheet was produced in the same manner as in Example 1 except that the adhesive D was used.
［実施例６］
実施例１の粘着シートの作製において粘着剤Ａを乾燥質量で１５ｇ／ｍ２となるように塗被、乾燥させた以外は、実施例１と同様にして粘着シートを作成した。
[Example 6]
In the preparation of the pressure-sensitive adhesive sheet of Example 1, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive A was coated and dried so as to have a dry mass of 15 g / m 2 .
［実施例７］
実施例１の粘着シートの作製において粘着剤Ａを乾燥質量で２５ｇ／ｍ２となるように塗被、乾燥させた以外は、実施例１と同様にして粘着シートを作成した。
[Example 7]
In the preparation of the pressure-sensitive adhesive sheet of Example 1, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive A was coated and dried so as to have a dry mass of 25 g / m 2 .
［実施例８］
実施例１の粘着シートの作製において粘着剤Ａを乾燥質量で１０ｇ／ｍ２となるように塗被、乾燥させた以外は、実施例１と同様にして粘着シートを作成した。
[Example 8]
In the preparation of the pressure-sensitive adhesive sheet of Example 1, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive A was coated and dried so as to have a dry mass of 10 g / m 2 .
［実施例９］
実施例１の粘着シートの作製において粘着剤Ａを乾燥質量で３０ｇ／ｍ２となるように塗被、乾燥させた以外は、実施例１と同様にして粘着シートを作成した。
[Example 9]
In the preparation of the pressure-sensitive adhesive sheet of Example 1, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive A was coated and dried so as to have a dry mass of 30 g / m 2 .
［比較例１］
実施例１の粘着シートの作製において市販のセルロースフィルム（製品名：ＮａｔｕｒｅＦｌｅｘ ４２ＮＶＳＷ、６５ｇ／ｍ２、フタムラ化学社製）の代わりに市販のポリエチレンテレフタレートフィルム（東洋紡績社製）を基材シートとして使用した以外は、実施例１と同様にして粘着シートを作製した
[Comparative Example 1]
In the production of the adhesive sheet of Example 1, a commercially available polyethylene terephthalate film (manufactured by Toyo Spinning Co., Ltd.) was used as a base sheet instead of a commercially available cellulose film (product name: NatureFlex 42 NVSW, 65 g / m 2 , manufactured by Futamura Chemical Co., Ltd.). An adhesive sheet was prepared in the same manner as in Example 1 except that
［比較例２］
実施例１の粘着シートの作製において市販のセルロースフィルム（製品名：ＮａｔｕｒｅＦｌｅｘ ４２ＮＶＳＷ、坪量６５ｇ／ｍ２、フタムラ化学社製）の代わりに市販の撥水紙（レインガード/王子エフテックス社製）を基材シートとして使用した以外は、実施例１と同様にして粘着シートを作製した。
[Comparative Example 2]
In the production of the adhesive sheet of Example 1, a commercially available water-repellent paper (Rainguard / Oji F-Tex Co., Ltd.) was used instead of the commercially available cellulose film (product name: NatureFlex 42 NVSW, basis weight 65 g / m 2 , manufactured by Futamura Chemical Co., Ltd.). Was used as the base sheet, and an adhesive sheet was prepared in the same manner as in Example 1.
［比較例３］
実施例１において粘着剤Ａの代わりに市販のアクリル系粘着剤（商品名：ＢＰＷ６１１１Ａ−１／トーヨーケム社製）を乾燥質量で２０ｇ／ｍ２となるように塗被、乾燥した以
外は、実施例１と同様にして粘着シートを作成した。
[Comparative Example 3]
Example 1 except that a commercially available acrylic pressure-sensitive adhesive (trade name: BPW6111A-1 / manufactured by Toyochem Co., Ltd.) was applied instead of the pressure-sensitive adhesive A so as to have a dry mass of 20 g / m 2 and dried. An adhesive sheet was prepared in the same manner as in 1.
［比較例４］
実施例１の粘着シートの作製において市販のセルロースフィルム（製品名：ＮａｔｕｒｅＦｌｅｘ ４２ＮＶＳＷ、坪量６５ｇ／ｍ２、フタムラ化学社製）の代わりに市販のポリ乳酸系フィルム（エコロージュ／三菱ケミカル社製）を基材シートとして用いた以外は、実施例１と同様にして粘着シートを作成した。
[Comparative Example 4]
In the production of the pressure-sensitive adhesive sheet of Example 1, a commercially available polylactic acid film (Ecologe / Mitsubishi Chemical Co., Ltd.) was used instead of the commercially available cellulose film (product name: NatureFlex 42 NVSW, basis weight 65 g / m 2 , manufactured by Futamura Chemical Co., Ltd.). An adhesive sheet was prepared in the same manner as in Example 1 except that it was used as a base sheet.
［比較例５］
実施例１において粘着剤Ａの代わりに市販のデンプン糊を乾燥質量で２０ｇ／ｍ２となるように塗被、乾燥した以外は、実施例１と同様にして粘着シートを作成した。
[Comparative Example 5]
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that a commercially available starch paste was applied in place of the pressure-sensitive adhesive A so as to have a dry mass of 20 g / m 2 and dried in Example 1.
［比較例６］
実施例１の粘着シートの作製において市販のセルロースフィルム（製品名：ＮａｔｕｒｅＦｌｅｘ ４２ＮＶＳＷ、坪量６５ｇ／ｍ２、フタムラ化学社製）の代わりに市販のセロハン（レンゴー社製、坪量坪量５６ｇ／ｍ２）を基材シートとして用いた以外は、実施例１と同様にして粘着シートを作成した。
[Comparative Example 6]
In the production of the adhesive sheet of Example 1, instead of the commercially available cellulose film (product name: NatureFlex 42 NVSW, basis weight 65 g / m 2 , manufactured by Futamura Chemical Co., Ltd.), commercially available cellophane (manufactured by Rengo Co., Ltd., basis weight 56 g / m) An adhesive sheet was prepared in the same manner as in Example 1 except that 2 ) was used as the base sheet.
このようにして得られた粘着シートについて、下記の評価を行い、得られた結果を表１に示した。 The adhesive sheet thus obtained was evaluated as follows, and the obtained results are shown in Table 1.
（評価試験項目）
〔接着力〕
ＪＩＳ−Ｚ−０２３７の常態粘着力の測定方法に準拠し、下記の二つの条件で保存した後の接着力をそれぞれ測定した。（単位：Ｎ／２５ｍｍ）
条件Ａ：粘着シートの製造後、温度２３±２℃、関係湿度６５±５％の雰囲気下に７日間保存した後、その接着力を測定した。
条件Ｂ：粘着シート製造後、温度４０±２℃、関係湿度９０±５％の雰囲気下に７日間保存した後、その接着力を測定した。
接着力は８Ｎ／２５ｍｍ以上であれば、実用上問題がない。
(Evaluation test items)
[Adhesive strength]
According to the method for measuring the normal adhesive strength of JIS-Z-0237, the adhesive strength after storage under the following two conditions was measured. (Unit: N / 25 mm)
Condition A: After manufacturing the adhesive sheet, it was stored in an atmosphere of a temperature of 23 ± 2 ° C. and a related humidity of 65 ± 5% for 7 days, and then its adhesive strength was measured.
Condition B: After producing the adhesive sheet, it was stored in an atmosphere of a temperature of 40 ± 2 ° C. and a related humidity of 90 ± 5% for 7 days, and then its adhesive strength was measured.
If the adhesive strength is 8N / 25mm or more, there is no practical problem.
〔粘着シートの吸水度〕
ＪＩＳ−Ｐ−８１４０の吸水度試験方法に準拠し、粘着シートの表面側（基材シート）の吸水度を測定した。なお、水の接触時間は３０秒で行った。
[Water absorption of adhesive sheet]
The water absorption on the surface side (base sheet) of the adhesive sheet was measured according to the water absorption test method of JIS-P-8140. The contact time of water was 30 seconds.
〔粘着シートのはっ水度〕
Ｊ．ＴＡＰＰＩ紙パルプ試験方法Ｎｏ．６８：２０００に従って、粘着シートの表面側（基材シート）のはっ水度を測定した。
[Water repellency of adhesive sheet]
J. TAPPI Pulp and Paper Test Method No. According to 68: 2000, the water repellency of the surface side (base sheet) of the adhesive sheet was measured.
（耐水性試験）
前記粘着シートの前記基材シートの前記粘着層が積層されていない面に熱転写プリンタ（型番：ＳＣＡＮ ＴＲＯＮＩＣＳ ＳＧ４１２Ｒ、サトー社製）でＪＡＮバーコードを印字した後、前記粘着シートの前記ＪＡＮバーコード印字部を含んで切り出した５０ｍｍ×５０ｍｍの粘着シートサンプルを前記粘着層を介して６０ｍｍ×６０ｍｍのポリエチレンテレフタレートフィルムに貼り付けた後、水温２３℃の水道水５００ｃｃの入ったビーカーに投入して２０秒浸漬した。
サンプルの耐水性を以下の基準で評価した。
○：粘着シートサンプルがポリエチレンテレフタレートフィルムから剥がれておらず、耐水性が良好である。
×：粘着シートサンプルがポリエチレンテレフタレートフィルムから剥がれており、耐水性に実用上問題がある。
(Water resistance test)
After printing a JAN barcode on the surface of the adhesive sheet on which the adhesive layer is not laminated with a thermal transfer printer (model number: SCAN TRONICS SG412R, manufactured by Sato Co., Ltd.), printing the JAN barcode on the adhesive sheet. A 50 mm × 50 mm pressure-sensitive adhesive sheet sample cut out including the portion was attached to a 60 mm × 60 mm polyethylene terephthalate film via the pressure-sensitive adhesive layer, and then placed in a beaker containing 500 cc of tap water at a water temperature of 23 ° C. for 20 seconds. Soaked.
The water resistance of the sample was evaluated according to the following criteria.
◯: The adhesive sheet sample is not peeled off from the polyethylene terephthalate film, and the water resistance is good.
X: The adhesive sheet sample is peeled off from the polyethylene terephthalate film, and there is a practical problem in water resistance.
（印刷保存性）
前記耐水性試験において２０秒浸漬した粘着シートサンプルをビーカーから取り出して温度２３±２℃、関係湿度６５±５％の雰囲気下で乾燥させてから、バーコードリーダー（型番：ＢＨＴ−６１５９ＵＭＷＢ、デンソー社製）で読取りを行い、以下の基準で評価した。
○：バーコードを読み取ることができ、印字保存性が良好である。
△：バーコードを読み取り成功率が７０％以上であり、実用に耐える。
×：バーコードを読み取ることができ、印字保存性に実用上問題がある。
(Print storage stability)
The pressure-sensitive adhesive sheet sample immersed for 20 seconds in the water resistance test is taken out from the beaker and dried in an atmosphere having a temperature of 23 ± 2 ° C. and a related humidity of 65 ± 5%, and then a barcode reader (model number: BHT-6159UMWB, Denso Corporation). The product was read and evaluated according to the following criteria.
◯: The barcode can be read and the print storage stability is good.
Δ: The success rate of reading the barcode is 70% or more, and it is practical.
X: Bar code can be read, and there is a practical problem in print storage stability.
（海洋分解性試験）
４０Ｌ水槽に蒸留水３５Ｌを入れ、人口海水の素（製品名：ＲＥＤ ＳＥＡ ＳＡＬＴ、Ｒｅｄ Ｓｅａ社製）を比重１．０２になるよう溶解して、人口海水を調整する。
次いで、水温を２６℃に調整し、水槽にライブロックを投入し、ポンプで水槽を循環させて海洋環境を作成する。
予め乾燥質量Ａを測定した１００ｍｍ×１００ｍｍの試験片を水槽に９０日間浸漬させた後、試験片を取り出して乾燥質量Ｂを測定し、残存率（乾燥質量Ｂ／乾燥質量Ａ）を測定する。残存率が２０％以下のものを合格とする。
(Ocean degradability test)
Add 35 L of distilled water to a 40 L water tank and dissolve artificial seawater (product name: RED SEA SALT, manufactured by Red Sea) to a specific gravity of 1.02 to adjust the artificial seawater.
Next, the water temperature is adjusted to 26 ° C., live rock is put into the water tank, and the water tank is circulated by a pump to create a marine environment.
A 100 mm × 100 mm test piece whose dry mass A has been measured in advance is immersed in a water tank for 90 days, then the test piece is taken out and the dry mass B is measured, and the residual ratio (dry mass B / dry mass A) is measured. Those with a survival rate of 20% or less are considered acceptable.
〔耐水性試験〕
５ｃｍ角に切った粘着シートを市販のポリエチレンテレフタレートフィルムに貼り付け、温度２３±２℃、関係湿度６５±５％の雰囲気下に２４時間放置後、２３゜Ｃの水に２０秒間浸漬し、取り出したときの状態を下記評価基準にて評価した。
○：粘着ラベルがフィルムから剥がれないで、評価前の状態を維持している。
△：粘着ラベルの一部に剥がれが見られる、もしくはラベル周囲が波打つ。
×：粘着ラベルが全てフィルムから剥がれる。
[Water resistance test]
An adhesive sheet cut into 5 cm squares is attached to a commercially available polyethylene terephthalate film, left in an atmosphere of a temperature of 23 ± 2 ° C. and a related humidity of 65 ± 5% for 24 hours, then immersed in water at 23 ° C. for 20 seconds and taken out. The state at that time was evaluated according to the following evaluation criteria.
◯: The adhesive label does not peel off from the film, and the state before evaluation is maintained.
Δ: Peeling is seen on a part of the adhesive label, or the circumference of the label is wavy.
X: All the adhesive labels are peeled off from the film.
〔ゲル分率〕
１０ｃｍ角に切った基材シート重量を測定する。・・・Ｗ１
１０ｃｍ角に切った粘着シートの重量を測定する。・・・Ｗ２
上記基材シートならびに粘着シートをそれぞれトルエンに２４時間浸漬させ、取り出した後に乾燥させてそれぞれの重量（基材シート：Ｗ３、粘着シート：Ｗ４）を測定する。 下記式に従いゲル分率を算出し、結果を表１に示した。
ゲル分率（％） ＝ （Ｗ４−Ｗ３）／（Ｗ２−Ｗ１）×１００
[Gel fraction]
The weight of the base sheet cut into 10 cm squares is measured.・ ・ ・ W1
Weigh the adhesive sheet cut into 10 cm squares.・ ・ ・ W2
The base sheet and the pressure-sensitive adhesive sheet are each immersed in toluene for 24 hours, taken out, and then dried to measure their respective weights (base material sheet: W3, pressure-sensitive adhesive sheet: W4). The gel fraction was calculated according to the following formula, and the results are shown in Table 1.
Gel fraction (%) = (W4-W3) / (W2-W1) x 100
（水性ペン筆記性）
前記粘着シートの前記基材シートの前記粘着層が積層されていない面に水性ペン（水性サインペン、ペンテル社製）で描画し、画像の滲み具合を以下の基準で評価した。
○：滲みが殆どなく水性ペン筆記性が良好である。
△：僅かに滲みが見られるが、実用上問題ない水性ペン筆記性を有する。
×：滲みが観察される、または、画像がかすれ実用上問題がある。
(Aqueous pen writing ability)
A water-based pen (water-based felt-tip pen, manufactured by Pentel) was used to draw on the surface of the base material sheet of the pressure-sensitive adhesive sheet on which the pressure-sensitive adhesive layer was not laminated, and the degree of blurring of the image was evaluated according to the following criteria.
◯: There is almost no bleeding and the water-based pen writing property is good.
Δ: Slight bleeding is observed, but it has a water-based pen writing property that does not cause any problem in practical use.
X: Blurring is observed or the image is faint and there is a practical problem.
表１の如く、本発明の粘着シートは、貼り付け時には必要な接着力を示し、経時による接着力の低下も少なく、実使用時の耐水性にも優れ、且つ使用後に海洋に廃棄されたとしても海洋環境下で分解される粘着シートであった。 As shown in Table 1, the adhesive sheet of the present invention exhibits the necessary adhesive strength at the time of sticking, the adhesive strength does not decrease with time, has excellent water resistance during actual use, and is discarded in the ocean after use. Was also an adhesive sheet that decomposed in the marine environment.
Claims (4)
前記基材シートがアミロース、ポリビニルアルコールまたはビスコースのいずれかを主原料とするフィルムであり、且つＪＩＳ Ｐ ８１４０に準拠して測定される吸水度が１０ｇ／ｍ２以下であり、前記粘着剤層のゲル分率が５０％以下である粘着シート。 An adhesive sheet having an adhesive layer on the base sheet and at least a part of the base sheet.
The base material sheet is a film containing any of amylose, polyvinyl alcohol or viscose as a main raw material, and the water absorption degree measured according to JIS P 8140 is 10 g / m 2 or less, and the pressure-sensitive adhesive layer. Adhesive sheet having a gel fraction of 50% or less.
前記共重合樹脂中に親水性モノマー単位を前記共重合樹脂中に有し前記親水性モノマー単位を粘着剤組成中に２０〜３０質量％含有する請求項１に記載の粘着シート。 The adhesive layer is composed mainly of a copolymer resin.
The pressure-sensitive adhesive sheet according to claim 1, wherein the copolymer resin contains a hydrophilic monomer unit in the copolymer resin, and the hydrophilic monomer unit is contained in the pressure-sensitive adhesive composition in an amount of 20 to 30% by mass.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113897A (en) * | 1994-10-14 | 1996-05-07 | Oji Kako Kk | Base material for release paper |
| JP2001089722A (en) * | 1999-09-21 | 2001-04-03 | Oji Paper Co Ltd | Pressure-sensitive adhesive label |
| JP2001172581A (en) * | 1999-12-22 | 2001-06-26 | Oji Paper Co Ltd | Pressure sensitive adhesive sheet or pressure sensitive adhesive tape |
| US20160186013A1 (en) * | 2014-12-30 | 2016-06-30 | Avery Dennison Corporation | Water-Activated Linerless Adhesive Articles and Related Methods |
| JP2018115278A (en) * | 2017-01-19 | 2018-07-26 | リンテック株式会社 | Adhesive film and method for sticking adhesive film to adherend |
-
2020
- 2020-01-27 JP JP2020010677A patent/JP7447505B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113897A (en) * | 1994-10-14 | 1996-05-07 | Oji Kako Kk | Base material for release paper |
| JP2001089722A (en) * | 1999-09-21 | 2001-04-03 | Oji Paper Co Ltd | Pressure-sensitive adhesive label |
| JP2001172581A (en) * | 1999-12-22 | 2001-06-26 | Oji Paper Co Ltd | Pressure sensitive adhesive sheet or pressure sensitive adhesive tape |
| US20160186013A1 (en) * | 2014-12-30 | 2016-06-30 | Avery Dennison Corporation | Water-Activated Linerless Adhesive Articles and Related Methods |
| JP2018115278A (en) * | 2017-01-19 | 2018-07-26 | リンテック株式会社 | Adhesive film and method for sticking adhesive film to adherend |
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