JP5530611B2 - Label forming adhesive sheet - Google Patents
Label forming adhesive sheet Download PDFInfo
- Publication number
- JP5530611B2 JP5530611B2 JP2008241988A JP2008241988A JP5530611B2 JP 5530611 B2 JP5530611 B2 JP 5530611B2 JP 2008241988 A JP2008241988 A JP 2008241988A JP 2008241988 A JP2008241988 A JP 2008241988A JP 5530611 B2 JP5530611 B2 JP 5530611B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- sheet
- mass
- 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.)
- Active
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- 239000000853 adhesive Substances 0.000 title claims description 30
- 230000001070 adhesive effect Effects 0.000 title claims description 28
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 137
- 239000010410 layer Substances 0.000 claims description 55
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 19
- 229920003232 aliphatic polyester Polymers 0.000 claims description 15
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 11
- 239000004626 polylactic acid Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- 239000000178 monomer Substances 0.000 description 30
- 239000003431 cross linking reagent Substances 0.000 description 26
- -1 polybutylene succinate Polymers 0.000 description 25
- 239000000839 emulsion Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- 239000004925 Acrylic resin Substances 0.000 description 14
- 229920000178 Acrylic resin Polymers 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920006381 polylactic acid film Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CCQJKEYNLSZZNO-UHFFFAOYSA-N 10-trimethoxysilyldecyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCCCOC(=O)C=C CCQJKEYNLSZZNO-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- MSWDKRMGRFOUHD-UHFFFAOYSA-N 2-aminoethyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCN MSWDKRMGRFOUHD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- NWIIFBPIDORBCY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O.OCC(O)CO NWIIFBPIDORBCY-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 1
- CSBJCQMIXISILC-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl prop-2-enoate Chemical compound C[Si](C)(Cl)CCCOC(=O)C=C CSBJCQMIXISILC-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- DGBFOBNYTYHFPN-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C=C DGBFOBNYTYHFPN-UHFFFAOYSA-N 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- YFISHOAHNLGUEL-UHFFFAOYSA-N 3-tributoxysilylpropyl prop-2-enoate Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCOC(=O)C=C YFISHOAHNLGUEL-UHFFFAOYSA-N 0.000 description 1
- LEPRPXBFZRAOGU-UHFFFAOYSA-N 3-trichlorosilylpropyl prop-2-enoate Chemical compound Cl[Si](Cl)(Cl)CCCOC(=O)C=C LEPRPXBFZRAOGU-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- HGEKXQRHZRDGKO-UHFFFAOYSA-N 3-tripropoxysilylpropyl prop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C=C HGEKXQRHZRDGKO-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- TUUKLRVBYCHYOG-UHFFFAOYSA-N 4-trimethoxysilylbutyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCOC(=O)C=C TUUKLRVBYCHYOG-UHFFFAOYSA-N 0.000 description 1
- OTWRKXPZLZXAFH-UHFFFAOYSA-N 5-trimethoxysilylpentyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCOC(=O)C=C OTWRKXPZLZXAFH-UHFFFAOYSA-N 0.000 description 1
- ALEBYBVYXQTORU-UHFFFAOYSA-N 6-hydrazinyl-6-oxohexanoic acid Chemical compound NNC(=O)CCCCC(O)=O ALEBYBVYXQTORU-UHFFFAOYSA-N 0.000 description 1
- INVAIHOVGZNBFS-UHFFFAOYSA-N 6-triethoxysilylhexyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCCCCOC(=O)C=C INVAIHOVGZNBFS-UHFFFAOYSA-N 0.000 description 1
- WCULYVVFGLYOBZ-UHFFFAOYSA-N 6-trimethoxysilylhexyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCOC(=O)C=C WCULYVVFGLYOBZ-UHFFFAOYSA-N 0.000 description 1
- JOVCTEPPTIOAPX-UHFFFAOYSA-N 8-trimethoxysilyloctyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCOC(=O)C=C JOVCTEPPTIOAPX-UHFFFAOYSA-N 0.000 description 1
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- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
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- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- NOBSUVLSUXZMQP-UHFFFAOYSA-N prop-2-enyl(dipropoxy)silane Chemical compound CCCO[SiH](CC=C)OCCC NOBSUVLSUXZMQP-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer 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
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明はラベル形成用粘着シートに関し、さらに詳しくは、基材として生分解性シートを用いてなる、熱履歴後であっても収縮率が低く、熱寸法安定性に優れるラベルを与えるラベル形成用粘着シートに関するものである。 The present invention relates to a pressure-sensitive adhesive sheet for label formation, and more specifically, for label formation that uses a biodegradable sheet as a base material, provides a label with low shrinkage even after heat history and excellent thermal dimensional stability. The present invention relates to an adhesive sheet.
各種物品に表示、宣伝などのために粘着ラベルが幅広く使用されている。粘着ラベルは粘着シートから形成されるものであり、粘着シートは通常印刷等が設けられるシート状基材、粘着剤層及び粘着剤層を保護する剥離シートにより構成されている。
シート状基材には、紙、プラスチックフィルム、金属箔等の種々のものが用いられているが、粘着シートを燃焼させて廃棄する場合、シート状基材がプラスチックフィルムであると有毒ガスが発生したり、金属箔では高温が必要であるなど総合的に環境汚染を引き起こす場合がある。また、シート状基材がプラスチックフィルムの場合、土中投棄などで廃棄すると、フィルムが分解しないことから生態系を破壊するなど環境破壊を起こすおそれがある。
そこで近年では、シート状基材として用いるプラスチックフィルムに生分解性物質から成るフィルム（生分解性フィルム）を用い、廃棄後は微生物によって自然に分解される粘着シートが盛んに開発されている。生分解性フィルムの中で、粘着性や強度の点でポリ乳酸フィルムをシート状基材として用いたものが多い（例えば、特許文献１参照）。
Adhesive labels are widely used for display and promotion on various articles. The pressure-sensitive adhesive label is formed from a pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive sheet is usually composed of a sheet-like substrate on which printing or the like is provided, a pressure-sensitive adhesive layer, and a release sheet that protects the pressure-sensitive adhesive layer.
Various materials such as paper, plastic film, and metal foil are used for the sheet-like substrate. When the adhesive sheet is burned and discarded, toxic gas is generated if the sheet-like substrate is a plastic film. However, the metal foil may cause environmental pollution comprehensively, such as the high temperature required. In addition, when the sheet-like substrate is a plastic film, if it is discarded by dumping in the soil, the film does not decompose, which may cause environmental destruction such as destruction of the ecosystem.
Therefore, in recent years, pressure-sensitive adhesive sheets that are biodegradable films (biodegradable films) that are used as sheet-like substrates and that are naturally decomposed by microorganisms after disposal have been actively developed. Many biodegradable films use a polylactic acid film as a sheet-like substrate in terms of adhesiveness and strength (see, for example, Patent Document 1).
シート状基材として生分解性フィルムを用い、その一方の面に粘着剤層が形成された粘着シートが生分解性が良好なものとして用いられているが、生分解性フィルムは、汎用のプラスチックフィルムに比べて、熱寸法安定性が不十分であるため、食品などのラベルに使用した場合に、電子レンジなどによる熱によってラベルが収縮してしまうという問題が生じる。
この問題を解決するために、生分解性を有するフィルム基材と、前記フィルム基材上に形成された粘着層とを有する粘着テープであって、前記フィルム基材は主たる繰り返し単位が一般式Ｏ−ＣＨＲ−ＣＯ−（ＲはＨまたは、炭素数１〜３のアルキル基）である脂肪族ポリエステルを主成分としたポリマーから成り、１２０℃でのフィルム長手方向の熱収縮率が５％以下である脂肪族ポリエステル二軸延伸フィルムを基材とし、その少なくとも片面に粘着層を設けてなることを特徴とする粘着テープが開示されている（例えば、特許文献２参照）。
しかしながら、前記の技術において、粘着剤層に必要とされる物性は詳細には開示されていない。
A biodegradable film is used as a sheet-like substrate, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed on one side thereof is used as a biodegradable material. Since the thermal dimensional stability is insufficient as compared with a film, there is a problem that the label shrinks due to heat from a microwave oven or the like when used for a label such as food.
In order to solve this problem, a pressure-sensitive adhesive tape having a biodegradable film base and an adhesive layer formed on the film base, wherein the film base has a general repeating unit of the general formula O It is composed of a polymer mainly composed of an aliphatic polyester that is —CHR—CO— (R is H or an alkyl group having 1 to 3 carbon atoms), and the thermal shrinkage in the film longitudinal direction at 120 ° C. is 5% or less. There has been disclosed an adhesive tape characterized in that an aliphatic polyester biaxially stretched film is used as a base material and an adhesive layer is provided on at least one surface thereof (see, for example, Patent Document 2).
However, the physical properties required for the pressure-sensitive adhesive layer in the above technique are not disclosed in detail.
一方、粘着剤層を構成する粘着剤としては、例えばアクリル系、ウレタン系、ゴム系、シリコーン系などがあるが、これらの中で、粘着力、保持力、耐候性、耐熱性などの性能の点から、アクリル系粘着剤が多用されている。このアクリル系粘着剤としては、従来溶剤型のものが主として用いられてきたが、近年、塗工時における有機溶剤の揮発が環境衛生や安全面で問題となっており、また、粘着シートにした場合でも、粘着剤層に僅かながら有機溶剤が含まれ、環境衛生面で問題となっていた。
これに対し、エマルション型のものは、環境衛生、安全面については特に問題はなく、又高濃度化による高速塗工及び脱溶剤による低コスト化が可能であることから、最近では、溶剤型に代えて、エマルション型のものが使用されるようになってきた。特に、食品関係に使用されるラベルには、無溶剤型の粘着剤を用いたラベルが好んで使用されている。
On the other hand, the emulsion type has no particular problems in terms of environmental hygiene and safety, and since high-speed coating by high concentration and cost reduction by desolvation are possible, recently it has been changed to the solvent type. Instead, an emulsion type has been used. In particular, labels using solvent-free pressure-sensitive adhesives are preferably used for labels used in food products.
本発明は、このような事情のもとで、基材として生分解性シートを用いてなる、熱履歴後であっても収縮率が低く、熱寸法安定性に優れるラベルを与えるラベル形成用粘着シートを提供することを目的とするものである。 Under such circumstances, the present invention uses a biodegradable sheet as a base material, and has a low shrinkage rate even after heat history and provides a label with excellent thermal dimensional stability. The purpose is to provide a sheet.
本発明者は、前記目的を達成するために鋭意研究を重ねた結果、生分解性シートの片面に、特にアクリル系エマルション型粘着剤を用いて、特定の性状を有する架橋された粘着剤層を設けることにより、その目的を達成し得ることを見出し、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、
［１］生分解性シートと、その片面に架橋された粘着剤層とを有する粘着シートであって、前記架橋された粘着剤層のゲル分率が５０質量％以上であり、かつ前記粘着シートのＪＩＳ Ｚ ０２３７に準拠して測定した保持力が、７万秒経過時点での該粘着シートのずれ量として０.５ｍｍ以下であり、前記生分解性シートに用いられる樹脂全体に、生分解性を有しない樹脂を５０質量％以下の範囲で含有し、架橋された粘着剤層を構成する粘着剤が、粘着付与剤を含まないことを特徴とするラベル形成用粘着シート、
［２］生分解性シートの厚さをＡ（μｍ）、架橋された粘着剤層の厚さをＢ（μｍ）とした場合、前記Ａが１０〜１５０μｍであり、かつＢ／Ａ比が０.１〜２.０である上記［１］項に記載のラベル形成用粘着シート、
［３］架橋された粘着剤層を構成する粘着剤が、アクリル系エマルション型粘着剤である上記［１］又は［２］項に記載のラベル形成用粘着シート、
［４］生分解性シートが、ポリ乳酸系脂肪族ポリエステル及びその誘導体の中から選ばれる少なくとも１種を５０質量％以上含むフィルムである上記［１］〜［３］項のいずれかに記載のラベル形成用粘着シート、及び
［５］架橋された粘着剤層に剥離シートが貼付されてなる上記［１］〜［４］項のいずれかに記載のラベル形成用粘着シート、
を提供するものである。
As a result of intensive studies to achieve the above object, the present inventor has formed a crosslinked pressure-sensitive adhesive layer having a specific property on one side of the biodegradable sheet, particularly using an acrylic emulsion-type pressure-sensitive adhesive. As a result, it was found that the object can be achieved, and the present invention has been completed based on this finding.
That is, the present invention
[1] A pressure-sensitive adhesive sheet having a biodegradable sheet and a pressure-sensitive adhesive layer crosslinked on one surface thereof, wherein the gel fraction of the cross-linked pressure-sensitive adhesive layer is 50% by mass or more, and the pressure-sensitive adhesive sheet The holding force measured in accordance with JIS Z 0237 is 0.5 mm or less as the amount of deviation of the pressure-sensitive adhesive sheet after 70,000 seconds, and the entire resin used in the biodegradable sheet is biodegradable. A pressure- sensitive adhesive sheet for forming a label , wherein the pressure-sensitive adhesive constituting the crosslinked pressure-sensitive adhesive layer does not contain a tackifier ,
[2] When the thickness of the biodegradable sheet is A (μm) and the thickness of the crosslinked pressure-sensitive adhesive layer is B (μm), the A is 10 to 150 μm and the B / A ratio is 0. The pressure-sensitive adhesive sheet for label formation according to the above [1], which is .1 to 2.0,
[ 3 ] The pressure-sensitive adhesive sheet for label formation according to the above [1] or [ 2 ], wherein the pressure-sensitive adhesive constituting the crosslinked pressure-sensitive adhesive layer is an acrylic emulsion-type pressure-sensitive adhesive,
[ 4 ] The biodegradable sheet according to any one of [1] to [ 3 ], wherein the biodegradable sheet is a film containing 50% by mass or more of at least one selected from polylactic acid-based aliphatic polyesters and derivatives thereof. The pressure-sensitive adhesive sheet for label formation, and the pressure-sensitive adhesive sheet for label formation according to any one of the above items [1] to [ 4 ], wherein a release sheet is attached to the [ 5 ] cross-linked pressure-sensitive adhesive layer,
Is to provide.
本発明によれば、基材として生分解性シートを用い、その片面に特定の性状を有する粘着剤層を設けることにより、熱履歴後であっても収縮率が低く、熱寸法安定性に優れるラベルを与えるラベル形成用粘着シートを提供することができる。 According to the present invention, by using a biodegradable sheet as a base material and providing a pressure-sensitive adhesive layer having a specific property on one side, the shrinkage rate is low even after heat history and the thermal dimensional stability is excellent. A label-forming pressure-sensitive adhesive sheet that provides a label can be provided.
本発明のラベル形成用粘着シート（以下、単に粘着シートと称することがある。）は、生分解性シートと、その片面に架橋された粘着剤層とを有する粘着シートであって、前記架橋された粘着剤層が、下記の性状を有することを特徴とする。
［生分解性シート］
本発明のラベル形成用粘着シートにおいては、基材として生分解性シートが使用される。この生分解性シートに用いられる材料としては、生分解性を有すると共に、製膜性が良好で、ラベルを形成した場合に、ラベルとしての機械特性や耐久性などを満たすものであればよく、特に制限されず、生物由来の材料であってもよく、石油由来の材料であってもよい。このような生分解性材料として、例えば脂肪族ポリエステル、微生物産生ポリエステル、芳香族−脂肪族ポリエステル、脂肪族ポリエステルカーボネート、脂肪族ポリエステルアミド、脂肪族ポリエステルエーテル、ポリアミノ酸、ポリビニルアルコール、デンプン、セルロース及び酢酸セルロース、ヒドロキシエチルセルロースやヒドロキシプロピルセルロース等のセルロース誘導体、キチン、キトサン、マンナン等の多糖類などが挙げられる。
The pressure-sensitive adhesive sheet for label formation of the present invention (hereinafter sometimes simply referred to as a pressure-sensitive adhesive sheet) is a pressure-sensitive adhesive sheet having a biodegradable sheet and a pressure-sensitive adhesive layer cross-linked on one side thereof. The pressure-sensitive adhesive layer has the following properties.
[Biodegradable sheet]
In the pressure-sensitive adhesive sheet for label formation of the present invention, a biodegradable sheet is used as a substrate. As a material used for this biodegradable sheet, as long as it has biodegradability, film-forming property is good, and a label is formed, it may satisfy the mechanical characteristics and durability as a label, The material is not particularly limited, and may be a biological material or a petroleum-derived material. Such biodegradable materials include, for example, aliphatic polyesters, microorganism-produced polyesters, aromatic-aliphatic polyesters, aliphatic polyester carbonates, aliphatic polyester amides, aliphatic polyester ethers, polyamino acids, polyvinyl alcohol, starch, cellulose and Examples thereof include cellulose derivatives such as cellulose acetate, hydroxyethyl cellulose and hydroxypropyl cellulose, and polysaccharides such as chitin, chitosan and mannan.
中でも、機械特性、耐久性、製膜性などの観点から脂肪族ポリエステル及びその誘導体、セルロース及びその誘導体、ポリビニルアルコール、キトサン等が好ましく、これらの中では脂肪族ポリエステル及びその誘導体がより好ましい。脂肪族ポリエステル及びその誘導体としては、ポリ乳酸系、ポリカプロラクトン系、ポリブチレンサクシネート系などが実用化されている。
これらの中でポリ乳酸系脂肪族ポリエステル及びその誘導体が特に好適である。
ポリ乳酸は、トウモロコシなどの植物を発酵して得られる乳酸を原料として製造され、そして微生物によって水と二酸化炭素に分解され、再び植物の育成を助けるという連鎖性を有することから、バイオリサイクル型として、本発明においては、好適に用いられる。
Of these, aliphatic polyesters and derivatives thereof, cellulose and derivatives thereof, polyvinyl alcohol, chitosan, and the like are preferable from the viewpoints of mechanical properties, durability, film-forming properties, etc. Among these, aliphatic polyesters and derivatives thereof are more preferable. As the aliphatic polyester and derivatives thereof, polylactic acid, polycaprolactone, polybutylene succinate and the like have been put into practical use.
Of these, polylactic acid-based aliphatic polyesters and derivatives thereof are particularly suitable.
Polylactic acid is produced using lactic acid obtained by fermenting plants such as corn as raw materials, and is decomposed into water and carbon dioxide by microorganisms, and has a linkage property that helps plants grow again. In the present invention, it is preferably used.
前記ポリ乳酸は、原料の乳酸として、Ｌ形、Ｄ形、ラセミ形のいずれを用いてもよく、また、化学合成法及び発酵法のいずれの方法で得られたものも用いることができるが、バイオリサイクルの観点から、トウモロコシなどの澱粉を乳酸発酵させて得られたものを用いることが好ましい。
本発明で用いることのできるポリ乳酸は、前記乳酸を原料とし、（１）環化反応によって得られたラクチドを開環重合させてポリマーを得る二段階プロセス、及び（２）乳酸を直接重合させてポリマーを得る一段階プロセス、のいずれの方法によって得られたものであってもよい。
このポリ乳酸の重量平均分子量は、通常５万〜８０万である。また、融点は、通常９０〜２００℃程度であり、ガラス転移温度は、通常４０〜８０℃程度である。
The polylactic acid may be any of L-form, D-form, and racemic form as raw material lactic acid, and those obtained by any method of chemical synthesis and fermentation can be used. From the viewpoint of biorecycling, it is preferable to use a product obtained by subjecting starch such as corn to lactic acid fermentation.
The polylactic acid that can be used in the present invention comprises the above-mentioned lactic acid as a raw material, (1) a two-stage process for obtaining a polymer by ring-opening polymerization of lactide obtained by a cyclization reaction, and (2) direct polymerization of lactic acid. It may be obtained by any one of the one-stage processes for obtaining the polymer.
The weight average molecular weight of this polylactic acid is usually 50,000 to 800,000. Moreover, melting | fusing point is about 90-200 degreeC normally, and glass transition temperature is about 40-80 degreeC normally.
本発明においては、前記の生分解性材料を１種用いて生分解性シート状基材を作製してもよく、２種以上を組み合わせて生分解性シート状基材を作製してもよいが、当該生分解性シートは、生分解性の観点から、前記の生分解性材料、特にポリ乳酸系脂肪族ポリエステル及びその誘導体の中から選ばれる少なくとも１種を５０質量％以上含むフィルムであることが好ましい。
また、当該生分解性材料のみでは、例えば強度や製膜性等が低い場合には、当該生分解性材料と、一般的な基材に用いられる生分解性を有しない樹脂等を混合して用いてもよい。当該生分解性材料と混合して用いることが可能な材料としては、例えばポリアクリル、ポリエステル、ポリウレタン、ポリオレフィン等が挙げられる。またこの場合、上記生分解性を有しない樹脂は、生分解性シートに用いられる樹脂全体の中で５０質量％以下、中でも３０質量％以下の範囲内で含有されていることが好ましい。上記生分解性を有しない材料の含有量を上記範囲内とすることにより、本発明の目的を損なうことのないものとすることができるからである。
In the present invention, a biodegradable sheet-like substrate may be produced using one of the biodegradable materials described above, or a biodegradable sheet-like substrate may be produced by combining two or more kinds. The biodegradable sheet is a film containing 50% by mass or more of at least one selected from the above biodegradable materials, particularly polylactic acid aliphatic polyesters and derivatives thereof, from the viewpoint of biodegradability. Is preferred.
In addition, when the biodegradable material alone is low in strength, film formability, etc., for example, the biodegradable material and a non-biodegradable resin used for a general base material are mixed. It may be used. Examples of materials that can be used by mixing with the biodegradable material include polyacryl, polyester, polyurethane, and polyolefin. In this case, the resin having no biodegradability is preferably contained within a range of 50% by mass or less, particularly 30% by mass or less, based on the entire resin used for the biodegradable sheet. This is because by setting the content of the material having no biodegradability within the above range, the object of the present invention can be prevented.
当該生分解性シートは、印刷性を付与するために、粘着剤層とは反対側の面に、各種印刷方式に対応するインク受理層を設けたものであってもよい。
また、当該生分解性シートは、その上に設けられる粘着剤層との密着性を向上させるために、所望により酸化法や凹凸化法などの表面処理を施すことができる。上記酸化法としては、例えばプラズマ処理、コロナ放電処理、クロム酸処理（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理などが挙げられ、また、凹凸化法としては、例えばサンドブラスト法、溶剤処理法などが挙げられる。これらの表面処理法は生分解性シートの種類に応じて適宜選ばれるが、一般にはコロナ放電処理法が効果及び操作性などの面から、好ましく用いられる。また、プライマー処理を施すこともできる。
本発明においては、当該生分解性シートの厚さは、適宜選定されるが、通常１０〜１５０μｍの範囲で選定され、より好ましくは１５〜１００μｍの範囲である。
The biodegradable sheet may be provided with an ink receiving layer corresponding to various printing methods on the surface opposite to the pressure-sensitive adhesive layer in order to impart printability.
In addition, the biodegradable sheet can be subjected to surface treatment such as an oxidation method or a concavo-convex method, if desired, in order to improve the adhesion to the pressure-sensitive adhesive layer provided thereon. Examples of the oxidation method include plasma treatment, corona discharge treatment, chromic acid treatment (wet process), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Treatment methods and the like. These surface treatment methods are appropriately selected according to the type of the biodegradable sheet, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, primer treatment can also be performed.
In the present invention, the thickness of the biodegradable sheet is appropriately selected, but is usually selected in the range of 10 to 150 μm, and more preferably in the range of 15 to 100 μm.
［粘着剤層］
本発明のラベル形成用粘着シートにおいては、前記生分解性シートの片面に、架橋された粘着剤層が形成される。
本発明においては、当該架橋された粘着剤層は、ゲル分率が５０質量％以上であることを要する。このゲル分率が５０質量％未満では粘着剤層の凝集力が不足してしまい、生分解性シートの、熱履歴による寸法変化を抑えることができず、ラベル形状の維持が困難であり、本発明の目的が達せられない。好ましいゲル分率は６０質量％以上である。一方、ゲル分率が高くなりすぎると、粘着剤層のタックが低下し、粘着性能や外観に悪影響を及ぼす場合があることから、ゲル分率は９５質量％以下であることが好ましく、９０質量％以下であることがより好ましい。
なお、本発明においては、上記ゲル分率は、下記の方法により測定される値である。
＜架橋された粘着剤層のゲル分率＞
サイズ５０ｍｍ×５０ｍｍ、厚さ５０μｍのポリ乳酸系フィルム［三菱樹脂社製、商品名「エコロージュＳＡ」］の片面に、本発明に係る粘着剤を塗布し、９０℃で１分間乾燥してなるテストピースを、ステンレス製金網の質量（Ａｇ）に貼り付け質量（Ｂｇ）を測定する。次いで、これを約２００ｃｍ3の酢酸エチルに浸漬し、２３℃にて２４時間放置する。続いて金網付きテストピースを取り出し、大気圧下で１１０℃、２時間加熱乾燥し、乾燥後の質量（Ｃｇ）を測定する。
次いで、テストピースをステンレス製金網から剥がし、残った粘着剤が除去されてなるポリ乳酸系フィルムのみの質量（Ｄｇ）を測定し、下記の式
ゲル分率（質量％）＝［(Ｃ−Ａ−Ｄ)／(Ｂ−Ａ−Ｄ)］×１００
により、ゲル分率を算出する。
[Adhesive layer]
In the label-forming pressure-sensitive adhesive sheet of the present invention, a crosslinked pressure-sensitive adhesive layer is formed on one side of the biodegradable sheet.
In the present invention, the crosslinked pressure-sensitive adhesive layer needs to have a gel fraction of 50% by mass or more. When the gel fraction is less than 50% by mass, the cohesive force of the pressure-sensitive adhesive layer is insufficient, the dimensional change due to the heat history of the biodegradable sheet cannot be suppressed, and the label shape is difficult to maintain. The object of the invention cannot be achieved. A preferable gel fraction is 60% by mass or more. On the other hand, if the gel fraction becomes too high, the tackiness of the pressure-sensitive adhesive layer is lowered, which may adversely affect the adhesive performance and appearance. Therefore, the gel fraction is preferably 95% by mass or less, and 90% by mass. % Or less is more preferable.
In the present invention, the gel fraction is a value measured by the following method.
<Gel fraction of crosslinked adhesive layer>
A test in which the pressure-sensitive adhesive according to the present invention is applied to one side of a polylactic acid-based film (trade name “Ecologe SA” manufactured by Mitsubishi Plastics, Inc.) having a size of 50 mm × 50 mm and a thickness of 50 μm, and dried at 90 ° C. for 1 minute. The piece is attached to the mass (Ag) of the stainless steel wire mesh and the mass (Bg) is measured. Then, it is immersed in about 200 cm 3 of ethyl acetate and left at 23 ° C. for 24 hours. Subsequently, a test piece with a wire net is taken out, dried by heating at 110 ° C. for 2 hours under atmospheric pressure, and the mass (Cg) after drying is measured.
Next, the test piece was peeled off from the stainless steel wire mesh, and the mass (Dg) of only the polylactic acid-based film from which the remaining adhesive was removed was measured, and the following formula Gel fraction (mass%) = [(CA −D) / (B−A−D)] × 100
To calculate the gel fraction.
また、本発明のラベル形成用粘着シートにおいては、ＪＩＳ Ｚ ０２３７に準拠して測定した保持力が、７万秒経過時点での該粘着シートのずれ量として０.５ｍｍ以下であることを要する。このずれ量が０.５ｍｍを超えると、生分解性シートの熱履歴による寸法変化を抑えることができず、本発明の目的が達せられない。好ましい保持力は、前記ずれ量で０.４ｍｍ以下である。
なお、本発明においては、上記保持力は、下記の方法により測定される値である。
＜粘着シートの保持力＞
本発明に係る粘着剤を、剥離シート上に塗布し、乾燥させたのち、生分解性フィルムに貼り合わせ粘着シートを作製する。次いで、この粘着シートを、ステンレス製鋼板（ＳＵＳ３８０）に、貼り付け面積が２５ｍｍ×２５ｍｍになるように貼付し、８０℃、Ｄｒｙ条件下で９.８Ｎの荷重をかけ、ＪＩＳ Ｚ ０２３７の保持力の測定法に準じて、７万秒後のフィルムのずれ量を測定する。
Moreover, in the adhesive sheet for label formation of this invention, the retention strength measured based on JISZ0237 needs to be 0.5 mm or less as deviation | shift amount of this adhesive sheet at the time of 70,000 second progress. If this deviation exceeds 0.5 mm, the dimensional change due to the thermal history of the biodegradable sheet cannot be suppressed, and the object of the present invention cannot be achieved. A preferable holding force is 0.4 mm or less in terms of the shift amount.
In the present invention, the holding force is a value measured by the following method.
<Holding power of adhesive sheet>
After applying the adhesive which concerns on this invention on a peeling sheet and making it dry, it bonds together to a biodegradable film and produces an adhesive sheet. Next, this adhesive sheet was affixed to a stainless steel plate (SUS380) so that the affixed area was 25 mm × 25 mm, and a load of 9.8 N was applied under conditions of 80 ° C. and Dry to maintain the holding power of JIS Z 0237. According to the measurement method, the amount of displacement of the film after 70,000 seconds is measured.
また、本発明のラベル形成用粘着シートにおいては、生分解性シートの厚さをＡ（μｍ）、架橋された粘着剤層の厚さをＢ（μｍ）とした場合、生分解性シートの熱履歴による寸法変化を効果的に抑え、かつ粘着シート全体の厚さを好適な範囲にするために、Ｂ／Ａ比が０.１〜２.０であることが好ましく、０.２〜１.０であることがより好ましい。 Further, in the pressure-sensitive adhesive sheet for label formation of the present invention, when the thickness of the biodegradable sheet is A (μm) and the thickness of the crosslinked pressure-sensitive adhesive layer is B (μm), the heat of the biodegradable sheet In order to effectively suppress the dimensional change due to the history and make the thickness of the entire pressure-sensitive adhesive sheet within a suitable range, the B / A ratio is preferably 0.1 to 2.0, and preferably 0.2 to 1. More preferably 0.
（アクリル系エマルション型粘着剤）
本発明のラベル形成用粘着シートにおいて、架橋された粘着剤層を構成する粘着剤としては、それから形成される粘着剤層が、前記性状を有するものであれば、その種類については特に制限はなく、様々な種類の粘着剤、例えばゴム系粘着剤、シリコーン系粘着剤及びアクリル系粘着剤などを用いることができるが、これらの中で、粘着剤としての性能、耐候性、ゲル分率の調節性などの観点からアクリル系粘着剤が好ましく、環境性の観点から、特にアクリル系エマルション型粘着剤が好適である。
(Acrylic emulsion type adhesive)
In the pressure-sensitive adhesive sheet for label formation of the present invention, the pressure-sensitive adhesive constituting the crosslinked pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive layer formed therefrom has the above properties. Various types of pressure-sensitive adhesives such as rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and acrylic pressure-sensitive adhesives can be used. Among them, performance as a pressure-sensitive adhesive, weather resistance, adjustment of gel fraction Acrylic adhesives are preferred from the standpoint of properties, and acrylic emulsion-type adhesives are particularly preferred from the environmental standpoint.
このアクリル系エマルション型粘着剤は、粘着付与剤の存在下、エチレン性不飽和単量体を反応性界面活性剤を用いて乳化重合することにより、かつ内部架橋剤又は外部架橋剤あるいはその両方を用いることにより、製造することができる。
なお、ここで内部架橋剤とは、重合時に、ポリマー分子内に架橋構造を導入し得る架橋型反応性単量体を指し、一方、外部架橋剤とは、重合体粒子間にも架橋構造を導入し得る化合物を指す。外部架橋剤を用いる場合には、架橋すべき重合体粒子は、分子内に架橋性官能基が導入されていることが必須となる。
エチレン性不飽和単量体としては、従来アクリル系エマルション型粘着剤の原料として慣用されている単量体、具体的には(メタ)アクリル酸アルキルエステル及び所望により官能性単量体や他の単量体を用いることができる。
This acrylic emulsion-type pressure-sensitive adhesive is obtained by emulsion polymerization of an ethylenically unsaturated monomer using a reactive surfactant in the presence of a tackifier, and an internal crosslinking agent and / or an external crosslinking agent. It can be manufactured by using it.
Here, the internal cross-linking agent refers to a cross-linkable reactive monomer that can introduce a cross-linked structure into the polymer molecule during polymerization, while the external cross-linking agent refers to a cross-linked structure between polymer particles. Refers to a compound that can be introduced. When an external crosslinking agent is used, it is essential that the polymer particles to be crosslinked have a crosslinkable functional group introduced into the molecule.
As the ethylenically unsaturated monomer, a monomer conventionally used as a raw material for an acrylic emulsion-type pressure-sensitive adhesive, specifically, a (meth) acrylic acid alkyl ester and optionally a functional monomer or other Monomers can be used.
前記(メタ)アクリル酸エステルとしては、アルキル基の炭素数が１〜２０の(メタ)アクリル酸エステルが好ましく、具体的には、(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)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(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)アクリル酸イソオクチル、(メタ)アクリル酸デシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリルなどが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The (meth) acrylic acid ester is preferably a (meth) acrylic acid ester having an alkyl group having 1 to 20 carbon atoms, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Propyl acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, ( Examples include decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
また、官能性単量体としては、例えば(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、(メタ)アクリル酸３−ヒドロキシプロピル、(メタ)アクリル酸２−ヒドロキシブチル、(メタ)アクリル酸３−ヒドロキシブチル、(メタ)アクリル酸４−ヒドロキシブチルなどの(メタ)アクリル酸ヒドロキシアルキルエステル；(メタ)アクリル酸アセトアセトキシメチル；アクリルアミド、メタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ,Ｎ−ジメチルアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ,Ｎ−ジメチルメタクリルアミド、Ｎ−メチロ−ルアクリルアミド、Ｎ−メチロ−ルメタクリルアミド、ジアセトンアクリルアミドなどのアクリルアミド類；(メタ)アクリル酸モノ又はジメチルアミノエチル、(メタ)アクリル酸モノ又はジエチルアミノエチル、(メタ)アクリル酸モノ又はジメチルアミノプロピル、(メタ)アクリル酸モノ又はジエチルアミノプロピルなどの(メタ)アクリル酸モノ又はジアルキルアミノアルキル；アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸などのエチレン性不飽和カルボン酸などが挙げられる。これらの単量体は単独で用いてもよく、２種以上を組み合わせて用いてもよい。
これらの官能性単量体における官能基は、外部架橋剤を用いる場合の架橋点となる。
Examples of the functional monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. (Meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; acetoacetoxymethyl (meth) acrylate; acrylamide, methacrylamide, N-methylacrylamide, Acrylamides such as N, N-dimethylacrylamide, N-methylmethacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide; (meth) acrylic acid mono Or dimethylaminoethyl, (meth) acrylic Mono- or dialkylaminoalkyl (meth) acrylates such as mono- or diethylaminoethyl phosphate, mono- or dimethylaminopropyl (meth) acrylate, mono- or diethylaminopropyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, maleic Examples thereof include ethylenically unsaturated carboxylic acids such as acid, itaconic acid and citraconic acid. These monomers may be used independently and may be used in combination of 2 or more type.
The functional group in these functional monomers serves as a crosslinking point when an external crosslinking agent is used.
さらに、その他の単量体としては、例えば酢酸ビニル、プロピオン酸ビニルなどのビニルエステル類；エチレン、プロピレン、イソブチレンなどのオレフィン類；塩化ビニル、ビニリデンクロリドなどのハロゲン化オレフィン類；スチレン、α−メチルスチレンなどのスチレン系単量体；ブタジエン、イソプレン、クロロプレンなどのジエン系単量体；アクリロニトリル、メタクリロニトリルなどのニトリル系単量体などが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。
また、内部架橋剤である架橋型反応性単量体としては、多官能性エチレン性不飽和単量体、ケト基含有エチレン性不飽和単量体、アルコキシシリル基含有エチレン性不飽和単量体などが挙げられる。
Furthermore, other monomers include, for example, vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene, α-methyl Examples thereof include styrene monomers such as styrene; diene monomers such as butadiene, isoprene and chloroprene; and nitrile monomers such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.
In addition, the cross-linkable reactive monomer that is an internal cross-linking agent includes a polyfunctional ethylenically unsaturated monomer, a keto group-containing ethylenically unsaturated monomer, and an alkoxysilyl group-containing ethylenically unsaturated monomer. Etc.
ここで、多官能性エチレン性不飽和単量体としては、例えば、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、１,３−ブチレングリコールジ(メタ)アクリレート、１,４−ブタンジオールジ(メタ)アクリレート、１,６−ヘキサンジオールジ(メタ)アクリレート、１,９−ノナンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、グリセリンメタクリレートアクリレート、トリス(メタ)アクリロイルオキシフォスフェート、グリセリンジ(メタ)アクリレート、ジアリルテレフタレート、テトラアリルオキシエタン、ジビニルベンゼン、トリ(メタ)アリルイソシアヌレート等が挙げられる。 Here, as the polyfunctional ethylenically unsaturated monomer, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Tet Methylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, glycerin methacrylate acrylate, tris (meth) acryloyloxyphosphate, glycerin di (meth) acrylate, diallyl terephthalate, tetraallyloxyethane, divinylbenzene, tri ( And (meth) allyl isocyanurate.
ケト基含有エチレン性不飽和単量体としては、例えばダイアセトンアクリルアミド、２−(アセトアセトキシ)エチル(メタ)アクリレート、アセトアセトキシメチル(メタ)アクリレート、アリルアセトアセテートなどが挙げられる。
アルコキシシリル基含有エチレン性不飽和単量体としては、例えば２−(メタ)アクリロキシエチルトリメトキシシラン、２−(メタ)アクリロキシエチルトリエトキシシラン、γ−(メタ)アクリロキシプロピルトリメトキシシラン、γ−(メタ)アクリロキシプロピルトリエトキシシラン、γ−(メタ)アクリロキシプロピルメチルジメトキシシラン、γ−(メタ)アクリロキシプロピルジメチルメトキシシラン、γ−(メタ)アクリロキシプロピルメチルジエトキシシラン、γ−(メタ)アクリロキシプロピルジメチルエトキシシラン、γ−(メタ)アクリロキシプロピルトリクロロシラン、γ−(メタ)アクリロキシプロピルメチルジクロロシラン、γ−(メタ)アクリロキシプロピルジメチルクロロシラン、γ−(メタ)アクリロキシプロピルトリプロピオキシシラン、γ−(メタ)アクリロキシプロピルメチルジプロピオキシシラン、γ−(メタ)アクリロキシプロピルトリブトキシシラン、(メタ)アクリロキシブチルトリメトキシシラン、(メタ)アクリロキシペンチルトリメトキシシラン、(メタ)アクリロキシヘキシルトリメトキシシラン、(メタ)アクリロキシヘキシルトリエトキシシラン、(メタ)アクリロキシオクチルトリメトキシシラン、(メタ)アクリロキシデシルトリメトキシシラン、(メタ)アクリロキシドデシルトリメトキシシラン、(メタ)アクリロキシオクタデシルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、ビニルメチルジプロポキシシラン等が挙げられる。
これらの内部架橋剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよいが、これらの中で、特にケト基含有エチレン性不飽和単量体が好適である。内部架橋剤の配合量は、全モノマー１００質量部に対し、０.５〜１０質量部とするのが好ましい。
Examples of the keto group-containing ethylenically unsaturated monomer include diacetone acrylamide, 2- (acetoacetoxy) ethyl (meth) acrylate, acetoacetoxymethyl (meth) acrylate, and allyl acetoacetate.
Examples of the alkoxysilyl group-containing ethylenically unsaturated monomer include 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane. , Γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyldimethylchlorosilane, γ- (meta ) Acryloxypropyltripropoxysilane, γ- (Meth) acryloxypropylmethyldipropoxyoxysilane, γ- (meth) acryloxypropyltributoxysilane, (meth) acryloxybutyltrimethoxysilane, (meth) acryloxypentyltrimethoxysilane, (meth) acryloxyhexyl Trimethoxysilane, (meth) acryloxyhexyltriethoxysilane, (meth) acryloxyoctyltrimethoxysilane, (meth) acryloxydecyltrimethoxysilane, (meth) acryloxydecyltrimethoxysilane, (meth) acryloxyoctadecyl Examples include trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldipropoxysilane.
These internal cross-linking agents may be used alone or in combination of two or more. Among these, keto group-containing ethylenically unsaturated monomers are particularly suitable. The amount of the internal crosslinking agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of all monomers.
前記エチレン性不飽和単量体の乳化重合において存在させる粘着付与剤については特に制限はなく、従来粘着剤における粘着付与剤として慣用されているものの中から、適宜選択して用いることができる。この粘着付与剤としては、ロジン系樹脂、キシレン樹脂、テルペン−フェノール樹脂、芳香族変性テルペン樹脂、石油樹脂、クマロンインデン樹脂、テルペン樹脂、スチレン樹脂、エチレン／酢酸ビニル樹脂、さらにはスチレン−ブタジエンブロックポリマー、スチレン−イソプレンブロックポリマー、エチレン−イソプレン−スチレンブロックポリマー、塩化ビニル／酢酸ビニル系ポリマー、アクリル系ゴムなどのエラストマー等が挙げられる。
この粘着付与剤を前記エチレン性不飽和単量体に均一に分散・溶解させるためには、前記エチレン性不飽和単量体に相溶する粘着付与剤を適宜選択して使用することが好ましい。これらの粘着付与剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
There is no restriction | limiting in particular about the tackifier made to exist in the emulsion polymerization of the said ethylenically unsaturated monomer, It can select suitably from what was conventionally used as the tackifier in a conventional adhesive. Examples of the tackifier include rosin resin, xylene resin, terpene-phenol resin, aromatic modified terpene resin, petroleum resin, coumarone indene resin, terpene resin, styrene resin, ethylene / vinyl acetate resin, and styrene-butadiene. Examples include block polymers, styrene-isoprene block polymers, ethylene-isoprene-styrene block polymers, vinyl chloride / vinyl acetate polymers, elastomers such as acrylic rubber, and the like.
In order to uniformly disperse and dissolve the tackifier in the ethylenically unsaturated monomer, it is preferable to select and use a tackifier that is compatible with the ethylenically unsaturated monomer. These tackifiers may be used individually by 1 type, and may be used in combination of 2 or more type.
当該アクリル系エマルション型粘着剤を構成するアクリル樹脂エマルションは、エチレン性不飽和単量体と粘着付与剤とを含む混合物を乳化重合させることにより、製造されるが、この乳化重合においては、乳化剤として反応性界面活性剤が好ましく用いられる。
この反応性界面活性剤については特に制限はなく、従来公知のイオン性、非イオン性の界面活性剤の中から、適宜選択して用いることができる。
このような反応性界面活性剤を用いることにより、耐水粘着力の良好なアクリル系エマルション型粘着剤が得られる。
これらの反応性界面活性剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The acrylic resin emulsion constituting the acrylic emulsion-type pressure-sensitive adhesive is produced by emulsion polymerization of a mixture containing an ethylenically unsaturated monomer and a tackifier. In this emulsion polymerization, A reactive surfactant is preferably used.
The reactive surfactant is not particularly limited, and can be appropriately selected from conventionally known ionic and nonionic surfactants.
By using such a reactive surfactant, an acrylic emulsion-type pressure-sensitive adhesive having good water-resistant adhesive strength can be obtained.
These reactive surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
本発明におけるアクリル系樹脂エマルションの製造においては、前記粘着付与剤は、エチレン性不飽和単量体１００質量部に対し、通常０.５〜１５質量部の割合で用いられる。粘着付与剤の使用量が０.５質量部以上であると低温粘着力の付与効果が発揮されるが、１５質量部を超えるとエマルションの乳化安定性が低下することがある。粘着付与剤の好ましい使用量は３〜１０質量部の範囲である。
一方、前記反応性界面活性剤は、エチレン性不飽和単量体１００質量部に対し、通常０.５〜４.５質量部の割合で用いられる。反応性界面活性剤の使用量が０.５質量部以上であると良好な乳化効果及び耐水粘着力の付与効果が発揮されるが、４.５質量部を超えると耐水粘着力が低下することがある。反応性界面活性剤の好ましい使用量は０.７〜３.５質量部の範囲である。
In the production of the acrylic resin emulsion in the present invention, the tackifier is usually used at a ratio of 0.5 to 15 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer. When the amount of the tackifier used is 0.5 parts by mass or more, the effect of imparting low-temperature adhesive strength is exhibited, but when it exceeds 15 parts by mass, the emulsion stability of the emulsion may be lowered. The preferable usage-amount of a tackifier is the range of 3-10 mass parts.
On the other hand, the reactive surfactant is usually used at a ratio of 0.5 to 4.5 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer. When the amount of the reactive surfactant used is 0.5 parts by mass or more, a good emulsifying effect and a water-adhesive strength-imparting effect are exhibited, but when it exceeds 4.5 parts by mass, the water-resistant adhesive strength decreases. There is. The preferred amount of reactive surfactant used is in the range of 0.7 to 3.5 parts by weight.
次に、このアクリル系樹脂エマルションの製造方法の好適な実施態様について説明する。
まず、水性媒体中に、所定の割合の前記アクリル系樹脂の原料として用いられるエチレン性不飽和単量体、粘着付与剤及び反応性界面活性剤を加え、高圧ホモジナイザー又は超音波などを用いて乳化処理を行い、乳化液を調製する。
次に、このようにして調製された乳化液を、重合開始剤の存在下に４０〜９０℃程度に加熱して重合を行う。この際、重合開始剤としては、従来使用されている公知のもの、例えば有機過酸化物、アゾ系化合物、過硫酸塩、各種レドックス系触媒などが用いられる。
なお、重合開始剤は、反応開始時に全量存在させておいてもよく、あるいは反応開始時に一部存在させ、反応過程で残りを一括添加又は分割添加してもよい。このようにして、目的とするアクリル系樹脂エマルションを得ることができる。
本発明においては、必要に応じ、外部架橋剤を、このアクリル系樹脂エマルションに添加することができる。
Next, the suitable embodiment of the manufacturing method of this acrylic resin emulsion is demonstrated.
First, an ethylenically unsaturated monomer, a tackifier and a reactive surfactant used as a raw material for the acrylic resin in a predetermined ratio are added to an aqueous medium, and emulsified using a high-pressure homogenizer or ultrasonic waves. Processing is performed to prepare an emulsion.
Next, the emulsion prepared in this manner is heated to about 40 to 90 ° C. in the presence of a polymerization initiator for polymerization. At this time, as the polymerization initiator, conventionally known ones such as organic peroxides, azo compounds, persulfates, various redox catalysts and the like are used.
The polymerization initiator may be present in its entirety at the start of the reaction, or may be partially present at the start of the reaction, and the remainder may be added all at once or dividedly during the reaction process. In this way, the intended acrylic resin emulsion can be obtained.
In the present invention, an external cross-linking agent can be added to the acrylic resin emulsion as necessary.
この外部架橋剤としては、例えばイソシアネート系化合物、エポキシ系化合物、メラミン系化合物、アジリジン系化合物、ヒドラジド系化合物、オキサゾリン系化合物、カルボジイミド系化合物、尿素系化合物、ジアルデヒド系化合物、金属キレート化合物、金属アルコキシド、金属塩などが挙げられる。これらは１種のみを単独で用いてもよく、２種以上を組み合わせて用いてもよいが、これらの中で、性能の点から、特にヒドラジド系化合物が好適である。ヒドラジド系化合物としては、アジピン酸ヒドラジド、アジピン酸ジヒドラジド、カルボヒドラジドなどが挙げられる。
外部架橋剤の配合量は、アクリル系樹脂エマルション１００質量部に対し０.２〜７.０質量部とするのが好ましい。
Examples of the external crosslinking agent include isocyanate compounds, epoxy compounds, melamine compounds, aziridine compounds, hydrazide compounds, oxazoline compounds, carbodiimide compounds, urea compounds, dialdehyde compounds, metal chelate compounds, metals Examples thereof include alkoxides and metal salts. These may be used alone or in combination of two or more. Among these, hydrazide compounds are particularly preferred from the viewpoint of performance. Examples of hydrazide compounds include adipic acid hydrazide, adipic acid dihydrazide, carbohydrazide, and the like.
The amount of the external crosslinking agent is preferably 0.2 to 7.0 parts by mass with respect to 100 parts by mass of the acrylic resin emulsion.
これらの外部架橋剤は、内部架橋剤を用いる場合には、用いてもよいし、用いなくてもよいが、内部架橋剤を用いない場合には必須となる。
上記架橋剤を併用する場合の配合量は、アクリル系樹脂エマルション１００質量部に対し、内部架橋剤は０.５〜５.０質量部、外部架橋剤は０.２〜０.４質量部とするのが好ましい。
前記の内部架橋剤は、重合時に加えられるが、この外部架橋剤は、乳化重合で得られたアクリル系樹脂エマルションに加えられる。
このアクリル系樹脂エマルションには、さらに必要に応じ、各種添加剤、例えば防腐・防かび剤、凍結融解安定剤、防錆剤、可塑剤、高沸点溶剤、顔料、充填剤などを添加することができる。
このようにして、所望のアクリル系エマルション型粘着剤が得られる。
These external crosslinking agents may or may not be used when an internal crosslinking agent is used, but are essential when an internal crosslinking agent is not used.
The compounding amount when the above crosslinking agent is used in combination is 0.5 to 5.0 parts by mass for the internal crosslinking agent and 0.2 to 0.4 parts by mass for the external crosslinking agent with respect to 100 parts by mass of the acrylic resin emulsion. It is preferable to do this.
The internal cross-linking agent is added during the polymerization, and the external cross-linking agent is added to the acrylic resin emulsion obtained by emulsion polymerization.
Various additives such as antiseptic / antifungal agents, freeze / thaw stabilizers, rust preventives, plasticizers, high-boiling solvents, pigments, fillers and the like may be added to the acrylic resin emulsion as necessary. it can.
In this way, a desired acrylic emulsion-type pressure-sensitive adhesive is obtained.
［ラベル形成用粘着シートの作製］
本発明においては、粘着剤、特に好ましくは前述したアクリル系エマルション型粘着剤を、生分解性シートの片面に直接塗布、乾燥して架橋された粘着剤層を形成するか、あるいは剥離シートの剥離剤層面に塗布、乾燥して架橋された粘着剤層を形成したのち、生分解性シートの片面に貼り合せることにより、目的のラベル形成用粘着シートを作製することができる。粘着剤層の形成方法としては、特に制限なく種々の方法を用いることができ、例えば、エアーナイフコーター、ブレードコーター、バーコーター、グラビアコーター、ロールコーター、ロールナイフコーター、カーテンコーター、ダイコーター、ナイフコーター、スクリーンコーター、マイヤーバーコーター、キスコーターなどが挙げられる。
粘着剤層の厚さとしては、本発明においては、前述したように、生分解性シートの熱履歴による寸法変化を抑制する観点から、架橋された粘着剤層の厚さをＢ（μｍ）、該生分解性シートの厚さをＡ（μｍ）とした場合、Ｂ／Ａ比が、好ましくは０.１〜２.０、より好ましくは０.２〜１.０になるように制御することが望ましい。
[Preparation of label-forming adhesive sheet]
In the present invention, the pressure-sensitive adhesive, particularly preferably the above-described acrylic emulsion-type pressure-sensitive adhesive, is directly applied to one side of the biodegradable sheet and dried to form a crosslinked pressure-sensitive adhesive layer, or the release sheet is peeled off. After the adhesive layer surface is coated and dried to form a crosslinked pressure-sensitive adhesive layer, it is bonded to one side of the biodegradable sheet, whereby a target pressure-sensitive adhesive sheet for label formation can be produced. Various methods can be used as the method for forming the pressure-sensitive adhesive layer without any particular limitation. For example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife Examples include coaters, screen coaters, Mayer bar coaters, and kiss coaters.
As the thickness of the pressure-sensitive adhesive layer, in the present invention, as described above, the thickness of the cross-linked pressure-sensitive adhesive layer is B (μm) from the viewpoint of suppressing dimensional change due to the thermal history of the biodegradable sheet. When the thickness of the biodegradable sheet is A (μm), the B / A ratio is preferably controlled to be 0.1 to 2.0, more preferably 0.2 to 1.0. Is desirable.
粘着剤層の表面は、剥離シートで覆うことが好ましい。この剥離シートは、粘着剤層の表面を保護することができると共にラベル形成時の工程シートの役割も果たす。
剥離シートとしては、いずれのものを使用してもよく、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン、ポリプロピレン、ポリアクリレートなどの各種樹脂よりなるフィルムや、ポリエチレンラミネート紙、ポリプロピレンラミネート紙、クレーコート紙、樹脂コート紙、グラシン紙、上質紙等の各種紙材を基材とし、この基材の粘着剤層との接合面に、必要により剥離処理が施されたものを用いることができる。
剥離処理としては、シリコーン系樹脂、長鎖アルキル系樹脂、フッ素系樹脂等の剥離剤よりなる剥離剤層の形成が挙げられる。剥離シートの厚さは、特に制限されず、適宜選定すればよい。
The surface of the pressure-sensitive adhesive layer is preferably covered with a release sheet. This release sheet can protect the surface of the pressure-sensitive adhesive layer and also serves as a process sheet during label formation.
Any release sheet may be used, for example, films made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polyacrylate, polyethylene laminated paper, polypropylene laminated paper, clay coated paper. In addition, various paper materials such as resin-coated paper, glassine paper, and high-quality paper can be used as the base material, and the surface of the base material bonded to the pressure-sensitive adhesive layer can be peeled off if necessary.
Examples of the release treatment include formation of a release agent layer made of a release agent such as a silicone resin, a long-chain alkyl resin, and a fluorine resin. The thickness of the release sheet is not particularly limited and may be appropriately selected.
このようにして得られた本発明のラベル形成用粘着シートは、基材として生分解性シートを用い、その片面に特定の性状を有する粘着剤層を設けることにより、得られるラベルは、熱履歴後であっても収縮率が低く、熱寸法安定性に優れる特徴を有している。このラベルを作製するには、例えばまず、ラベル印刷機などで粘着シートに印刷後、所定形状ラベルに打ち抜きを施し、ラベル部以外のカス部分を除去するカス上げを行うことにより、剥離シート上に複数のラベルが貼付してなるラベリングマシン用ラベル連続体を得る。次いで、このラベル連続体から、ラベリングマシンにより個別のラベルを分離する方法などを用いることができる。 The pressure-sensitive adhesive sheet for label formation of the present invention thus obtained uses a biodegradable sheet as a substrate, and a label obtained by providing a pressure-sensitive adhesive layer having a specific property on one side has a thermal history. Even after this, the shrinkage rate is low and the thermal dimensional stability is excellent. In order to produce this label, for example, after printing on an adhesive sheet with a label printing machine or the like, a predetermined shape label is punched, and the residue is removed by removing the residue other than the label portion. A label continuum for a labeling machine obtained by attaching a plurality of labels is obtained. Next, a method of separating individual labels from the label continuum by a labeling machine can be used.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例における諸特性は、以下に示す方法に従って求めた。
（１）粘着剤層のゲル分率
明細書本文記載の方法に従って測定した。
（２）粘着シートの保持力
本発明に係る粘着剤を、剥離シート上に乾燥後の厚さが２０μｍになるように塗布し、９０℃で１分間乾燥させたのち、厚さ５０μｍの生分解性フィルム［三菱樹脂社製、商品名「エコロージュＳＡ」］に貼り合わせ粘着シートを作製する。次いで、この粘着シートを、ステンレス製鋼板（ＳＵＳ３８０）に、貼り付け面積が２５ｍｍ×２５ｍｍになるように貼付し、８０℃、Ｄｒｙ条件下で９.８Ｎの荷重をかけ、ＪＩＳ Ｚ ０２３７の保持力の測定法に準じて、７万秒後のフィルムのずれ量を測定する。
（３）ラベルの収縮率
実施例及び比較例の粘着シートを、ステンレス鋼板（ＳＵＳ６００）の試験板にサンプルサイズＭＤ＝６０ｍｍ、ＣＤ＝６０ｍｍ（ＭＤ＝フィルム製造時の流れ方向、ＣＤ＝フィルム製造時の幅方向）になるように貼付する。
次に、貼付した粘着シートのＭＤ方向、ＣＤ方向に沿って直線を十字に描き、それぞれ５０ｍｍの位置に印を付け、ＭＤ方向、ＣＤ方向の寸法を測定する。次いで、この試験板を１０５℃、Ｄｒｙ条件下で１０日間放置後、取り出し、４時間後に該粘着シート上に記載した５０ｍｍ×５０ｍｍ線のＭＤ方向、ＣＤ方向の寸法を測定し、下記の式よりラベルの収縮率を算出する。
ラベルの収縮率（％）＝［（乾燥後の寸法−乾燥前の寸法）／乾燥前寸法］×１００
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics in each example were calculated | required according to the method shown below.
(1) Gel fraction of adhesive layer It measured according to the method of the statement text.
(2) Holding power of pressure-sensitive adhesive sheet The pressure-sensitive adhesive according to the present invention is applied onto a release sheet so that the thickness after drying is 20 μm, dried at 90 ° C. for 1 minute, and then biodegraded to a thickness of 50 μm. A sticky adhesive sheet is prepared by bonding to an adhesive film [Mitsubishi Resin Co., Ltd., trade name “Ecologe SA”]. Next, this adhesive sheet was affixed to a stainless steel plate (SUS380) so that the affixed area was 25 mm × 25 mm, and a load of 9.8 N was applied under conditions of 80 ° C. and Dry to maintain the holding power of JIS Z 0237. According to the measurement method, the amount of displacement of the film after 70,000 seconds is measured.
(3) Shrinkage rate of label The pressure-sensitive adhesive sheets of Examples and Comparative Examples were sample size MD = 60 mm, CD = 60 mm (MD = flow direction during film production, CD = film production time) on a stainless steel plate (SUS600) test plate. Affixed so that it is in the width direction.
Next, a straight line is drawn in a cross along the MD direction and the CD direction of the attached adhesive sheet, marks are respectively placed at positions of 50 mm, and the dimensions in the MD direction and the CD direction are measured. Next, the test plate was left to stand for 10 days at 105 ° C. and Dry, taken out, and after 4 hours, the dimensions in the MD direction and CD direction of the 50 mm × 50 mm line described on the pressure-sensitive adhesive sheet were measured. Calculate the shrinkage of the label.
Shrinkage rate (%) of label = [(size after drying−size before drying) / size before drying] × 100
実施例１
（１）粘着剤の製造
アクリル酸ｎ−ブチル７０質量部、メタクリル酸メチル１５質量部、アクリル酸２−エチルヘキシル１２質量部、アクリル酸２質量部及び内部架橋剤としてのダイアセトンアクリルアミド１質量部からなるエチレン性不飽和単量体混合物を、アニオン系反応性乳化剤［ＡＤＥＫＡ社製、商品名「アデカリアソープＳＥ１０Ｎ」］３質量部（固形分）、イオン交換水１２５質量部、過硫酸アンモニウム０.５質量部及び第二リン酸ナトリウム０.３質量部と混合し、撹拌して乳化液を調製した。この乳化液に重合開始剤（過硫酸カリウム）０.２質量部を加えた後、８０℃で３時間加熱し、平均粒子径２００ｎｍの重合体を有するアクリル系樹脂エマルション（固形分濃度＝４８質量％）を得た。
（２）粘着シートの作製
上記（１）で得られたアクリル系樹脂エマルション１００質量部に、架橋剤としてアジピン酸ジヒドラジド１質量部を混合し、シリコーン系剥離シート［リンテック社製、商品名「ＳＰ−８ＬＫ２」］上に乾燥後の厚さが２０μｍになるように塗布し、９０℃で１分間乾燥させたのち、厚さ５０μｍのポリ乳酸系フィルム［三菱樹脂社製、商品名「エコロージュＳＡ ５０μｍ厚」脂肪族ポリエステル含有量９５質量％以上］に貼り合わせて、粘着シートを作製した。室温放置７日後、この粘着シートについて、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。これらの結果を第１表に示す。
Example 1
(1) Production of pressure-sensitive adhesive From 70 parts by mass of n-butyl acrylate, 15 parts by mass of methyl methacrylate, 12 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of acrylic acid, and 1 part by mass of diacetone acrylamide as an internal crosslinking agent 3 parts by mass (solid content) of anionic reactive emulsifier [manufactured by ADEKA, trade name “ADEKA rear soap SE10N”], 125 parts by mass of ion-exchanged water, 0.5% ammonium persulfate An emulsion was prepared by mixing with mass parts and 0.3 parts by mass of dibasic sodium phosphate and stirring. After adding 0.2 parts by mass of a polymerization initiator (potassium persulfate) to this emulsion, an acrylic resin emulsion having a polymer with an average particle size of 200 nm (solid content concentration = 48 mass) is heated at 80 ° C. for 3 hours. %).
(2) Preparation of pressure-sensitive adhesive sheet 100 parts by mass of the acrylic resin emulsion obtained in (1) above was mixed with 1 part by mass of adipic acid dihydrazide as a crosslinking agent, and a silicone-based release sheet [trade name “SP manufactured by Lintec Corporation] -8LK2 "], and after drying at 90 ° C. for 1 minute, a polylactic acid film having a thickness of 50 μm [trade name“ Ecologe SA 50 μm, manufactured by Mitsubishi Plastics, Inc. ” A pressure-sensitive adhesive sheet was prepared by bonding to a “thick” aliphatic polyester content of 95% by mass or more]. Seven days after standing at room temperature, the pressure-sensitive adhesive layer was determined for the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the shrinkage ratio of the label. These results are shown in Table 1.
実施例２
アニオン系反応性乳化剤［ＡＤＥＫＡ社製、商品名「アデカリアソープＳＥ１０Ｎ」］の量を１.５質量部とすると共に、ノニオン性の非反応性乳化剤［花王社製、商品名「エマルゲン９２０」］０.５質量部（固形分）を併用した以外は、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
Example 2
The amount of anionic reactive emulsifier [ADEKA, trade name “ADEKA rear soap SE10N”] is 1.5 parts by mass, and nonionic non-reactive emulsifier [trade name “Emulgen 920”, manufactured by Kao Corporation]. A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that 0.5 part by mass (solid content) was used together. After 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the shrinkage of the label The rate was determined. The results are shown in Table 1.
実施例３
エチレン性不飽和単量体混合物を、アクリル酸ｎ−ブチル５０質量部、メタクリル酸メチル１５質量部、アクリル酸２−エチルヘキシル３２質量部、アクリル酸２質量部及び内部架橋剤としてのアリルアセトアセテート１質量部の混合物とした以外は、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
Example 3
The ethylenically unsaturated monomer mixture was mixed with 50 parts by mass of n-butyl acrylate, 15 parts by mass of methyl methacrylate, 32 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of acrylic acid and allyl acetoacetate 1 as an internal crosslinking agent. A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the mixture was in parts by mass, and after 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the label shrinkage were determined. The results are shown in Table 1.
実施例４
ｎ−ブチルアクリレート／アクリル酸共重合体（組成質量比９９／１）を、固形分濃度で３０質量％含む酢酸エチル溶液１００質量部に対して、イソシアネート系架橋剤［綜研化学社製、商品名「ＴＤ−７５」、固形分濃度７５質量％］１.０質量部を加えて、均一になるまで撹拌し、塗工液（感圧接着剤）を調製した。次いで、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
実施例５
乾燥後の粘着剤層の厚さを１０μｍとした以外は、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
実施例６
乾燥後の粘着剤層の厚さを５０μｍとした以外は、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
実施例７
アクリル酸２−エチルヘキシル７７.５質量部、アクリル酸メチル１５質量部、メタアクリル酸メチル７.５質量部、アクリル酸１.５質量部及び内部架橋剤として２−アセトアセトキシエチルメタクリレート０.３質量部からなる混合物と、アニオン性の反応性乳化剤［ＡＤＥＫＡ社製、商品名「アデカリアソープＳＲ−１０」］８質量部（固形分）と、イオン交換水１２５質量部と、第二リン酸ナトリウム０.３質量部及び過硫酸アンモニウム０.５質量部とを混合し、撹拌して乳化液を調製した。この乳化液に重合開始剤（過硫酸カリウム）０.２質量部を加えた後、８０℃で３時間加熱し、平均粒子径が２００ｎｍの重合体を有するアクリル系樹脂エマルションを得た（固形分濃度：４４質量％）。
このアクリル樹脂系エマルションからなる塗工液を、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
Example 4
For 100 parts by mass of an ethyl acetate solution containing 30% by mass of a solid content concentration of n-butyl acrylate / acrylic acid copolymer (composition mass ratio 99/1), an isocyanate crosslinking agent [trade name, manufactured by Soken Chemical Co., Ltd. "TD-75", solid content concentration 75 mass%] 1.0 mass part was added, and it stirred until it became uniform, and prepared the coating liquid (pressure sensitive adhesive). Next, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1. After 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the shrinkage rate of the label were determined. The results are shown in Table 1.
Example 5
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was 10 μm. After 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the label Shrinkage was determined. The results are shown in Table 1.
Example 6
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer after drying was 50 μm. After 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the label Shrinkage was determined. The results are shown in Table 1.
Example 7
77.5 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of methyl acrylate, 7.5 parts by weight of methyl methacrylate, 1.5 parts by weight of acrylic acid, and 0.3 parts by weight of 2-acetoacetoxyethyl methacrylate as an internal crosslinking agent Part mixture, anionic reactive emulsifier [manufactured by ADEKA, trade name “ADEKA rear soap SR-10”] 8 parts by mass (solid content), 125 parts by mass of ion-exchanged water, and dibasic sodium phosphate 0.3 parts by mass and 0.5 parts by mass of ammonium persulfate were mixed and stirred to prepare an emulsion. After adding 0.2 parts by mass of a polymerization initiator (potassium persulfate) to this emulsion, the mixture was heated at 80 ° C. for 3 hours to obtain an acrylic resin emulsion having a polymer having an average particle size of 200 nm (solid content). Concentration: 44% by mass).
A pressure-sensitive adhesive sheet was prepared from the coating solution comprising this acrylic resin emulsion in the same manner as in Example 1. After 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the shrinkage rate of the label were obtained. It was. The results are shown in Table 1.
比較例１
（１）粘着剤の製造
アクリル酸２−エチルヘキシル６５質量部、アクリル酸ブチル２５質量部、及びアクリル酸エチル１０質量部からなる共重合体に、ロジン系粘着付与剤３０質量部を添加した固形分濃度で３０質量％の酢酸エチル溶液１００質量部に対して、イソシアネート系架橋剤［綜研化学社製、商品名「ＴＤ−７５」、固形分濃度７５質量％］１.０質量部を加えて、均一になるまで撹拌し、塗工液を調製した。次いで、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
Comparative Example 1
(1) Manufacture of adhesive agent Solid content which added 30 mass parts of rosin system tackifiers to the copolymer which consists of 65 mass parts of 2-ethylhexyl acrylate, 25 mass parts of butyl acrylate, and 10 mass parts of ethyl acrylate. To 100 parts by mass of an ethyl acetate solution having a concentration of 30% by mass, 1.0 part by mass of an isocyanate-based crosslinking agent [manufactured by Soken Chemical Co., Ltd., trade name “TD-75”, solid content concentration: 75% by mass] It stirred until it became uniform and the coating liquid was prepared. Next, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1. After 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the shrinkage rate of the label were determined. The results are shown in Table 1.
比較例２
天然ゴム［伊藤商事社製、ムーニー粘度ＭＬ1+4（１００℃）：６０］１００質量部に、液状イソブレン［クラレ社製、商品名「ＬＩＲ−４０３」］を１５０質量部、粘着付与樹脂としてテルペン系樹脂［ヤスハラケミカル社製、商品名「ＹＳレジン ＰＸ−１１５０」］１２５質量部、酸化防止剤［チバ・スペシャルティ・ケミカルズ社製、フェノール系酸化防止剤「ＩＲＧＡＮＯＸ１０７６」］２.５質量部、架橋剤として［東洋インキ製造社製、商品名「ＢＸＸ５１３４」］１.５質量部、トルエン８７５質量部を混練して粘着剤溶液を作製した。
次いで、実施例１と同様にして粘着シートを作製し、室温放置７日後、粘着剤層のゲル分率、粘着シートの保持力及びラベルの収縮率を求めた。結果を第１表に示す。
Comparative Example 2
100 parts by mass of natural rubber [manufactured by ITO Corporation, Mooney viscosity ML 1 + 4 (100 ° C.): 60], 150 parts by mass of liquid isobrene [manufactured by Kuraray Co., Ltd., trade name “LIR-403”] as a tackifier resin 125 parts by mass of a terpene resin [trade name “YS Resin PX-1150” manufactured by Yasuhara Chemical Co., Ltd.], 2.5 parts by mass of an antioxidant [manufactured by Ciba Specialty Chemicals Inc., phenolic antioxidant “IRGANOX1076”] 1.5 parts by mass of [Toyo Ink Mfg. Co., Ltd., trade name “BXX5134]] and 875 parts by mass of toluene were mixed as an agent to prepare an adhesive solution.
Next, a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1. After 7 days at room temperature, the gel fraction of the pressure-sensitive adhesive layer, the holding power of the pressure-sensitive adhesive sheet, and the shrinkage rate of the label were determined. The results are shown in Table 1.
参考例
実施例１〜４及び比較例１、２において、基材の生分解性シートとして用いられるポリ乳酸系フィルム［三菱樹脂社製、商品名「エコロージュＳＡ ５０μｍ厚」］単体について、ＭＤ＝６０ｍｍ、ＣＤ＝６０ｍｍに切り出したサンプルに、ＭＤ方向、ＣＤ方向に沿って直線を十字に描き、それぞれ５０ｍｍの位置に印を付け、ＭＤ方向、ＣＤ方向の寸法を測定した。次いで、１０５℃、Ｄｒｙ条件下で１０日間後、取り出し、４時間後に、フィルム単体上に記載した５０ｍｍ×５０ｍｍ線のＭＤ方向、ＣＤ方向の収縮率を求めた。その結果も合わせて第１表に示す。
Reference Example In Examples 1 to 4 and Comparative Examples 1 and 2, a polylactic acid film used as a biodegradable sheet for a base material [manufactured by Mitsubishi Plastics Co., Ltd., trade name “Ecologe SA 50 μm thickness”] alone, MD = 60 mm The sample cut into CD = 60 mm was drawn with a straight line along the MD direction and the CD direction, marked at a position of 50 mm, and the dimensions in the MD direction and the CD direction were measured. Subsequently, after 10 days under 105 ° C. and Dry conditions, the film was taken out, and after 4 hours, the shrinkage in the MD direction and the CD direction of the 50 mm × 50 mm line described on the single film was determined. The results are also shown in Table 1.
第１表から、本発明のラベル形成用粘着シート（実施例１〜７）は、比較例及び基材フィルム単体のものに比べて、ラベルのＭＤ方向の収縮率（寸法変化率）及びＣＤ方向の収縮率（寸法変化率）共に、はるかに小さいことが分かる。 From Table 1, the pressure-sensitive adhesive sheets for label formation of the present invention (Examples 1 to 7) were compared with the comparative example and the base film alone, and the shrinkage rate (dimensional change rate) in the MD direction and the CD direction of the label. It can be seen that both the shrinkage rate (dimensional change rate) of the sample is much smaller.
本発明のラベル形成用粘着シートは、基材として生分解性シートを用い、その片面に特定の性状を有する粘着剤層を設けることにより、熱履歴後であっても収縮率が低く、熱寸法安定性に優れるラベルを提供することができる。 The pressure-sensitive adhesive sheet for label formation of the present invention uses a biodegradable sheet as a base material, and is provided with a pressure-sensitive adhesive layer having a specific property on one side thereof. A label having excellent stability can be provided.
Claims (5)
架橋された粘着剤層を構成する粘着剤が、粘着付与剤を含まないことを特徴とするラベル形成用粘着シート。 A pressure-sensitive adhesive sheet having a biodegradable sheet and a pressure-sensitive adhesive layer cross-linked on one side thereof, wherein the gel fraction of the cross-linked pressure-sensitive adhesive layer is 50% by mass or more, and JIS Z of the pressure-sensitive adhesive sheet The holding force measured according to 0237 is 0.5 mm or less as the amount of deviation of the adhesive sheet when 70,000 seconds have elapsed, and the entire resin used for the biodegradable sheet does not have biodegradability. Containing the resin in a range of 50% by mass or less ,
A pressure- sensitive adhesive sheet for forming a label , wherein the pressure-sensitive adhesive constituting the crosslinked pressure-sensitive adhesive layer does not contain a tackifier.
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| WO2012133273A1 (en) * | 2011-03-30 | 2012-10-04 | リンテック株式会社 | Emulsion adhesive composition and re-peelable adhesive sheet |
| US9403348B2 (en) | 2012-09-21 | 2016-08-02 | Lg Hausys, Ltd. | Biodegradable sheets having adhesive layer |
| JP6345969B2 (en) * | 2013-06-05 | 2018-06-20 | ニッタ株式会社 | Manufacturing method of adhesive tape |
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| JP3410160B2 (en) * | 1993-07-28 | 2003-05-26 | リンテック株式会社 | Biodegradable adhesive label |
| JP3534340B2 (en) * | 1994-12-13 | 2004-06-07 | 株式会社日本触媒 | Composition for pressure-sensitive adhesive for flexible PVC, pressure-sensitive adhesive product and bonded product |
| JP4378575B2 (en) * | 1999-03-31 | 2009-12-09 | 東洋紡績株式会社 | Manufacturing method of adhesive tape |
| JP2003327933A (en) * | 2002-05-16 | 2003-11-19 | Lintec Corp | Pressure sensitive adhesive sheet |
| JP4134606B2 (en) * | 2002-06-18 | 2008-08-20 | 東亞合成株式会社 | Active energy ray-curable pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
| JP2004034631A (en) * | 2002-07-08 | 2004-02-05 | Nitto Denko Corp | Surface protection film for optical film |
| JP5116239B2 (en) * | 2006-02-08 | 2013-01-09 | 日本合成化学工業株式会社 | Method for producing emulsion-type pressure-sensitive adhesive composition, and pressure-sensitive adhesive composition |
| JP5311530B2 (en) * | 2006-02-23 | 2013-10-09 | リンテック株式会社 | Adhesive sheet |
| JP4953717B2 (en) * | 2006-05-19 | 2012-06-13 | リンテック株式会社 | Optical functional film bonding adhesive, optical functional film and method for producing the same |
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