JP2013018985A - Adhesive and label - Google Patents
Adhesive and label Download PDFInfo
- Publication number
- JP2013018985A JP2013018985A JP2012194115A JP2012194115A JP2013018985A JP 2013018985 A JP2013018985 A JP 2013018985A JP 2012194115 A JP2012194115 A JP 2012194115A JP 2012194115 A JP2012194115 A JP 2012194115A JP 2013018985 A JP2013018985 A JP 2013018985A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- pressure
- sensitive adhesive
- experimental example
- label
- 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 abstract description 91
- 230000001070 adhesive effect Effects 0.000 title abstract description 91
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 38
- 239000005017 polysaccharide Substances 0.000 claims abstract description 38
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 235000011187 glycerol Nutrition 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001540 sodium lactate Substances 0.000 claims abstract description 8
- 235000011088 sodium lactate Nutrition 0.000 claims abstract description 8
- 229940005581 sodium lactate Drugs 0.000 claims abstract description 8
- 150000004676 glycans Chemical class 0.000 claims abstract 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 89
- 239000010410 layer Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 235000013305 food Nutrition 0.000 abstract description 23
- 230000032683 aging Effects 0.000 abstract description 17
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 5
- 239000012790 adhesive layer Substances 0.000 abstract description 4
- 150000004804 polysaccharides Chemical class 0.000 description 36
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 24
- 229920002472 Starch Polymers 0.000 description 24
- 235000010413 sodium alginate Nutrition 0.000 description 24
- 239000000661 sodium alginate Substances 0.000 description 24
- 229940005550 sodium alginate Drugs 0.000 description 24
- 235000019698 starch Nutrition 0.000 description 24
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 22
- 239000008107 starch Substances 0.000 description 22
- 239000001879 Curdlan Substances 0.000 description 21
- 229920002558 Curdlan Polymers 0.000 description 21
- 235000019316 curdlan Nutrition 0.000 description 21
- 229940078035 curdlan Drugs 0.000 description 21
- 238000006266 etherification reaction Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000003002 pH adjusting agent Substances 0.000 description 9
- 235000010443 alginic acid Nutrition 0.000 description 7
- 229920000615 alginic acid Polymers 0.000 description 7
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 7
- 239000001354 calcium citrate Substances 0.000 description 7
- 229920001542 oligosaccharide Polymers 0.000 description 7
- 150000002482 oligosaccharides Chemical class 0.000 description 7
- 235000013337 tricalcium citrate Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 150000002772 monosaccharides Chemical class 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 6
- 235000019801 trisodium phosphate Nutrition 0.000 description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 5
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 5
- 229940072056 alginate Drugs 0.000 description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000001630 malic acid Substances 0.000 description 5
- 235000011090 malic acid Nutrition 0.000 description 5
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 4
- 240000003768 Solanum lycopersicum Species 0.000 description 4
- -1 for example Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000036962 time dependent Effects 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 244000061456 Solanum tuberosum Species 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 229940100486 rice starch Drugs 0.000 description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- DBTMGCOVALSLOR-UHFFFAOYSA-N 32-alpha-galactosyl-3-alpha-galactosyl-galactose Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(OC2C(C(CO)OC(O)C2O)O)OC(CO)C1O DBTMGCOVALSLOR-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RXVWSYJTUUKTEA-UHFFFAOYSA-N D-maltotriose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(O)C(CO)O1 RXVWSYJTUUKTEA-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FYGDTMLNYKFZSV-UHFFFAOYSA-N mannotriose Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(O)C(O)C2O)CO)C(O)C1O FYGDTMLNYKFZSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
この発明は粘着剤及びラベルに係り、特に、青果物等の食品に直接貼付させるラベル等の粘着剤層に使用する粘着剤において、可食性であり、耐湿性や耐老化性にも優れ、青果物等の食品に対して長期にわたって安定した十分な接着力が得られるようにした点に特徴を有するものである。 The present invention relates to a pressure-sensitive adhesive and a label, and in particular, in a pressure-sensitive adhesive used for a pressure-sensitive adhesive layer such as a label to be directly attached to foods such as fruits and vegetables, it is edible, excellent in moisture resistance and aging resistance, It is characterized in that a sufficient and stable adhesive force can be obtained over a long period of time.
ラベル基材の片面に粘着剤層が設けられたラベルが様々な分野で使用されており、近年においては、生産者等を表示したラベルを、直接青果物等の食品に貼付させることが行われている。 Labels with a pressure-sensitive adhesive layer provided on one side of a label base material are used in various fields. In recent years, labels displaying producers and the like are directly attached to foods such as fruits and vegetables. Yes.
ここで、ラベルの粘着剤層に用いる粘着剤としては、一般に、アクリル酸エステル共重合体のエラストマーを用いたアクリル系の粘着剤や、天然ゴム等のエラストマーを用いたゴム系の粘着剤が使用されている。 Here, as the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the label, generally, an acrylic pressure-sensitive adhesive using an acrylic ester copolymer elastomer or a rubber-based pressure sensitive adhesive using an elastomer such as natural rubber is used. Has been.
しかし、上記のような粘着剤は、食品添加物として認可されたものではなく、口に入れて食するには不向きな材料である。そして、このような粘着剤を用いたラベルを青果物等の食品に直接貼付させた場合、このラベルを剥がす際に、粘着剤の一部が青果物等の食品に残る可能性があり、このような食品をそのまま食することは、食の安全・安心の点から問題となるおそれがある。 However, the above-mentioned pressure-sensitive adhesive is not approved as a food additive and is a material unsuitable for eating in the mouth. And when a label using such an adhesive is directly attached to a food such as fruits and vegetables, a part of the adhesive may remain in the food such as fruits and vegetables when the label is peeled off. Eating food as it is may be problematic from the viewpoint of food safety and security.
また、近年においては、コラーゲン加水分解物と乳酸ナトリウムとを用いた可食性の粘着剤が提案されている（例えば、特許文献１参照。）。 In recent years, an edible adhesive using a collagen hydrolyzate and sodium lactate has been proposed (see, for example, Patent Document 1).
しかし、上記の粘着剤は、必ずしも十分な接着力を有しているとはいえず、このような粘着剤を用いたラベルを、上記のように青果物等の食品に直接貼付した場合、ラベルが簡単に剥がれたりするという問題があった。 However, the above-mentioned pressure-sensitive adhesive does not necessarily have sufficient adhesive force, and when a label using such a pressure-sensitive adhesive is directly attached to food such as fruits and vegetables as described above, the label is not There was a problem that it peeled off easily.
さらに、可食性で青果物等の食品に対する接着力を高めた粘着剤として、本出願人は、乳酸ナトリウム及び／又はグリセリンを用いた溶剤に、少なくとも多糖類を溶解させた粘着剤を開発した（例えば、特許文献２参照。）。 Further, as an adhesive that is edible and has improved adhesion to foods such as fruits and vegetables, the present applicant has developed an adhesive in which at least a polysaccharide is dissolved in a solvent using sodium lactate and / or glycerin (for example, , See Patent Document 2).
しかし、このような粘着剤においても、耐湿性や耐老化性が必ずしも十分ではなく、食品等に対して長期にわたって安定した十分な接着力を得ることは困難であった。
この発明は、ラベル等を青果物等の食品に直接貼付させる場合における上記のような問題を解決することを課題とするものであり、可食性であり、耐湿性や耐老化性にも優れ、青果物等の食品に対して長期にわたって安定した十分な接着力が得られる粘着剤及びこのような粘着剤を用いたラベルを提供することを課題とするものである。 An object of the present invention is to solve the above-described problems in the case where labels and the like are directly attached to foods such as fruits and vegetables, which are edible, excellent in moisture resistance and aging resistance, It is an object of the present invention to provide a pressure-sensitive adhesive that can provide a stable and sufficient adhesive force over a long period of time for foods such as the above and a label using such a pressure-sensitive adhesive.
この発明に係る粘着剤においては、グリセリン及び／又は乳酸ナトリウムと水とを含む溶剤に、少なくともエーテル化された多糖類を溶解させた。 In engaging Ru viscosity Chakuzai to this invention, the solvent containing the glycerine and / or sodium lactate and water to dissolve the polysaccharide is at least etherified.
また、この発明に係るラベルにおいては、ラベル基材の片面に設ける粘着剤層に上記のような粘着剤を用いるようにしたのである。 In the label according to the present invention, the above-mentioned pressure-sensitive adhesive is used for the pressure-sensitive adhesive layer provided on one side of the label substrate.
この発明の粘着剤においては、上記のようにグリセリン及び／又は乳酸ナトリウムを含む溶剤に、少なくともエーテル化された多糖類を溶解させたため、上記のように粘着剤の老化が抑制されて、青果物等の食品に対して長期にわたって安定した十分な接着力が得られるようになる。 In viscous Chakuzai of this invention, the solvent containing glycerin and / or sodium lactate as described above, since the dissolved polysaccharide which is at least etherified, aging of the adhesive as described above is suppressed, Sufficient and stable adhesive force can be obtained for foods such as fruits and vegetables over a long period of time.
また、この発明に係るラベルにおいては、ラベル基材の片面に設ける粘着剤層に上記のような粘着剤を用いるようにしたため、このラベルを青果物等の食品に直接貼付させた場合に、十分な接着力が長期にわたって得られ、このラベルが簡単に剥がれるのが防止される。 Further, in the label according to the present invention, since the above-mentioned pressure-sensitive adhesive is used for the pressure-sensitive adhesive layer provided on one side of the label base material, it is sufficient when the label is directly attached to food such as fruits and vegetables. Adhesive strength is obtained over a long period of time, preventing the label from being easily peeled off.
また、このラベルを青果物等の食品から剥がす際に、粘着剤の一部が青果物等の食品に残ったとしても、この粘着剤が可食性で安全性が高いため、このような食品をそのまま食しても、食の安全・安心の点から問題となることもない。 In addition, when this label is peeled from foods such as fruits and vegetables, even if a part of the adhesive remains in foods such as fruits and vegetables, the adhesive is edible and highly safe. However, there is no problem in terms of food safety and security.
以下、この発明の実施形態に係る粘着剤及びラベルについて具体的に説明する。なお、この発明に係る粘着剤及びラベルは、特に下記の実施形態に示したものに限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施できるものである。 Hereinafter, the adhesive and the label according to the embodiment of the present invention will be specifically described. The pressure-sensitive adhesive and label according to the present invention are not particularly limited to those shown in the following embodiments, and can be appropriately changed and implemented without departing from the scope of the invention.
ここで、この実施形態における粘着剤において、多糖類を溶解させる溶剤にグリセリン及び／又は乳酸ナトリウムを含む溶剤を用いるようにしたのは、これらの溶剤が優れた保水能力を有し、上記の多糖類を可塑化すると同時に、粘着性を発揮させることができるためである。 Here, in the pressure-sensitive adhesive in this embodiment, the solvent containing glycerin and / or sodium lactate is used as the solvent for dissolving the polysaccharide because these solvents have an excellent water retention capability, This is because the saccharide can be plasticized and at the same time exert adhesiveness.
そして、上記のような溶剤に溶解させる多糖類としては、各種の多糖類を用いることができ、例えば、ワキシスターチ，馬鈴薯系澱粉，米系澱粉，タピオカ系澱粉などの各種澱粉、グリコーゲン、グアーガム、ローカストビーンガム、プルラン、デキストラン、アラビアガラクタンなどを用いることができるが、耐水性の高い各種澱粉を用いることが好ましく、特に、前記のように耐老化性に優れたワキシスターチを用いることが好ましい。 Various polysaccharides can be used as the polysaccharide dissolved in the solvent as described above. For example, various starches such as waxy starch, potato starch, rice starch, tapioca starch, glycogen, guar gum, locust Bean gum, pullulan, dextran, arabic galactan, and the like can be used, but it is preferable to use various starches having high water resistance, and it is particularly preferable to use waxy starch having excellent aging resistance as described above.
また、粘着剤の耐老化性をさらに向上させるために、前記のようにエーテル化させた多糖類を用いる。ここで、多糖類をエーテル化させる割合については特に限定されないが、エーテル化度が低いと、粘着剤の耐老化性を向上させる効果が少ない一方、エーテル化度が高くなりすぎると、粘着剤の接着力が低下するおそれがあるため、好ましくはエーテル化度を０．５〜１５％程度にし、より好ましくは１〜１０％程度にする。 Moreover, in order to further improve the aging resistance of the pressure-sensitive adhesive, the polysaccharide etherified as described above is used. Here, the ratio of the etherification of the polysaccharide is not particularly limited, but if the degree of etherification is low, the effect of improving the aging resistance of the adhesive is small, while if the degree of etherification is too high, Since the adhesive force may be reduced, the degree of etherification is preferably about 0.5 to 15%, more preferably about 1 to 10%.
そして、上記のような多糖類をグリセリン及び／又は乳酸ナトリウムを含む溶剤に溶解させるにあたり、溶解させる多糖類の量が少ないと、十分な接着力が得られなくなる一方、溶解させる多糖類の量が多くなりすぎると、この粘着剤の粘度が高くなり過ぎて、ラベル基材等への塗工が困難になるため、上記の溶剤と多糖類との重量比が、好ましくは９：１〜６：４の範囲、より好ましくは８５：１５〜６５：３５の範囲になるようにする。 And when dissolving the polysaccharide as described above in a solvent containing glycerin and / or sodium lactate, if the amount of polysaccharide to be dissolved is small, sufficient adhesive force cannot be obtained, while the amount of polysaccharide to be dissolved is If the amount is too large, the viscosity of the pressure-sensitive adhesive becomes too high and it becomes difficult to apply to the label substrate, so the weight ratio of the solvent to the polysaccharide is preferably 9: 1 to 6: 4 and more preferably 85:15 to 65:35.
また、上記の粘着剤における耐老化性をさらに向上させるためには、前記のように粘着剤にｐＨ調整剤を加えるなどにより、粘着剤をアルカリ性に調整することが好ましい。そして、粘着剤のｐＨを調整するアルカリ側のｐＨ調整剤としては、例えば、水酸化ナトリウムＮａＯＨ、リン酸三ナトリウムＮａ3ＰＯ4、リン酸三カリウムＫ3ＰＯ4、リン酸水素二ナトリウムＮａ2ＨＰＯ4、リン酸水素二カリウムＫ2ＨＰＯ4、ピロリン酸ナトリウムＮａ4Ｐ2Ｏ7、ピロリン酸カリウムＫ4Ｐ2Ｏ7、トリポリリン酸ナトリウムＮａ5Ｐ3Ｏ10、炭酸ナトリウムＮａ2ＣＯ3、アルカリイオン水などを用いることができ、特に、安全性の観点からは、食品への添加が認められているリン酸三ナトリウムＮａ3ＰＯ4又はリン酸三カリウムＫ3ＰＯ4を用いることが好ましく、また酸性側のｐＨ調整剤としては、例えば、リンゴ酸、クエン酸、グルコン酸などを用いることができる。 Moreover, in order to further improve the aging resistance in the above-mentioned pressure-sensitive adhesive, it is preferable to adjust the pressure-sensitive adhesive to alkaline by adding a pH adjuster to the pressure-sensitive adhesive as described above. Examples of the alkali-side pH adjuster for adjusting the pH of the pressure-sensitive adhesive include sodium hydroxide NaOH, trisodium phosphate Na 3 PO 4 , tripotassium phosphate K 3 PO 4 , and disodium hydrogen phosphate Na 2. HPO 4 , dipotassium hydrogen phosphate K 2 HPO 4 , sodium pyrophosphate Na 4 P 2 O 7 , potassium pyrophosphate K 4 P 2 O 7 , sodium tripolyphosphate Na 5 P 3 O 10 , sodium carbonate Na 2 CO 3 , Alkaline ion water or the like can be used. In particular, from the viewpoint of safety, it is preferable to use trisodium phosphate Na 3 PO 4 or tripotassium phosphate K 3 PO 4 that is allowed to be added to food. Further, as the acidic pH adjuster, for example, malic acid, citric acid, gluconic acid and the like can be used.
また、上記の第１の粘着剤においては、耐湿性を向上させるために、上記の溶剤にアルギン酸塩やカードランを溶解させるようにする。 Moreover, in said 1st adhesive, in order to improve moisture resistance, it is made to melt | dissolve alginate and curdlan in said solvent.
ここで、アルギン酸塩としては、粘着剤の耐湿性をさらに向上させるため、前記のように架橋させたものを用いることが好ましく、アルギン酸塩を架橋させる架橋剤としては、例えば、クエン酸カルシウム、炭酸カルシウムなどの2価以上のカチオン性金属塩を用い
ることができ、特に、反応性や溶剤への溶解性の点からクエン酸カルシウムを用いることが好ましい。
Here, as the alginate, in order to further improve the moisture resistance of the pressure-sensitive adhesive, it is preferable to use those crosslinked as described above. Examples of the crosslinking agent for crosslinking alginate include calcium citrate, carbonate A divalent or higher cation metal salt such as calcium can be used, and calcium citrate is particularly preferable from the viewpoint of reactivity and solubility in a solvent.
また、上記のようにアルギン酸塩やカードランを溶解させるにあたり、これらの溶解量が少ないと、耐湿性を向上させる効果が少ない一方、これらの溶解量が多くなりすぎると、粘着剤の接着力が低下するおそれがあるため、アルギン酸塩の場合には、上記の多糖類に対して０．２〜１５重量％の範囲、カードランの場合には、上記の多糖類に対して１〜２０重量％の範囲にすることが好ましい。 In addition, when dissolving alginate or curdlan as described above, if the amount of these dissolved is small, the effect of improving the moisture resistance is small. On the other hand, if the amount of these dissolved is too large, the adhesive strength of the adhesive is reduced. In the case of alginate, it is in the range of 0.2 to 15% by weight with respect to the polysaccharide. In the case of curdlan, 1 to 20% by weight with respect to the polysaccharide. It is preferable to be in the range.
特に、カードランを用いた場合には、粘着剤の粘度の上昇が抑制されて、ラベル基材などへの塗工が容易になると共に、耐湿性に加えて粘着剤の接着力も向上する点で好ましい。 In particular, when curdlan is used, an increase in the viscosity of the pressure-sensitive adhesive is suppressed, making it easy to apply to a label substrate, etc., and improving the adhesive strength of the pressure-sensitive adhesive in addition to moisture resistance. preferable.
また、上記の粘着剤の粘度を調整したり、接着力を向上させたりするために、上記の溶剤に単糖類及び／又は少糖類を溶解させることができる。そして、上記の単糖類としては、例えば、グルコース、フルクトース、ガラクトース、マンノース等を用いることができる。また、上記の少糖類としては、例えば、トレハロース、マルトース、スクロース、ラクトース、セロビオース、マルトトリオース、ラフィノース、澱粉を分解させた各種のデキストリン等のオリゴ糖を用いることができる。 Moreover, in order to adjust the viscosity of said adhesive or to improve adhesive force, a monosaccharide and / or oligosaccharide can be dissolved in said solvent. And as said monosaccharide, glucose, fructose, galactose, mannose etc. can be used, for example. Examples of the oligosaccharide include oligosaccharides such as trehalose, maltose, sucrose, lactose, cellobiose, maltotriose, raffinose, and various dextrins obtained by decomposing starch.
また、上記のように単糖類及び／又は少糖類を溶解させるにあたり、単糖類及び／又は少糖類の量が少ないと、粘着剤における粘度の調整が十分に行えなくなり、また接着力を高める効果が十分に得られなくなる一方、単糖類及び／又は少糖類の量が多くなりすぎると、粘着剤の粘度が高くなりすぎて、ラベル基材等への粘着剤の塗工が困難になるため、上記の多糖類と、単糖類及び／又は少糖類との重量比を、好ましくは６：１〜１：５の範囲、より好ましくは３：１〜１：４の範囲になるようにする。 In addition, in dissolving monosaccharides and / or oligosaccharides as described above, if the amount of monosaccharides and / or oligosaccharides is small, the viscosity of the pressure-sensitive adhesive cannot be sufficiently adjusted, and the effect of increasing the adhesive strength can be obtained. On the other hand, when the amount of monosaccharides and / or oligosaccharides is too large, the viscosity of the pressure-sensitive adhesive becomes too high and it becomes difficult to apply the pressure-sensitive adhesive to the label substrate, etc. The weight ratio of the polysaccharide to the monosaccharide and / or oligosaccharide is preferably in the range of 6: 1 to 1: 5, more preferably in the range of 3: 1 to 1: 4.
また、上記の粘着剤においては、必要に応じて、モルノンなどの防腐剤、ソルビン酸カリウム，ソルビン酸などの保存剤、キトサンなどの抗菌剤を添加させることもできる。 Moreover, in said adhesive, antiseptic | preservatives, such as mornon, preservatives, such as potassium sorbate and sorbic acid, and antibacterial agents, such as chitosan, can also be added as needed.
また、この発明の実施形態に係るラベル１０においては、図１に示すように、ラベル基材１１の片面に上記のような粘着剤を用いた粘着剤層１２を設けるようにしている。 Further, in the label 10 according to the embodiment of the present invention, as shown in FIG. 1, an adhesive layer 12 using the above-mentioned adhesive is provided on one side of a label substrate 11.
そして、この実施形態のラベル１０においては、粘着剤層１２に上記のような粘着剤を用いたため、このラベル１０を青果物等の食品（図示せず）に直接貼付させた場合においても、この粘着剤が老化したり、水分によって接着性が低下したりするのが防止され、このラベル１０が青果物等の食品から簡単に剥がれるということがなく、長期にわたって十分な接着力が得られると共に、このラベル１０を青果物等の食品から剥がす際に、粘着剤の一部が青果物等の食品に残ったとしても、この粘着剤が可食性で安全性が高いため、このような食品をそのまま食しても、食の安全・安心の点から問題となることもない。 In the label 10 of this embodiment, since the above-mentioned adhesive is used for the adhesive layer 12, even when this label 10 is directly attached to foods such as fruits and vegetables (not shown), this adhesive The agent is prevented from aging and the adhesiveness is lowered due to moisture, and the label 10 is not easily peeled off from foods such as fruits and vegetables. Even when a part of the adhesive remains in the food such as fruits and vegetables when peeling 10 from the food such as fruits and vegetables, the adhesive is edible and highly safe. There is no problem in terms of food safety and security.
次に、この発明の実施例に係る具体的な粘着剤を説明する前に、参考例に係る具体的な粘着剤について説明し、参考例の粘着剤が優れた特性を示すことを、比較例を挙げて明らかにする。 Next, before describing the specific adhesive according to an embodiment of the present invention, it describes the specific pressure-sensitive adhesive according to a reference example, to show a pressure-sensitive adhesive excellent properties of Reference Example, Comparative Example To clarify.
（参考例１）
参考例１においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、架橋及びα化されたワキシスターチ（日澱化学（株）製：スターチＭＨ-Ａ）３０ｇを加
えて攪拌し、これを糊化させた後、これに４重量％のアルギン酸ナトリウム水溶液１２．５ｇ（アルギン酸ナトリウム０．５ｇ）と、アルギン酸ナトリウムの架橋剤であるクエン酸カルシウム０．０７ｇ（アルギン酸ナトリウムに対して０．３当量）とを加えて攪拌し、参考例１の粘着剤を調製した。なお、この粘着剤のｐＨは６．５であった。
( Reference Example 1)
In Reference Example 1, 30 g of waxy starch (manufactured by Nissho Chemical Co., Ltd .: Starch MH-A) cross-linked and pregelatinized as a polysaccharide was added to a solvent consisting of 35 g of glycerin and 35 g of water and stirred. After being gelatinized, 12.5 g of a 4% by weight aqueous sodium alginate solution (0.5 g of sodium alginate) and 0.07 g of calcium citrate which is a cross-linking agent for sodium alginate (0.3% relative to sodium alginate) Equivalent) was added and stirred to prepare the pressure-sensitive adhesive of Reference Example 1. The pressure-sensitive adhesive had a pH of 6.5.
（参考例２）
参考例２においては、上記の参考例１において、上記の４重量％のアルギン酸ナトリウム水溶液を２５ｇ（アルギン酸ナトリウム１ｇ）、アルギン酸ナトリウムの架橋剤であるクエン酸カルシウムを０．１４ｇ（アルギン酸ナトリウムに対して０．３当量）加えるようにし、それ以外は、上記の参考例１と同様にして、参考例２の粘着剤を調製した。なお、この粘着剤のｐＨは６．５であった。
( Reference Example 2)
In Reference Example 2, in the above Reference Example 1, 25 g of the 4 wt% aqueous sodium alginate solution (1 g of sodium alginate) and 0.14 g of calcium citrate which is a cross-linking agent for sodium alginate (based on sodium alginate) 0.3 equivalent) was added, and the adhesive of Reference Example 2 was prepared in the same manner as Reference Example 1 above. The pressure-sensitive adhesive had a pH of 6.5.
（参考例３）
参考例３においては、上記の参考例１において、上記の４重量％のアルギン酸ナトリウム水溶液を３７．５ｇ（アルギン酸ナトリウム１．５ｇ）、アルギン酸ナトリウムの架橋剤であるクエン酸カルシウムを０．２１ｇ（アルギン酸ナトリウムに対して０．３当量）加えるようにし、それ以外は、上記の参考例１と同様にして、参考例３の粘着剤を調製した。なお、この粘着剤のｐＨは６．６であった。
( Reference Example 3)
In Reference Example 3, in the above Reference Example 1, 37.5 g (1.5 g of sodium alginate) of the above 4% by weight sodium alginate aqueous solution and 0.21 g (alginic acid) of calcium citrate which is a cross-linking agent for sodium alginate. The pressure-sensitive adhesive of Reference Example 3 was prepared in the same manner as in Reference Example 1 except that 0.3 equivalent) was added. The pressure-sensitive adhesive had a pH of 6.6.
（参考例４）
参考例４においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、架橋及びα化されたワキシスターチ（日澱化学（株）製：スターチＭＨ-Ａ）２７ｇを加
えて攪拌し、これを糊化させた後、これに１重量％の水酸化ナトリウムと６重量％のカードランを含む水溶液６２．６ｇ（カードラン３．７５ｇ）を加えて攪拌し、さらにアルカリ側のｐＨ調整剤である水酸化ナトリウムを全体に対して０．５重量％加えて、参考例４の粘着剤を調製した。なお、この粘着剤のｐＨは１２．５であった。
( Reference Example 4)
In Reference Example 4, 27 g of waxy starch (manufactured by Nissho Chemical Co., Ltd .: Starch MH-A) cross-linked and pregelatinized as a polysaccharide was added to a solvent consisting of 35 g of glycerin and 35 g of water and stirred. After adding 62.6 g of an aqueous solution containing 1% by weight of sodium hydroxide and 6% by weight of curdlan (3.75 g of curdlan), the mixture was further stirred with a pH adjuster on the alkali side. A pressure sensitive adhesive of Reference Example 4 was prepared by adding 0.5% by weight of certain sodium hydroxide to the whole. The pressure-sensitive adhesive had a pH of 12.5.
（参考例５）
参考例５においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、架橋及びα化されたワキシスターチ（日澱化学（株）製：スターチＭＨ-Ａ）２７ｇを加
えて攪拌し、これを糊化させた後、これに１重量％のリン酸三ナトリウムＮａ3ＰＯ4と６重量％のカードランを含む水溶液６２．６ｇ（カードラン３．７５ｇ）を加えて攪拌し、さらにアルカリ側のｐＨ調整剤であるリン酸三ナトリウムＮａ3ＰＯ4を全体に対して１重量％加えて、参考例５の粘着剤を調製した。なお、この粘着剤のｐＨは１１．２であった。
( Reference Example 5)
In Reference Example 5, 27 g of waxy starch (manufactured by Nissho Chemical Co., Ltd .: Starch MH-A) cross-linked and pregelatinized as a polysaccharide was added to a solvent composed of 35 g of glycerin and 35 g of water and stirred. After adding 62.6 g of an aqueous solution containing 1% by weight of trisodium phosphate Na 3 PO 4 and 6% by weight of curdlan (3.75 g of curdlan), the mixture was further stirred on the alkali side. A pressure-sensitive adhesive of Reference Example 5 was prepared by adding 1% by weight of trisodium phosphate Na 3 PO 4 , which is a pH adjusting agent. The pressure-sensitive adhesive had a pH of 11.2.
（比較例１）
比較例１においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、架橋及びα化されたワキシスターチ（日澱化学（株）製：スターチＭＨ-Ａ）３０ｇを加
えて攪拌し、これを糊化させて、比較例１の粘着剤を調製した。なお、この粘着剤のｐＨは５．５であった。
(Comparative Example 1)
In Comparative Example 1, 30 g of crosslinked and pregelatinized waxy starch (manufactured by Nissho Chemical Co., Ltd .: Starch MH-A) was added as a polysaccharide to a solvent composed of 35 g of glycerin and 35 g of water, and this was stirred. The pressure-sensitive adhesive of Comparative Example 1 was prepared. The pressure-sensitive adhesive had a pH of 5.5.
次に、上記のように調製した参考例１〜５及び比較例１の各粘着剤をそれぞれラベル基材の片面に付与した各ラベルをトマトに貼り付け、これを５℃に設定した冷蔵庫で１日冷却させた後、これを常温で放置させて結露させ、この状態で各ラベルをトマトから剥離させて、各粘着剤の耐湿性の評価を行い、その結果を下記の表１に示した。 Next, each label provided with the adhesives of Reference Examples 1 to 5 and Comparative Example 1 prepared as described above on one side of the label base material was affixed to tomato, and this was set in a refrigerator set at 5 ° C. After being allowed to cool for a day, it was allowed to stand at room temperature for condensation, and in this state, each label was peeled off from the tomato, and the moisture resistance of each adhesive was evaluated. The results are shown in Table 1 below.
なお、耐湿性の評価については、トマトから剥離させた時における、各粘着剤の糸引き状態を調べ、糸引きがなかった場合を○、糸引きが生じた面積が４割以下の場合を△、糸引きが生じた面積が４割を超える場合を×で示した。 For evaluation of moisture resistance, the threading state of each pressure-sensitive adhesive when peeled from the tomato was examined. A case where there was no threading, and a case where the area where threading occurred was 40% or less. The case where the area where stringing occurred exceeded 40% was indicated by x.
なお、カードランを加えた参考例５の粘着剤において、糸引きが生じた面積は1割未満
であった。
In the adhesive of Reference Example 5 to which curdlan was added, the area where stringing occurred was less than 10%.
この結果、アルギン酸ナトリウムやカードランを加えた参考例１〜５の各粘着剤は、アルギン酸ナトリウムやカードランを加えていない比較例１の粘着剤に比べて、トマトから剥離させた時における粘着剤の糸引きが少なくなって、耐湿性が改善されていた。 As a result, each adhesive of Reference Examples 1 to 5 to which sodium alginate or curdlan was added was a pressure-sensitive adhesive when peeled from tomato, compared to the adhesive of Comparative Example 1 to which sodium alginate or curdlan was not added. As a result, the thread resistance was reduced and the moisture resistance was improved.
次に、粘着剤にアルギン酸ナトリウムを加えると共に使用する多糖類の種類を変更させた実験を行い、エーテル化させた多糖類を用いたこの発明の実施例に係る具体的な粘着剤において、粘着剤の耐老化性が向上して、長期にわたって十分な接着力が得られることを明らかにする。 Next, an experiment was performed in which sodium alginate was added to the adhesive and the type of polysaccharide used was changed, and in the specific adhesive according to the embodiment of the present invention using the etherified polysaccharide, It is clarified that the aging resistance is improved and sufficient adhesive strength can be obtained over a long period of time.
（実験例Ａ１）
実験例Ａ１においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、エーテル化されたワキシスターチ（日澱化学（株）製：デリカＳＥ エーテル化度５％）２７ｇと、エーテル化及び架橋されたワキシスターチ（日澱化学（株）製：アミコールＡ エーテル化度５％）３ｇとを加えて攪拌し、これを糊化させた後、これに４重量％のアルギン酸ナトリウム水溶液１２．５ｇ（アルギン酸ナトリウム０．５ｇ）と、アルギン酸ナトリウムの架橋剤であるクエン酸カルシウム０．０７ｇ（アルギン酸ナトリウムに対して０．３当量）とを加えて攪拌し、さらに酸性側のｐＨ調整剤であるリンゴ酸を全体に対して０．２重量％加えて、実験例Ａ１の粘着剤を調製した。なお、この粘着剤のｐＨは３．４であった。
(Experimental example A1)
In Experimental Example A1, 27 g of etherified waxy starch (manufactured by Nissho Chemical Co., Ltd .: Delica SE etherification degree 5%) as a polysaccharide in a solvent composed of 35 g of glycerin and 35 g of water, and etherification and crosslinking 3 g of waxy starch (Nissho Chemical Co., Ltd .: Amcol A etherification degree 5%) was added and stirred to gelatinize it, and then 12.5 g of 4% by weight aqueous sodium alginate solution (alginic acid) 0.5 g of sodium) and 0.07 g of calcium citrate which is a cross-linking agent for sodium alginate (0.3 equivalents with respect to sodium alginate) are added and stirred, and further, malic acid which is a pH adjuster on the acidic side is added. The adhesive of Experimental Example A1 was prepared by adding 0.2% by weight to the whole. The pressure-sensitive adhesive had a pH of 3.4.
（実験例Ａ２）
実験例Ａ２においては、多糖類として、エーテル化及び架橋された馬鈴薯系澱粉（日澱化学（株）製：デリカＭ９ エーテル化度５％）２７ｇと、エーテル化及び架橋されたワキシスターチ（日澱化学（株）製：アミコールＡ エーテル化度５％）３ｇとを用いるようにし、それ以外は、上記の実験例Ａ１と同様にして、実験例Ａ２の粘着剤を調製した。なお、この粘着剤のｐＨは３．６であった。
(Experimental example A2)
In Experimental Example A2, as a polysaccharide, 27 g of etherified and crosslinked potato starch (manufactured by Nissho Chemical Co., Ltd .: Delica M9 degree of etherification 5%) and etherified and crosslinked waxy starch (Nissho Chemical) The pressure-sensitive adhesive of Experimental Example A2 was prepared in the same manner as in Experimental Example A1 except that 3 g of Amicol A (degree of etherification 5%) was used. The pressure-sensitive adhesive had a pH of 3.6.
（実験例Ａ３）
実験例Ａ３においては、多糖類として、エーテル化された米系澱粉（日澱化学（株）製：デリカＲＢ エーテル化度４％）２７ｇと、エーテル化及び架橋されたワキシスターチ（日澱化学（株）製：アミコールＡ エーテル化度５％）３ｇとを用いるようにし、それ以外は、上記の実験例Ａ１と同様にして、実験例Ａ３の粘着剤を調製した。なお、この粘着剤のｐＨは３．６であった。
(Experimental example A3)
In Experimental Example A3, as a polysaccharide, 27 g of etherified rice starch (manufactured by Nissho Chemical Co., Ltd .: Delica RB 4 degree of etherification), and etherified and crosslinked waxy starch (Nissho Chemical Co., Ltd.) ) Manufactured by: Amicol A 5 degree of etherification), except that 3 g was used, and the adhesive of Experimental Example A3 was prepared in the same manner as in Experimental Example A1 above. The pressure-sensitive adhesive had a pH of 3.6.
（実験例Ａ４）
実験例Ａ４においては、多糖類として、エーテル化されたタピオカ系澱粉（日澱化学（株）製：Ｇ８００ エーテル化度５％）２７ｇと、エーテル化及び架橋されたワキシスターチ（日澱化学（株）製：アミコールＡ エーテル化度５％）３ｇとを用いるようにし、それ以外は、上記の実験例Ａ１と同様にして、実験例Ａ４の粘着剤を調製した。なお、この粘着剤のｐＨは３．１であった。
(Experimental example A4)
In Experimental Example A4, as a polysaccharide, 27 g of etherified tapioca starch (manufactured by Nissho Chemical Co., Ltd .: G800 degree of etherification 5%), and etherified and cross-linked waxy starch (Nissho Chemical Co., Ltd.) The pressure-sensitive adhesive of Experimental Example A4 was prepared in the same manner as in Experimental Example A1 except that 3 g of Amicol A (degree of etherification 5%) was used. The pressure-sensitive adhesive had a pH of 3.1.
（実験例Ａ５）
実験例Ａ５においては、多糖類として、架橋及びα化されているがエーテル化されていない前記のワキシスターチ（日澱化学（株）製：スターチＭＨ-Ａ）３０ｇを用いるよう
にし、それ以外は、上記の実験例Ａ１と同様にして、実験例Ａ５の粘着剤を調製した。なお、この粘着剤のｐＨは３．３であった。
(Experiment A5)
In Experimental Example A5, 30 g of the above waxy starch (manufactured by Nissho Chemical Co., Ltd .: Starch MH-A) that is crosslinked and pregelatinized but not etherified is used as the polysaccharide. In the same manner as in Experimental Example A1, a pressure-sensitive adhesive of Experimental Example A5 was prepared. The pressure-sensitive adhesive had a pH of 3.3.
そして、上記のように調製した実験例Ａ１〜Ａ５の各粘着剤を温度２５℃、湿度５０％の雰囲気下において保管し、所定の保管日を経過した時点において、各粘着剤の接着力を調べ、その結果を図２に示した。 And each adhesive of Experimental Examples A1 to A5 prepared as described above is stored in an atmosphere of a temperature of 25 ° C. and a humidity of 50%, and the adhesive strength of each adhesive is examined when a predetermined storage date has passed. The results are shown in FIG.
ここで、各粘着剤の接着力については、ホットメルト粘着剤の溶融粘度試験方法（ＪＩＳ Ｚ０２３７）に規定される１８０度引き剥がし法に準拠し、試験片にＳＵＳを用い、それぞれ引張り速度３００ｍｍ／ｍｉｎの条件でＳＵＳ接着力（ｇ／２５ｍｍ）を測定した。 Here, the adhesive strength of each pressure-sensitive adhesive is based on the 180-degree peeling method defined in the melt viscosity test method for hot melt pressure-sensitive adhesive (JIS Z0237). SUS adhesive strength (g / 25 mm) was measured under the condition of min.
そして、実験例Ａ１の粘着剤におけるＳＵＳ接着力の経時変化を太線で、実験例Ａ２の粘着剤におけるＳＵＳ接着力の経時変化を細線で、実験例Ａ３の粘着剤におけるＳＵＳ接着力の経時変化を１点鎖線で、実験例Ａ４の粘着剤におけるＳＵＳ接着力の経時変化を２点鎖線で、実験例Ａ５の粘着剤におけるＳＵＳ接着力の経時変化を破線で示した。 The change over time of the SUS adhesive force in the pressure sensitive adhesive of Experimental Example A1 is indicated by a thick line, the time change of the SUS adhesive force in the pressure sensitive adhesive of Experimental Example A2 is indicated by a thin line, and the time change of the SUS adhesive strength in the pressure sensitive adhesive of Experimental Example A3 is indicated. The one-dot chain line shows the time-dependent change of the SUS adhesive force in the pressure-sensitive adhesive of Experimental Example A4 by a two-dot chain line, and the time-change of the SUS adhesive force in the pressure-sensitive adhesive of Experimental Example A5 is shown by the broken line.
この結果、エーテル化された多糖類を用いた実験例Ａ１〜Ａ４の各粘着剤は、エーテル化されていない多糖類を用いた実験例Ａ５の粘着剤に比べて、耐老化性が向上し、長期にわたって安定した接着力が得られた。特に、エーテル化されたワキシスターチを多く使用した実験例Ａ１の粘着剤は、長期の保管後においても高い接着力が得られた。 As a result, each adhesive of Experimental Examples A1 to A4 using an etherified polysaccharide has improved aging resistance compared to the adhesive of Experimental Example A5 using a non-etherified polysaccharide, A stable adhesive force was obtained over a long period of time. In particular, the adhesive of Experimental Example A1 using a large amount of etherified waxy starch obtained high adhesive strength even after long-term storage.
次に、エーテル化された多糖類を用いると共に、カードランを加えた粘着剤におけるｐＨを調整してアルカリ性、酸性、中性に変更させた実験を行い、カードランを加えた粘着剤をアルカリ性にした場合に、粘着剤の耐老化性が向上して、長期にわたって十分な接着力が得られることを明らかにする。 Next, while using the etherified polysaccharide, the pH of the pressure-sensitive adhesive added with curdlan was adjusted to be alkaline, acidic, and neutral, and the pressure-sensitive adhesive added with curdlan was made alkaline. In this case, it is clarified that the aging resistance of the pressure-sensitive adhesive is improved and sufficient adhesive force can be obtained over a long period of time.
（実験例Ｂ１）
実験例Ｂ１においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、エーテル化及び架橋された馬鈴薯系澱粉（日澱化学（株）製：デリカＭ９ エーテル化度５％）２７ｇと、エーテル化及び架橋されたワキシスターチ（日澱化学（株）製：アミコールＡ エーテル化度５％）３ｇとを加えて攪拌し、これを糊化させた後、これに１重量％のリン酸三ナトリウムＮａ3ＰＯ4と６重量％のカードランを含む水溶液６２．６ｇ（カードラン３．７５ｇ）を加えて攪拌し、さらに酸性側のｐＨ調整剤であるリンゴ酸を全体に対して０．０７重量％加えて、実験例Ｂ１の粘着剤を調製した。なお、この粘着剤のｐＨは９．８でアルカリ性であった。
(Experimental example B1)
In Experimental Example B1, 27 g of potato-based starch (manufactured by Nissho Chemical Co., Ltd .: Delica M9 degree of etherification 5%) etherified and crosslinked as a polysaccharide in a solvent consisting of 35 g of glycerin and 35 g of water; 3 g of etherified and cross-linked waxy starch (manufactured by Nissho Chemical Co., Ltd .: Amycol A etherification degree 5%) was added and stirred to gelatinize it, and then 1 wt% of trisodium phosphate 62.6 g of an aqueous solution containing Na 3 PO 4 and 6% by weight of curdlan (3.75 g of curdlan) was added and stirred, and further, malic acid, which is a pH adjuster on the acidic side, was 0.07 wt. % Was added to prepare the adhesive of Experimental Example B1. The pressure-sensitive adhesive had a pH of 9.8 and was alkaline.
（実験例Ｂ２）
実験例Ｂ２においては、酸性側のｐＨ調整剤であるリンゴ酸を全体に対して０．１７重量％加えるようにし、それ以外は、上記の実験例Ｂ１と同様にして、実験例Ｂ２の粘着剤を調製した。なお、この粘着剤のｐＨは７．１で中性であった。
(Experiment B2)
In Experimental Example B2, malic acid, which is a pH adjusting agent on the acidic side, was added in an amount of 0.17% by weight, and the adhesive of Experimental Example B2 was otherwise the same as in Experimental Example B1. Was prepared. The pressure-sensitive adhesive had a pH of 7.1 and was neutral.
（実験例Ｂ３）
実験例Ｂ３においては、酸性側のｐＨ調整剤であるリンゴ酸を全体に対して０．６０重量％加えるようにし、それ以外は、上記の実験例Ｂ１と同様にして、実験例Ｂ３の粘着剤を調製した。なお、この粘着剤のｐＨは４．０で酸性であった。
(Experiment B3)
In Experimental Example B3, 0.60% by weight of malic acid, which is a pH adjuster on the acidic side, was added to the whole, and otherwise, in the same manner as in Experimental Example B1, the adhesive of Experimental Example B3 Was prepared. The pressure-sensitive adhesive had a pH of 4.0 and was acidic.
そして、上記のように調製した実験例Ｂ１〜Ｂ３の各粘着剤を、上記の場合と同様に、温度２５℃、湿度５０％の雰囲気下において保管し、所定の保管日を経過した時点において、各粘着剤のＳＵＳ接着力（ｇ／２５ｍｍ）を測定し、実験例Ｂ１のアルカリ性の粘着剤におけるＳＵＳ接着力の経時変化を実線で、実験例Ｂ２の中性の粘着剤におけるＳＵＳ接着力の経時変化を１点鎖線で、実験例Ｂ３の酸性の粘着剤におけるＳＵＳ接着力の経時変化を破線で図３に示した。 And each adhesive of Experimental Examples B1 to B3 prepared as described above was stored in an atmosphere at a temperature of 25 ° C. and a humidity of 50% as in the above case, and at the time when a predetermined storage date had passed, The SUS adhesive strength (g / 25 mm) of each pressure-sensitive adhesive was measured, the change over time of the SUS adhesive strength in the alkaline pressure-sensitive adhesive of Experimental Example B1 was represented by a solid line, and the time course of SUS adhesive strength in the neutral pressure-sensitive adhesive of Experimental Example B2 FIG. 3 shows the change over time of the SUS adhesive force in the acidic pressure-sensitive adhesive of Experimental Example B3 with a dashed line, and the change with the dashed line.
この結果、エーテル化された多糖類を用いると共に、カードランを加えた粘着剤をアルカリ性に調整した実験例Ｂ１の粘着剤は、上記の粘着剤を中性や酸性に調整した実験例Ｂ２，Ｂ３の粘着剤に比べて、接着力が高くなると共に、耐老化性が向上し、長期にわたって安定した接着力が得られた。 As a result, the pressure-sensitive adhesive of Experimental Example B1 using an etherified polysaccharide and adjusting the pressure-sensitive adhesive added with curdlan to alkalinity is experimental examples B2 and B3 where the pressure-sensitive adhesive is adjusted to be neutral or acidic. As compared with the pressure-sensitive adhesive, the adhesive force was increased, the aging resistance was improved, and a stable adhesive force was obtained over a long period of time.
次に、エーテル化された多糖類を用いた粘着剤に、カードランを加えた場合と、アルギン酸ナトリウムを加えた場合とについて実験を行い、粘着剤における耐老化性の評価を行った。 Next, an experiment was conducted on the case where curdlan was added to the pressure-sensitive adhesive using the etherified polysaccharide and the case where sodium alginate was added, and the aging resistance of the pressure-sensitive adhesive was evaluated.
（実験例Ｃ１）
実験例Ｃ１においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、エーテル化及び架橋された馬鈴薯系澱粉（日澱化学（株）製：デリカＭ９ エーテル化度５％）２７ｇと、エーテル化及び架橋されたワキシスターチ（日澱化学（株）製：アミコールＡ エーテル化度５％）３ｇとを加えて攪拌し、これを糊化させた後、これに１重量％のリン酸三ナトリウムＮａ3ＰＯ4と５重量％のカードランを含む水溶液５０ｇ（カードラン２．５ｇ）を加えて攪拌し、実験例Ｃ１の粘着剤を調製した。なお、この粘着剤のｐＨは１０．１０であった。
(Experimental example C1)
In Experimental Example C1, 27 g of potato-based starch (manufactured by Nissho Chemical Co., Ltd .: Delica M9 degree of etherification 5%) etherified and crosslinked as a polysaccharide in a solvent consisting of 35 g of glycerin and 35 g of water; 3 g of etherified and cross-linked waxy starch (manufactured by Nissho Chemical Co., Ltd .: Amycol A etherification degree 5%) was added and stirred to gelatinize it, and then 1 wt% of trisodium phosphate 50 g of an aqueous solution containing Na 3 PO 4 and 5% by weight of curdlan (2.5 g of curdlan) was added and stirred to prepare an adhesive of Experimental Example C1. The pressure-sensitive adhesive had a pH of 10.10.
（実験例Ｃ２）
実験例Ｃ２においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、多糖類として、エーテル化及び架橋された馬鈴薯系澱粉（日澱化学（株）製：デリカＭ９ エーテル化度５％）２７ｇと、エーテル化及び架橋されたワキシスターチ（日澱化学（株）製：アミコールＡ エーテル化度５％）３ｇとを加えて攪拌し、これを糊化させた後、これに４重量％のアルギン酸ナトリウム水溶液１２．５ｇ（アルギン酸ナトリウム０．５ｇ）と、アルギン酸ナトリウムの架橋剤であるクエン酸カルシウム０．０７ｇ（アルギン酸ナトリウムに対して０．３当量）とを加えて攪拌し、実験例Ｃ２の粘着剤を調製した。なお、この粘着剤のｐＨは３．５７であった。
(Experimental example C2)
In Experimental Example C2, 27 g of potato-based starch (manufactured by Nissho Chemical Co., Ltd .: Delica M9 degree of etherification 5%) etherified and crosslinked as a polysaccharide in a solvent consisting of 35 g of glycerin and 35 g of water; 3 g of etherified and crosslinked waxy starch (manufactured by Nissho Chemical Co., Ltd .: Amycol A etherification degree 5%) was added and stirred to gelatinize it, and then 4 wt% aqueous sodium alginate solution 12 0.5 g (0.5 g of sodium alginate) and 0.07 g of calcium citrate which is a cross-linking agent of sodium alginate (0.3 equivalents with respect to sodium alginate) were added and stirred to prepare an adhesive for Experimental Example C2. did. The pressure-sensitive adhesive had a pH of 3.57.
そして、上記のように調製した実験例Ｃ１，Ｃ２の各粘着剤を、上記の場合と同様に、温度２５℃、湿度５０％の雰囲気下において保管し、所定の保管日を経過した時点において、各粘着剤のＳＵＳ接着力（ｇ／２５ｍｍ）を測定し、実験例Ｃ１のカードランを加えた粘着剤におけるＳＵＳ接着力の経時変化を太線で、実験例Ｃ２のアルギン酸ナトリウムを加えた粘着剤におけるＳＵＳ接着力の経時変化を細線で図４に示した。 And each adhesive of Experimental Examples C1 and C2 prepared as described above was stored in an atmosphere at a temperature of 25 ° C. and a humidity of 50% as in the above case, and at the time when a predetermined storage date had passed, The SUS adhesive strength (g / 25 mm) of each pressure-sensitive adhesive was measured, and the change over time of the SUS adhesive strength in the pressure-sensitive adhesive added with the curdlan of Experimental Example C1 is indicated by a thick line, and the pressure-sensitive adhesive added with sodium alginate in Experimental Example C2 The change with time of the SUS adhesive force is shown by a thin line in FIG.
この結果、エーテル化された多糖類を用いると共に、カードランを加えた実験例Ｃ１の粘着剤は、高い接着力を示すと共に、耐老化性が向上し、長期にわたって安定した接着力が得られた。また、エーテル化された多糖類を用いると共に、アルギン酸ナトリウムを加えた実験例Ｃ２の粘着剤は、耐老化性が向上し、初期の接着力を超えるような高い接着力が長期にわたって得られた。 As a result, the pressure-sensitive adhesive of Experimental Example C1 using the etherified polysaccharide and adding curdlan showed high adhesive force, improved aging resistance, and stable adhesive force was obtained over a long period of time. . In addition, the pressure-sensitive adhesive of Experimental Example C2 using the etherified polysaccharide and sodium alginate was improved in aging resistance, and high adhesive strength exceeding the initial adhesive strength was obtained over a long period of time.
１０ ラベル
１１ ラベル基材
１２ 粘着剤層
10 Label 11 Label substrate 12 Adhesive layer
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012194115A JP5599118B2 (en) | 2012-09-04 | 2012-09-04 | Adhesives and labels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012194115A JP5599118B2 (en) | 2012-09-04 | 2012-09-04 | Adhesives and labels |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007028632A Division JP5158748B2 (en) | 2007-02-08 | 2007-02-08 | Adhesives and labels |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013018985A true JP2013018985A (en) | 2013-01-31 |
| JP5599118B2 JP5599118B2 (en) | 2014-10-01 |
Family
ID=47690712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012194115A Active JP5599118B2 (en) | 2012-09-04 | 2012-09-04 | Adhesives and labels |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5599118B2 (en) |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5971658A (en) * | 1982-10-16 | 1984-04-23 | Nichiden Kagaku Kk | Preparation of noodles |
| JPS61250080A (en) * | 1985-04-30 | 1986-11-07 | Nichiban Co Ltd | Pressure-sensitive adhesive tape, sheet or label |
| JPS63112673A (en) * | 1986-10-29 | 1988-05-17 | Sekisui Chem Co Ltd | Hydrophilic tacky composition |
| JPS63210179A (en) * | 1987-02-27 | 1988-08-31 | Fuji Photo Film Co Ltd | Developing ink for lithographic plate |
| JPH01289457A (en) * | 1988-02-04 | 1989-11-21 | Takeda Chem Ind Ltd | Edible film |
| JPH02133484A (en) * | 1988-11-14 | 1990-05-22 | Kemitetsuku Hanbai Kk | Powdery adhesive |
| JPH0598221A (en) * | 1991-10-11 | 1993-04-20 | Sekisui Chem Co Ltd | Water-soluble self-adhesive tape for masking |
| JPH06145610A (en) * | 1992-11-13 | 1994-05-27 | Sekisui Chem Co Ltd | Substrate for water-soluble tacky adhesive tape |
| JPH07289180A (en) * | 1994-04-26 | 1995-11-07 | Nippon Suisan Kaisha Ltd | Method for boiling rice in good taste |
| JP2000228961A (en) * | 1999-02-09 | 2000-08-22 | Kyodo Milk Industry Co Ltd | Freeze-dried soybean-curd and its production |
| JP2002515925A (en) * | 1996-05-06 | 2002-05-28 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | Adhesive based on maltodextran |
| JP2004248665A (en) * | 2002-12-26 | 2004-09-09 | Tsukioka:Kk | Edible film, method for producing the edible film and film containing the edible film |
| JP2004321067A (en) * | 2003-04-24 | 2004-11-18 | Uha Mikakuto Co Ltd | Candy-containing fruit confectionery |
| JP2004350555A (en) * | 2003-05-28 | 2004-12-16 | Nissin Food Prod Co Ltd | Method for producing cook-free packaged boiled/chilled buckwheat noodle |
| JP2005102617A (en) * | 2003-09-30 | 2005-04-21 | Sanei Gen Ffi Inc | Thermal-resistant filling material |
| JP2005320406A (en) * | 2004-05-07 | 2005-11-17 | Osaka Sealing Printing Co Ltd | Adhesive and adhesive label using the same |
| JP2006109785A (en) * | 2004-10-15 | 2006-04-27 | Sanei Gen Ffi Inc | Method for producing easily meltable solid drink |
| JP2006117724A (en) * | 2004-10-19 | 2006-05-11 | Osaka Sealing Printing Co Ltd | Adhesive and label |
-
2012
- 2012-09-04 JP JP2012194115A patent/JP5599118B2/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5971658A (en) * | 1982-10-16 | 1984-04-23 | Nichiden Kagaku Kk | Preparation of noodles |
| JPS61250080A (en) * | 1985-04-30 | 1986-11-07 | Nichiban Co Ltd | Pressure-sensitive adhesive tape, sheet or label |
| JPS63112673A (en) * | 1986-10-29 | 1988-05-17 | Sekisui Chem Co Ltd | Hydrophilic tacky composition |
| JPS63210179A (en) * | 1987-02-27 | 1988-08-31 | Fuji Photo Film Co Ltd | Developing ink for lithographic plate |
| JPH01289457A (en) * | 1988-02-04 | 1989-11-21 | Takeda Chem Ind Ltd | Edible film |
| JPH02133484A (en) * | 1988-11-14 | 1990-05-22 | Kemitetsuku Hanbai Kk | Powdery adhesive |
| JPH0598221A (en) * | 1991-10-11 | 1993-04-20 | Sekisui Chem Co Ltd | Water-soluble self-adhesive tape for masking |
| JPH06145610A (en) * | 1992-11-13 | 1994-05-27 | Sekisui Chem Co Ltd | Substrate for water-soluble tacky adhesive tape |
| JPH07289180A (en) * | 1994-04-26 | 1995-11-07 | Nippon Suisan Kaisha Ltd | Method for boiling rice in good taste |
| JP2002515925A (en) * | 1996-05-06 | 2002-05-28 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | Adhesive based on maltodextran |
| JP2000228961A (en) * | 1999-02-09 | 2000-08-22 | Kyodo Milk Industry Co Ltd | Freeze-dried soybean-curd and its production |
| JP2004248665A (en) * | 2002-12-26 | 2004-09-09 | Tsukioka:Kk | Edible film, method for producing the edible film and film containing the edible film |
| JP2004321067A (en) * | 2003-04-24 | 2004-11-18 | Uha Mikakuto Co Ltd | Candy-containing fruit confectionery |
| JP2004350555A (en) * | 2003-05-28 | 2004-12-16 | Nissin Food Prod Co Ltd | Method for producing cook-free packaged boiled/chilled buckwheat noodle |
| JP2005102617A (en) * | 2003-09-30 | 2005-04-21 | Sanei Gen Ffi Inc | Thermal-resistant filling material |
| JP2005320406A (en) * | 2004-05-07 | 2005-11-17 | Osaka Sealing Printing Co Ltd | Adhesive and adhesive label using the same |
| JP2006109785A (en) * | 2004-10-15 | 2006-04-27 | Sanei Gen Ffi Inc | Method for producing easily meltable solid drink |
| JP2006117724A (en) * | 2004-10-19 | 2006-05-11 | Osaka Sealing Printing Co Ltd | Adhesive and label |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5599118B2 (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2625762T3 (en) | Aqueous starch-based adhesive compositions and uses thereof | |
| JP5158748B2 (en) | Adhesives and labels | |
| US3503769A (en) | Method of modifying alkylene glycol alginates | |
| JP6340514B2 (en) | Tapioca pearl, method for producing the same and food containing tapioca pearl | |
| CN104004469A (en) | Preparation method for glutinous rice glue | |
| WO2009031039A3 (en) | Tablet coatings made from modified carboxymethylcellulose materials | |
| JP5553399B2 (en) | Adhesives and labels | |
| JP5164098B2 (en) | Adhesives and labels | |
| JP4793803B2 (en) | Adhesives and labels | |
| EP2422628B1 (en) | Modification of carbohydrates using continuous generation of hydroxyl radicals | |
| JP5061897B2 (en) | Composition for capsule film | |
| JP5599118B2 (en) | Adhesives and labels | |
| WO2013096438A1 (en) | Formulation for the prevention of delamination in starch-based adhesives | |
| JP5550166B2 (en) | Adhesives and labels | |
| US10702455B2 (en) | Gel composition, sheet, and production method therefor | |
| JP5582591B2 (en) | Adhesives and labels | |
| JP5060063B2 (en) | Adhesive composition | |
| JP6085705B2 (en) | Gel composition and sheet, and production method thereof | |
| JP2015123058A (en) | Powder for molding confectionery and combined confectionery using the same | |
| JP2003002901A (en) | Method for lowering viscosity of polysaccharide, viscosity-lowering agent for polysaccharide and polysaccharide lowered in viscosity | |
| BR112021015154A2 (en) | COMPOSITION AND SALT COMPONENT | |
| TW202342677A (en) | Liquid paste for paper | |
| Shinde | Production kinetics and functional properties of carboxymethyl sorghum starch | |
| US20210189013A1 (en) | Method for preparing physically modified starch by using heating and freezing-thawing and adding various edible gums | |
| JP2006083336A (en) | Starch aqueous adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140307 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140421 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140811 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140811 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5599118 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |