JP5164098B2 - Adhesives and labels - Google Patents
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- JP5164098B2 JP5164098B2 JP2007288515A JP2007288515A JP5164098B2 JP 5164098 B2 JP5164098 B2 JP 5164098B2 JP 2007288515 A JP2007288515 A JP 2007288515A JP 2007288515 A JP2007288515 A JP 2007288515A JP 5164098 B2 JP5164098 B2 JP 5164098B2
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- pressure
- sensitive adhesive
- starch
- adhesive
- label
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- 239000000853 adhesive Substances 0.000 title claims description 46
- 230000001070 adhesive effect Effects 0.000 title claims description 46
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 72
- 229920002472 Starch Polymers 0.000 claims description 53
- 235000019698 starch Nutrition 0.000 claims description 53
- 239000008107 starch Substances 0.000 claims description 51
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003002 pH adjusting agent Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 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 claims description 11
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 11
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 11
- 229920002558 Curdlan Polymers 0.000 claims description 10
- 239000001879 Curdlan Substances 0.000 claims description 10
- 229940078035 curdlan Drugs 0.000 claims description 10
- 235000019316 curdlan Nutrition 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 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 description 8
- 239000001540 sodium lactate Substances 0.000 claims description 8
- 235000011088 sodium lactate Nutrition 0.000 claims description 8
- 229940005581 sodium lactate Drugs 0.000 claims description 8
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000013305 food Nutrition 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 235000012055 fruits and vegetables Nutrition 0.000 description 18
- 230000032683 aging Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 6
- 238000006266 etherification reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 241000227653 Lycopersicon Species 0.000 description 3
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920001542 oligosaccharide Polymers 0.000 description 3
- 150000002482 oligosaccharides Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- -1 mornon Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium 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
- 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
- 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
- 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
- 244000043261 Hevea brasiliensis Species 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
- 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
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 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
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 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
- 239000003795 chemical substances by application Substances 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
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 238000012423 maintenance Methods 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
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 229940069338 potassium sorbate Drugs 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
- 229940100486 rice starch Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 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
- 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
Images
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、可食性で安全性に優れると共に、耐湿性及び耐老化性にも優れ、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 an adhesive and a label, and in particular, in an adhesive used for an adhesive layer such as a label to be directly attached to food such as fruits and vegetables, it is edible and excellent in safety, and also has moisture resistance and aging resistance. It is excellent and is characterized in that a sufficient adhesive force stable over a long period of time can be obtained for foods such as fruits and vegetables.
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. ing.
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、特許文献１に示されるように、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。 In recent years, as shown in Patent Document 1, an edible adhesive using a collagen hydrolyzate and sodium lactate has been proposed.
しかし、この特許文献１に示される粘着剤の場合、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, in the case of the pressure sensitive adhesive shown in Patent Document 1, it cannot be said that it has sufficient adhesive force, and a label using such a pressure sensitive adhesive is directly applied to foods such as fruits and vegetables as described above. When affixed, there was a problem that the label easily peeled off.
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、特許文献２に示されるように、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。 Furthermore, as disclosed in Patent Document 2, the present applicant has dissolved at least a polysaccharide in a solvent using sodium lactate and / or glycerin as an adhesive that is edible and has improved adhesion to foods such as fruits and vegetables. Developed a pressure sensitive adhesive.
しかし、この特許文献２に示される粘着剤においても、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、可食性で安全性に優れると共に、耐湿性及び耐老化性にも優れ、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。 This invention is to solve the above-mentioned problems when directly attaching labels and the like to foods such as fruits and vegetables, and is edible and excellent in safety, as well as moisture and aging resistance. Another object of the present invention is to provide a pressure-sensitive adhesive that can provide a sufficient and stable adhesive force over a long period of time for food such as fruits and vegetables, and a label using such a pressure-sensitive adhesive.
この発明に係る粘着剤においては、上記のような課題を解決するため、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、少なくとも澱粉とカードランとｐＨ調整剤とを溶解させて、ｐＨが１１．５〜１２．６の範囲になるようにした。 In the pressure-sensitive adhesive according to the present invention, in order to solve the above-described problems, at least starch, curdlan, and a pH adjuster are dissolved in a solvent containing glycerin and / or sodium lactate and water, and the pH is reduced. The range was from 11.5 to 12.6 .
なお、この発明の粘着剤においては、上記のｐＨを１１．５〜１２．６の範囲にすることがより好ましい。 In the pressure-sensitive adhesive of the present invention, the pH is more preferably in the range of 11.5 to 12.6.
ここで、この発明における粘着剤において、上記の澱粉としては、ワキシ架橋澱粉、エーテル化架橋澱粉及びワキシエーテル化架橋澱粉から選択される少なくとも１種を用いることが好ましく、特に、ワキシエーテル化架橋澱粉を用いることがより好ましい。 Here, in the pressure-sensitive adhesive of the present invention, as the starch, it is preferable to use at least one selected from waxy crosslinked starch, etherified crosslinked starch and waxy etherified crosslinked starch, and in particular, waxy etherified crosslinked starch is used. It is more preferable.
また、この発明の粘着剤において、上記のｐＨ調整剤としては、リン酸三カリウムＫ3ＰＯ4を用いることが好ましい。 In the pressure-sensitive adhesive of the present invention, it is preferable to use tripotassium phosphate K 3 PO 4 as the pH adjuster.
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、少なくとも澱粉とカードランとｐＨ調整剤とを溶解させて、ｐＨが１１．２〜１３．０の範囲になるようにしたため、上記のカードランにより非水溶性の膜が形成されて粘着剤の耐湿性が向上すると共に、アルカリ性にしたことによって耐老化性が向上され、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なる。特に、この粘着剤におけるｐＨを１１．５〜１２．６の範囲にすると、粘着剤における耐湿性が一層向上されるようになる。 In the pressure-sensitive adhesive of this invention, at least starch, curdlan, and pH adjuster are dissolved in the solvent containing glycerin and / or sodium lactate as described above, and the pH is in the range of 11.2 to 13.0. As a result, a water-insoluble film is formed by the curdlan and the moisture resistance of the pressure-sensitive adhesive is improved, and the aging resistance is improved by making it alkaline, and it can be applied to foods such as fruits and vegetables for a long time. A stable and sufficient adhesive force can be obtained. In particular, when the pH of the pressure-sensitive adhesive is in the range of 11.5 to 12.6, the moisture resistance of the pressure-sensitive adhesive is further improved.
また、この粘着剤において、澱粉として、ワキシ架橋澱粉、エーテル化架橋澱粉及びワキシエーテル化架橋澱粉から選択される少なくとも１種を用いると、粘着剤の耐老化性が一層向上し、なかでも、ワキシエーテル化架橋澱粉が粘着剤の耐老化性を向上させる上で特に好ましく、青果物等の食品に対してより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 this pressure-sensitive adhesive, when at least one selected from waxy crosslinked starch, etherified crosslinked starch and waxy etherified crosslinked starch is used as the starch, the aging resistance of the pressure-sensitive adhesive is further improved. Cross-linked starch is particularly preferable in improving the aging resistance of the pressure-sensitive adhesive, and a sufficient adhesive force that is stable over a long period of time can be obtained for foods such as fruits and vegetables.
また、この発明の粘着剤において、上記のｐＨ調整剤としてリン酸三カリウムＫ3ＰＯ4を用いると、粘着剤のｐＨを上記の範囲に調整することが簡単に行えると共に、食品への添加が認められているため、食の安全・安心の点から問題となることもない。 In addition, in the pressure-sensitive adhesive of the present invention, when tripotassium phosphate K 3 PO 4 is used as the pH adjusting agent, the pH of the pressure-sensitive adhesive can be easily adjusted to the above range, and can be added to foods. Because it is approved, there is no problem in terms of food safety and security.
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、この発明の粘着剤において、澱粉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、上記の澱粉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 of the present invention, a solvent containing glycerin and / or sodium lactate is used as a solvent for dissolving starch, because these solvents have excellent water retention ability, and the above starch is plasticized. This is because the adhesiveness can be exhibited simultaneously.
そして、澱粉としては、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を用いることができるが、粘着剤の耐老化性を向上させるために、上記のようにワキシ架橋澱粉、エーテル化架橋澱粉及びワキシエーテル化架橋澱粉から選択される少なくとも１種を用いることが好ましく、特に、ワキシエーテル化架橋澱粉を用いることがより好ましい。なお、エーテル化架橋澱粉やワキシエーテル化架橋澱粉において、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。 As the starch, for example, various starches such as waxy starch, potato-based starch, rice-based starch, tapioca-based starch can be used, but in order to improve the aging resistance of the adhesive, It is preferable to use at least one selected from starch, etherified crosslinked starch, and waxy etherified crosslinked starch, and it is more preferable to use waxy etherified crosslinked starch. In etherified crosslinked starch and waxy etherified crosslinked starch, the ratio of etherification is not particularly limited, but if the degree of etherification is low, the effect of improving the aging resistance of the pressure-sensitive adhesive is small, while the degree of etherification is high. If it becomes too much, the adhesive strength of the pressure-sensitive adhesive may be reduced, so the degree of etherification is preferably about 0.5 to 15%, more preferably about 1 to 10%.
そして、上記の澱粉をグリセリン及び／又は乳酸ナトリウムを含む溶剤に溶解させるにあたり、溶解させる澱粉の量が少ないと、十分な接着力が得られなくなる一方、溶解させる澱粉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、上記の溶剤と澱粉との重量比が、好ましくは９０：１０〜６０：４０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 above-mentioned starch in a solvent containing glycerin and / or sodium lactate, if the amount of starch to be dissolved is small, sufficient adhesive force cannot be obtained, while if the amount of starch to be dissolved is too large, Since the viscosity of the pressure-sensitive adhesive becomes too high and it becomes difficult to apply to the label substrate, the weight ratio of the solvent to starch is preferably in the range of 90:10 to 60:40, more preferably Is in the range of 85:15 to 65:35.
また、上記の粘着剤における耐湿性及び耐老化性をさらに向上させるためには、前記のようにｐＨ調整剤を加えて、粘着剤のｐＨを１１．２〜１３．０の範囲、好ましくは１１．５〜１２．６の範囲にする。 Further, in order to further improve the moisture resistance and aging resistance in the above-mentioned pressure-sensitive adhesive, a pH adjuster is added as described above, and the pH of the pressure-sensitive adhesive is in the range of 11.2 to 13.0, preferably 11. The range is from 5 to 12.6.
ここで、このように粘着剤のｐＨを調整するｐＨ調整剤としては、安全性の観点から、食品への添加が認められている水酸化ナトリウムＮａＯＨ、リン酸三ナトリウムＮａ3ＰＯ4、リン酸三カリウムＫ3ＰＯ4、炭酸ナトリウムＮａ2ＣＯ3、リン酸水素二ナトリウムＮａ2ＨＰＯ4、リン酸水素二カリウムＫ2ＨＰＯ4、ピロリン酸四ナトリウムＮａ4Ｐ2Ｏ7、ピロリン酸四カリウムＫ4Ｐ2Ｏ7、トリポリリン酸ナトリウムＮａ5Ｐ3Ｏ10、炭酸水素ナトリウムＮａＨＣＯ3などを用いることが好ましい。より好ましくは、食品への添加が認められているが、使用制限がある水酸化ナトリウムＮａＯＨを除く、上記のｐＨ調整剤を用いるようにする。 Here, as a pH adjuster for adjusting the pH of the pressure-sensitive adhesive in this manner, sodium hydroxide NaOH, trisodium phosphate Na 3 PO 4 , phosphoric acid, which are allowed to be added to foods from the viewpoint of safety, are used. Tripotassium K 3 PO 4 , sodium carbonate Na 2 CO 3 , disodium hydrogen phosphate Na 2 HPO 4 , dipotassium hydrogen phosphate K 2 HPO 4 , tetrasodium pyrophosphate Na 4 P 2 O 7 , tetrapotassium pyrophosphate K It is preferable to use 4 P 2 O 7 , sodium tripolyphosphate Na 5 P 3 O 10 , sodium bicarbonate NaHCO 3 or the like. More preferably, the above pH adjuster is used except sodium hydroxide NaOH, which is allowed to be added to foods but is restricted in use.
さらに、上記のｐＨ調整剤の中でも、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、特に、溶解性が高く、粘着剤のｐＨの調整が容易に行える点からリン酸三カリウムＫ3ＰＯ4を用いることがより好ましい。また、添加するｐＨ調整剤の量は、ｐＨ調整剤の種類によって異なるが、例えば、リン酸三カリウムＫ3ＰＯ4の場合、一般に上記の澱粉に対して５．３〜４４重量％の範囲、好ましくは８〜２８重量％の範囲になるようにする。 Furthermore, among the above pH adjusters, it is preferable to use trisodium phosphate Na 3 PO 4 or tripotassium phosphate K 3 PO 4 , and in particular, the solubility is high and the pH of the pressure-sensitive adhesive can be easily adjusted. From the viewpoint, it is more preferable to use tripotassium phosphate K 3 PO 4 . The amount of the pH adjusting agent to be added varies depending on the type of the pH adjusting agent. For example, in the case of tripotassium phosphate K 3 PO 4 , it is generally in the range of 5.3 to 44% by weight based on the starch, Preferably, it is in the range of 8 to 28% by weight.
また、この発明の粘着剤において、グリセリン及び／又は乳酸ナトリウムを含む溶剤にカードランを溶解させるにあたり、カードランの溶解量が少ないと、粘着剤の耐湿性を向上させる効果が少なくなる一方、カードラン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、カードランの量を上記の澱粉に対して１〜２０重量％の範囲にすることが好ましい。なお、このようにカードランを用いた場合には、粘着剤の粘度が上昇するのが抑制されて、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。 Further, in the pressure-sensitive adhesive of the present invention, when the curdlan is dissolved in a solvent containing glycerin and / or sodium lactate, the effect of improving the moisture resistance of the pressure-sensitive adhesive is reduced when the curdlan is dissolved in a small amount. If the dissolved amount of run is too large, the adhesive strength of the pressure-sensitive adhesive may be reduced. Therefore, the amount of curdlan is preferably in the range of 1 to 20% by weight with respect to the starch. When curdlan is used in this way, the viscosity of the pressure-sensitive adhesive is prevented from increasing, making it easy to apply to a label substrate, etc., and adhering the pressure-sensitive adhesive in addition to moisture resistance. Power is also improved.
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、上記の粘着剤の粘度を調整したり、接着力を向上させたりする等のために、上記の溶剤に、ワキシ架橋澱粉、エーテル化架橋澱粉及びワキシエーテル化架橋澱粉の少なくとも１種と共に、これ以外の澱粉を溶解させることもできる。 In addition, in order to adjust the viscosity of the above-mentioned pressure-sensitive adhesive or improve the adhesive force, the above-mentioned solvent is mixed with at least one of waxy crosslinked starch, etherified crosslinked starch and waxy etherified crosslinked starch. Other starches can be dissolved.
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.
そして、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。
And in the
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。
In the
また、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。
Moreover, even when a part of the adhesive remains in the food such as fruits and vegetables when the
次に、この発明の実施例に係る具体的な粘着剤について説明し、実施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, specific adhesives according to examples of the present invention will be described, and it will be clarified by giving comparative examples that the adhesives of the examples exhibit excellent characteristics.
（実施例１）
実施例１においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、澱粉として、ワキシエーテル化架橋澱粉（松谷化学工業（株）製：パインエース５）を２５ｇ加えて攪拌し、これを糊化させた後、これに６．２５重量％のカードラン水溶液を８０ｇ（カードラン固形分５ｇ）と、ｐＨ調整剤のリン酸三カリウムＫ3ＰＯ4を２．４ｇ（澱粉に対して９．６重量％）とを加えて攪拌し、実施例１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。
Example 1
In Example 1, 25 g of waxy etherified cross-linked starch (Matsutani Chemical Industry Co., Ltd .: Pine Ace 5) was added as a starch to a solvent consisting of 35 g of glycerin and 35 g of water, and the resulting mixture was gelatinized. Thereafter, 80 g of a 6.25 wt% curdlan aqueous solution (5 g of curdlan solid content) and 2.4 g of tripotassium phosphate K 3 PO 4 pH adjusting agent (9.6 wt% based on starch) And the mixture was stirred to prepare the pressure-sensitive adhesive of Example 1. The pressure-sensitive adhesive had a pH of 11.2.
（実施例２）
実施例２においては、ｐＨ調整剤のリン酸三カリウムＫ3ＰＯ4を４．０ｇ（澱粉に対して１６．０重量％）加えるようにし、それ以外は、上記の実施例１の場合と同様にして、実施例２の粘着剤を調製した。なお、この粘着剤のｐＨは１１．９であった。
(Example 2)
In Example 2, 4.0 g (16.0% by weight with respect to starch) of tripotassium phosphate K 3 PO 4 as a pH adjusting agent was added, and the other cases were the same as in Example 1 above. Thus, the pressure-sensitive adhesive of Example 2 was prepared. The pressure-sensitive adhesive had a pH of 11.9.
（実施例３）
実施例３においては、ｐＨ調整剤のリン酸三カリウムＫ3ＰＯ4を５．６ｇ（澱粉に対して２２．４重量％）加えるようにし、それ以外は、上記の実施例１の場合と同様にして、実施例３の粘着剤を調製した。なお、この粘着剤のｐＨは１２．０であった。
(Example 3)
In Example 3, 5.6 g (22.4% by weight with respect to starch) of tripotassium phosphate K 3 PO 4 as a pH adjusting agent was added, and the other cases were the same as in Example 1 above. Thus, the pressure-sensitive adhesive of Example 3 was prepared. The pressure-sensitive adhesive had a pH of 12.0.
（実施例４）
実施例４においては、ｐＨ調整剤に水酸化ナトリウムＮａＯＨを用い、この水酸化ナトリウムＮａＯＨを１．２ｇ（澱粉に対して４．８重量％）加えるようにし、それ以外は、上記の実施例１の場合と同様にして、実施例４の粘着剤を調製した。なお、この粘着剤のｐＨは１２．６であった。
Example 4
In Example 4, sodium hydroxide NaOH was used as a pH adjuster, and 1.2 g of this sodium hydroxide NaOH was added (4.8% by weight based on starch). Otherwise, Example 1 above was used. The adhesive of Example 4 was prepared in the same manner as described above. The pressure-sensitive adhesive had a pH of 12.6.
（実施例５）
実施例５においては、グリセリン３５ｇと水３５ｇとからなる溶剤に、澱粉として、ワキシエーテル化架橋澱粉（松谷化学工業（株）製：パインエース５）を２２ｇと、ワキシ架橋澱粉（日澱化学（株）製：スターチＭＨ−Ａ）３ｇとを加えるようにし、上記の実施例２の場合と同様に、ｐＨ調整剤のリン酸三カリウムＫ3ＰＯ4を４．０ｇ（澱粉に対して１６．０重量％）加えて、実施例５の粘着剤を調製した。なお、この粘着剤のｐＨは１１．９であった。
(Example 5)
In Example 5, 22 g of waxy etherified crosslinked starch (Matsutani Chemical Industry Co., Ltd .: Pine Ace 5) was used as a starch in a solvent consisting of 35 g of glycerin and 35 g of water, and waxy crosslinked starch (Nippon Chemical Co., Ltd.). ): Starch MH-A) 3 g was added, and in the same manner as in Example 2 above, 4.0 g of tripotassium phosphate K 3 PO 4 as a pH adjuster (16.0 based on starch) In addition, the pressure-sensitive adhesive of Example 5 was prepared. The pressure-sensitive adhesive had a pH of 11.9.
（比較例１）
比較例１においては、ｐＨ調整剤のリン酸三カリウムＫ3ＰＯ4を１．２ｇ（澱粉に対して４．８重量％）加えるようにし、それ以外は、上記の実施例１の場合と同様にして、比較例１の粘着剤を調製した。なお、この粘着剤のｐＨは１０．８であった。
(Comparative Example 1)
In Comparative Example 1, 1.2 g of tripotassium phosphate K 3 PO 4 as a pH adjusting agent was added (4.8% by weight with respect to starch), and the others were the same as in Example 1 above. Thus, a pressure-sensitive adhesive of Comparative Example 1 was prepared. The pressure-sensitive adhesive had a pH of 10.8.
次に、上記のように調製した実施例１〜５及び比較例１の各粘着剤について、それぞれ耐湿性及び耐老化性の評価を行い、その結果を下記の表１に示した。 Next, the adhesives of Examples 1 to 5 and Comparative Example 1 prepared as described above were evaluated for moisture resistance and aging resistance, respectively, and the results are shown in Table 1 below.
ここで、各粘着剤の耐湿性については、上記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るようにした。 Here, about the moisture resistance of each adhesive, after sticking each label which gave each said adhesive to the single side | surface of a label base material on a tomato respectively and making this cool for one day with the refrigerator set to 5 degreeC This was allowed to stand at room temperature for condensation, and in this state, each label was peeled off from the tomato.
そして、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。 And, for evaluation of moisture resistance, the state of stringing of each pressure-sensitive adhesive when peeled from the tomato was examined, ○ when there was no stringing, and △ when the area where stringing occurred was 40% or less The case where the area where stringing occurred exceeded 40% was indicated by x.
また、各粘着剤の耐老化性については、各粘着剤を温度２３℃、湿度５０％の雰囲気下において２週間保管し、各粘着剤の保管前と保管後における接着力を調べ、保管前の接着力に対して、保管後における接着力が８０％以上維持された場合を○で示し、保管後における接着力の維持が８０％未満の場合を×で示した。 In addition, regarding the aging resistance of each pressure-sensitive adhesive, each pressure-sensitive adhesive is stored for 2 weeks in an atmosphere at a temperature of 23 ° C. and a humidity of 50%, and the adhesive strength before and after storage of each pressure-sensitive adhesive is examined. The case where the adhesive strength after storage was maintained at 80% or more with respect to the adhesive strength was indicated by ○, and the case where the maintenance of adhesive strength after storage was less than 80% was indicated by ×.
この結果、澱粉に耐老化性に優れたワキシエーテル化架橋澱粉を用いた実施例１〜５及び比較例１の各粘着剤においては、何れも保管前の接着力に対して、保管後における接着力が８０％以上維持されており、何れも耐老化性は良好であった。また、実施例２〜５の各粘着剤においては、４週間保管後における接着力も、保管前の接着力に対して８０％以上維持されており、耐老化性は極めて良好であった。 As a result, in each of the pressure-sensitive adhesives of Examples 1 to 5 and Comparative Example 1 using a waxy etherified cross-linked starch excellent in aging resistance, the adhesive strength after storage is higher than the adhesive strength before storage. Was maintained at 80% or more, and all had good aging resistance. In each of the pressure-sensitive adhesives of Examples 2 to 5, the adhesive strength after storage for 4 weeks was maintained at 80% or more with respect to the adhesive strength before storage, and the aging resistance was extremely good.
一方、耐湿性については、粘着剤のｐＨが１０．８である比較例１の粘着剤の場合、剥離時における粘着剤の糸引きが多く発生したのに対して、粘着剤のｐＨが１１．２〜１３．０の範囲になった実施例１〜５の各粘着剤においては、剥離時における粘着剤の糸引きの発生が少なくなっており、比較例１の粘着剤に比べて耐湿性が向上しており、特に、ｐＨが１１．５〜１２．６の範囲になった実施例２〜５の各粘着剤においては、糸引きの発生がなく耐湿性がさらに向上していた。 On the other hand, regarding the moisture resistance, in the case of the pressure-sensitive adhesive of Comparative Example 1 in which the pH of the pressure-sensitive adhesive was 10.8, a lot of threading of the pressure-sensitive adhesive occurred during peeling, whereas the pH of the pressure-sensitive adhesive was 11. In each of the pressure-sensitive adhesives of Examples 1 to 5 in the range of 2 to 13.0, occurrence of stringing of the pressure-sensitive adhesive at the time of peeling was reduced, and moisture resistance was higher than that of the pressure-sensitive adhesive of Comparative Example 1. In particular, in each of the pressure-sensitive adhesives of Examples 2 to 5 having a pH in the range of 11.5 to 12.6, there was no occurrence of stringing, and the moisture resistance was further improved.
１０ ラベル
１１ ラベル基材
１２ 粘着剤層
10
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