JP6657871B2 - Packaging materials and packaging containers - Google Patents
Packaging materials and packaging containers Download PDFInfo
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- JP6657871B2 JP6657871B2 JP2015235762A JP2015235762A JP6657871B2 JP 6657871 B2 JP6657871 B2 JP 6657871B2 JP 2015235762 A JP2015235762 A JP 2015235762A JP 2015235762 A JP2015235762 A JP 2015235762A JP 6657871 B2 JP6657871 B2 JP 6657871B2
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- fine particles
- hydrophobic fine
- water
- packaging material
- repellent layer
- Prior art date
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- 239000005022 packaging material Substances 0.000 title claims description 79
- 238000004806 packaging method and process Methods 0.000 title claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 196
- 239000010419 fine particle Substances 0.000 claims description 195
- 239000010410 layer Substances 0.000 claims description 93
- 239000005871 repellent Substances 0.000 claims description 90
- 239000011230 binding agent Substances 0.000 claims description 70
- 239000002245 particle Substances 0.000 claims description 46
- 239000012790 adhesive layer Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 150000004703 alkoxides Chemical class 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 32
- 238000011156 evaluation Methods 0.000 description 23
- 239000000843 powder Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- -1 polyethylene terephthalate Polymers 0.000 description 16
- 230000002940 repellent Effects 0.000 description 16
- 235000013618 yogurt Nutrition 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000001993 wax Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- 239000004831 Hot glue Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229920002301 cellulose acetate Polymers 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000005033 polyvinylidene chloride Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012793 heat-sealing layer Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- IZNXGXORLKRGRH-UHFFFAOYSA-N CC(C)O[V](OC(C)C)(OC(C)C)(OC(C)C)OC(C)C Chemical compound CC(C)O[V](OC(C)C)(OC(C)C)(OC(C)C)OC(C)C IZNXGXORLKRGRH-UHFFFAOYSA-N 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NIHCCIIEOQYYEL-UHFFFAOYSA-N P.C(C)O.C(C)O.C(C)O Chemical compound P.C(C)O.C(C)O.C(C)O NIHCCIIEOQYYEL-UHFFFAOYSA-N 0.000 description 1
- HUKJQVKQHYLZSZ-UHFFFAOYSA-N P.CO.CO.CO Chemical compound P.CO.CO.CO HUKJQVKQHYLZSZ-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 240000000851 Vaccinium corymbosum Species 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- VZLNSPSVSKXECI-UHFFFAOYSA-N ethanol;iron Chemical compound [Fe].CCO.CCO VZLNSPSVSKXECI-UHFFFAOYSA-N 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000004170 rice bran wax Substances 0.000 description 1
- 235000019384 rice bran wax Nutrition 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- YNPXMOHUBANPJB-UHFFFAOYSA-N zinc;butan-1-olate Chemical compound [Zn+2].CCCC[O-].CCCC[O-] YNPXMOHUBANPJB-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、包装材料及び包装容器に関する。 The present invention relates to a packaging material and a packaging container.
液体、半固体又はゲル状の内容物が封入された包装容器の蓋材には、該内容物の付着を抑制する機能を有するものがある。例えば下記特許文献１に記載される蓋材では、熱封緘層（ホットメルト層）の外面（内容物と対向する面側）に、疎水性湿式シリカ粒子と疎水性乾式シリカ粒子との混合組成物からなる内容物付着防止用の粒子被覆層が形成されている。この特許文献１では、上記粒子被覆層が撥水性を奏することによって、内容物が蓋材に付着することを抑制している。 Some lids of packaging containers in which liquid, semi-solid or gel-like contents are sealed have a function of suppressing the adhesion of the contents. For example, in the lid material described in Patent Literature 1 below, a mixed composition of hydrophobic wet silica particles and hydrophobic dry silica particles is provided on the outer surface (the surface facing the content) of the heat sealing layer (hot melt layer). A particle coating layer for preventing adhesion of contents is formed. In Patent Literature 1, the particle coating layer exhibits water repellency, thereby preventing the contents from adhering to the lid material.
上記特許文献１に記載される蓋材においては、熱封緘層の溶融成分の一部が粒子被覆層に含浸しており、上記シリカ粒子の脱落を抑制している。しかしながら、粒子被覆層において上記溶融成分が含浸しない領域が多い場合、粒子被覆層に割れ等が発生しやすくなる（すなわち、粒子被覆層の膜強度が低くなる）。この場合、シリカ粒子の多くが脱落し、蓋材に粉落ちが発生するおそれがある。一方、粒子被覆層において上記溶融成分が含浸する領域を大きくした場合、撥水性を発揮するシリカ粒子の多くは、撥水性を奏さない熱封緘層に埋もれてしまう。この場合、蓋材は十分な撥水性を発揮できないおそれがある。 In the lid material described in Patent Literature 1, a part of the molten component of the heat sealing layer is impregnated in the particle coating layer, thereby suppressing the silica particles from falling off. However, when there are many regions where the molten component is not impregnated in the particle coating layer, cracks and the like are likely to occur in the particle coating layer (that is, the film strength of the particle coating layer is reduced). In this case, most of the silica particles may fall off and powder may fall off the lid material. On the other hand, when the region where the above-mentioned molten component is impregnated in the particle coating layer is enlarged, many of the silica particles exhibiting water repellency are buried in the heat sealing layer which does not exhibit water repellency. In this case, the lid material may not be able to exhibit sufficient water repellency.
本発明は、良好な撥水性を発揮でき、粉落ちを抑制できる包装材料及び包装容器を提供することを目的とする。 An object of the present invention is to provide a packaging material and a packaging container that can exhibit good water repellency and suppress powder falling.
本発明の一態様に係る包装材料は、基材と、基材上に設けられる接着層と、接着層上に設けられ、疎水性微粒子及びバインダーを有する撥水層と、を備え、疎水性微粒子は、第１疎水性微粒子と、第１疎水性微粒子の平均粒径よりも少なくとも５０倍以上大きい平均粒径を有する第２疎水性微粒子とを含み、第１疎水性微粒子の平均粒径は、５ｎｍ以上２００ｎｍ以下であり、撥水層において、バインダーの質量は、第２疎水性微粒子の質量よりも大きい。 A packaging material according to one embodiment of the present invention includes a base material, an adhesive layer provided on the base material, and a water-repellent layer provided on the adhesive layer and having hydrophobic fine particles and a binder, Comprises a first hydrophobic fine particle, and a second hydrophobic fine particle having an average particle diameter at least 50 times larger than the average particle diameter of the first hydrophobic fine particle, and the average particle diameter of the first hydrophobic fine particle is: 5 nm or more and 200 nm or less, and in the water-repellent layer, the mass of the binder is larger than the mass of the second hydrophobic fine particles.
この包装材料では、撥水層は、上記の第１疎水性微粒子及び第２疎水性微粒子を含む疎水性微粒子と、バインダーとを有している。ここで、撥水層において、バインダーの質量は、第２疎水性微粒子の質量よりも大きい。このような条件を満たす包装材料の撥水層においては、第１疎水性微粒子及び第２疎水性微粒子がバインダーによって良好に固定されるので、当該撥水層には割れ等が生じにくい。これにより、第１疎水性微粒子の粉落ちを抑制できるだけでなく、第１疎水性微粒子の平均粒径よりも大きい平均粒径を有する第２疎水性微粒子の粉落ちも発生しにくくなる。このため、撥水層を構成する疎水性微粒子（特に第２疎水性微粒子）によって、当該撥水層は、良好な撥水性を発揮できる。したがって、上記包装材料によれば、良好な撥水性を発揮できると共に、粉落ちを抑制できる。 In this packaging material, the water-repellent layer has the hydrophobic fine particles including the first hydrophobic fine particles and the second hydrophobic fine particles, and a binder. Here, in the water-repellent layer, the mass of the binder is larger than the mass of the second hydrophobic fine particles. In the water-repellent layer of the packaging material that satisfies such conditions, the first hydrophobic fine particles and the second hydrophobic fine particles are satisfactorily fixed by the binder, so that the water-repellent layer is less likely to crack. Thereby, not only can the powder drop of the first hydrophobic fine particles be suppressed, but also the powder drop of the second hydrophobic fine particles having an average particle diameter larger than the average particle diameter of the first hydrophobic fine particles is less likely to occur. For this reason, the hydrophobic particles (particularly, the second hydrophobic fine particles) constituting the water-repellent layer allow the water-repellent layer to exhibit good water repellency. Therefore, according to the above-mentioned packaging material, good water repellency can be exhibited, and powder falling can be suppressed.
また、疎水性微粒子とバインダーとの合計質量に対する疎水性微粒子の質量の割合は、３０％よりも大きくてもよい。この場合、撥水層における疎水性微粒子の割合が大きくなるので、当該撥水層がより良好な撥水性を発揮できる。 Further, the ratio of the mass of the hydrophobic fine particles to the total mass of the hydrophobic fine particles and the binder may be larger than 30%. In this case, since the ratio of the hydrophobic fine particles in the water-repellent layer increases, the water-repellent layer can exhibit better water repellency.
また、バインダーの質量に対する第２疎水性微粒子の質量の割合は７０％未満であってもよい。この場合、バインダーによって第２疎水性微粒子を確実に固定できるので、第２疎水性微粒子の粉落ちを抑制できる。 Further, the ratio of the mass of the second hydrophobic fine particles to the mass of the binder may be less than 70%. In this case, since the second hydrophobic fine particles can be reliably fixed by the binder, powder falling of the second hydrophobic fine particles can be suppressed.
第２疎水性微粒子の平均粒径は、２μｍ以上１０μｍ以下であってもよい。この場合、第２疎水性微粒子の粉落ちを抑制しつつ、撥水層の撥水性を向上できる。 The average particle size of the second hydrophobic fine particles may be 2 μm or more and 10 μm or less. In this case, the water repellency of the water-repellent layer can be improved while suppressing powder dropping of the second hydrophobic fine particles.
また、撥水層の厚さは、０．５μｍ以上２０μｍ以下でもよい。この場合、撥水層は、撥水性を良好に発揮できる。 Further, the thickness of the water-repellent layer may be 0.5 μm or more and 20 μm or less. In this case, the water repellent layer can exhibit good water repellency.
また、撥水層に対向する接着層の表面は、凸部及び凹部が設けられた凹凸面であり、撥水層において、凸部上の第１部分の厚さは、凹部上の第２部分の厚さよりも小さくてもよい。この場合、撥水層は、接着層の表面に沿った形状を有するので、撥水層の構造に起因した撥水性が向上する。また、第１部分に含まれる疎水性微粒子はバインダーによって固定されやすくなるので、撥水層の第１部分における膜強度を向上できる。 The surface of the adhesive layer facing the water-repellent layer is an uneven surface provided with convex portions and concave portions. In the water-repellent layer, the thickness of the first portion on the convex portion is the second portion on the concave portion. May be smaller than the thickness of In this case, since the water repellent layer has a shape along the surface of the adhesive layer, the water repellency due to the structure of the water repellent layer is improved. Further, since the hydrophobic fine particles contained in the first portion are easily fixed by the binder, the film strength in the first portion of the water-repellent layer can be improved.
また、本発明の他の一態様に係る包装容器は、上記段落に記載されるいずれかの包装材料を蓋材として用いる。この場合、接着層の表面上に好適に維持される撥水層によって、容器中に収容された内容物が蓋材に付着することを良好に抑制できる。 A packaging container according to another embodiment of the present invention uses any of the packaging materials described in the above paragraph as a lid. In this case, the water-repellent layer suitably maintained on the surface of the adhesive layer can favorably prevent the contents contained in the container from adhering to the lid.
本発明によれば、良好な撥水性を発揮でき、粉落ちを抑制できる包装材料及び包装容器を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the packaging material and packaging container which can exhibit favorable water repellency and can suppress powder fall can be provided.
以下、添付図面を参照して、本発明の好適な実施形態について詳細に説明する。なお、以下の説明において、同一要素又は同一機能を有する要素には、同一符号を用いることとし、重複する説明は省略する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, the same elements or elements having the same functions will be denoted by the same reference symbols, without redundant description.
図１は、本実施形態に係る包装材料の概略断面図である。図１に示されるように、包装材料１は、基材２と、基材２上に設けられる接着層３と、接着層３上に設けられる撥水層４とを備えている。包装材料１の表面には、例えば印刷又は貼り合わせの加工を施して、文字及び模様等の意匠性が付与されていてもよい。 FIG. 1 is a schematic sectional view of the packaging material according to the present embodiment. As shown in FIG. 1, the packaging material 1 includes a base material 2, an adhesive layer 3 provided on the base material 2, and a water-repellent layer 4 provided on the adhesive layer 3. The surface of the packaging material 1 may be subjected to, for example, printing or laminating to impart design properties such as characters and patterns.
基材２は、支持体となる物であれば特に制限はなく、例えば紙、樹脂を含むフィルム、又は金属箔の少なくとも一種を有する。紙としては、上質紙、特殊上質紙、コート紙、アート紙、キャストコート紙、模造紙、又はクラフト紙等が挙げられる。樹脂を含むフィルムとしては、ポリオレフィン、酸変性ポリオレフィン、ポリエステル、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリアミド（ＰＡ）、ポリ塩化ビニル（ＰＶＣ）、セルロースアセテート、及びセロファン樹脂の少なくとも一種を含むフィルムが挙げられる。このフィルムは延伸フィルムでもよいし、非延伸フィルムでもよい。金属箔としては、例えばアルミ箔又はニッケル箔等が挙げられる。基材２が積層体である場合、例えば接着剤等が用いられてもよい。 The substrate 2 is not particularly limited as long as it is a support, and has at least one kind of paper, a film containing a resin, or a metal foil. Examples of the paper include high quality paper, special high quality paper, coated paper, art paper, cast coated paper, imitation paper, and kraft paper. Examples of the resin-containing film include polyolefin, acid-modified polyolefin, polyester, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamide (PA), polyvinyl chloride (PVC), cellulose acetate, and cellophane resin. A film containing at least one kind is exemplified. This film may be a stretched film or a non-stretched film. Examples of the metal foil include an aluminum foil and a nickel foil. When the substrate 2 is a laminate, for example, an adhesive or the like may be used.
また、基材２は、バリア性フィルム、無機蒸着フィルム、又は金属箔等のバリア膜を有してもよい。このバリア膜は、液体及び空気が包装材料１を通過することを阻害する機能、及び光が包装材料１を透過することを抑制する機能等を有している。 Further, the substrate 2 may have a barrier film such as a barrier film, an inorganic vapor deposition film, or a metal foil. The barrier film has a function of preventing liquid and air from passing through the packaging material 1 and a function of suppressing light from passing through the packaging material 1.
バリア性フィルムとしては、例えばポリ塩化ビニリデン（ＰＶＤＣ）、エチレンビニルアルコール共重合体（ＥＶＯＨ）、ポリアクリロニトリル（ＰＡＮ）、又はポリビニルアルコール（ＰＶＡ）等から構成されるフィルムが挙げられる。また、バリア性フィルムとして、ＰＥＴフィルム、ポリエチレン又はポリプロピレン等の延伸オレフィン樹脂フィルム、ポリアミドフィルム、ポリ塩化ビニルフィルム、セルロースアセテートフィルム、又はセロファンフィルム等を用いてもよい。この場合、これらのフィルムの表面にＰＶＤＣコート、ＰＶＡコート、アクリル酸系樹脂コート等を施してもよい。 Examples of the barrier film include a film composed of polyvinylidene chloride (PVDC), ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), or the like. Further, as the barrier film, a PET film, a stretched olefin resin film such as polyethylene or polypropylene, a polyamide film, a polyvinyl chloride film, a cellulose acetate film, a cellophane film, or the like may be used. In this case, a PVDC coat, a PVA coat, an acrylic resin coat, or the like may be applied to the surface of these films.
また、バリア性フィルムとして、ＰＶＤＣ共押出フィルム、ＥＶＯＨ共押出フィルム、ナイロン（ＯＮＹ）系共押出フィルム、又はＯＰＰ共押出フィルム等を用いてもよい。 Further, as the barrier film, a PVDC coextruded film, an EVOH coextruded film, a nylon (ONY) coextruded film, an OPP coextruded film, or the like may be used.
無機蒸着フィルムは、例えば延伸オレフィン樹脂フィルム、ポリアミドフィルム、ポリ塩化ビニルフィルム、セルロースアセテートフィルム、又はセロファンフィルムに対して、アルミニウム、アルミナ、又はシリカ等が蒸着されることによって形成されるフィルムである。 The inorganic vapor-deposited film is a film formed by, for example, vapor-depositing aluminum, alumina, silica, or the like on a stretched olefin resin film, a polyamide film, a polyvinyl chloride film, a cellulose acetate film, or a cellophane film.
図２は、本実施形態に係る包装材料の使用例を示す概略図である。図２に示されるように、バリア膜が含まれた基材２を備える包装材料１は、例えば内容物６が収容されたカップ状の容器７の蓋材として用いられる。この場合、包装材料１の接着層３が容器７の上部に設けられた縁７ａに接着することにより、包装材料１は容器７を封止している。包装材料１のバリア膜は、内容物６の基材２内への浸透を阻害する機能、内容物６の酸化劣化を防止する機能、内容物６の水分の揮発を抑える機能、または、内容物６の光劣化を防止する機能の少なくとも一つを呈することができる。 FIG. 2 is a schematic diagram illustrating an example of use of the packaging material according to the present embodiment. As shown in FIG. 2, the packaging material 1 including the base material 2 including the barrier film is used as, for example, a lid of a cup-shaped container 7 in which contents 6 are stored. In this case, the packaging material 1 seals the container 7 by bonding the adhesive layer 3 of the packaging material 1 to the edge 7 a provided on the upper part of the container 7. The barrier film of the packaging material 1 has a function of inhibiting the penetration of the contents 6 into the base material 2, a function of preventing the contents 6 from being oxidized and degraded, a function of suppressing the volatilization of moisture of the contents 6, or a content. 6 can exhibit at least one of the functions of preventing light deterioration.
図１に戻って、接着層３は、包装材料１によって容器等の対象物を包装する際に接着性を発揮する層である。接着層３の撥水層４に対向する表面３ａは凹凸面となっている。つまり、接着層３の表面３ａには、複数の凸部１１及び複数の凹部１２が設けられている。接着層３の厚さ方向（以下、単に厚さ方向とする）に沿った凸部１１の頂点から凹部１２の底面までの距離ｄは、１μｍ以上１００μｍ以下である。本実施形態においては、凸部１１及び凹部１２は、厚さ方向において垂直な方向に延在し、距離ｄの中心を通過する基準線ｃを基準として定められる。具体的には、接着層３において、厚さ方向に沿って基準線ｃよりも基材２と反対側を凸部１１とし、基準線ｃよりも基材２側を凹部１２とする。隣接する凸部１１同士の頂点間距離は、例えば、０．１ｍｍ以上、０．３ｍｍ以上、０．４ｍｍ以上、又は０．５ｍｍ以上であり、且つ、１．０ｍｍ以下である。 Returning to FIG. 1, the adhesive layer 3 is a layer that exhibits adhesiveness when packaging an object such as a container with the packaging material 1. The surface 3a of the adhesive layer 3 facing the water-repellent layer 4 is an uneven surface. That is, a plurality of convex portions 11 and a plurality of concave portions 12 are provided on the surface 3 a of the adhesive layer 3. The distance d from the top of the projection 11 to the bottom of the recess 12 along the thickness direction of the adhesive layer 3 (hereinafter simply referred to as the thickness direction) is 1 μm or more and 100 μm or less. In the present embodiment, the protrusions 11 and the recesses 12 extend in a direction perpendicular to the thickness direction, and are determined based on a reference line c passing through the center of the distance d. Specifically, in the adhesive layer 3, the side opposite to the base line 2 with respect to the reference line c along the thickness direction is defined as a convex portion 11, and the side of the base material 2 with respect to the reference line c is defined as a concave portion 12. The distance between the vertices of the adjacent convex portions 11 is, for example, 0.1 mm or more, 0.3 mm or more, 0.4 mm or more, or 0.5 mm or more, and 1.0 mm or less.
接着層３は、主成分としてホットメルト接着剤を含んでいる。ホットメルト接着剤には、ワックス、熱可塑性樹脂、及び粘着付与材の少なくとも一種が含まれている。ホットメルト接着剤の軟化点は、例えば、７０℃以上、８０℃以上、又は１００℃以上であり、且つ、１２０℃以下である。 The adhesive layer 3 contains a hot melt adhesive as a main component. The hot melt adhesive contains at least one of a wax, a thermoplastic resin, and a tackifier. The softening point of the hot melt adhesive is, for example, 70 ° C. or more, 80 ° C. or more, or 100 ° C. or more, and 120 ° C. or less.
ワックスとしては、例えば天然ワックス又は合成ワックス等が用いられる。天然ワックスとしては、例えばキャンデリラロウ、カルナバロウ、米ぬかロウ、又はミツロウ等が挙げられる。合成ワックスとしては、例えばパラフィン、マイクロクリスタリン、ポリエチレンワックス、ポリプロピレンワックス、モンタンワックス、又はフィッシャートロプスワックス等が挙げられる。 As the wax, for example, a natural wax or a synthetic wax is used. Examples of the natural wax include candelilla wax, carnauba wax, rice bran wax, and beeswax. Examples of the synthetic wax include paraffin, microcrystalline, polyethylene wax, polypropylene wax, montan wax, and Fischer-Tropsch wax.
熱可塑性樹脂は、例えばポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、ポリスチレン（ＰＳ）、アクリロニトリル・スチレン共重合体（ＡＳ）、アクリロニトリル・ブタジエン・スチレン共重合体（ＡＢＳ）、ポリエチレン、エチレン・酢酸ビニル共重合体（ＥＶＡ）、ポリプロピレン、ポリアセタール（ＰＯＭ）、ポリメチルメタクリレート（ＰＭＭＡ）、メタクリル・スチレン共重合体（ＭＳ）、酢酸セルロース（ＣＡ）、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート、ポリエステル、ポリアミド、ポリウレタン（ＰＵ）、及びＰＣＴＦＥ，ＰＴＦＥ，ＦＥＰ，ＰＦＡ，ＥＴＦＥ，ＰＶＤＦ等のフッ素系樹脂から用途に応じて選定される。 The thermoplastic resin is, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene (PS), acrylonitrile / styrene copolymer (AS), acrylonitrile / butadiene / styrene copolymer (ABS), polyethylene, ethylene / vinyl acetate Copolymer (EVA), polypropylene, polyacetal (POM), polymethyl methacrylate (PMMA), methacryl / styrene copolymer (MS), cellulose acetate (CA), polycarbonate (PC), polyethylene terephthalate, polyester, polyamide, polyurethane (PU) and fluororesins such as PCTFE, PTFE, FEP, PFA, ETFE, and PVDF depending on the application.
粘着付与材は、ロジン誘導体、ポリテルペン樹脂、及び石油樹脂等から用途に応じて選定される。 The tackifier is selected from a rosin derivative, a polyterpene resin, a petroleum resin and the like according to the application.
図１に示されるように、撥水層４は、少なくとも撥水性を発揮する層であり、接着層３の表面３ａを覆うように形成されている。撥水層４の厚さは、例えば０．５μｍ以上２０μｍ以下である。撥水層４の厚さがこの範囲内である場合、包装材料１は、撥水性を十分に発揮できると共に、接着層３による良好な接着性を発揮する。撥水層４は、平面視にて接着層３の表面３ａの３０％以上、好ましくは５０％以上、より好ましくは７０％以上を覆うように設けられる。包装材料１が上述した容器７等と接着する場合、包装材料１の内容物と接触しないことが明らかである部位には撥水層４が設けられていなくてもよい。 As shown in FIG. 1, the water-repellent layer 4 is a layer exhibiting at least water repellency, and is formed so as to cover the surface 3 a of the adhesive layer 3. The thickness of the water-repellent layer 4 is, for example, 0.5 μm or more and 20 μm or less. When the thickness of the water repellent layer 4 is within this range, the packaging material 1 can sufficiently exhibit water repellency and exhibit good adhesiveness by the adhesive layer 3. The water-repellent layer 4 is provided so as to cover 30% or more, preferably 50% or more, more preferably 70% or more of the surface 3a of the adhesive layer 3 in plan view. When the packaging material 1 adheres to the above-described container 7 or the like, the water-repellent layer 4 may not be provided at a portion where it is apparent that the packaging material 1 does not come into contact with the contents of the packaging material 1.
本実施形態では、撥水層４の厚さは一定ではない。撥水層４を、凸部１１上に位置する第１部分２１と、凹部１２上に位置する第２部分２２とに区画した場合、第１部分２１の厚さは第２部分２２の厚さよりも小さくなっている。例えば、第１部分２１の厚さは、第２部分２２の厚さの０．１倍〜０．８倍である。撥水層４は、その少なくとも一部に空隙を有してもよい。 In the present embodiment, the thickness of the water-repellent layer 4 is not constant. When the water-repellent layer 4 is divided into a first portion 21 located on the convex portion 11 and a second portion 22 located on the concave portion 12, the thickness of the first portion 21 is larger than the thickness of the second portion 22. Is also getting smaller. For example, the thickness of the first portion 21 is 0.1 to 0.8 times the thickness of the second portion 22. The water-repellent layer 4 may have a void in at least a part thereof.
図３は、図１に示す包装材料における撥水層の具体例を示す図である。図３に示されるように、撥水層４は、第１疎水性微粒子３１及び第２疎水性微粒子３２を含む疎水性微粒子３０と、バインダー３３とを有している。撥水層４の撥水性に寄与する疎水性微粒子３０において、第２疎水性微粒子３２は、第１疎水性微粒子３１の平均粒径よりも少なくとも５０倍以上（もしくは少なくとも１００倍以上）大きい平均粒径を有する。第１疎水性微粒子３１の平均粒径は、例えば５ｎｍ以上２００ｎｍ以下であり、第２疎水性微粒子３２の平均粒径は、例えば２μｍ以上１０μｍ以下である。第１疎水性微粒子３１及び第２疎水性微粒子３２の平均粒径が上記範囲内であることにより、第１疎水性微粒子３１及び第２疎水性微粒子３２の両方がバインダー３３によって良好に固定され、撥水層４から脱落しにくくなる。加えて、第１疎水性微粒子３１及び第２疎水性微粒子３２は撥水層４中を良好に分散でき、第１疎水性微粒子３１及び第２疎水性微粒子３２をハンドリングよく用いることができる。また、撥水層４内に複数の平均粒径を有する疎水性微粒子３０を用いることにより、撥水層４内にはフラクタル構造が形成されやすくなるので、結果として撥水層４の撥水性が高まる。なお、第１疎水性微粒子３１及び第２疎水性微粒子３２を含む疎水性微粒子３０における平均粒径は、例えば５μｍ（５０００ｎｍ）以下であればよい。 FIG. 3 is a diagram showing a specific example of a water-repellent layer in the packaging material shown in FIG. As shown in FIG. 3, the water-repellent layer 4 has hydrophobic fine particles 30 including first hydrophobic fine particles 31 and second hydrophobic fine particles 32, and a binder 33. In the hydrophobic fine particles 30 that contribute to the water repellency of the water-repellent layer 4, the second hydrophobic fine particles 32 have an average particle size that is at least 50 times (or at least 100 times) larger than the average particle size of the first hydrophobic fine particles 31. Have a diameter. The average particle size of the first hydrophobic fine particles 31 is, for example, 5 nm or more and 200 nm or less, and the average particle size of the second hydrophobic fine particles 32 is, for example, 2 μm or more and 10 μm or less. When the average particle diameter of the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 is within the above range, both the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 are favorably fixed by the binder 33, It becomes difficult to fall off from the water repellent layer 4. In addition, the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 can be dispersed well in the water-repellent layer 4, and the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 can be used with good handling. Further, by using the hydrophobic fine particles 30 having a plurality of average particle diameters in the water-repellent layer 4, a fractal structure is easily formed in the water-repellent layer 4, and as a result, the water repellency of the water-repellent layer 4 is improved. Increase. The average particle size of the hydrophobic fine particles 30 including the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 may be, for example, 5 μm (5000 nm) or less.
第１疎水性微粒子３１の平均粒径は、撥水層４の表面に露出している第１疎水性微粒子３１の粒径から算出される。第１疎水性微粒子３１の粒径は、例えば走査電子顕微鏡（ＳＥＭ）による目視観察にて計測された値と定義する。第１疎水性微粒子３１の平均粒径の測定法として、まずＳＥＭにて任意の５箇所を測定する。次に、各観察表面にて確認される疎水性微粒子１００個の粒径を測定する。そして、各観察表面の全計測値の平均値を算出することによって、第１疎水性微粒子３１の平均粒径を求める。なお、第１疎水性微粒子３１の粒径は、透過電子顕微鏡（ＴＥＭ）を用いて測定してもよい。 The average particle size of the first hydrophobic fine particles 31 is calculated from the particle size of the first hydrophobic fine particles 31 exposed on the surface of the water-repellent layer 4. The particle size of the first hydrophobic fine particles 31 is defined as a value measured by visual observation using, for example, a scanning electron microscope (SEM). As a method for measuring the average particle diameter of the first hydrophobic fine particles 31, first, five arbitrary points are measured by SEM. Next, the particle diameter of 100 hydrophobic fine particles confirmed on each observation surface is measured. Then, by calculating the average value of all the measured values of each observation surface, the average particle size of the first hydrophobic fine particles 31 is obtained. The particle size of the first hydrophobic fine particles 31 may be measured using a transmission electron microscope (TEM).
また、第２疎水性微粒子３２の平均粒径は、レーザ回折・散乱法による粒度分布測定により算出される。この場合、第２疎水性微粒子３２を分散溶媒であるメタノールに分散した液体にレーザ光を照射することによって発生する回折・散乱光の強度分布を測定し、当該測定値から第２疎水性微粒子３２の平均粒径を求める。 The average particle size of the second hydrophobic fine particles 32 is calculated by measuring the particle size distribution by a laser diffraction / scattering method. In this case, the intensity distribution of diffraction / scattered light generated by irradiating a laser beam to a liquid in which the second hydrophobic fine particles 32 are dispersed in methanol as a dispersion solvent is measured, and the second hydrophobic fine particles 32 are determined from the measured values. Is determined.
第１疎水性微粒子３１及び第２疎水性微粒子３２は、いずれも無機酸化物を主成分としている。この無機酸化物は、例えば酸化珪素（シリカ）、酸化アルミニウム、酸化チタン、及び酸化マグネシウムの内少なくとも１種を含んでいる。無機酸化物が酸化珪素である場合、合成シリカ又は天然シリカが用いられる。合成シリカは、例えば燃焼法若しくはアーク法等の乾式製法、又は、沈殿法若しくはゲル法等の湿式製法によって合成される。一般的に、乾式製法により製造された合成シリカの平均粒径は、湿式製法により製造された合成シリカの平均粒径よりも小さくなる。したがって、第１疎水性微粒子３１は乾式製法により形成され、第２疎水性微粒子３２は湿式製法により形成されてもよい。 Each of the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 has an inorganic oxide as a main component. The inorganic oxide contains, for example, at least one of silicon oxide (silica), aluminum oxide, titanium oxide, and magnesium oxide. When the inorganic oxide is silicon oxide, synthetic silica or natural silica is used. Synthetic silica is synthesized by, for example, a dry method such as a combustion method or an arc method, or a wet method such as a precipitation method or a gel method. Generally, the average particle size of the synthetic silica produced by the dry process is smaller than the average particle size of the synthetic silica produced by the wet process. Therefore, the first hydrophobic fine particles 31 may be formed by a dry manufacturing method, and the second hydrophobic fine particles 32 may be formed by a wet manufacturing method.
第１疎水性微粒子３１及び第２疎水性微粒子３２の表面には疎水化処理が施されている。疎水化処理としては、乾式法、湿式法等が挙げられる。無機酸化物を主成分とした微粒子の全面を処理するために、ＣＶＤ法又はプラズマ法等による乾式法を用いてもよい。このような疎水化処理を行うことによって、微粒子の表面に疎水性官能基を結合させ、付着防止機能を付与している。 The surfaces of the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 are subjected to a hydrophobic treatment. Examples of the hydrophobic treatment include a dry method and a wet method. In order to treat the entire surface of the fine particles containing an inorganic oxide as a main component, a dry method such as a CVD method or a plasma method may be used. By performing such a hydrophobic treatment, a hydrophobic functional group is bonded to the surface of the fine particles, and an adhesion preventing function is provided.
微粒子の表面に結合する疎水性官能基は、例えばジメチルシリル基（（ＣＨ３）２Ｓｉ（Ｏ−Ｒ）２）、トリメチルシリル基（（ＣＨ３）３Ｓｉ（Ｏ−Ｒ））、ジメチルポリシロキサン基（（ＣＨ３）２−Ｓｉ−Ｏ−Ｓｉ（Ｏ−Ｒ）３）、ジメチルシロキサン基、アミノアルキルシリル基、アルキルシリル基、又はメタクリルシリル基である。このような官能基を微粒子の表面に結合させることにより、撥水層４の臨界表面張力（表面エネルギー）を小さくする。なお、Ｒは低級アルキル基であり、例えば炭素数が１〜４のアルキル基である。 Examples of the hydrophobic functional group bonded to the surface of the fine particles include a dimethylsilyl group ((CH 3 ) 2 Si (OR) 2 ), a trimethylsilyl group ((CH 3 ) 3 Si (OR)), and dimethylpolysiloxane. Group ((CH 3 ) 2 —Si—O—Si (OR) 3 ), a dimethylsiloxane group, an aminoalkylsilyl group, an alkylsilyl group, or a methacrylsilyl group. By bonding such a functional group to the surface of the fine particles, the critical surface tension (surface energy) of the water-repellent layer 4 is reduced. In addition, R is a lower alkyl group, for example, an alkyl group having 1 to 4 carbon atoms.
バインダー３３は、撥水層４内の第１疎水性微粒子３１及び第２疎水性微粒子３２を強固に固定するために用いられる物質である。このバインダー３３として、例えば１種以上の金属アルコキシドが用いられる。この金属アルコキシドは加水分解物でもよい。この場合、金属アルコキシドの加水分解物と、水／アルコール混合溶媒とが含まれるバインダーであってもよい。また、必要に応じてシランカップリング剤、又はバインダー３３の反応を制御するための触媒等の添加剤がさらに含まれてもよい。 The binder 33 is a substance used for firmly fixing the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 in the water-repellent layer 4. As the binder 33, for example, one or more metal alkoxides are used. The metal alkoxide may be a hydrolyzate. In this case, a binder containing a hydrolyzate of a metal alkoxide and a mixed solvent of water / alcohol may be used. If necessary, an additive such as a silane coupling agent or a catalyst for controlling the reaction of the binder 33 may be further included.
金属アルコキシドは、Ｍ（ＯＲ）ｎで示される。Ｍは金属原子であり、ｎは自然数である。Ｍは、例えば、Ｌｉ、Ｎａ、Ｃｕ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｇａ、Ｙ、Ｓｉ、Ｇｅ、Ｐｂ、Ｐ、Ｓｂ、Ｔａ、Ｗ、Ｌａ、Ｎｄ、Ｔｉ等である。ｎはＭの原子価である。Ｒは低級アルキル基であり、例えば炭素数が１〜４のアルキル基である。 Metal alkoxides are denoted by M (OR) n. M is a metal atom, and n is a natural number. M is, for example, Li, Na, Cu, Mg, Ca, Sr, Ba, Zn, B, Al, Ga, Y, Si, Ge, Pb, P, Sb, Ta, W, La, Nd, Ti, etc. is there. n is the valence of M. R is a lower alkyl group, for example, an alkyl group having 1 to 4 carbon atoms.
金属アルキコシドの具体例として、例えば、メチルトリメトキシシラン等のアルコキシシラン、アルミニウムプロポキシド、チタンイソプロポキシド、亜鉛ｔ−ブトキシド、亜鉛ｎ−ブトキシド、カルシウムエトキシド、鉄エトキシド、バナジウムイソプロポキシド、錫ｔ−ブトキシド、リチウムエトキシド、ベリリウムエトキシド、ホウ素エトキシド、燐エトキシド、燐メトキシド、マグネシウムメトキシド、又はマグネシウムエトキシド等が挙げられる。本実施形態では、上記金属アルコキシドの中で、例えばテトラエトキシシラン（ＴＥＯＳ）、トリイソプロポキシアルミニウム、及び３−グリシドキシプロピルトリメトキシシランの少なくとも一種を用いている。 Specific examples of metal alkoxysides include, for example, alkoxysilanes such as methyltrimethoxysilane, aluminum propoxide, titanium isopropoxide, zinc t-butoxide, zinc n-butoxide, calcium ethoxide, iron ethoxide, vanadium isopropoxide, and tin. Examples include t-butoxide, lithium ethoxide, beryllium ethoxide, boron ethoxide, phosphorus ethoxide, phosphorus methoxide, magnesium methoxide, and magnesium ethoxide. In the present embodiment, among the metal alkoxides, for example, at least one of tetraethoxysilane (TEOS), triisopropoxyaluminum, and 3-glycidoxypropyltrimethoxysilane is used.
また、バインダー３３として、例えばアクリル樹脂、メラミン樹脂、アミノ樹脂、エポキシ樹脂、スチレン樹脂、セルロース樹脂、塩化ビニル樹脂、エチレン酢酸ビニル共重合体、塩酢ビ樹脂（塩化ビニルと酢酸ビニルとの共重合物）、ＳＢＲ樹脂、メラミン樹脂、フェノール樹脂、シリコーン樹脂、ポリウレタン、ポリエチレン、ポリプロピレン、ポリエステル、又はポリビニルアルコール等の少なくとも一種が用いられてもよい。 Further, as the binder 33, for example, an acrylic resin, a melamine resin, an amino resin, an epoxy resin, a styrene resin, a cellulose resin, a vinyl chloride resin, an ethylene-vinyl acetate copolymer, a polyvinyl chloride resin (copolymerization of vinyl chloride and vinyl acetate) ), SBR resin, melamine resin, phenol resin, silicone resin, polyurethane, polyethylene, polypropylene, polyester, polyvinyl alcohol, or the like.
撥水層４において、疎水性微粒子３０とバインダー３３との質量比は、特に限定されない。本実施形態では、上記質量比（疎水性微粒子：バインダー）は、例えば３０：７０〜９０：１０である。換言すると、撥水層４において、疎水性微粒子３０とバインダー３３との合計質量に対する疎水性微粒子３０の質量の割合は、例えば３０％以上９０％以下の任意の値である。したがって、撥水層４において、疎水性微粒子３０とバインダー３３との質量比は、３０：７０〜８０：２０でもよく、３０：７０〜７０：３０でもよく、３０：７０〜６０：４０でもよく、３０：７０〜５０：５０でもよく、３０：７０〜４０：６０でもよく、４０：６０〜９０：１０でもよく、４０：６０〜８０：２０でもよく、５０：５０〜９０：１０でもよく、５０：５０〜８０：２０でもよく、５０：５０〜７０：３０でもよく、５０：５０〜６０：４０でもよく、６０：４０〜９０：１０でもよく、７０：３０〜９０：１０でもよい。なお、撥水層４における疎水性微粒子３０の割合を大きくし、当該撥水層４の撥水性をより発揮させるために、疎水性微粒子３０とバインダー３３との合計質量に対する疎水性微粒子３０の質量の割合は、３０％よりも大きくてもよい。 In the water-repellent layer 4, the mass ratio between the hydrophobic fine particles 30 and the binder 33 is not particularly limited. In the present embodiment, the mass ratio (hydrophobic fine particles: binder) is, for example, 30:70 to 90:10. In other words, in the water-repellent layer 4, the ratio of the mass of the hydrophobic fine particles 30 to the total mass of the hydrophobic fine particles 30 and the binder 33 is an arbitrary value of, for example, 30% or more and 90% or less. Therefore, in the water-repellent layer 4, the mass ratio of the hydrophobic fine particles 30 to the binder 33 may be 30:70 to 80:20, 30:70 to 70:30, or 30:70 to 60:40. 30:70 to 50:50, 30:70 to 40:60, 40:60 to 90:10, 40:60 to 80:20, 50:50 to 90:10 , 50: 50-80: 30, 50: 50-70: 30, 50: 50-60: 40, 60: 40-90: 10, 70: 30-90: 10. . In order to increase the ratio of the hydrophobic fine particles 30 in the water-repellent layer 4 and to make the water-repellent layer 4 exhibit more water repellency, the mass of the hydrophobic fine particles 30 with respect to the total mass of the hydrophobic fine particles 30 and the binder 33 is increased. May be greater than 30%.
疎水性微粒子３０において、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比は、特に限定されない。本実施形態では、上記質量比（第１疎水性微粒子：第２疎水性微粒子）は、例えば５０：５０〜９０：１０である。換言すると、疎水性微粒子３０において、第１疎水性微粒子３１と第２疎水性微粒子３２との合計質量に対する第２疎水性微粒子３２の質量の割合は、１０％以上５０％以下の任意の値である。したがって、疎水性微粒子３０において、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比は、５０：５０〜８０：２０でもよく、５０：５０〜７０：３０でもよく、６０：４０〜７０：３０でもよい。第１疎水性微粒子３１と第２疎水性微粒子３２との質量比は、疎水性微粒子３０とバインダー３３との質量比に応じて調整されてもよい。 In the hydrophobic fine particles 30, the mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 is not particularly limited. In the present embodiment, the mass ratio (first hydrophobic fine particles: second hydrophobic fine particles) is, for example, 50:50 to 90:10. In other words, in the hydrophobic fine particles 30, the ratio of the mass of the second hydrophobic fine particles 32 to the total mass of the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 is an arbitrary value of 10% or more and 50% or less. is there. Therefore, in the hydrophobic fine particles 30, the mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 may be 50:50 to 80:20, may be 50:50 to 70:30, and may be 60:40. It may be up to 70:30. The mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 may be adjusted according to the mass ratio between the hydrophobic fine particles 30 and the binder 33.
上述したように第２疎水性微粒子３２の平均粒径は、第１疎水性微粒子３１の平均粒径よりも比較的大きい。このため、撥水層４において第２疎水性微粒子３２は比較的脱落しやすくなっている。そこで、撥水層４では、バインダー３３の質量を第２疎水性微粒子３２の質量よりも大きくなるようにしている。これにより、第２疎水性微粒子３２がバインダー３３により良好に固定される。より強固に第２疎水性微粒子３２をバインダー３３により固定するために、撥水層４において、バインダー３３の質量に対する第２疎水性微粒子３２の質量の割合が７０％未満であってもよい。 As described above, the average particle size of the second hydrophobic fine particles 32 is relatively larger than the average particle size of the first hydrophobic fine particles 31. For this reason, the second hydrophobic fine particles 32 in the water-repellent layer 4 are relatively easily dropped. Therefore, in the water-repellent layer 4, the mass of the binder 33 is set to be larger than the mass of the second hydrophobic fine particles 32. As a result, the second hydrophobic fine particles 32 are satisfactorily fixed by the binder 33. In order to more firmly fix the second hydrophobic fine particles 32 with the binder 33, the ratio of the mass of the second hydrophobic fine particles 32 to the mass of the binder 33 in the water-repellent layer 4 may be less than 70%.
次に、本実施形態に係る包装材料１の形成方法の一例、及び該包装材料１による容器７の封止方法の一例を、図１及び図２を用いながら説明する。まず、基材２を準備する。基材２は、単層でもよく、接着剤によって互いに接着された積層体でもよい。もしくは、基材２は、例えばＰＥＴフィルム等のプラスチックフィルムに金属又は金属酸化物等が蒸着されたフィルムでもよい。 Next, an example of a method of forming the packaging material 1 according to the present embodiment and an example of a method of sealing the container 7 with the packaging material 1 will be described with reference to FIGS. First, the base material 2 is prepared. The substrate 2 may be a single layer or a laminate bonded to each other by an adhesive. Alternatively, the substrate 2 may be a film in which metal or metal oxide is deposited on a plastic film such as a PET film.
次に、基材２の一方の主面上に接着層３を形成する。例えば、加熱されたグラビア版を用いたダイレクトグラビア方式で、上述したホットメルト接着剤を基材２上にコーティングする。これにより、凹凸面である表面３ａを有する接着層３を形成する。 Next, the adhesive layer 3 is formed on one main surface of the substrate 2. For example, the above-described hot melt adhesive is coated on the base material 2 by a direct gravure method using a heated gravure plate. Thus, the adhesive layer 3 having the surface 3a that is an uneven surface is formed.
次に、第１疎水性微粒子３１、第２疎水性微粒子３２、及びバインダー３３が混入された液体を準備する。この液体の溶媒は、例えばメタノール、エタノール、プロパノール、若しくはイソプロピルアルコール（ＩＰＡ）等のアルコール溶媒、酢酸エチル、トルエン、アセトン等の有機溶媒、又は水である。この液体は、接着層３を形成する前に準備してもよい。 Next, a liquid in which the first hydrophobic fine particles 31, the second hydrophobic fine particles 32, and the binder 33 are mixed is prepared. The liquid solvent is, for example, an alcohol solvent such as methanol, ethanol, propanol, or isopropyl alcohol (IPA), an organic solvent such as ethyl acetate, toluene, or acetone, or water. This liquid may be prepared before forming the adhesive layer 3.
次に、上記液体を接着層３の表面３ａにコーティングする。例えば、グラビアコート、バーコート、キスリバースコート、ダイコート、ドクターブレードコート、刷毛塗り、ディップコート、スプレーコート、スピンコート、又は押出しラミネーション等の公知の方法によって、上記液体を表面３ａにコーティングする。 Next, the liquid is coated on the surface 3 a of the adhesive layer 3. For example, the surface 3a is coated with the liquid by a known method such as gravure coating, bar coating, kiss reverse coating, die coating, doctor blade coating, brush coating, dip coating, spray coating, spin coating, or extrusion lamination.
次に、上記液体の溶媒を除去することにより、接着層３上に空隙を有する撥水層４を形成する。例えば、ヒータ若しくは温風等を用いた加熱乾燥、又は自然乾燥によって、上記溶媒を除去する。以上により、基材２、接着層３、及び撥水層４を有する包装材料１を形成する。 Next, the water-repellent layer 4 having voids is formed on the adhesive layer 3 by removing the liquid solvent. For example, the solvent is removed by heating drying using a heater or hot air, or by natural drying. Thus, the packaging material 1 having the base material 2, the adhesive layer 3, and the water-repellent layer 4 is formed.
次に、形成した包装材料１の撥水層４側と容器７とを対向させ、撥水層４と容器７の縁７ａとを接触させる。そして、包装材料１を加熱すると共に容器７に押し付けることによって、包装材料１の軟化した接着層３が容器７の縁７ａに接着する。具体的には、包装材料１を容器７に押し付ける際に、撥水層４において容器７の縁７ａに接する部分が割れ、クラックが生じる。このクラックから溶融したホットメルト接着剤が流れ込むことにより、接着層３が容器７の縁７ａに接着する。これにより、図２に示される内容物６が封止された包装容器１００を形成する。なお、撥水層４において容器７の縁７ａに接する部分の殆どは、ホットメルト接着剤の流入に伴って縁７ａの外部に押し出される。 Next, the water repellent layer 4 side of the formed packaging material 1 and the container 7 are opposed to each other, and the water repellent layer 4 and the edge 7a of the container 7 are brought into contact with each other. Then, by heating the packaging material 1 and pressing it against the container 7, the softened adhesive layer 3 of the packaging material 1 adheres to the edge 7 a of the container 7. Specifically, when the packaging material 1 is pressed against the container 7, a portion of the water-repellent layer 4 that is in contact with the edge 7 a of the container 7 is broken, and a crack occurs. When the molten hot melt adhesive flows from the crack, the adhesive layer 3 adheres to the edge 7 a of the container 7. Thereby, the packaging container 100 in which the contents 6 shown in FIG. 2 are sealed is formed. Most of the portion of the water-repellent layer 4 in contact with the edge 7a of the container 7 is pushed out of the edge 7a with the inflow of the hot melt adhesive.
以上に説明した本実施形態に係る包装材料１では、撥水層４は、第１疎水性微粒子３１及び第２疎水性微粒子３２を含む疎水性微粒子３０と、バインダー３３とを有している。また、撥水層４において、バインダー３３の質量は、第２疎水性微粒子３２の質量よりも大きい。このような条件を満たす包装材料１の撥水層４においては、第１疎水性微粒子３１及び第２疎水性微粒子３２がバインダー３３によって良好に固定されるので、当該撥水層４には割れ等が生じにくい。また、第１疎水性微粒子３１の粉落ちを抑制できるだけでなく、第１疎水性微粒子３１の平均粒径よりも大きい平均粒径を有する第２疎水性微粒子３２の粉落ちも発生しにくくなる。このため、撥水層４を構成する疎水性微粒子３０（特に第２疎水性微粒子３２）によって、当該撥水層４は、良好な撥水性を発揮できる。したがって、本実施形態に係る包装材料１によれば、良好な撥水性を発揮できると共に、粉落ちを抑制できる。 In the packaging material 1 according to the present embodiment described above, the water-repellent layer 4 has the hydrophobic fine particles 30 including the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32, and the binder 33. In the water-repellent layer 4, the mass of the binder 33 is larger than the mass of the second hydrophobic fine particles 32. In the water-repellent layer 4 of the packaging material 1 that satisfies such conditions, the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 are fixed well by the binder 33. Is unlikely to occur. Further, not only can the first hydrophobic fine particles 31 be prevented from powder falling off, but also the second hydrophobic fine particles 32 having an average particle diameter larger than the average particle diameter of the first hydrophobic fine particles 31 are less likely to fall off. For this reason, the hydrophobic fine particles 30 (particularly, the second hydrophobic fine particles 32) constituting the water repellent layer 4 allow the water repellent layer 4 to exhibit good water repellency. Therefore, according to the packaging material 1 according to the present embodiment, good water repellency can be exhibited, and powder falling can be suppressed.
また、疎水性微粒子３０とバインダー３３との合計質量に対する疎水性微粒子３０の質量の割合は、３０％よりも大きくてもよい。この場合、撥水層４における疎水性微粒子３０の割合が大きくなるので、撥水層４がより良好な撥水性を発揮できる。 Further, the ratio of the mass of the hydrophobic fine particles 30 to the total mass of the hydrophobic fine particles 30 and the binder 33 may be larger than 30%. In this case, since the ratio of the hydrophobic fine particles 30 in the water-repellent layer 4 is increased, the water-repellent layer 4 can exhibit better water repellency.
また、バインダー３３の質量に対する第２疎水性微粒子３２の質量の割合が７０％未満であってもよい。この場合、バインダー３３によって第２疎水性微粒子３２を確実に固定できるので、第２疎水性微粒子３２の粉落ちを抑制できる。 Further, the ratio of the mass of the second hydrophobic fine particles 32 to the mass of the binder 33 may be less than 70%. In this case, since the second hydrophobic fine particles 32 can be reliably fixed by the binder 33, powder dropping of the second hydrophobic fine particles 32 can be suppressed.
また、第２疎水性微粒子３２の平均粒径は、２μｍ以上１０μｍ以下であってもよい。この場合、第２疎水性微粒子３２の粉落ちを抑制しつつ、撥水層４の撥水性を向上できる。 The average particle size of the second hydrophobic fine particles 32 may be 2 μm or more and 10 μm or less. In this case, it is possible to improve the water repellency of the water repellent layer 4 while suppressing the second hydrophobic fine particles 32 from falling off.
また、撥水層４の厚さは、０．５μｍ以上２０μｍ以下でもよい。この場合、撥水層４は、撥水性を良好に発揮できる。 Further, the thickness of the water-repellent layer 4 may be 0.5 μm or more and 20 μm or less. In this case, the water repellent layer 4 can exhibit good water repellency.
また、撥水層４に対向する接着層３の表面３ａは、凸部１１及び凹部１２が設けられた凹凸面であり、撥水層４において、凸部１１上の第１部分２１の厚さは、凹部１２上の第２部分２２の厚さよりも小さくてもよい。この場合、撥水層４は、接着層３の表面３ａに沿った形状を有するので、撥水層４の構造に起因した撥水性が向上する。また、第１部分２１に含まれる疎水性微粒子３０はバインダー３３によって結合しやすくなるので、撥水層４の第１部分２１における膜強度を向上できる。 The surface 3a of the adhesive layer 3 facing the water-repellent layer 4 is an uneven surface provided with the convex portions 11 and the concave portions 12, and the thickness of the first portion 21 on the convex portions 11 in the water-repellent layer 4. May be smaller than the thickness of the second portion 22 on the recess 12. In this case, since the water repellent layer 4 has a shape along the surface 3a of the adhesive layer 3, the water repellency due to the structure of the water repellent layer 4 is improved. In addition, since the hydrophobic fine particles 30 included in the first portion 21 are easily bonded by the binder 33, the film strength of the first portion 21 of the water-repellent layer 4 can be improved.
また、図２に示される包装容器１００は、本実施形態に係る包装材料１を蓋材として用いたものであってもよい。この場合、接着層３の表面３ａ上に好適に維持される撥水層４によって、容器７中に収容された内容物６が包装材料１に付着することを良好に抑制できる。また、落下等の衝撃、積載における加圧、及び保管時の高温等の環境に耐え、良好なシール性を発揮する包装容器１００を得ることができる。また、内容物６を使用する時は、包装材料１を容器７から容易に剥離して開封できる機能を有する。 The packaging container 100 shown in FIG. 2 may use the packaging material 1 according to the present embodiment as a lid. In this case, the water-repellent layer 4 suitably maintained on the surface 3a of the adhesive layer 3 can favorably prevent the contents 6 accommodated in the container 7 from adhering to the packaging material 1. Further, it is possible to obtain the packaging container 100 that withstands an environment such as an impact such as a drop, a pressurization during loading, and a high temperature during storage, and exhibits a good sealing property. When the contents 6 are used, the packaging material 1 has a function of easily peeling off and opening the packaging material 1 from the container 7.
本発明は、上記実施形態に限定されるものではない。例えば、包装材料１の接着層３の表面３ａは凹凸面でなくてもよく、平坦面であってもよい。 The present invention is not limited to the above embodiment. For example, the surface 3a of the adhesive layer 3 of the packaging material 1 may not be an uneven surface but may be a flat surface.
本発明を以下の実施例によりさらに詳細に説明するが、本発明はこれらの例に限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
（実施例１）
厚み１２μｍのＰＥＴフィルムの片面に、厚さ７μｍのアルミニウム箔をドライラミネートにて貼り付けた。そして、アルミニウム箔に、厚さ２５μｍの低密度ポリエチレンフィルム（ＬＤＰＥフィルム）を押し出し法にて成膜することにより、図１に示される基材２を形成した。この基材２のＬＤＰＥフィルム上に、接着層３を形成した。この接着層３は、７５線／インチのグラビア板を用いたグラビアコートによって形成されており、接着層３の表面３ａに形成された凸部１１の頂点間距離を約０．５ｍｍとした。また、接着層３を構成するホットメルト樹脂として、東洋アドレ株式会社製トヨメルトＨ２３２を用いた。
(Example 1)
An aluminum foil having a thickness of 7 μm was attached to one side of a PET film having a thickness of 12 μm by dry lamination. Then, a low-density polyethylene film (LDPE film) having a thickness of 25 μm was formed on an aluminum foil by an extrusion method to form the substrate 2 shown in FIG. The adhesive layer 3 was formed on the LDPE film of the substrate 2. The adhesive layer 3 is formed by gravure coating using a gravure plate of 75 lines / inch, and the distance between the vertices of the protrusions 11 formed on the surface 3a of the adhesive layer 3 is about 0.5 mm. In addition, Toyo Melt H232 manufactured by Toyo Adress Co., Ltd. was used as a hot melt resin constituting the adhesive layer 3.
次に、微粒子として、平均粒径が１２ｎｍである第１シリカ微粒子（製品名：ＲＹ２００Ｓ、日本アエロジル株式会社製）と、平均粒径が４μｍである第２シリカ微粒子（製品名：サイロホ−ビック２００、富士シリシア化学株式会社製）とを準備した。これらのシリカ微粒子と、金属アルコキシド加水分解液とを２−プロパノールに加えて分散させることにより、第１シリカ微粒子及び第２シリカ微粒子が分散した液体を作成した。これにより、第１シリカ微粒子及び第２シリカ微粒子の表面には、ジメチルポリシロキサンにより疎水化処理が施され、それぞれ第１疎水性微粒子３１及び第２疎水性微粒子３２とした。また、金属アルコキシド加水分解液は、バインダー３３として機能するテトラエトキシシラン（ＴＥＯＳ）を、０．１規定濃度の塩酸溶液に加えて加水分解させることによって形成した。上記液体では、下記表１に示されるように、第１疎水性微粒子３１と第２疎水性微粒子３２とを併せた疎水性微粒子３０と、バインダー３３との質量比は、５０：５０となるように調整した。また、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比は、５０：５０となるように調整した。このため、バインダー３３と第２疎水性微粒子３２との質量比（バインダー：第２疎水性微粒子）は、５０：（５０／２）＝５０：２５となるように調整した。すなわち、撥水層４において、バインダー３３の質量に対する第２疎水性微粒子３２の質量の割合は５０％であり、バインダー３３の質量は第２疎水性微粒子３２の質量よりも大きくなるように調整した。 Next, as fine particles, first silica fine particles having an average particle diameter of 12 nm (product name: RY200S, manufactured by Nippon Aerosil Co., Ltd.) and second silica fine particles having an average particle diameter of 4 μm (product name: Silophobic 200) And Fuji Silysia Chemical Ltd.). These silica fine particles and the metal alkoxide hydrolyzate were added to 2-propanol and dispersed to prepare a liquid in which the first silica fine particles and the second silica fine particles were dispersed. As a result, the surfaces of the first silica fine particles and the second silica fine particles were subjected to a hydrophobic treatment with dimethylpolysiloxane to obtain first hydrophobic fine particles 31 and second hydrophobic fine particles 32, respectively. The metal alkoxide hydrolyzate was formed by adding tetraethoxysilane (TEOS), which functions as the binder 33, to a 0.1N hydrochloric acid solution and hydrolyzing it. In the above liquid, as shown in Table 1 below, the mass ratio between the hydrophobic fine particles 30 including the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 and the binder 33 is 50:50. Was adjusted. The mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 was adjusted to be 50:50. For this reason, the mass ratio of the binder 33 to the second hydrophobic fine particles 32 (binder: second hydrophobic fine particles) was adjusted to be 50: (50/2) = 50: 25. That is, in the water-repellent layer 4, the ratio of the mass of the second hydrophobic fine particles 32 to the mass of the binder 33 is 50%, and the mass of the binder 33 is adjusted to be larger than the mass of the second hydrophobic fine particles 32. .
次に、上記液体を接着層３の表面３ａに塗布した後、６０℃の熱風に曝して２−プロパノール等の溶媒を蒸発させた。これにより、撥水層４が接着層３上に形成された包装材料１を得た。上記液体内の固形分塗布量が２ｇ／ｍ２になるように、該液体をマイクログラビアコートによって塗布した。 Next, after applying the above liquid to the surface 3a of the adhesive layer 3, it was exposed to hot air at 60 ° C. to evaporate a solvent such as 2-propanol. Thereby, the packaging material 1 in which the water-repellent layer 4 was formed on the adhesive layer 3 was obtained. The liquid was applied by microgravure coating so that the solid applied amount in the liquid was 2 g / m 2 .
（実施例２〜５，７〜１０ならびに参考例６，１１〜１３）
実施例２〜５，７〜１０ならびに参考例６，１１〜１３のそれぞれでは、疎水性微粒子３０とバインダー３３との質量比、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比、及びバインダー３３の質量に対する第２疎水性微粒子３２の質量の割合を、下記表１に示される通りに調整した以外は、実施例１と同様にして包装材料１を形成した。なお、実施例２〜５，７〜１０ならびに参考例６，１１〜１３のそれぞれにおいて、実施例１と同様に、バインダー３３の質量は第２疎水性微粒子３２の質量よりも大きくなるように調整した。
(Examples 2 to 5, 7 to 10 and Reference Examples 6, 11 to 13)
In each of Examples 2 to 5, 7 to 10 and Reference Examples 6, 11 to 13, the mass ratio between the hydrophobic fine particles 30 and the binder 33 and the mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 A packaging material 1 was formed in the same manner as in Example 1 except that the mass ratio of the second hydrophobic fine particles 32 to the mass of the binder 33 was adjusted as shown in Table 1 below. In each of Examples 2 to 5, 7 to 10, and Reference Examples 6, 11 to 13, the mass of the binder 33 was adjusted so as to be larger than the mass of the second hydrophobic fine particles 32, as in Example 1. did.
（比較例１）
下記表２に示されるように、疎水性微粒子３０とバインダー３３との質量比を１００：０となるように調整したこと（すなわち、バインダー３３を用いなかったこと）、及び第１疎水性微粒子３１と第２疎水性微粒子３２との質量比を１００：０となるように調整したこと（すなわち、第２疎水性微粒子３２のみを用いたこと）以外は、実施例１と同様にして包装材料１を形成した。
(Comparative Example 1)
As shown in Table 2 below, the mass ratio between the hydrophobic fine particles 30 and the binder 33 was adjusted to be 100: 0 (that is, the binder 33 was not used), and the first hydrophobic fine particles 31 were used. The packaging material 1 was prepared in the same manner as in Example 1 except that the mass ratio between the first hydrophobic fine particles 32 and the second hydrophobic fine particles 32 was adjusted to be 100: 0 (that is, only the second hydrophobic fine particles 32 were used). Was formed.
（比較例２〜１１）
比較例２〜１１のそれぞれでは、疎水性微粒子３０とバインダー３３との質量比、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比、及びバインダー３３の質量に対する第２疎水性微粒子３２の質量の割合を、下記表２に示される通りに調整した以外は、実施例１と同様にして包装材料１を形成した。以下に、各比較例にて実施例１と大きく異なる点を説明する。
(Comparative Examples 2 to 11)
In each of Comparative Examples 2 to 11, the mass ratio between the hydrophobic fine particles 30 and the binder 33, the mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32, and the second hydrophobic fine particles with respect to the mass of the binder 33 A packaging material 1 was formed in the same manner as in Example 1 except that the mass ratio of 32 was adjusted as shown in Table 2 below. Hereinafter, points that are significantly different from Example 1 in each comparative example will be described.
比較例２〜４ではバインダー３３を用いずに包装材料１を形成し、比較例４〜９では第２疎水性微粒子３２を用いずに包装材料１を形成した。また、比較例１０では、疎水性微粒子３０とバインダー３３との質量比を７０：３０に調整すると共に、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比を５０：５０に調整して包装材料１を形成した。比較例１１では、疎水性微粒子３０とバインダー３３との質量比を８０：２０に調整すると共に、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比を５０：５０に調整して包装材料１を形成した。比較例１０，１１では、バインダー３３の質量が第２疎水性微粒子３２の質量よりも小さくなるように調整した。 In Comparative Examples 2 to 4, the packaging material 1 was formed without using the binder 33, and in Comparative Examples 4 to 9, the packaging material 1 was formed without using the second hydrophobic fine particles 32. In Comparative Example 10, the mass ratio between the hydrophobic fine particles 30 and the binder 33 was adjusted to 70:30, and the mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 was adjusted to 50:50. Thus, a packaging material 1 was formed. In Comparative Example 11, the mass ratio between the hydrophobic fine particles 30 and the binder 33 was adjusted to 80:20, and the mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32 was adjusted to 50:50. A packaging material 1 was formed. In Comparative Examples 10 and 11, the mass of the binder 33 was adjusted to be smaller than the mass of the second hydrophobic fine particles 32.
（評価方法）
実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１の包装材料１を下記の方法で試験し、評価した。
(Evaluation method)
The packaging materials 1 of Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11 were tested and evaluated by the following methods.
（撥水層の表面観察）
図４は、実施例１の包装材料の撥水層側の面の凹部を走査型電子顕微鏡（株式会社日立ハイテクノロジーズ製Ｓ−４８００）によって撮影した写真である。図４の倍率は１０００倍である。図４に示されるように、撥水層４の表面には、第２疎水性微粒子３２が複数確認された。これらの第２疎水性微粒子３２の形状は不定形であるので、図４においては、当該第２疎水性微粒子３２は略板状に観察された。
(Observation of the surface of the water-repellent layer)
FIG. 4 is a photograph taken by a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) of the concave portion on the water-repellent layer side of the packaging material of Example 1. The magnification in FIG. 4 is 1000 times. As shown in FIG. 4, a plurality of second hydrophobic fine particles 32 were confirmed on the surface of the water-repellent layer 4. Since the shape of the second hydrophobic fine particles 32 is indefinite, in FIG. 4, the second hydrophobic fine particles 32 are observed in a substantially plate shape.
（撥水性試験）
上述の実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１の包装材料１において、撥水層４が設けられた側の撥水性を確認した。まず、ヨーグルト（ソフトタイプヨーグルト ブルーベリー味）が収容されたカップ状のプラスチック容器を、包装材料１により封止して密閉した。具体的には、包装材料１の撥水層４を上記容器に接触させ、５０ｋｇ加重、１９０℃、１秒の条件にて、上記容器の上面に設けられた縁に包装材料１を熱封止した。包装材料１によって封止された各容器を５℃まで冷却した後、包装材料１が下方に位置するように当該容器を反転させて６０分間平坦な台に静置した。反転した容器を６０分間静置させた後、当該容器を正転させてすぐに包装材料１を容器から剥がした。包装材料１を容器から完全に剥がした際にヨーグルトが包装材料１に付着していた面積に基づいて、実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１の撥水性を評価した。
(Water repellency test)
In the packaging materials 1 of Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11, the water repellency of the side on which the water repellent layer 4 was provided was confirmed. First, a cup-shaped plastic container containing yogurt (soft type yogurt blueberry flavor) was sealed and sealed with the packaging material 1. Specifically, the water-repellent layer 4 of the packaging material 1 is brought into contact with the container, and the packaging material 1 is heat-sealed to the edge provided on the upper surface of the container under the conditions of a load of 50 kg, 190 ° C. and 1 second. did. After each container sealed with the packaging material 1 was cooled down to 5 ° C., the container was inverted so that the packaging material 1 was positioned below, and allowed to stand on a flat table for 60 minutes. After the inverted container was allowed to stand for 60 minutes, the container was rotated forward and the packaging material 1 was immediately peeled from the container. Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11 based on the area where the yogurt adhered to the packaging material 1 when the packaging material 1 was completely removed from the container. Was evaluated for water repellency.
ヨーグルトが包装材料１に付着していた面積は、目視により観察して評価した。具体的には、容器を反転させていた際にヨーグルトに接触していた包装材料１の面積に対して、包装材料１を容器から完全に剥がした際にヨーグルトが包装材料１に付着していた面積の割合を目視で観察した。また、実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１のそれぞれにおいては、ヨーグルトが収容されたプラスチック容器を１２個準備したことにより、上記評価を１２回行った。このため、各実施例、各参考例及び各比較例は、１２回の評価の平均値に基づいて評価された。 The area where the yogurt had adhered to the packaging material 1 was visually observed and evaluated. Specifically, the yogurt adhered to the packaging material 1 when the packaging material 1 was completely peeled from the container with respect to the area of the packaging material 1 that was in contact with the yogurt when the container was inverted. The area ratio was visually observed. In each of Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11, the above evaluation was performed 12 times by preparing 12 plastic containers containing yogurt. went. For this reason, each Example , each Reference Example, and each Comparative Example were evaluated based on the average of 12 evaluations.
実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１に対する撥水性試験の評価結果は、以下に示すＡ〜Ｃの基準に沿って判定した。本撥水性試験では、Ａ又はＢであれば撥水層４が良好な撥水性を有すると判定した。
Ａ：ヨーグルトが包装材料１に付着していた面積の割合が２０％以下。
Ｂ：ヨーグルトが包装材料１に付着していた面積の割合が２０％より大きく４０％未満。
Ｃ：ヨーグルトが包装材料１に付着していた面積の割合が４０％以上。
The evaluation results of the water repellency test for Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11 were determined according to the following criteria A to C. In this water repellency test, it was determined that the water repellent layer 4 had good water repellency if it was A or B.
A: The ratio of the area where the yogurt has adhered to the packaging material 1 is 20% or less.
B: The ratio of the area where the yogurt adhered to the packaging material 1 is more than 20% and less than 40%.
C: The ratio of the area where the yogurt adhered to the packaging material 1 is 40% or more.
図５（ａ）は、実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１の撥水性試験結果を示す表である。図５（ａ）に示されるように、実施例１〜５，７〜１０ならびに参考例６，１１〜１３の評価は、Ａ又はＢのいずれかであった。具体的には、実施例１〜５，７〜１０ならびに参考例６，１１の評価はＡであり、参考例１２，１３の評価はＢであった。また、比較例２〜４，１０，１１の評価はＡであり、比較例１の評価はＢであり、比較例５〜９の評価はＣであった。 FIG. 5A is a table showing the results of the water repellency tests of Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11. As shown in FIG. 5A , the evaluation of Examples 1 to 5, 7 to 10 and Reference Examples 6, 11 to 13 was either A or B. Specifically, the evaluation of Examples 1 to 5, 7 to 10 and Reference Examples 6 and 11 was A, and the evaluation of Reference Examples 12 and 13 was B. The evaluations of Comparative Examples 2 to 4, 10, and 11 were A, the evaluation of Comparative Example 1 was B, and the evaluations of Comparative Examples 5 to 9 were C.
実施例１〜５，７〜１０ならびに参考例６，１１〜１３を比較すると、参考例１２，１３においては、バインダー３３の質量に対する疎水性微粒子３０の質量が比較的小さい。このため、参考例１２，１３では、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比にかかわらず、実施例１〜５，７〜１０ならびに参考例６，１１よりも撥水性が発揮されなかったと考えられる。これらの結果より、実施例１〜５，７〜１０と参考例６，１１を含み且つ参考例１２，１３を含まない条件、例えば疎水性微粒子３０とバインダー３３との合計質量に対する疎水性微粒子３０の質量の割合が３０％よりも大きい場合、包装材料１の撥水性はより良好に発揮されると考えられる。 Comparing Examples 1 to 5, 7 to 10 and Reference Examples 6, 11 to 13, in Reference Examples 12 and 13, the mass of the hydrophobic fine particles 30 with respect to the mass of the binder 33 is relatively small. Therefore, in Reference Examples 12 and 13, water repellency is higher than in Examples 1 to 5, 7 to 10 and Reference Examples 6 and 11 regardless of the mass ratio of the first hydrophobic fine particles 31 to the second hydrophobic fine particles 32. It is considered that was not exhibited. From these results, the conditions that include Examples 1 to 5, 7 to 10 and Reference Examples 6 and 11 but do not include Reference Examples 12 and 13, for example, the hydrophobic fine particles 30 with respect to the total mass of the hydrophobic fine particles 30 and the binder 33 When the mass ratio is larger than 30%, the water repellency of the packaging material 1 is considered to be exhibited more favorably.
また、バインダー３３及び第２疎水性微粒子３２を用いていない比較例４の評価はＡである一方で、バインダー３３を用いると共に第２疎水性微粒子３２を用いていない比較例５〜９の評価は全てＣであった。これらの結果より、バインダー３３を用いる場合、疎水性微粒子３０が第１疎水性微粒子３１だけでなく第２疎水性微粒子３２も含むことにより、撥水層４は良好な撥水性を発揮できると考えられる。 The evaluation of Comparative Example 4 not using the binder 33 and the second hydrophobic fine particles 32 was A, while the evaluation of Comparative Examples 5 to 9 not using the binder 33 and using the second hydrophobic fine particles 32 was A. All were C. From these results, it is considered that when the binder 33 is used, the hydrophobic particles 30 include not only the first hydrophobic particles 31 but also the second hydrophobic particles 32, so that the water repellent layer 4 can exhibit good water repellency. Can be
（粉落ち試験）
実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１のそれぞれに実施した上述の撥水性試験において、包装材料１を容器から完全に剥がした際に、容器に収容されているヨーグルトの表面全体に対して撥水層とみられる浮遊物が存在した割合を目視で確認した。粉落ち試験の評価結果は、以下に示すＡ〜Ｃの基準に沿って判定した。この粉落ち試験では、Ａ又はＢであれば撥水層４の粉落ちが抑制できていると判定した。なお、評価がＢである場合、容器中のヨーグルト表面には疎水性微粒子３０に起因したと考えられる油状浮遊膜が形成されていた。また、評価がＣである場合、上記油膜に加えて、ヨーグルト表面に白色の粉状物が目視にて観察された。
Ａ：ヨーグルトに浮遊物が存在した割合が０％。
Ｂ：ヨーグルトに浮遊物が存在した割合が２５％以下。
Ｃ：ヨーグルトに浮遊物が存在した割合が２５％より大きい。
(Powder drop test)
In the above-described water repellency tests performed on each of Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11, when the packaging material 1 was completely peeled off from the container, The proportion of suspended matter that appeared to be a water-repellent layer on the entire surface of the contained yogurt was visually confirmed. The evaluation results of the powder drop test were determined in accordance with the following criteria A to C. In this powder drop test, it was determined that the powder drop of the water-repellent layer 4 could be suppressed if it was A or B. When the evaluation was B, an oily floating film considered to be caused by the hydrophobic fine particles 30 was formed on the surface of the yogurt in the container. When the evaluation was C, a white powdery substance was visually observed on the yogurt surface in addition to the oil film.
A: The percentage of suspended matter in the yogurt is 0%.
B: The proportion of suspended matter in the yogurt is 25% or less.
C: The percentage of suspended matter in the yogurt is greater than 25%.
図５（ｂ）は、実施例１〜５，７〜１０、参考例６，１１〜１３及び比較例１〜１１の粉落ち試験結果を示す表である。図５（ｂ）に示されるように、実施例１〜５，７〜１０ならびに参考例６，１１〜１３の評価は、Ａ又はＢになっていた。具体的には、実施例１〜５，７〜１０ならびに参考例１２，１３の評価はＡであり、参考例６，１１の評価はＢであった。また、比較例５〜８の評価はＡであり、比較例９の評価はＢであり、比較例１〜４，１０，１１の評価はＣであった。 FIG. 5B is a table showing the powder drop test results of Examples 1 to 5, 7 to 10, Reference Examples 6, 11 to 13, and Comparative Examples 1 to 11. As shown in FIG. 5B, the evaluations of Examples 1 to 5, 7 to 10 and Reference Examples 6, 11 to 13 were A or B. Specifically, the evaluation of Examples 1 to 5, 7 to 10 and Reference Examples 12 and 13 was A, and the evaluation of Reference Examples 6 and 11 was B. The evaluations of Comparative Examples 5 to 8 were A, the evaluation of Comparative Example 9 was B, and the evaluations of Comparative Examples 1 to 4, 10, and 11 were C.
上述したように、実施例１〜５，７〜１０ならびに参考例６，１１〜１３においてはバインダー３３の質量は第２疎水性微粒子３２の質量よりも大きい一方で、比較例１０，１１においてはバインダー３３の質量は第２疎水性微粒子３２の質量よりも小さい。これらの結果より、バインダー３３の質量は第２疎水性微粒子３２の質量よりも小さい場合、第２疎水性微粒子３２がバインダー３３によって十分に固定されなくなり、比較例１０，１１の評価がＣになったと考えられる。 As described above, in Examples 1 to 5, 7 to 10 and Reference Examples 6 , 11 to 13, the mass of the binder 33 is larger than the mass of the second hydrophobic fine particles 32, while in Comparative Examples 10 and 11, The mass of the binder 33 is smaller than the mass of the second hydrophobic fine particles 32. From these results, when the mass of the binder 33 is smaller than the mass of the second hydrophobic fine particles 32, the second hydrophobic fine particles 32 are not sufficiently fixed by the binder 33, and the evaluation of Comparative Examples 10 and 11 is C. It is considered that
実施例１〜５，７〜１０ならびに参考例６，１１〜１３を比較すると、参考例６，１１の評価はＢであった。これは、バインダー３３の質量に対する第２疎水性微粒子３２の質量の割合が７０％以上と大きくなっており、疎水性微粒子３０（特に第２疎水性微粒子３２）の一部がバインダー３３によって固定されなかったからだと考えられる。これらの結果より、バインダー３３の質量に対する第２疎水性微粒子３２の質量の割合が７０％未満である場合、粉落ちが発生しなくなったと考えられる。 When Examples 1 to 5, 7 to 10 and Reference Examples 6, 11 to 13 were compared, the evaluation of Reference Examples 6 and 11 was B. This is because the ratio of the mass of the second hydrophobic fine particles 32 to the mass of the binder 33 is as large as 70% or more, and a part of the hydrophobic fine particles 30 (particularly, the second hydrophobic fine particles 32) is fixed by the binder 33. It is thought that it was not. From these results, it is considered that when the ratio of the mass of the second hydrophobic fine particles 32 to the mass of the binder 33 is less than 70%, powder dropping does not occur.
また、バインダー３３を用いていない比較例１〜４においては、バインダー３３により疎水性微粒子３０が接着層３上に固定されない。このため、第１疎水性微粒子３１と第２疎水性微粒子３２との質量比にかかわらず、撥水層４から粉落ちが発生し、比較例１〜４の評価はＣになったと考えられる。 In Comparative Examples 1 to 4 in which the binder 33 was not used, the hydrophobic fine particles 30 were not fixed on the adhesive layer 3 by the binder 33. For this reason, regardless of the mass ratio between the first hydrophobic fine particles 31 and the second hydrophobic fine particles 32, powder fall occurred from the water-repellent layer 4, and it is considered that Comparative Examples 1 to 4 were evaluated as C.
１…包装材料、２…基材、３…接着層、３ａ…表面、４…撥水層、６…内容物、７…容器、７ａ…縁、１１…凸部、１２…凹部、２１…第１部分、２２…第２部分、３０…疎水性微粒子、３１…第１疎水性微粒子、３２…第２疎水性微粒子、３３…バインダー、１００…包装容器。 DESCRIPTION OF SYMBOLS 1 ... Packaging material, 2 ... Base material, 3 ... Adhesive layer, 3a ... Surface, 4 ... Water-repellent layer, 6 ... Contents, 7 ... Container, 7a ... Edge, 11 ... Convex part, 12 ... Concave part, 21 ... No. 1 part, 22 ... second part, 30 ... hydrophobic fine particles, 31 ... first hydrophobic fine particles, 32 ... second hydrophobic fine particles, 33 ... binder, 100 ... packaging container.
Claims (6)
前記基材上に設けられる接着層と、
前記接着層上に設けられ、疎水性微粒子及び金属アルコキシドを含むバインダーを有する撥水層と、
を備え、
前記疎水性微粒子は、第１疎水性微粒子と、前記第１疎水性微粒子の平均粒径よりも少なくとも５０倍以上大きい平均粒径を有する第２疎水性微粒子とを含み、
前記第１疎水性微粒子の平均粒径は、５ｎｍ以上２００ｎｍ以下であり、
前記撥水層において、前記バインダーの質量は、前記第２疎水性微粒子の質量よりも大きく、
前記疎水性微粒子と前記バインダーとの合計質量に対する前記疎水性微粒子の質量の割合は、３０％よりも大きく６０％以下であり、
前記バインダーの質量に対する前記第２疎水性微粒子の質量の割合は、１０％以上７０％未満である、
包装材料。 A substrate,
An adhesive layer provided on the base material,
A water-repellent layer provided on the adhesive layer and having a binder containing hydrophobic fine particles and a metal alkoxide ,
With
The hydrophobic fine particles include a first hydrophobic fine particle, and a second hydrophobic fine particle having an average particle size at least 50 times larger than the average particle size of the first hydrophobic fine particle,
The average particle size of the first hydrophobic fine particles is 5 nm or more and 200 nm or less,
Wherein the water-repellent layer, the mass of the binder is much larger than the mass of the second hydrophobic particulate,
The ratio of the mass of the hydrophobic fine particles to the total mass of the hydrophobic fine particles and the binder is greater than 30% and 60% or less;
The ratio of the mass of the second hydrophobic fine particles to the mass of the binder is 10% or more and less than 70%,
Packaging material.
前記撥水層において、前記凸部上の第１部分の厚さは、前記凹部上の第２部分の厚さよりも小さい、請求項１〜４のいずれか一項に記載の包装材料。 The surface of the adhesive layer facing the water-repellent layer is an uneven surface provided with convex portions and concave portions,
In the water-repellent layer, the thickness of the first portion on the convex portion is smaller than the thickness of the second portion on said concave portion, the packaging material according to any one of claims 1-4.
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| JP5441843B2 (en) * | 2010-07-07 | 2014-03-12 | 昭和電工パッケージング株式会社 | Contents adhesion prevention lid material and manufacturing method thereof |
| JP4878650B1 (en) * | 2010-08-12 | 2012-02-15 | 森永乳業株式会社 | Lid for cup-shaped container and method for manufacturing the same |
| JP5929076B2 (en) * | 2011-09-29 | 2016-06-01 | 凸版印刷株式会社 | Lid material |
| JP5880218B2 (en) * | 2012-03-30 | 2016-03-08 | 凸版印刷株式会社 | Water repellent laminate |
| JP6064461B2 (en) * | 2012-09-06 | 2017-01-25 | 凸版印刷株式会社 | Lid material and sealed container using the same |
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