JP5674221B2 - Laminates and packaging materials - Google Patents
Laminates and packaging materials Download PDFInfo
- Publication number
- JP5674221B2 JP5674221B2 JP2010218768A JP2010218768A JP5674221B2 JP 5674221 B2 JP5674221 B2 JP 5674221B2 JP 2010218768 A JP2010218768 A JP 2010218768A JP 2010218768 A JP2010218768 A JP 2010218768A JP 5674221 B2 JP5674221 B2 JP 5674221B2
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- Prior art keywords
- thermoplastic resin
- fine particles
- oxide fine
- particles
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000005022 packaging material Substances 0.000 title claims description 45
- 239000010410 layer Substances 0.000 claims description 155
- 229920005992 thermoplastic resin Polymers 0.000 claims description 108
- 230000002209 hydrophobic effect Effects 0.000 claims description 91
- 239000010419 fine particle Substances 0.000 claims description 89
- 239000002245 particle Substances 0.000 claims description 87
- 239000003242 anti bacterial agent Substances 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 14
- 239000012790 adhesive layer Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 5
- 238000004438 BET method Methods 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 27
- 238000001035 drying Methods 0.000 description 23
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- -1 carrero Substances 0.000 description 15
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- 235000013618 yogurt Nutrition 0.000 description 15
- 229910002012 Aerosil® Inorganic materials 0.000 description 13
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- 239000004922 lacquer Substances 0.000 description 12
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
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- 238000010586 diagram Methods 0.000 description 6
- 239000002648 laminated material Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
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- 239000004831 Hot glue Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
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- 239000002537 cosmetic Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
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- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 description 2
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- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
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- 239000011888 foil Substances 0.000 description 2
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- 239000002778 food additive Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
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- 239000000057 synthetic resin Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
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- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
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- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 1
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229940126575 aminoglycoside Drugs 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WZPBZJONDBGPKJ-VEHQQRBSSA-N aztreonam Chemical compound O=C1N(S([O-])(=O)=O)[C@@H](C)[C@@H]1NC(=O)C(=N/OC(C)(C)C(O)=O)\C1=CSC([NH3+])=N1 WZPBZJONDBGPKJ-VEHQQRBSSA-N 0.000 description 1
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- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- YZBQHRLRFGPBSL-RXMQYKEDSA-N carbapenem Chemical compound C1C=CN2C(=O)C[C@H]21 YZBQHRLRFGPBSL-RXMQYKEDSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 238000011081 inoculation Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000003835 ketolide antibiotic agent Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 150000003952 β-lactams Chemical class 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、積層体及び包装材料に関する。特に、テーブルクロス、ナプキン、エプロン、テーブルカバー、床マット、壁面クロス、壁紙、ラベル、剥離紙、タグ、椅子カバー、防水シート、傘、スキーウェア、建築材、ベッドカバー、靴表面材、靴カバー、防水着、撥水フィルム、撥水シート等に用いる積層体ならびに食品、飲料品、医薬品、化粧品、化学品等を包装するために用いる包装材料に関する。 The present invention relates to a laminate and a packaging material. In particular, tablecloth, napkin, apron, table cover, floor mat, wall cloth, wallpaper, label, release paper, tag, chair cover, tarpaulin, umbrella, ski wear, building material, bed cover, shoe surface material, shoe cover The present invention relates to a laminate used for waterproof clothing, water-repellent films, water-repellent sheets and the like and packaging materials used for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals and the like.
従来より多種多様の包装材料が知られているが、その内容物も多岐にわたる。例えば、ゼリー菓子、プリン、ヨーグルト、液体洗剤、練り歯磨き、カレールー、シロップ、ワセリン、洗顔クリーム、洗顔ムース等のように、食品、飲料品、医薬品、化粧品、化学品等がある。また、内容物の性状も、例えば固体、半固体、液体、粘性体、ゲル状物等のように様々なものがある。 A wide variety of packaging materials are known in the past, but their contents are also diverse. For example, there are foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like such as jelly confectionery, pudding, yogurt, liquid detergent, toothpaste, carrero, syrup, petrolatum, face wash cream, face wash mousse and the like. Also, there are various properties of the contents such as a solid, a semi-solid, a liquid, a viscous material, a gel-like material, and the like.
これらの内容物を包装するための包装材料においては、密封性が要求されるほかに、内容物、包装形態、用途等に応じて熱接着性、遮光性、耐熱性、耐久性等が要求される。ところが、これらの特性を満たしている包装材料であっても、次のような問題がある。すなわち、内容物が包装材料に付着するという問題である。内容物が包装材料に付着すれば、内容物をすべて使い切ることが困難になり、それだけ無駄が生じることになる。また、内容物をすべて使い切るためには包装材料に付着した内容物を別途に回収しなければならず、手間がかかる。このため、包装材料では、上記のような密封性等のほか、内容物が包装材料に付着しにくい性質（非付着性）を備えていることが必要である。 The packaging materials for packaging these contents are required to have hermeticity as well as thermal adhesiveness, light shielding, heat resistance, durability, etc. depending on the contents, packaging form, application, etc. The However, even packaging materials that satisfy these characteristics have the following problems. That is, there is a problem that the contents adhere to the packaging material. If the contents adhere to the packaging material, it becomes difficult to use up all the contents, resulting in waste. In addition, in order to use up all the contents, the contents attached to the packaging material must be collected separately, which is troublesome. For this reason, the packaging material needs to have a property (non-adhesiveness) that the contents are difficult to adhere to the packaging material in addition to the above-described sealing property and the like.
これに対し、接着層を介して一体化された基材層とヒートシール層とを備えた蓋材において、ヒートシール層が、付着防止効果を有するグリセリン酸エステル、ポリグリセリン脂肪酸エステル、ペンタエリスリトール脂肪酸エステル、ポリオキシプロピレン・ポリオキシエチレンブロックポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、脂肪酸アミド等を含むポリオレフィンからなり、その厚さが１０μｍよりも厚く、接着層と該ヒートシール層との間にポリオレフィンからなる中間層が設けられていることを特徴とする充填物付着防止蓋材が提案されている（特許文献１）。 On the other hand, in a lid provided with a base material layer and a heat seal layer integrated through an adhesive layer, the heat seal layer has an anti-adhesion effect, glyceric acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid. It is made of polyolefin containing ester, polyoxypropylene / polyoxyethylene block polymer, sorbitan fatty acid ester, polyoxyethylene alkyl ether, fatty acid amide, etc., and its thickness is thicker than 10 μm, between the adhesive layer and the heat seal layer There has been proposed a filler adhesion prevention lid material characterized in that an intermediate layer made of polyolefin is provided (Patent Document 1).
しかし、特許文献１のような蓋材では、付着防止効果が十分なものとは言えない。この点において、実用化を進める上ではさらなる改善が必要である。 However, it cannot be said that the cover material as in Patent Document 1 has a sufficient adhesion preventing effect. In this respect, further improvement is necessary for practical use.
従って、本発明の主な目的は、従来技術よりも優れた非付着性を持続的に発揮できる積層体を提供することにある。 Therefore, the main object of the present invention is to provide a laminate capable of continuously exhibiting non-adhesiveness superior to that of the prior art.
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定の構造を有する積層体ないし包装材料を採用することにより上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by employing a laminate or a packaging material having a specific structure, and has completed the present invention. It was.
すなわち、本発明は、下記の積層体ないし包装材料に係る。
１． 熱接着層として機能する熱可塑性樹脂を含有する層の表面の少なくとも一部に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子が付着している積層体であって、有機成分及び無機成分の少なくとも１種を含む平均粒子径が０．５〜１００μｍの充填粒子が前記熱可塑性樹脂を含有する層に含まれており、前記積層体を熱接着するに際して、熱接着される領域上に存在する疎水性酸化物微粒子が熱可塑性樹脂を含有する層中に埋め込まれ、熱可塑性樹脂を含有する層が最表面となることにより熱接着を行うことができる積層体。
２． 前記熱可塑性樹脂を含有する層の表面の少なくとも一部にさらに抗菌剤粒子が付着している、前記項１に記載の積層体。
３． 疎水性酸化物微粒子の付着量が０．０１〜１０ｇ／ｍ２である、前記項１又は２に記載の積層体。
４． 疎水性酸化物微粒子が三次元網目状構造からなる多孔質層を形成している、前記項１〜３のいずれかに記載の積層体。
５． 疎水性酸化物微粒子のＢＥＴ法による比表面積が５０〜３００ｍ２／ｇである、前記項１〜４のいずれかに記載の積層体。
６． 疎水性酸化物微粒子が疎水性シリカである、前記項１〜５のいずれかに記載の積層体。
７． 疎水性シリカがその表面にトリメチルシリル基を有する、前記項６に記載の積層体。
８． 前記熱可塑性樹脂を含有する層中における前記充填粒子の含有量は、固形分重量基準で１〜８０重量％である、前記項１〜７のいずれかに記載の積層体。
９． 前記項１〜８のいずれかに記載の積層体を含む包装材料。
That is, the present invention relates to the following laminate or packaging material.
1. A laminate in which hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are attached to at least a part of the surface of a layer containing a thermoplastic resin functioning as a heat-adhesive layer , comprising an organic component and an inorganic component Filled particles having an average particle size of 0.5 to 100 μm including at least one kind are included in the layer containing the thermoplastic resin, and are present on a region to be thermally bonded when the laminate is thermally bonded. A laminated body in which hydrophobic oxide fine particles are embedded in a layer containing a thermoplastic resin, and the layer containing the thermoplastic resin becomes the outermost surface, whereby thermal bonding can be performed .
2. Item 2. The laminate according to Item 1, wherein antibacterial particles are further attached to at least a part of the surface of the layer containing the thermoplastic resin .
3. Item 3. The laminate according to Item 1 or 2, wherein the amount of hydrophobic oxide fine particles attached is 0.01 to 10 g / m 2 .
4). Item 4. The laminate according to any one of Items 1 to 3, wherein the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure.
5. Item 5. The laminate according to any one of Items 1 to 4, wherein the hydrophobic oxide fine particles have a specific surface area of 50 to 300 m 2 / g by BET method.
6). Item 6. The laminate according to any one of Items 1 to 5, wherein the hydrophobic oxide fine particles are hydrophobic silica.
7). Item 7. The laminate according to Item 6, wherein the hydrophobic silica has a trimethylsilyl group on the surface thereof.
8). Item 8. The laminate according to any one of Items 1 to 7 , wherein the content of the filler particles in the layer containing the thermoplastic resin is 1 to 80% by weight based on the weight of solid content .
9. A packaging material comprising the laminate according to any one of Items 1 to 8.
本発明の積層体及び包装材料は、良好な撥水性及び非付着性（又は防汚性）を発揮することができる。特に、熱可塑性樹脂を含む層（以下「熱可塑性樹脂層」ともいう。）に有機成分及び無機成分の少なくとも１種を含む充填粒子が含有されている場合は、疎水性酸化物微粒子の脱落を効果的に抑制ないしは防止することができる結果、良好な撥水性及び非付着性をより効果的に持続させることが可能となる。 The laminate and the packaging material of the present invention can exhibit good water repellency and non-adhesiveness (or antifouling property). In particular, when a layer containing a thermoplastic resin (hereinafter also referred to as “thermoplastic resin layer”) contains filled particles containing at least one of an organic component and an inorganic component, the hydrophobic oxide fine particles are removed. As a result of being able to effectively suppress or prevent, good water repellency and non-adhesiveness can be maintained more effectively.
また、本発明の積層体又は包装材料において、熱可塑性樹脂層の表面の少なくとも一部に、疎水性酸化物微粒子とともに抗菌剤粒子を付着させることにより、優れた抗菌作用を発揮させることが可能となる。 Moreover, in the laminate or the packaging material of the present invention, it is possible to exert an excellent antibacterial action by attaching antibacterial agent particles together with hydrophobic oxide fine particles to at least a part of the surface of the thermoplastic resin layer. Become.
また、本発明の積層体又は包装材料において、熱可塑性樹脂層を熱接着層として利用する場合は、良好な熱接着性を維持しながらも、優れた非付着性を持続的に発揮することができる。すなわち、熱接着層の種類、厚み等の制限を受けることなく、熱接着性を実用上阻害せずに、高い非付着性を得ることができる。より具体的には、熱接着時において、熱接着される領域上に存在する疎水性酸化物微粒子は当該熱接着層中に埋め込まれるので熱接着を阻害しない一方、熱接着される領域外に存在する疎水性酸化物微粒子はそのまま熱接着層上に保持されているのでその高い非付着性を発揮することができる。 In the laminate or packaging material of the present invention, when a thermoplastic resin layer is used as a thermal adhesive layer, excellent non-adhesiveness can be continuously exhibited while maintaining good thermal adhesiveness. it can. That is, high non-adhesiveness can be obtained without impeding the thermal adhesiveness practically without being restricted by the type and thickness of the thermal adhesive layer. More specifically, at the time of thermal bonding, the hydrophobic oxide fine particles existing on the heat-bonded region are embedded in the heat-bonding layer and thus do not inhibit the heat-bonding, but exist outside the heat-bonded region. Since the hydrophobic oxide fine particles are held on the thermal adhesive layer as they are, their high non-adhesiveness can be exhibited.
このような積層体は、例えばテーブルクロス、ナプキン、エプロン、テーブルカバー、床マット、壁面クロス、壁紙、ラベル、剥離紙、タグ、椅子カバー、防水シート、傘、スキーウェア、建築材、ベッドカバー、靴表面材、靴カバー、防水着、撥水フィルム、撥水シート等に好適に用いることができる。また、この積層体は、そのまま又は加工することにより、食品、飲料品、医薬品、化粧品、化学品等を包装するための包装材料としても好適に用いることができる。 Such laminates include, for example, tablecloths, napkins, aprons, table covers, floor mats, wall cloths, wallpaper, labels, release paper, tags, chair covers, tarpaulins, umbrellas, ski wear, building materials, bed covers, It can be suitably used for shoe surface materials, shoe covers, waterproof clothing, water repellent films, water repellent sheets and the like. Moreover, this laminated body can be suitably used as a packaging material for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals and the like as they are or by processing them.
１ 基材層
２ 熱可塑性樹脂層
３ 疎水性酸化物微粒子
４ 容器
５ 内容物
６ 充填粒子
７ 抗菌剤粒子
DESCRIPTION OF SYMBOLS 1 Base material layer 2 Thermoplastic resin layer 3 Hydrophobic oxide fine particle 4 Container 5 Contents 6 Filling particle 7 Antibacterial agent particle
１．積層体・包装材料
本発明の積層体は、熱可塑性樹脂を含有する層（以下「熱可塑性樹脂層」ともいう。）の表面の少なくとも一部に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子が付着していることを特徴とする。
1. Laminate / Packaging Material The laminate of the present invention comprises a hydrophobic oxide having an average primary particle diameter of 3 to 100 nm on at least a part of the surface of a layer containing a thermoplastic resin (hereinafter also referred to as “thermoplastic resin layer”). It is characterized by adhering fine particles.
図１に本発明の積層体の一例の断面構造の模式図を示す。図１の積層体では、基材層１の一方面に、充填粒子６を含んだ熱可塑性樹脂層２が積層されており、その熱可塑性樹脂層２の表面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子３が付着している。熱可塑性樹脂層２は包装材料（積層体）の一方の最外層に積層されている。最外層である熱可塑性樹脂層２において、他の層（図１では基材層）と隣接していない側の面（最外面）に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子３が付着している。疎水性酸化物微粒子３は熱可塑性樹脂層２に付着して固定されている。すなわち、疎水性酸化物微粒子と内容物とが接触しても疎水性酸化物微粒子が脱落しないように付着している。図１において、疎水性酸化物微粒子３は、一次粒子が含まれていても良いが、その凝集体（二次粒子）が多く含まれていることが望ましい。特に、疎水性酸化物微粒子が三次元網目状構造からなる多孔質層をなしていることがより好ましい。すなわち、熱可塑性樹脂層２の上には疎水性酸化物微粒子により形成された三次元網目状構造からなる多孔質層が積層されていることが好ましい。 FIG. 1 shows a schematic diagram of a cross-sectional structure of an example of the laminate of the present invention. In the laminate of FIG. 1, the thermoplastic resin layer 2 including the filler particles 6 is laminated on one surface of the base material layer 1, and the average primary particle diameter of 3 to 100 nm is formed on the surface of the thermoplastic resin layer 2. Hydrophobic oxide fine particles 3 are attached. The thermoplastic resin layer 2 is laminated on one outermost layer of the packaging material (laminate). In the thermoplastic resin layer 2 that is the outermost layer, hydrophobic oxide fine particles 3 having an average primary particle diameter of 3 to 100 nm are formed on the surface (outermost surface) that is not adjacent to another layer (base material layer in FIG. 1). It is attached. Hydrophobic oxide fine particles 3 are adhered and fixed to the thermoplastic resin layer 2. That is, even if the hydrophobic oxide fine particles and the content come into contact with each other, the hydrophobic oxide fine particles are attached so as not to fall off. In FIG. 1, the hydrophobic oxide fine particles 3 may contain primary particles, but it is desirable that the hydrophobic oxide fine particles 3 contain many aggregates (secondary particles). In particular, it is more preferable that the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure. That is, it is preferable that a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles is laminated on the thermoplastic resin layer 2.
本発明においては、熱可塑性樹脂層中に充填粒子を含有させる場合は、熱可塑性樹脂層の表面（疎水性酸化物微粒子が付着する面）がその断面において凹凸状になり、その凹部に疎水性酸化物微粒子が凝集状態で入り込むことにより、非付着性を長期間維持すると考えられる。すなわち、内容物のほか、工程中の機器又は装置との接触が生じても、当該凹部に入り込んだ疎水性酸化物微粒子は当該凹部に入り込んで固定された状態を維持することによって疎水性酸化物微粒子の脱落を効果的に抑制ないしは防止できる結果、優れた非付着性を持続的に発揮することができる。換言すれば、良好な非付着性を比較的長期にわたり発揮することができる。 In the present invention, when the filler particles are contained in the thermoplastic resin layer, the surface of the thermoplastic resin layer (surface on which hydrophobic oxide fine particles adhere) becomes uneven in the cross section, and the recesses are hydrophobic. It is considered that the non-adhesiveness is maintained for a long time by the oxide fine particles entering in an aggregated state. That is, in addition to the contents, the hydrophobic oxide fine particles that have entered the concave portion enter the concave portion and maintain the fixed state even when contact with the device or apparatus in the process occurs. As a result of effectively suppressing or preventing the falling off of the fine particles, excellent non-adhesiveness can be exhibited continuously. In other words, good non-adhesiveness can be exhibited over a relatively long period.
図２には、本発明の積層体を容器の蓋材として用いて作製された包装体の断面構造の模式図を示す。なお、図２では、疎水性酸化物微粒子３及び充填粒子６の表記は省略されている。容器４に内容物５が充填され、その開口部と積層体の熱可塑性樹脂層２とが接するような状態で密封される。つまり、熱可塑性樹脂層２に付着している疎水性酸化物微粒子が内容物５と接触可能な状態で本発明の積層体（包装材料）が使用されることになる。このような場合であっても、熱可塑性樹脂層２は疎水性酸化物微粒子によって保護され、優れた非付着性を有するので、たとえ内容物が熱可塑性樹脂層２近傍に接触しても（接近しても）、内容物の熱可塑性樹脂層への付着が疎水性酸化物微粒子（又は疎水性酸化物微粒子からなる多孔質層）によって遮られ、なおかつ、はじかれる。このため、内容物が熱可塑性樹脂層近傍に付着したままの状態とならずに、疎水性酸化物微粒子（又は疎水性酸化物微粒子からなる多孔質層）にはじかれて内容物が容器内に戻る。なお、容器４の材質としては、金属、合成樹脂、ガラス、紙、それらの複合材等から適宜選択でき、その材質に応じて熱可塑性樹脂層の種類、成分等を適宜調整することができる。 In FIG. 2, the schematic diagram of the cross-sectional structure of the package produced using the laminated body of this invention as a cover material of a container is shown. In FIG. 2, the notation of the hydrophobic oxide fine particles 3 and the filler particles 6 is omitted. The container 4 is filled with the contents 5 and sealed in such a state that the opening and the thermoplastic resin layer 2 of the laminate are in contact with each other. That is, the laminate (packaging material) of the present invention is used in a state where the hydrophobic oxide fine particles adhering to the thermoplastic resin layer 2 can come into contact with the contents 5. Even in such a case, since the thermoplastic resin layer 2 is protected by the hydrophobic oxide fine particles and has excellent non-adhesiveness, even if the contents are in contact with the vicinity of the thermoplastic resin layer 2 (approaching) Even so, adhesion of the contents to the thermoplastic resin layer is blocked and repelled by the hydrophobic oxide fine particles (or a porous layer made of hydrophobic oxide fine particles). For this reason, the content does not remain in the vicinity of the thermoplastic resin layer, but is repelled by hydrophobic oxide fine particles (or a porous layer made of hydrophobic oxide fine particles) and the content is placed in the container. Return. In addition, as a material of the container 4, it can select suitably from a metal, a synthetic resin, glass, paper, those composite materials, etc., The kind of a thermoplastic resin layer, a component, etc. can be adjusted suitably according to the material.
図４には、本発明の積層体の他の一例の断面構造の模式図を示す。図１との相違点は、基材層１の一方面に積層されている充填粒子６を含んだ熱可塑性樹脂層２の表面にさらに抗菌剤粒子７が付着している点である。図４では、疎水性酸化物微粒子３に加えてさらに抗菌剤粒子７が付着し、疎水性酸化物微粒子３とともに抗菌剤粒子７が熱可塑性樹脂層２に付着して固定されている。すなわち、抗菌剤粒子が内容物と接触しても、抗菌剤粒子が脱落しないように熱可塑性樹脂層２の表面に付着している。 In FIG. 4, the schematic diagram of the cross-section of another example of the laminated body of this invention is shown. The difference from FIG. 1 is that the antibacterial agent particles 7 are further adhered to the surface of the thermoplastic resin layer 2 including the filler particles 6 laminated on one surface of the base material layer 1. In FIG. 4, the antibacterial agent particle 7 is further adhered in addition to the hydrophobic oxide fine particle 3, and the antibacterial agent particle 7 is adhered and fixed to the thermoplastic resin layer 2 together with the hydrophobic oxide fine particle 3. That is, even when the antibacterial agent particles come into contact with the contents, the antibacterial agent particles adhere to the surface of the thermoplastic resin layer 2 so that the antibacterial agent particles do not fall off.
図４に示すように、熱可塑性樹脂層中に充填粒子を含有させる場合は、熱可塑性樹脂層の表面（疎水性酸化物微粒子及び抗菌剤粒子が付着する面）がその断面において凹凸状になり、その凹部に疎水性酸化物微粒子と抗菌剤粒子が入り込むことにより、非付着性と抗菌性を長期間維持すると考えられる。すなわち、内容物のほか、工程中の機器又は装置との接触が生じても、当該凹部に入り込んだ疎水性酸化物微粒子と抗菌剤粒子は当該凹部に入り込んで固定された状態を維持することによって疎水性酸化物微粒子と抗菌剤粒子の脱落を効果的に抑制ないしは防止できる結果、優れた非付着性と抗菌性を持続的に発揮することができる。換言すれば、良好な非付着性と抗菌性を比較的長期にわたり発揮することができる。 As shown in FIG. 4, when the filler particles are contained in the thermoplastic resin layer, the surface of the thermoplastic resin layer (the surface on which the hydrophobic oxide fine particles and antibacterial agent particles adhere) becomes uneven in the cross section. It is considered that non-adhesiveness and antibacterial properties are maintained for a long period of time when hydrophobic oxide fine particles and antibacterial agent particles enter the recesses. That is, in addition to the contents, even if contact with the device or device in the process occurs, the hydrophobic oxide fine particles and the antibacterial agent particles that have entered the concave portion enter the concave portion and maintain a fixed state. As a result of effectively suppressing or preventing the removal of the hydrophobic oxide fine particles and the antibacterial agent particles, excellent non-adhesiveness and antibacterial properties can be continuously exhibited. In other words, good non-adhesiveness and antibacterial properties can be exhibited for a relatively long time.
熱可塑性樹脂（層）
熱可塑性樹脂は、公知の熱可塑性樹脂を採用することができる。例えば、アクリル樹脂、ポリスチレン、ＡＢＳ樹脂、塩化ビニル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアミド系樹脂、ポリカーボネート、ポリアセタール、フッ素系樹脂、シリコン樹脂、ポリエステル系樹脂等のほか、これらのブレンド樹脂、これらを構成するモノマーの組合せを含む共重合体、変性樹脂等を用いることができる。
Thermoplastic resin (layer)
A known thermoplastic resin can be adopted as the thermoplastic resin. For example, acrylic resin, polystyrene, ABS resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate, polyacetal, fluorine resin, silicone resin, polyester resin, and blended resins of these Copolymers, modified resins and the like containing combinations of monomers to be used can be used.
熱可塑性樹脂層の厚みは特に限定的ではないが、生産性、コスト等の観点より０．０１μｍ〜５ｍｍ程度とすることが好ましく、０．０１μｍ〜２ｍｍ程度とすることがさらに好ましい。また、熱可塑性樹脂層を熱接着層として機能させる場合は、熱接着性を考慮し、１〜１５０μｍの厚みとするのが好ましい。特に、本発明の包装材料では、熱接着するに際して、熱接着される領域上に存在する疎水性酸化物微粒子が熱可塑性樹脂層中に埋め込まれ、熱可塑性樹脂層が最表面となることにより熱接着を行うことができる。このため、上記厚みの範囲内において、疎水性酸化物微粒子を熱可塑性樹脂層にできるだけ多く埋め込むことができる厚みに設定することが望ましい。 The thickness of the thermoplastic resin layer is not particularly limited, but is preferably about 0.01 μm to 5 mm, more preferably about 0.01 μm to 2 mm from the viewpoint of productivity, cost, and the like. Moreover, when making a thermoplastic resin layer function as a thermoadhesion layer, it is preferable to set it as thickness of 1-150 micrometers in view of thermoadhesiveness. In particular, in the packaging material of the present invention, when thermally bonding, the hydrophobic oxide fine particles present on the region to be thermally bonded are embedded in the thermoplastic resin layer, and the thermoplastic resin layer becomes the outermost surface. Gluing can be performed. For this reason, it is desirable to set the thickness within the above thickness range so that the hydrophobic oxide fine particles can be embedded in the thermoplastic resin layer as much as possible.
熱可塑性樹脂層中における熱可塑性樹脂の含有量は、熱可塑性樹脂の種類、充填粒子及びその他の添加剤の使用の有無等によって異なるが、通常は２０〜１００重量％とし、特に３０〜９９重量％とすることが好ましく、さらに好ましくは５０〜９９重量％とする。 The content of the thermoplastic resin in the thermoplastic resin layer varies depending on the type of thermoplastic resin, the presence or absence of filler particles and other additives, etc., but is usually 20 to 100% by weight, particularly 30 to 99% by weight. %, And more preferably 50 to 99% by weight.
本発明では、必要に応じて、熱可塑性樹脂（層）を補強したり、他の特性（耐水分透過性、耐酸素透過性、遮光性、断熱性、耐衝撃性等）を付与する目的で、熱可塑性樹脂（層）に他の層（基材層と称す）を積層することもできる。この場合、通常は、図１に示すように基材層／熱可塑性樹脂層／疎水性酸化物微粒子を順次積層した３層構造とすれば良い。 In the present invention, for the purpose of reinforcing a thermoplastic resin (layer) or imparting other properties (moisture permeability resistance, oxygen permeability resistance, light shielding property, heat insulating property, impact resistance, etc.) as necessary. Further, another layer (referred to as a base material layer) can be laminated on the thermoplastic resin (layer). In this case, usually, a three-layer structure in which a base material layer / thermoplastic resin layer / hydrophobic oxide fine particles are sequentially laminated as shown in FIG.
基材層を用いる場合、基材層としては、公知の材料を採用することができる。例えば、紙、合成紙、樹脂フィルム、蒸着層付き樹脂フィルム、合成樹脂板、アルミニウム箔、その他の金属箔、金属板、織布、不織布、皮、合成皮革、木材、ガラス板等の単体又はこれらの複合材料・積層材料を好適に用いることができる。 When using a base material layer, a well-known material is employable as a base material layer. For example, paper, synthetic paper, resin film, resin film with vapor deposition layer, synthetic resin plate, aluminum foil, other metal foil, metal plate, woven fabric, non-woven fabric, leather, synthetic leather, wood, glass plate, etc. The composite material / laminate material can be suitably used.
基材層には、公知の包装材料、建築材料、服飾材、日用品等で採用されている各層が任意の位置に積層されていても良い。例えば、印刷層、印刷保護層（いわゆるＯＰ層）、着色層、接着剤層、接着強化層、プライマーコート層、アンカーコート層、防滑剤層、滑剤層、防曇剤層等が挙げられる。 In the base material layer, each layer employed in known packaging materials, building materials, clothing materials, daily necessities, and the like may be laminated at an arbitrary position. For example, a printing layer, a printing protective layer (so-called OP layer), a colored layer, an adhesive layer, an adhesion reinforcing layer, a primer coat layer, an anchor coat layer, an anti-slip agent layer, a lubricant layer, an anti-fogging agent layer and the like can be mentioned.
基材層の積層方法、基材層と熱可塑性樹脂層との積層方法も限定的でなく、例えばドライラミネート法、押し出しラミネート法、ウエットラミネート法、ヒートラミネート法等の公知の方法を採用することができる。 The method for laminating the base material layer and the method for laminating the base material layer and the thermoplastic resin layer are not limited. For example, a known method such as a dry laminating method, an extrusion laminating method, a wet laminating method, or a heat laminating method should be adopted. Can do.
熱可塑性樹脂層を熱接着層として機能させる場合は、公知の熱接着性材料を採用することができる。例えば、公知のシーラントフィルムのほか、ラッカータイプ接着剤、イージーピール接着剤、ホットメルト接着剤等の接着剤により形成される層を採用することができる。すなわち、本明細書においては、熱可塑性樹脂には、樹脂成分を含有する公知の熱接着剤も含む。本発明では、この中でも、ラッカータイプ接着剤又はホットメルト接着剤を採用するのが好ましく、特にラッカータイプ接着剤により形成される熱接着層を好適に採用することができる。ホットメルト層を形成する場合には、ホットメルト接着剤を溶融状態で塗布した後、冷却固化するまでに疎水性酸化物微粒子を付与すれば熱接着層に疎水性酸化物微粒子をそのまま付着させることができるため、本発明積層体（又は包装材料）の連続的な生産が容易となる。 When making a thermoplastic resin layer function as a heat bond layer, a well-known heat bond material can be adopted. For example, in addition to a known sealant film, a layer formed of an adhesive such as a lacquer type adhesive, an easy peel adhesive, or a hot melt adhesive can be employed. That is, in the present specification, the thermoplastic resin includes a known thermal adhesive containing a resin component. In the present invention, among these, it is preferable to employ a lacquer type adhesive or a hot melt adhesive, and in particular, a thermal adhesive layer formed by a lacquer type adhesive can be suitably employed. When forming a hot melt layer, after applying the hot melt adhesive in a molten state, if the hydrophobic oxide fine particles are applied before cooling and solidifying, the hydrophobic oxide fine particles are allowed to adhere to the thermal adhesive layer as they are. Therefore, continuous production of the laminate (or packaging material) of the present invention is facilitated.
充填粒子
本発明では、必要に応じて熱可塑性樹脂層に充填粒子を含有させることもできる。熱可塑性樹脂層中に充填粒子を分散させることにより、より優れた耐摩耗性等を熱可塑性樹脂層に付与することができる。
Filled particles In the present invention, if necessary, filled particles can be contained in the thermoplastic resin layer. By dispersing the filler particles in the thermoplastic resin layer, more excellent wear resistance and the like can be imparted to the thermoplastic resin layer.
充填粒子としては、有機成分及び無機成分の少なくとも１種を含む充填粒子を採用することができる。 As the filler particles, filler particles containing at least one of an organic component and an inorganic component can be employed.
無機成分としては、例えば１）アルミニウム、銅、鉄、チタン、銀、カルシウム等の金属又はこれらを含む合金又は金属間化合物、２）酸化珪素、酸化アルミニウム、酸化ジルコニウム、酸化チタン、酸化鉄等の酸化物、３）リン酸カルシウム、ステアリン酸カルシウム等の無機酸塩又は有機酸塩、４）ガラス、５）窒化アルミニウム、窒化硼素、炭化珪素、窒化珪素等のセラミック等を好適に用いることができる。 Examples of inorganic components include 1) metals such as aluminum, copper, iron, titanium, silver, and calcium, or alloys or intermetallic compounds containing these metals, and 2) silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, iron oxide, and the like. Oxides, 3) inorganic acid salts or organic acid salts such as calcium phosphate and calcium stearate, 4) glass, 5) ceramics such as aluminum nitride, boron nitride, silicon carbide and silicon nitride can be suitably used.
有機成分としては、例えばアクリル系樹脂、ウレタン系樹脂、メラミン系樹脂、アミノ樹脂、エポキシ樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、ポリプロピレン系樹脂、ポリエステル系樹脂、セルロース系樹脂、塩化ビニル系樹脂、ポリビニルアルコール、エチレン−酢酸ビニル共重合体、エチレン−ビニルアルコール共重合体、エチレン−アクリル酸エチル共重合体、ポリアクリロニトリル、ポリアミド等の有機高分子成分（又は樹脂成分）を好適に用いることができる。 Examples of organic components include acrylic resins, urethane resins, melamine resins, amino resins, epoxy resins, polyethylene resins, polystyrene resins, polypropylene resins, polyester resins, cellulose resins, vinyl chloride resins, and polyvinyl resins. Organic polymer components (or resin components) such as alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, polyacrylonitrile, and polyamide can be suitably used.
本発明の充填粒子は、無機成分からなる粒子あるいは有機成分からなる粒子のほか、無機成分及び有機成分の両者を含む粒子を用いることができる。この中でも特に、アクリル系樹脂粒子、親水性シリカ粒子、リン酸カルシウム粒子、炭粉、焼成カルシウム粒子、未焼成カルシウム粒子、ステアリン酸カルシウム粒子等の少なくとも１種を用いることがより好ましい。 As the filler particles of the present invention, particles containing both an inorganic component and an organic component can be used in addition to particles made of an inorganic component or particles made of an organic component. Among these, it is particularly preferable to use at least one of acrylic resin particles, hydrophilic silica particles, calcium phosphate particles, carbon powder, calcined calcium particles, uncalcined calcium particles, calcium stearate particles, and the like.
充填粒子の平均粒子径（レーザー回折式粒度分布計による）は０．５〜１００μｍ程度が好ましく、１〜５０μｍがさらに好ましく、５〜３０μｍが最も好ましい。０．５μｍ未満では取扱い性、前述の凹凸形成等の点で不向きである。他方、１００μｍを超える場合は、充填粒子の脱落、分散性等の点で不向きである。 The average particle diameter of the packed particles (by a laser diffraction particle size distribution analyzer) is preferably about 0.5 to 100 μm, more preferably 1 to 50 μm, and most preferably 5 to 30 μm. If it is less than 0.5 μm, it is unsuitable in terms of handleability, the above-described formation of irregularities, and the like. On the other hand, when exceeding 100 micrometers, it is unsuitable at points, such as drop-off | omission of a filling particle and a dispersibility.
充填粒子の形状は限定的でなく、例えば球状、回転楕円体状、不定形状、涙滴状、扁平状、中空状、多孔質状等のいずれであっても良い。 The shape of the filled particles is not limited, and may be any of spherical shape, spheroid shape, indefinite shape, teardrop shape, flat shape, hollow shape, porous shape, and the like.
熱可塑性樹脂層中における充填粒子の含有量は、熱可塑性樹脂又は充填粒子の種類、所望の物性等に応じて適宜変更できるが、一般的には固形分重量基準で１〜８０重量％が好ましく、３〜５０重量％がさらに好ましい。 The content of the filler particles in the thermoplastic resin layer can be appropriately changed according to the kind of thermoplastic resin or filler particles, desired physical properties, etc., but generally 1 to 80% by weight based on the solid content weight is preferable. 3 to 50% by weight is more preferable.
充填粒子を含有させる方法は、特に限定されないが、一般的には熱可塑性樹脂層を形成するための原料（熱可塑性樹脂を含む組成物）に充填粒子を配合する方法等が挙げられる。混合する方法は、乾式混合又は湿式混合のいずれであっても良い。一般的に熱可塑性樹脂層の主成分は１）熱可塑性樹脂又はそれを構成するモノマーもしくはオリゴマー、２）溶剤、３）必要に応じて架橋剤等からなるため、それらの混合物中に充填粒子を添加混合すれば良い。 The method for containing the filler particles is not particularly limited, and generally includes a method of blending the filler particles with a raw material (composition containing a thermoplastic resin) for forming the thermoplastic resin layer. The mixing method may be either dry mixing or wet mixing. In general, the main component of the thermoplastic resin layer is 1) a thermoplastic resin or a monomer or oligomer constituting the thermoplastic resin, 2) a solvent, 3) a cross-linking agent, etc., if necessary. What is necessary is just to add and mix.
疎水性酸化物微粒子
熱可塑性樹脂層に付着する疎水性酸化物微粒子は、一次粒子平均径が通常３〜１００ｎｍであり、好ましくは５〜５０ｎｍであり、より好ましくは５〜２０ｎｍである。一次粒子平均径を上記範囲とすることにより、疎水性酸化物微粒子が適度な凝集状態となり、その凝集体中にある空隙に空気等の気体を保持することができる結果、優れた非付着性を得ることができる。すなわち、この凝集状態は、熱可塑性樹脂層に付着した後も維持されるので、優れた非付着性を発揮することができる。本発明において、疎水性酸化物微粒子は、熱可塑性樹脂（層）の片面あるいは両面に付着させることができる。
Hydrophobic oxide fine particles The hydrophobic oxide fine particles adhering to the thermoplastic resin layer usually have an average primary particle diameter of 3 to 100 nm, preferably 5 to 50 nm, and more preferably 5 to 20 nm. By setting the average primary particle diameter in the above range, the hydrophobic oxide fine particles are in an appropriate aggregated state, and can hold a gas such as air in the voids in the aggregate, resulting in excellent non-adhesiveness. Can be obtained. That is, since this aggregated state is maintained even after adhering to the thermoplastic resin layer, excellent non-adhesiveness can be exhibited. In the present invention, the hydrophobic oxide fine particles can be attached to one side or both sides of the thermoplastic resin (layer).
なお、本発明において、一次粒子平均径の測定は、走査型電子顕微鏡（ＦＥ−ＳＥＭ）で実施することができ、走査型電子顕微鏡の分解能が低い場合には透過型電子顕微鏡等の他の電子顕微鏡を併用して実施しても良い。具体的には、粒子形状が球状の場合はその直径、非球状の場合はその最長径と最短径との平均値を直径とみなし、走査型電子顕微鏡等による観察により任意に選んだ２０個分の粒子の直径の平均を一次粒子平均径とする。 In the present invention, the average primary particle diameter can be measured with a scanning electron microscope (FE-SEM). When the resolution of the scanning electron microscope is low, other electrons such as a transmission electron microscope are used. You may carry out together with a microscope. Specifically, when the particle shape is spherical, the diameter is considered as the diameter, and when the particle shape is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter, and 20 arbitrarily selected by observation with a scanning electron microscope or the like. The average diameter of the particles is defined as the average primary particle diameter.
疎水性酸化物微粒子の比表面積（ＢＥＴ法）は特に制限されないが、通常５０〜３００ｍ２／ｇとし、特に１００〜３００ｍ２／ｇとすることが好ましい。 The specific surface area of the hydrophobic oxide fine particles (BET method) is not particularly limited, and usually 50 to 300 m 2 / g, it is preferable that the particular 100 to 300 m 2 / g.
疎水性酸化物微粒子としては、疎水性を有するものであれば特に限定されず、表面処理により疎水化されたものであっても良い。例えば、親水性酸化物微粒子をシランカップリング剤等で表面処理を施し、表面状態を疎水性とした微粒子を用いることもできる。酸化物の種類も、疎水性を有するものであれば限定されない。例えばシリカ（二酸化ケイ素）、アルミナ、チタニア等の少なくとも１種を用いることができる。これらは公知又は市販のものを採用することができる。例えば、シリカとしては、製品名「ＡＥＲＯＳＩＬ Ｒ９７２」、「ＡＥＲＯＳＩＬ Ｒ９７２Ｖ」、「ＡＥＲＯＳＩＬ Ｒ９７２ＣＦ」、「ＡＥＲＯＳＩＬ Ｒ９７４」、「ＡＥＲＯＳＩＬ ＲＸ２００」、「ＡＥＲＯＳＩＬ ＲＹ２００」（以上、日本アエロジル株式会社製）、「ＡＥＲＯＳＩＬ Ｒ２０２」、「ＡＥＲＯＳＩＬ Ｒ８０５」、「ＡＥＲＯＳＩＬ Ｒ８１２」、「ＡＥＲＯＳＩＬ Ｒ８１２Ｓ」、（以上、エボニック デグサ社製）等が挙げられる。チタニアとしては、製品名「ＡＥＲＯＸＩＤＥ ＴｉＯ２ Ｔ８０５」（エボニック デグサ社製）等が例示できる。アルミナとしては、製品名「ＡＥＲＯＸＩＤＥ Ａｌｕ Ｃ」（エボニック デグサ社製）等をシランカップリング剤で処理して粒子表面を疎水性とした微粒子が例示できる。 The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be those hydrophobized by surface treatment. For example, fine particles in which hydrophilic oxide fine particles are subjected to a surface treatment with a silane coupling agent or the like to make the surface state hydrophobic can also be used. The type of oxide is not limited as long as it has hydrophobicity. For example, at least one of silica (silicon dioxide), alumina, titania and the like can be used. These may be known or commercially available. For example, as silica, product names “AEROSIL R972”, “AEROSIL R972V”, “AEROSIL R972CF”, “AEROSIL R974”, “AEROSIL RX200”, “AEROSIL RY200” (above, manufactured by Nippon Aerosil Co., Ltd.), “AEROSIL R202” "AEROSIL R805", "AEROSIL R812", "AEROSIL R812S" (above, manufactured by Evonik Degussa). Examples of titania include “AEROXIDE TiO 2 T805” (manufactured by Evonik Degussa). Examples of alumina include fine particles in which the product name “AEROXIDE Alu C” (manufactured by Evonik Degussa) is treated with a silane coupling agent to make the particle surface hydrophobic.
この中でも、疎水性シリカ微粒子を好適に用いることができる。とりわけ、より優れた非付着性が得られるという点において、表面にトリメチルシリル基を有する疎水性シリカ微粒子が好ましい。これに対応する市販品としては、例えば前記「ＡＥＲＯＳＩＬ Ｒ８１２」、「ＡＥＲＯＳＩＬ Ｒ８１２Ｓ」（いずれもエボニック デグサ社製）等が挙げられる。 Among these, hydrophobic silica fine particles can be preferably used. In particular, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable in that better non-adhesiveness can be obtained. Examples of commercially available products corresponding to this include “AEROSIL R812” and “AEROSIL R812S” (both manufactured by Evonik Degussa).
熱可塑性樹脂層に付着させる疎水性酸化物微粒子の付着量（乾燥後重量）は限定的ではないが、通常０．０１〜１０ｇ／ｍ２とするのが好ましく、０．２〜１．５ｇ／ｍ２とするのがより好ましく、０．２〜１ｇ／ｍ２とするのが最も好ましい。上記範囲内に設定することによって、より優れた非付着性が長期にわたって得ることができる上、疎水性酸化物微粒子の脱落抑制、コスト等の点でもいっそう有利となる。熱可塑性樹脂層に付着した疎水性酸化物微粒子は、三次元網目構造を有する多孔質層を形成していることが好ましく、その厚みは０．１〜５μｍ程度が好ましく、０．２〜２．５μｍ程度がさらに好ましい。このようなポーラスな層状態で付着することにより、当該層に空気を多く含むことができ、より優れた非付着性を発揮することができる。 The amount (weight after drying) of the hydrophobic oxide fine particles to be adhered to the thermoplastic resin layer is not limited, but is usually preferably 0.01 to 10 g / m 2, and preferably 0.2 to 1.5 g / m 2. m 2 is more preferable, and 0.2 to 1 g / m 2 is most preferable. By setting within the above range, more excellent non-adhesiveness can be obtained over a long period of time, and it is further advantageous in terms of suppression of falling off of hydrophobic oxide fine particles and cost. The hydrophobic oxide fine particles adhering to the thermoplastic resin layer preferably form a porous layer having a three-dimensional network structure, and the thickness is preferably about 0.1 to 5 μm, and 0.2 to 2. More preferably, it is about 5 μm. By adhering in such a porous layer state, the layer can contain a lot of air, and more excellent non-adhesiveness can be exhibited.
また、疎水性酸化物微粒子は、熱可塑性樹脂層の全面（基材層側と反対側の面の全面）に付着していても良いし、熱可塑性樹脂層が熱接着される領域（いわゆる接着しろ）を除いた領域に付着していても良い。本発明では、熱可塑性樹脂層の全面に付着している場合でも、熱接着される領域上に存在する疎水性酸化物微粒子のほとんど又は全部が当該熱可塑性樹脂層中に埋没するので熱接着が阻害されることはなく、工業的生産上でも熱可塑性樹脂層の全面に付着している方が望ましい。 Further, the hydrophobic oxide fine particles may be attached to the entire surface of the thermoplastic resin layer (the entire surface on the side opposite to the base material layer side), or a region where the thermoplastic resin layer is thermally bonded (so-called adhesion). You may adhere to the area | region except the margin. In the present invention, even when adhering to the entire surface of the thermoplastic resin layer, most or all of the hydrophobic oxide fine particles present on the region to be thermally bonded are buried in the thermoplastic resin layer, so that thermal adhesion is achieved. It is not obstructed, and it is desirable that it adheres to the entire surface of the thermoplastic resin layer even in industrial production.
抗菌剤粒子
本発明では、必要に応じて抗菌性を付与するために熱可塑性樹脂層に抗菌剤粒子を付着させることもできる。
Antibacterial Particles In the present invention, antibacterial particles can be attached to the thermoplastic resin layer as needed to impart antibacterial properties.
抗菌剤粒子としては、抗菌作用を有するものであれば特に限定されず、公知の抗菌剤を利用することもできる。例えば、銀系、銅系、ホウ酸カルシウム系、酸化亜鉛系等の無機系抗菌剤；イソチアン酸アリル系、β-ラクタム系、ペニシリン系、セフェム系、カルバペネム系、モノバクタム系、アミノグリコシド系、クロラムフェニコール系、マクロライド系、ケトライド系、ピリドンカルボン酸系、オキサゾリジノン系等の有機系抗菌剤；有機無機ハイブリッド型抗菌剤；キトサン、ヒノキチオ−ル等の天然系抗菌剤を使用することができる。これらの中でも、特に食品添加物用の抗菌剤あるいは可食性の抗菌剤が適しており、このような抗菌剤として市販品も使用することができる。例えば、大阪化成株式会社製炭化水素系抗菌剤「商品名：マルカサイドＰ３００、８１２Ａ」、バイオベンチャーバンク株式会社製アミノ酸系抗菌剤「商品名：パワーアンチ」、西日本イシダ株式会社製カラシ抽出物抗菌剤「ハイパー２４ＳＴ食品添加物」、株式会社シナネンゼオミック製銀ゼオライト系抗菌剤「ゼオミック」等を用いるのが好ましい。 The antibacterial agent particles are not particularly limited as long as they have an antibacterial action, and known antibacterial agents can also be used. For example, silver, copper, calcium borate, zinc oxide and other inorganic antibacterial agents; allyl isocyanate, β-lactam, penicillin, cephem, carbapenem, monobactam, aminoglycoside, chloram Organic antibacterial agents such as phenicol, macrolide, ketolide, pyridonecarboxylic acid, and oxazolidinone; organic-inorganic hybrid antibacterial agents; natural antibacterial agents such as chitosan and hinokitiol can be used. Among these, antibacterial agents for food additives or edible antibacterial agents are particularly suitable, and commercially available products can also be used as such antibacterial agents. For example, hydrocarbon antibacterial agent “trade name: Marcaside P300, 812A” manufactured by Osaka Kasei Co., Ltd., amino acid antibacterial agent “trade name: Power Anti” manufactured by Bioventure Bank Co., Ltd., mustard extract antibacterial manufactured by West Japan Ishida Co., Ltd. It is preferable to use the agent “Hyper 24ST food additive”, silver zeolite antibacterial agent “Zeomic” manufactured by Sinanen Zeomic Co., Ltd. and the like.
抗菌剤粒子の平均粒子径は限定的ではないが、通常０．５〜１０μｍであり、好ましくは２〜７μｍであり、より好ましくは５〜７μｍとすれば良い。平均粒子径を上記範囲に設定することにより、抗菌剤粒子がより効果的に熱可塑性樹脂層表面の凹凸の凹部に入り込み、脱落が抑止され、優れた抗菌性を長期間発揮させることが可能となる。本発明において、抗菌剤粒子は、疎水性酸化物微粒子と同様、熱可塑性樹脂（層）の片面あるいは両面に付着させることができる。 The average particle size of the antibacterial agent particles is not limited, but is usually 0.5 to 10 μm, preferably 2 to 7 μm, more preferably 5 to 7 μm. By setting the average particle size in the above range, the antibacterial agent particles can more effectively enter the concave and convex recesses on the surface of the thermoplastic resin layer, and can be prevented from falling off, and can exhibit excellent antibacterial properties for a long period of time. Become. In the present invention, the antibacterial agent particles can be attached to one side or both sides of the thermoplastic resin (layer), similarly to the hydrophobic oxide fine particles.
なお、本発明において、平均粒子径の測定は、走査型電子顕微鏡（ＦＥ−ＳＥＭ）で実施することができ、走査型電子顕微鏡の分解能が低い場合には透過型電子顕微鏡等の他の電子顕微鏡を併用して実施しても良い。具体的には、粒子形状が球状の場合はその直径、非球状の場合はその最長径と最短径との平均値を直径とみなし、走査型電子顕微鏡等による観察により任意に選んだ２０個分の粒子の直径の平均を一次粒子平均径とする。 In the present invention, the average particle size can be measured with a scanning electron microscope (FE-SEM). When the resolution of the scanning electron microscope is low, another electron microscope such as a transmission electron microscope is used. May be used in combination. Specifically, when the particle shape is spherical, the diameter is considered as the diameter, and when the particle shape is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter, and 20 arbitrarily selected by observation with a scanning electron microscope or the like. The average diameter of the particles is defined as the average primary particle diameter.
熱可塑性樹脂層に付着させる抗菌剤粒子の付着量（乾燥後重量）は限定的ではないが、通常０．０１〜１０ｇ／ｍ２とするのが好ましく、０．１〜１．５ｇ／ｍ２とするのがより好ましく、０．１〜１．０ｇ／ｍ２とするのが最も好ましい。上記範囲内に設定することによって、より優れた抗菌性を長期にわたって得ることができる上、抗菌剤粒子の脱落抑制、コスト等の点でもいっそう有利となる。また、抗菌剤粒子は、疎水性酸化物微粒子と同様、熱可塑性樹脂層の全面（基材層側と反対側の面の全面）に付着していても良いし、熱可塑性樹脂層が熱接着される領域（いわゆる接着しろ）を除いた領域に付着していても良い。本発明では、熱可塑性樹脂層の全面に付着している場合でも、熱接着される領域上に存在する抗菌剤粒子のほとんど又は全部が当該熱可塑性樹脂層中に埋没するので熱接着が阻害されることはなく、工業的生産上でも熱可塑性樹脂層の全面に付着している方が望ましい。 The adhesion amount (weight after drying) of the antibacterial agent particles to be adhered to the thermoplastic resin layer is not limited, but is usually preferably 0.01 to 10 g / m 2, and preferably 0.1 to 1.5 g / m 2. Is more preferable, and 0.1 to 1.0 g / m 2 is most preferable. By setting within the above range, it is possible to obtain superior antibacterial properties over a long period of time, and it is further advantageous in terms of suppression of dropping off of the antibacterial agent particles, cost, and the like. In addition, the antibacterial agent particles may be attached to the entire surface of the thermoplastic resin layer (the entire surface opposite to the base material layer side), as in the case of the hydrophobic oxide fine particles, or the thermoplastic resin layer is thermally bonded. You may adhere to the area | region except the area | region (what is called bonding margin). In the present invention, even when adhering to the entire surface of the thermoplastic resin layer, most or all of the antibacterial agent particles present on the region to be thermally bonded are buried in the thermoplastic resin layer, so that the thermal adhesion is inhibited. In view of industrial production, it is desirable to adhere to the entire surface of the thermoplastic resin layer.
包装材料及びその他の用途
本発明の積層体は、そのままで又は加工を施した上で包装材料をはじめ、他の様々な用途に用いることができる。他の用途としては、非付着性、防汚性、撥水性等が要求される分野であれば限定的でなく、例えばテーブルクロス、ナプキン、エプロン、テーブルカバー、床マット、壁面クロス、壁紙、ラベル、剥離紙、タグ、椅子カバー、防水シート、傘、スキーウェア、建築材、ベッドカバー、靴表面材、靴カバー、防水着、撥水フィルム、撥水シート等を挙げることができる。
Packaging Material and Other Applications The laminate of the present invention can be used for various other applications including packaging materials as they are or after being processed. Other uses are not limited as long as non-adhesiveness, antifouling properties, water repellency, etc. are required. For example, table cloth, napkin, apron, table cover, floor mat, wall cloth, wallpaper, label , Release paper, tag, chair cover, waterproof sheet, umbrella, ski wear, building material, bed cover, shoe surface material, shoe cover, waterproof clothing, water repellent film, water repellent sheet, and the like.
２．積層体・包装材料の製造方法
本発明の積層体（包装材料）は、例えば、少なくとも熱可塑性樹脂層を有する積層体ないし包装材料を製造する方法であって、当該熱可塑性樹脂層表面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子を付着させる工程（以下「付着工程」ともいう。）を含む製造方法によって好適に得ることができる。
2. Laminate / Packaging Material Manufacturing Method The laminate (packaging material) of the present invention is, for example, a method for producing a laminate or a packaging material having at least a thermoplastic resin layer, and primary particles on the surface of the thermoplastic resin layer. It can be suitably obtained by a production method including a step of attaching hydrophobic oxide fine particles having an average diameter of 3 to 100 nm (hereinafter also referred to as “attachment step”).
また、抗菌剤粒子を付着させる場合は、抗菌剤粒子を付着させる工程（この場合は、前記付着工程とまとめて「付着工程」という。）を含む製造方法によって、本発明の積層体（包装材料）を得ることができる。この場合、疎水性酸化物微粒子と抗菌剤粒子とは、同時に付着させても良いし、別々の工程で付着させても良い。また、別々の工程で実施する場合も、いずれを先に付着させても良い。 In addition, when the antibacterial agent particles are adhered, the laminate (packaging material) of the present invention is produced by a manufacturing method including a step of adhering the antibacterial agent particles (in this case, collectively referred to as the “adhesion step”). ) Can be obtained. In this case, the hydrophobic oxide fine particles and the antimicrobial agent particles may be attached at the same time or may be attached in separate steps. Moreover, when implementing by a separate process, any may be made to adhere first.
熱可塑性樹脂層は、フィルム状あるいはシート状のものであればそのまま用いることもできる。必要に応じて公知の基材層を公知の方法に従って積層することができる。例えば、単層基材又はドライラミネート法、押し出しラミネート法、ウエットラミネート法、ヒートラミネート法等により作製された積層材料に対して、前記１．で説明した方法により熱可塑性樹脂層を形成すれば良い。充填粒子を用いる場合は、充填粒子は前述のとおり、熱可塑性樹脂層を形成するための原料に予め含有させれば良い。 The thermoplastic resin layer can be used as it is if it is in the form of a film or a sheet. If necessary, a known substrate layer can be laminated according to a known method. For example, with respect to a laminated material produced by a single layer base material or a dry laminating method, an extrusion laminating method, a wet laminating method, a heat laminating method, etc. What is necessary is just to form a thermoplastic resin layer by the method demonstrated in (4). When using the filler particles, the filler particles may be previously contained in the raw material for forming the thermoplastic resin layer as described above.
疎水性酸化物微粒子及び抗菌剤粒子の付着工程を実施する方法は特に限定されない。例えば、ロールコーティング、グラビアコーティング、バーコート、ドクターブレードコーティング、刷毛塗り、粉体静電法等の公知の方法を採用することができる。ロールコーティング等を採用する場合は、疎水性酸化物微粒子を溶媒に分散させてなる分散体を用いて熱可塑性樹脂層上に塗膜を形成した後に乾燥する方法により付着工程を実施することができる。この場合の溶媒は限定されず、水のほか、例えばアルコール（エタノール）、シクロヘキサン、トルエン、アセトン、ＩＰＡ、プロピレングリコール、ヘキシレングリコール、ブチルジグリコール、ペンタメチレングリコール、ノルマルペンタン、ノルマルヘキサン、ヘキシルアルコール等の有機溶剤を適宜選択することができる。この際、微量の分散剤、着色剤、沈降防止剤、粘度調整剤等を併用することもできる。溶媒に対する疎水性酸化物微粒子の分散量は通常１０〜１００ｇ／Ｌ程度とすれば良い。また、溶媒に対する抗菌剤粒子の分散量は通常５〜１００ｇ／Ｌ程度とすれば良い。乾燥する場合は、自然乾燥又は強制乾燥（加熱乾燥）のいずれであっても良いが、工業的には強制乾燥するのが良い。乾燥温度は、熱可塑性樹脂層に影響を与えない範囲であれば制限されないが、通常は１５０℃以下、特に８０〜１２０℃とすることが好ましい。なお、疎水性酸化物微粒子と抗菌剤粒子とは、同時に（同一の溶媒を使用して）付着させても良いし、別々の工程（同一あるいは別々の溶媒を使用して）で付着させても良い。 The method for carrying out the attaching step of the hydrophobic oxide fine particles and the antibacterial agent particles is not particularly limited. For example, known methods such as roll coating, gravure coating, bar coating, doctor blade coating, brush coating, and electrostatic powder method can be employed. When roll coating or the like is employed, the adhesion step can be performed by a method of drying after forming a coating film on the thermoplastic resin layer using a dispersion obtained by dispersing hydrophobic oxide fine particles in a solvent. . The solvent in this case is not limited, and in addition to water, for example, alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal pentane, normal hexane, hexyl alcohol An organic solvent such as can be selected as appropriate. At this time, a very small amount of a dispersant, a colorant, an anti-settling agent, a viscosity modifier and the like can be used in combination. The dispersion amount of the hydrophobic oxide fine particles with respect to the solvent is usually about 10 to 100 g / L. Moreover, what is necessary is just to make the dispersion amount of the antimicrobial agent particle | grains with respect to a solvent into about 5-100 g / L normally. When drying, either natural drying or forced drying (heat drying) may be used, but industrially forced drying is preferable. The drying temperature is not limited as long as it does not affect the thermoplastic resin layer, but is usually 150 ° C. or less, and preferably 80 to 120 ° C. The hydrophobic oxide fine particles and the antibacterial agent particles may be attached at the same time (using the same solvent), or may be attached in separate steps (using the same or different solvents). good.
本発明の製造方法では、前記の付着工程中及び／又は付着工程後に積層体を加熱することもできる。積層体を加熱することにより熱可塑性樹脂層に対する疎水性酸化物微粒子及び抗菌剤粒子の付着力（固定力）をより高めることができる。この場合の加熱温度Ｔは、熱可塑性樹脂層の種類等に応じて適宜設定することができ、通常は用いる熱可塑性樹脂層の融点Ｔｍ（溶融開始温度）℃に対してＴｍ−５０≦Ｔ≦Ｔｍ＋５０の範囲とすることが好ましい。 In the manufacturing method of this invention, a laminated body can also be heated during the said adhesion process and / or after an adhesion process. By heating the laminate, the adhesion force (fixing force) of the hydrophobic oxide fine particles and the antibacterial agent particles to the thermoplastic resin layer can be further increased. The heating temperature T in this case can be appropriately set according to the type of the thermoplastic resin layer and the like, and usually Tm-50 ≦ T ≦ with respect to the melting point Tm (melting start temperature) ° C. of the thermoplastic resin layer to be used. A range of Tm + 50 is preferable.
このようにして得られた積層体は、そのままで又は加工を施して包装材料として用いることができる。加工方法は、公知の包装材料の場合と同様の方法を採用することができる。例えば、エンボス加工、ハーフカット加工、ノッチ加工等を施しても差し支えない。 The laminate thus obtained can be used as a packaging material as it is or after being processed. As the processing method, the same method as in the case of a known packaging material can be adopted. For example, embossing, half-cutting, notching, etc. may be performed.
以下に実施例及び比較例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。 The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.
実施例１〜９及び比較例１
熱可塑性樹脂層を有する積層体に対して疎水性酸化物微粒子を付着させたサンプルを作製した。具体的には下記のようにして各サンプルを作製した。
Examples 1 to 9 and Comparative Example 1
A sample was prepared by attaching hydrophobic oxide fine particles to a laminate having a thermoplastic resin layer. Specifically, each sample was produced as follows.
（１）積層体の作製
（実施例１、比較例１）
坪量５５ｇ／ｍ２の紙の一方面に表印刷及びＯＰコート（オーバープリントコート）を施し、他方表面にポリウレタン系ドライラミネート接着剤（乾燥後重量３．５ｇ／ｍ２；Ｄと略称）を用いて、アルミニウムを蒸着した厚み１６μｍのポリエチレンテレフタレートフィルム（ＡＬ蒸着ＰＥＴと略称）の蒸着面と貼り合わせた。さらにこの貼り合せ材のポリエチレンテレフタレートフィルム上に熱可塑性樹脂層としてヒートシールラッカー（主成分：ポリエステル系樹脂１６０重量部＋アクリル系樹脂１０重量部＋溶剤（トルエン＋ＭＥＫの混合溶剤）４０重量部：ラッカーと略称）を乾燥後重量約３ｇ／ｍ２（乾燥条件は１５０℃×１０秒）となるように塗布した。これによって、「ＯＰ／印刷／紙／Ｄ／ＡＬ蒸着ＰＥＴ／ラッカー」なる構成の積層体を得た。
（実施例２〜６）
上記ヒートシールラッカー中にアクリル樹脂ビーズ（平均粒子径：３０μｍ、積水化成工業株式会社製）をさらに１〜２０重量部（表中に示す）添加混合し、乾燥後重量３ｇ／ｍ２（乾燥条件は１５０℃×１０秒）となるように塗布した以外は、実施例１と同様に積層体を作製した。
（実施例７〜８）
上記実施例１において、ヒートシールラッカー中にアクリル樹脂ビーズ（平均粒子径：１５μｍ、積水化成工業株式会社製）をさらに１０重量部添加混合し、乾燥後重量３ｇ／ｍ２（乾燥条件は１５０℃×１０秒）となるように塗布した以外は、実施例１と同様にして積層体を作製した。
（実施例９）
上記実施例１において、ヒートシールラッカー中にアクリル樹脂ビーズ（平均粒子径：８μｍ、積水化成工業株式会社製）をさらに１０重量部添加混合し、乾燥後重量３ｇ／ｍ２（乾燥条件は１５０℃×１０秒）となるように塗布した以外は、実施例１と同様にして積層体を作製した。
(1) Production of laminate (Example 1, Comparative Example 1)
Applying front printing and OP coating (overprint coating) on one side of paper with a basis weight of 55 g / m 2 , polyurethane-based dry laminate adhesive (weight after drying: 3.5 g / m 2 ; abbreviated as D) on the other surface Then, it was bonded to a vapor deposition surface of a 16 μm thick polyethylene terephthalate film (abbreviated as AL vapor deposition PET) on which aluminum was vapor deposited. Further, a heat seal lacquer (main component: 160 parts by weight of polyester resin + 10 parts by weight of acrylic resin + solvent (mixed solvent of toluene + MEK)) 40 parts by weight of lacquer as a thermoplastic resin layer on the polyethylene terephthalate film of the bonding material And a weight of about 3 g / m 2 (drying condition is 150 ° C. × 10 seconds). As a result, a laminate having a configuration of “OP / printing / paper / D / AL vapor deposition PET / lacquer” was obtained.
(Examples 2 to 6)
1-20 parts by weight (shown in the table) of acrylic resin beads (average particle size: 30 μm, manufactured by Sekisui Kasei Kogyo Co., Ltd.) is further added and mixed in the heat seal lacquer, and the weight after drying is 3 g / m 2 (drying conditions). Was manufactured in the same manner as in Example 1 except that coating was performed so that the temperature was 150 ° C. × 10 seconds.
(Examples 7 to 8)
In Example 1, 10 parts by weight of acrylic resin beads (average particle size: 15 μm, manufactured by Sekisui Chemical Co., Ltd.) were further added and mixed in the heat seal lacquer, and the weight after drying was 3 g / m 2 (drying condition was 150 ° C. A laminated body was produced in the same manner as in Example 1 except that the coating was performed so that × 10 seconds).
Example 9
In Example 1, 10 parts by weight of acrylic resin beads (average particle diameter: 8 μm, manufactured by Sekisui Chemical Co., Ltd.) were further added and mixed in the heat seal lacquer, and the weight after drying was 3 g / m 2 (drying condition was 150 ° C. A laminated body was produced in the same manner as in Example 1 except that the coating was performed so that × 10 seconds).
（２）疎水性酸化物微粒子の付着
（実施例１〜９）
疎水性酸化物微粒子（製品名「ＡＥＲＯＳＩＬ Ｒ８１２Ｓ」エボニック デグサ社製、ＢＥＴ比表面積：２２０ｍ２／ｇ、一次粒子平均径：７ｎｍ）５ｇをエタノール１００ｍＬに分散させてコート液を調製した。このコート液を前記（１）で作製された積層体の熱可塑性樹脂層の面に乾燥後重量で０．１１〜０．４ｇ／ｍ２（表中に示す）になるようにバーコート方式で付与した後、１００℃で１０秒程度をかけて乾燥させてエタノールを蒸発させることにより、サンプル（包装材料）を得た。
（比較例１）
実施例１の積層体において、疎水性酸化物微粒子を付着させていないものを試験用サンプルとした。
(2) Adhesion of hydrophobic oxide fine particles (Examples 1 to 9)
A coating solution was prepared by dispersing 5 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m 2 / g, primary particle average diameter: 7 nm) in 100 mL of ethanol. This coating solution is applied to the surface of the thermoplastic resin layer of the laminate prepared in (1) above by a bar coating method so that the weight after drying is 0.11 to 0.4 g / m 2 (shown in the table). After the application, the sample (packaging material) was obtained by drying at 100 ° C. for about 10 seconds to evaporate ethanol.
(Comparative Example 1)
In the laminate of Example 1, a sample to which hydrophobic oxide fine particles were not adhered was used as a test sample.
（３）疎水性酸化物微粒子からなる多孔質層の観察
実施例の包装材料において、疎水性酸化物微粒子からなる層の構造をＦＥ−ＳＥＭにより観察した。その結果、いずれの包装材料についても、疎水性酸化物微粒子により形成された三次元網目構造を有する多孔質層が観察された。その一例として、実施例４の包装材料の一部断面観察写真を図３に示す。なお、同様の構造が形成されていることは他の実施例でも観察された。
(3) Observation of porous layer made of hydrophobic oxide fine particles In the packaging material of the example, the structure of the layer made of hydrophobic oxide fine particles was observed by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles was observed for any packaging material. As an example, a partial cross-sectional observation photograph of the packaging material of Example 4 is shown in FIG. In addition, it was observed also in another Example that the same structure was formed.
試験例１（開封強度）
各実施例及び比較例で得られたサンプルについて開封強度を調べた。
各包装材料から蓋材の形状（タブ付きの縦６２ｍｍ×横６７ｍｍの矩形）に切り抜いた蓋材を用いて包装体を作製した。具体的には、フランジ付きポリスチレン製容器（フランジ幅４ｍｍ、フランジ外径６０ｍｍ×６５ｍｍ□、高さ約４８ｍｍ、内容積約１００ｃｍ３になるように成形したもの）のフランジ上に前記蓋材をヒートシールすることによって包装体をそれぞれ作製した。前記ヒートシール条件は、温度２１０℃及び圧力２ｋｇ／ｃｍ２にて１秒間で２ｍｍ幅のリング（凹状）シールとした。各包装体上の蓋材のタブを開封始点からみて仰角４５度の方向に１００ｍｍ／分の速度で引っ張り、開封時の最大荷重を開封強度（Ｎ）とし、各包装体についてｎ＝６点測定し、その平均値を求めた。その結果を表１及び表２に示す。
Test example 1 (opening strength)
The opening strength of the samples obtained in each example and comparative example was examined.
A package was produced using a lid material cut out from each packaging material into a lid shape (rectangular length 62 mm × width 67 mm with a tab). Specifically, the lid material is heated on the flange of a flanged polystyrene container (formed with a flange width of 4 mm, a flange outer diameter of 60 mm × 65 mm □, a height of about 48 mm, and an internal volume of about 100 cm 3 ). Each package was produced by sealing. The heat seal condition was a ring (concave) seal with a width of 2 mm in 1 second at a temperature of 210 ° C. and a pressure of 2 kg / cm 2 . Pull the tab of the lid on each package from the opening start point and pull it at a speed of 100 mm / min in the direction of an elevation angle of 45 degrees. The maximum load at the time of opening is the opening strength (N), and n = 6 points for each package The average value was obtained. The results are shown in Tables 1 and 2.
試験例２（密封性（封緘強度））
試験例１で作製した包装体を試験サンプルとし、｛乳及び乳製品の成分規格等に関する省令（昭和５４年４月１６日厚生省令第１７号）｝の封緘強度試験法に準じて封緘強度試験を行った。但し、容器内に空気を流入し続け、空気漏れする時点の内圧（ｍｍＨｇ）を測定した。各包装体についてｎ＝３点測定したが、いずれも測定上限値３００ｍｍＨｇ以上であった。その結果を表１及び表２に示す。
Test Example 2 (Sealing property (sealing strength))
Using the package produced in Test Example 1 as a test sample, sealing strength test according to the sealing strength test method of {Ministerial Ordinance on Milk and Dairy Product Component Standards (April 16, 1979 Ministry of Health and Welfare Ordinance No. 17)} Went. However, the internal pressure (mmHg) at the time when air continued to flow into the container and air leaked was measured. Although n = 3 points were measured for each package, all of the measurement upper limit values were 300 mmHg or more. The results are shown in Tables 1 and 2.
試験例３（初期ヨーグルト非付着性）
各積層体の熱可塑性樹脂層側を試験面とし、この面を上面として水平な平台にクリップで固定し、市販のヨーグルト（製品名「おいしいカスピ海」ソフトヨーグルト、グリコ乳業株式会社製１滴：約０．４ｇ）を至近距離から垂らし、水平な平台を傾け、ヨーグルト液滴が転げ落ちた場合は合格、平台を９０度傾けても転げ落ちずに垂れ流れた場合を不合格とした。その結果を表１及び表２に示す。
Test Example 3 (Initial yogurt non-adhesiveness)
A thermoplastic resin layer side of each laminate is used as a test surface, and this surface is used as an upper surface and fixed to a horizontal flat plate with a clip. A commercially available yogurt (product name “Delicious Caspian Sea” soft yogurt, Glico Dairy Co., Ltd., 1 drop: About 0.4 g) was dropped from the nearest distance, the horizontal flatbed was tilted, and the yogurt droplets were accepted as falling, and the case where the yogurt droplets were dropped without falling even when the flatbed was tilted 90 degrees was regarded as unacceptable. The results are shown in Tables 1 and 2.
試験例４（倒立試験）
試験例１で用いたフランジ付きポリスチレン製容器中に市販のヨーグルト（製品名「おいしいカスピ海」ソフトヨーグルト、グリコ乳業株式会社製）を８５ｇそれぞれ充填し、試験例１と同様にして蓋材をヒートシールした。各包装体を１０秒間天地逆（開口部が地の方向の状態）にして保持した後、各包装体の天地を戻した状態（＝開口部が天方向の状態）で、手指で蓋材を開封し、各蓋材の熱可塑性樹脂層側の面の状態を目視で観察した。ヨーグルトが付着していない場合を合格、ヨーグルトが付着している状態を不合格とした。その結果を表１及び表２に示す。
Test example 4 (inverted test)
85 g of commercially available yogurt (product name “Delicious Caspian Sea” soft yogurt, manufactured by Glico Dairy Co., Ltd.) is filled in the flanged polystyrene container used in Test Example 1, and the lid material is heated in the same manner as in Test Example 1. Sealed. Hold each package for 10 seconds upside down (opening is in the direction of the ground), then return the top and bottom of each package (= opening is in the direction of the top) and hold the lid with your fingers. The container was opened, and the state of the surface of each lid member on the thermoplastic resin layer side was visually observed. The case where yogurt was not attached was determined to be acceptable, and the state where yogurt was adhered was regarded as unacceptable. The results are shown in Tables 1 and 2.
試験例５（振動試験）
試験例４と同様に各包装体を作製し、これらの各包装体を振動試験機（アイデックス株式会社製ＢＦ−３０Ｕ）を用いて２０分間、３０Ｈｚ（１分間に３０回の上下往復振動）、２．２ｍｍ振幅（上下方向）、加速度約１Ｇの条件にて振動させた後、蓋材を手指で開封し、各蓋材に付着したヨーグルトの重量を測定した。０．５ｇ／ｃｕｐ未満を合格、０．５ｇ／ｃｕｐ以上を不合格とした。その結果を表１及び表２に示す。
Test example 5 (vibration test)
Each package is prepared in the same manner as in Test Example 4, and each of these packages is subjected to a vibration tester (BF-30U manufactured by IDEX Co., Ltd.) for 20 minutes and 30 Hz (30 reciprocating vibrations up and down 30 times per minute). After vibrating under the conditions of 2.2 mm amplitude (vertical direction) and acceleration of about 1 G, the lid material was opened with fingers, and the weight of yogurt adhering to each lid material was measured. Less than 0.5 g / cup was accepted and 0.5 g / cup or more was rejected. The results are shown in Tables 1 and 2.
試験例６（耐磨耗試験）
各積層体の熱可塑性樹脂層側の面を試験面とし、学振形耐磨耗試験機（JIS K 5701-1）で往復回数１００回、荷重２００ｇ、相手材：クロムメッキ面の条件にて耐磨耗試験を実施した。耐磨耗試験後に試験例３と同じヨーグルト非付着性試験を行い、ヨーグルト液滴が転げ落ちた場合は合格、平台を９０度傾けても転げ落ちずに垂れ流れた場合を不合格とした。その結果を表１及び表２に示す。
Test Example 6 (Abrasion Resistance Test)
Using the surface of the thermoplastic resin layer side of each laminate as the test surface, using the Gakushin type abrasion resistance tester (JIS K 5701-1), the number of reciprocations is 100 times, the load is 200 g, and the mating material is chrome-plated surface. A wear resistance test was performed. The same yogurt non-adhesion test as in Test Example 3 was performed after the abrasion resistance test. The yogurt droplets were judged to pass, and the case where the yogurt droplets tumbled without falling even when tilted by 90 degrees was rejected. The results are shown in Tables 1 and 2.
試験例７（接触角）
各積層体の熱可塑性樹脂層側を試験面とし、接触角測定装置（固液界面解析装置「Ｄｒｏｐ Ｍａｓｔｅｒ３００」協和界面科学株式会社製）を用いて純水の接触角を測定した。その結果を表１及び表２に示す。
Test Example 7 (Contact angle)
The contact angle measuring device (solid-liquid interface analyzer “Drop Master 300” manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of pure water using the thermoplastic resin layer side of each laminate as a test surface. The results are shown in Tables 1 and 2.
表１及び表２の結果からも明らかなように、従来品（比較例）では非付着性（撥ヨーグルト性）は全く発揮せず、純水の接触角も８５度であるのに対し、本発明（実施例）では高い非付着性を発揮していることがわかる。開封強度、密封性（封緘強度）の点においても実用上差し支えのない良好な性能を示していることがわかる。また、接触角の結果からも、本発明の積層体及び包装材料が高い撥水性を示すことがわかる。 As is apparent from the results of Tables 1 and 2, the conventional product (comparative example) does not exhibit non-adhesiveness (yogurt repellent property) at all, and the contact angle of pure water is 85 degrees. It can be seen that the invention (Example) exhibits high non-adhesiveness. It can be seen that in terms of unsealing strength and sealing performance (sealing strength), good performance with no practical impediment is shown. Moreover, it turns out that the laminated body and packaging material of this invention show high water repellency also from the result of a contact angle.
特に、本発明の積層体及び包装材料の熱可塑性樹脂層側の最外面（疎水性酸化物微粒子が付着した面）は純水の接触角が１５０度以上を示し、従来の包装材料には見られない優れた内容物非付着性を有する。また、熱可塑性樹脂層に充填粒子として無機粒子あるいは有機粒子を含有させた場合は、耐摩耗性が飛躍的に向上し、疎水性酸化物微粒子の脱落を効果的に抑制ないしは防止できる結果、良好な非付着性を持続的に得られることがわかる。 In particular, the outermost surface on the thermoplastic resin layer side of the laminate and the packaging material of the present invention (the surface on which the hydrophobic oxide fine particles are attached) has a contact angle of pure water of 150 degrees or more, which is not seen in conventional packaging materials. It has excellent non-adhesive content. In addition, when inorganic particles or organic particles are contained as filler particles in the thermoplastic resin layer, the wear resistance is remarkably improved, and the falling off of hydrophobic oxide fine particles can be effectively suppressed or prevented. It can be seen that continuous non-adhesiveness can be obtained.
実施例１０〜１２及び比較例２
熱可塑性樹脂層を有する積層体に対して疎水性酸化物微粒子と抗菌剤粒子を付着させたサンプルを作製した。具体的には下記のようにして各サンプルを作製した。
Examples 10 to 12 and Comparative Example 2
A sample was prepared by attaching hydrophobic oxide fine particles and antibacterial agent particles to a laminate having a thermoplastic resin layer. Specifically, each sample was produced as follows.
（１）積層体の作製
（比較例２）
厚み３８μｍのポリエチレンテレフタレートフィルム（ＰＥＴ）上に熱可塑性樹脂層としてアクリル樹脂ビーズ入りヒートシールラッカー（主成分：ポリエステル系樹脂１６０重量部＋アクリル系樹脂１０重量部＋アクリル樹脂ビーズ（平均粒子径：２０μｍ、積水化成工業株式会社製）を１１重量部＋溶剤（トルエン＋ＭＥＫの混合溶剤）４０重量部：ラッカーと略称）を乾燥後重量約３ｇ／ｍ２（乾燥条件は１５０℃×１０秒）となるように塗布した。これによって、「ＰＥＴ／ビーズ入りラッカー」なる構成の積層体を得た。
（実施例１０〜１２）
疎水性酸化物微粒子（製品名「ＡＥＲＯＳＩＬ Ｒ８１２Ｓ」エボニック デグサ社製、ＢＥＴ比表面積：２２０ｍ２／ｇ、一次粒子平均径：７ｎｍ）５ｇと銀ゼオライト系抗菌剤粒子（製品名「ゼオミック」株式会社シナネンゼオミック製、平均粒子径：３μｍ）を１．０〜５．０ｇ（表３に重量比を記載）を、エタノール１００ｍＬに分散させてコート液を調製した。このコート液を比較例２と同様に作製した積層体の熱可塑性樹脂層の面に乾燥後重量で０．５〜０．８ｇ／ｍ２（表３に記載）になるようにバーコート方式で付与した後、１００℃で１０秒程度をかけて乾燥させてエタノールを蒸発させることにより、サンプル（包装材料）を得た。
(1) Production of laminate (Comparative Example 2)
A heat seal lacquer containing acrylic resin beads as a thermoplastic resin layer on a polyethylene terephthalate film (PET) having a thickness of 38 μm (main component: 160 parts by weight of polyester resin + 10 parts by weight of acrylic resin + acrylic resin beads (average particle diameter: 20 μm) , Sekisui Kasei Kogyo Co., Ltd.) 11 parts by weight + solvent (toluene + MEK mixed solvent) 40 parts by weight: abbreviated as lacquer) after drying, the weight is about 3 g / m 2 (drying conditions are 150 ° C. × 10 seconds) It was applied as follows. Thus, a laminate having a configuration of “PET / beaded lacquer” was obtained.
(Examples 10 to 12)
Hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m 2 / g, primary particle average diameter: 7 nm) A coating solution was prepared by dispersing 1.0 to 5.0 g (weight ratio shown in Table 3) of Zeomic, average particle size: 3 μm in 100 mL of ethanol. This coating liquid was applied to the surface of the thermoplastic resin layer of the laminate produced in the same manner as in Comparative Example 2 by a bar coating method so that the weight after drying was 0.5 to 0.8 g / m 2 (described in Table 3). After the application, the sample (packaging material) was obtained by drying at 100 ° C. for about 10 seconds to evaporate ethanol.
疎水性酸化物微粒子からなる多孔質層の観察
実施例１０〜１２の包装材料において、疎水性酸化物微粒子からなる層の構造をＦＥ−ＳＥＭにより観察した。その結果、いずれの包装材料についても、疎水性酸化物微粒子により形成された三次元網目構造を有する多孔質層が観察された。
Observation of porous layer made of hydrophobic oxide fine particles In the packaging materials of Examples 10 to 12, the structure of the layer made of hydrophobic oxide fine particles was observed by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles was observed for any packaging material.
試験例１〜７
各実施例及び比較例で得られたサンプルについて前記試験例１〜７と同様の試験を実施した。その結果を表３に示す。
Test Examples 1-7
Tests similar to those of Test Examples 1 to 7 were performed on the samples obtained in each Example and Comparative Example. The results are shown in Table 3.
試験例８（抗菌性試験）
実施例１０〜１２及び比較例２の各積層体の熱可塑性樹脂層側を試験面とし、次の条件により抗菌性試験を実施した。その結果を表５に示す。表４には、接種直後対照区の菌数と２４時間後対照区の菌数を示しており、抗菌性試験が有効であることがわかる。
１）試験方法：ＪＩＳ Ｚ２８０１−２０００（Ｎ＝１）
２）菌液濃度：１／５００ＮＢ
３）菌液滴下量：０．３ｍｌ
４）保存温度：３５±１℃
５）保存湿度：＞９０％
６）使用細菌：黄色ブドウ球菌（NBRC12732）
大腸菌（NBRC3972）
７）備考：殺菌方法は紫外線１０分間照射
被覆フィルムとしてメンブランフィルター（φ２５ｍｍ円形を使用）
Test Example 8 (Antimicrobial test)
The thermoplastic resin layer side of each laminate of Examples 10 to 12 and Comparative Example 2 was used as a test surface, and an antibacterial test was performed under the following conditions. The results are shown in Table 5. Table 4 shows the number of bacteria in the control group immediately after inoculation and the number of bacteria in the control group 24 hours later, which shows that the antibacterial test is effective.
1) Test method: JIS Z2801-2000 (N = 1)
2) Bacterial fluid concentration: 1 / 500NB
3) Bacteria droplet amount: 0.3 ml
4) Storage temperature: 35 ± 1 ° C
5) Storage humidity:> 90%
6) Bacteria used: Staphylococcus aureus (NBRC12732)
E. coli (NBRC3972)
7) Remarks: Sterilization method is UV irradiation for 10 minutes
Membrane filter as coating film (φ25mm circle is used)
判定０：抗菌効果有り（ＪＩＳ Ｚ２８０１の効果（抗菌活性値２．０以上）をいう。
Determination 0: An antibacterial effect is present (an effect of JIS Z2801 (antibacterial activity value of 2.0 or more)).
Claims (9)
The packaging material containing the laminated body in any one of Claims 1-8.
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