JPS63288749A - Water-resistant adhesive biaxially drawn film - Google Patents
Water-resistant adhesive biaxially drawn filmInfo
- Publication number
- JPS63288749A JPS63288749A JP12419787A JP12419787A JPS63288749A JP S63288749 A JPS63288749 A JP S63288749A JP 12419787 A JP12419787 A JP 12419787A JP 12419787 A JP12419787 A JP 12419787A JP S63288749 A JPS63288749 A JP S63288749A
- Authority
- JP
- Japan
- Prior art keywords
- water
- film
- resin
- polyester
- compound
- 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.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 20
- 239000000853 adhesive Substances 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 18
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- 239000011342 resin composition Substances 0.000 claims abstract description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000011229 interlayer Substances 0.000 abstract description 6
- 229920006397 acrylic thermoplastic Polymers 0.000 abstract 1
- 229920002313 fluoropolymer Polymers 0.000 abstract 1
- 239000004811 fluoropolymer Substances 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract 1
- 229920005573 silicon-containing polymer Polymers 0.000 abstract 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 abstract 1
- 150000003673 urethanes Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 60
- 238000000034 method Methods 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 17
- -1 polyethylene terephthalate Polymers 0.000 description 17
- 238000000576 coating method Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 9
- 229920006267 polyester film Polymers 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000011104 metalized film Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 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
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は数群された熱可塑性樹脂フィルム、特に耐水性
、耐熱水性に優れた接着力を何する二軸配向された熱Ｉ
Ｉ）塑性樹脂フィルムに関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a biaxially oriented thermoplastic resin film that has several groups of thermoplastic resin films, particularly a biaxially oriented thermoplastic resin film that has excellent adhesive strength and excellent water resistance and hot water resistance.
I) Regarding plastic resin film.
（従来の技術）
熱ｉＩ■塑性樹脂フィルム、特に二軸配向されたポリエ
ステル、ポリアミド、ポリオレフィン等のフィルムは包
装材料用、装飾用、金属蒸着用、写真用、製図用、電気
用、磁気テープ用その他の各種の１’ｎＸＺ用途等の非
常に多岐にわたる分野での応用がなされている。しかし
これらいずれの場合においても熱可塑性樹脂フィルムが
すべての性質において満足されているわけではない。殆
んどの用途の場合、フィルムはり１体で用いられること
は少なく、何等からの２次加工がなされる。このためそ
の加Ｉ一時における作業性、製品の性能及び品質の安定
性等の点から、特に表面の接着特性は重要な課題とされ
ている。例えば接着性に関しては、包装用途の場合は印
刷インキとの間の接着性が、金属蒸着をする場合には蒸
着層との接着性が、写真用フィルムベースきして用いる
場合にはゼラチン層との接着性が、製図用として用いる
場合にはマット化剤層との接着性が、磁気テープ用とし
て用いる場合には磁性中料層との接着性等がそれぞれｌ
な課題であり、他の特性に悪影響なく接着性を改良する
事が必妥になる。(Prior art) Thermal II plastic resin films, especially biaxially oriented polyester, polyamide, polyolefin, etc. films, are used for packaging materials, decoration, metal deposition, photography, drafting, electricity, and magnetic tape. It has been applied in a wide variety of fields including various other 1'nXZ uses. However, in all of these cases, the thermoplastic resin film does not satisfy all properties. In most applications, a single film beam is rarely used, and some secondary processing is performed. Therefore, from the viewpoint of workability during application, product performance, quality stability, etc., the adhesive properties of the surface are particularly important issues. For example, with regard to adhesion, in the case of packaging applications, it is adhesion with printing ink, in the case of metal vapor deposition, it is adhesion with the vapor deposited layer, and when it is used as a photographic film base, it is the adhesion with the gelatin layer. When used for drafting, the adhesion with the matting agent layer, and when used for magnetic tape, the adhesion with the magnetic medium layer, etc.
Therefore, it is essential to improve adhesion without adversely affecting other properties.
特に金属等で蒸着されたポリエチレンテレフタレートの
ごときポリエステルフィルムに易ヒートシール材料とし
てのポリオレフィン層が積層されたフィルム積層体は食
品包装、工業部品包装、保護被膜専の用途においてその
優れた酸素防止性、水分防市性、史には可視光、紫外線
等に対する光線遮へい性の故に多用されているが、例え
ば食品包装分野においては内包する食品類の殺菌を目的
としてなされる煮沸処理等の熱水処理によって容易に剥
離してしまう欠点がある。特にこれら剥離現象において
問題となる個所は、基材であるポリエステルフィルムと
金属蒸着層との界面における耐水、耐熱水接着力の不足
によって引きおこされる場合が多い。In particular, film laminates in which a polyolefin layer as an easily heat-sealable material is laminated on a polyester film such as polyethylene terephthalate vapor-deposited with metal etc. have excellent oxygen prevention properties and are used for food packaging, industrial parts packaging, and protective coating applications. Moisture-repellent properties are widely used in history due to their ability to shield visible light and ultraviolet rays, but for example, in the food packaging field, they are used in hot water treatments such as boiling to sterilize the food products they contain. It has the disadvantage that it peels off easily. In particular, these peeling phenomena are often caused by insufficient water resistance and hot water adhesive strength at the interface between the polyester film as the base material and the metal vapor deposited layer.
基材ポリエステルフィルムと金属蒸着層との接着性を改
りする方法としては英国特許第１３７０８９３号に記載
されたフィルムの加熱による方法などの各種の方法が提
案されいるが、いずれもまだ充分とはいえないものであ
り、特に耐水、耐熱水接着力において不充分であった。Various methods have been proposed to improve the adhesion between the base polyester film and the metal vapor deposited layer, such as the method of heating the film described in British Patent No. 1,370,893, but none of them are yet satisfactory. In particular, it was insufficient in terms of water resistance and hot water resistant adhesive strength.
一方、ポリエステルフィルムの印刷インキや写真用乳剤
、マット化剤、磁性塗料その他の各種塗料に対する接着
性を改善する事を目的とした各種の方法も提案されてお
り、特に印刷フィルムにおいては印刷層の熱水処理時の
剥離を改良する方法として特公昭５５−４５８３号公報
、特公昭５５−１２８７０号公報等に見られるような特
定の共重合ポリエステルをフィルム用ポリエステル原料
にブレンドする方法も提案されているが、このような方
法も対象が金属蒸着層の場合には充分な耐水、耐熱水接
着性を得られるには至っていない。On the other hand, various methods have been proposed to improve the adhesion of polyester films to printing inks, photographic emulsions, matting agents, magnetic paints, and other paints. As a method of improving peeling during hot water treatment, a method has also been proposed in which a specific copolymerized polyester is blended into a polyester raw material for film, as seen in Japanese Patent Publications No. 55-4583 and Japanese Patent Publication No. 55-12870. However, even with this method, sufficient water resistance and hot water resistant adhesion cannot be obtained when the target is a metal vapor deposited layer.
史に各塗料用途においてアルキルチタネート系、ウレタ
ン系等のいわゆるアンカーコート剤をフィルム表面に塗
布する方法が用いられる。しかし、これらは、一般的に
は、その性能が未だ不充分であるばかりでな（、ある場
合には有効であっても、他の場合にはまったく効果がな
いなどの汎用性に乏しく、特に金属蒸着層に対しては、
殆んどその効果を発押し得ないのが現状である。またそ
れ自身加水分解、貯蔵性等の点で非常に不安定なものが
多い。さらには、これらはいずれも高価格であり、一般
に有機溶剤系で用いられるためその引火性、Ｆｕ性等の
危険が多く、作業性、公害、省エネルギー等の立場から
も非常に不都合なものである。Historically, in various coating applications, a method has been used in which a so-called anchor coating agent such as an alkyl titanate type or urethane type agent is applied to the film surface. However, in general, these methods not only have insufficient performance, but also lack versatility, such as being effective in some cases but not at all in others. For the metal deposited layer,
The current situation is that it is hardly possible to achieve that effect. Moreover, many of them are very unstable in terms of hydrolysis, storage stability, etc. Furthermore, all of these are expensive, and because they are generally used in organic solvents, there are many dangers such as flammability and Fu, and they are extremely inconvenient from the standpoint of workability, pollution, and energy conservation. .
また、最近これらのアンカーコート剤に代るポリエステ
ルに良好な接着性を有する下塗り剤として、特開昭４８
−３７４８０号公報に一例がみられるようなポリエステ
ル系、ポリエーテルエステル共重合体系専が提案されて
いる。しかしながら、これらの重合体は、一般的にはポ
リエステルフィルムに対する接着性は良好であるが、他
の２次加工時における−１−塗り剤に対しては対象によ
り不充分な場合があり、汎用性に乏しい。特に比較的極
性の高い成分の塗料や、金属蒸着層に対しては、接着性
が不充分である場合が多い。又、これら加工剤に適用で
きる溶剤も、毒性、引火性の強いものが多く特公昭５４
−１６５５７号公報にもみられるごとく、加工剤を組成
的に変化させ水溶化させる試みも数多くなされているが
、この場合には、当然のことながら、得られた下塗り塗
膜の耐水性が乏しく、金属蒸着フィルムが水分に接する
ごとき最終用途では剥離欠点を発生しやすい。In addition, recently, as an undercoat agent with good adhesion to polyester as an alternative to these anchor coating agents, JP-A-48
Polyester and polyether ester copolymer systems have been proposed, an example of which can be seen in Japanese Patent No. 37480. However, although these polymers generally have good adhesion to polyester films, they may be insufficient for -1-coatings used in other secondary processing, depending on the target, and are not very versatile. Poor. In particular, adhesion is often insufficient for paints with relatively highly polar components and metal vapor deposited layers. In addition, many of the solvents that can be applied to these processing agents are highly toxic and flammable.
As seen in Publication No. 16557, many attempts have been made to make the finishing agent water-soluble by changing its composition, but in this case, as a matter of course, the water resistance of the resulting undercoat film is poor. In end-use applications where metallized films come into contact with moisture, peeling defects are likely to occur.
一方、これらの方法とは別に、ポリオレフィン系フィル
ムを中心としたプラスチックフィルムに対し、ヒートシ
ール性、ガスバリア性等を付与する目的で塩化ビニリデ
ン系樹脂を塗工する際のアンカーコーティング剤として
、アクリル酸エステル又はメタクリル酸エステル及び、
アクリル酸又はメタクリル酸、メチロールアクリルアミ
ド、アクリルアミド又はメタクリルアミド等の共重合体
により成る水容性アクリル系重合体（特開昭４８−−ｓ
ｏｘ２７ｑ公＋Ｖ）等のアクリル系アンカーコ−ト剤が
提案されている。しかしこの場合には、水溶性であるた
めに、当然のことながら耐水性を姿する用途には問題を
生じやすい。と同時に完全な水溶液系の場合には、疎水
性フィルム基材に対する濡れが悪く、均一な塗膜が得ら
れ難い。又、これらアクリル系化合物を、界面活性剤を
乳化剤として含む系で乳化重合を杼ない、粒子状エマル
ジョンを塗布する方法（特開昭５２−１５５６３３号公
報）等も提案されているが、含まれる界面活性剤のため
に、やはり耐水性が問題となり良好な耐水、耐熱水層間
接着力を有する金属蒸着フィルムが得られていない。On the other hand, apart from these methods, acrylic acid is used as an anchor coating agent when applying vinylidene chloride resin to plastic films, mainly polyolefin films, for the purpose of imparting heat sealing properties, gas barrier properties, etc. ester or methacrylic acid ester and
A water-soluble acrylic polymer consisting of a copolymer of acrylic acid or methacrylic acid, methylol acrylamide, acrylamide or methacrylamide (JP-A-48-S
Acrylic anchor coating agents such as ox27q+V) have been proposed. However, in this case, since it is water-soluble, problems tend to occur in applications requiring water resistance. At the same time, in the case of a completely aqueous solution system, it is difficult to wet the hydrophobic film substrate and it is difficult to obtain a uniform coating film. In addition, a method has been proposed in which these acrylic compounds are coated with a particulate emulsion without emulsion polymerization in a system containing a surfactant as an emulsifier (Japanese Unexamined Patent Publication No. 155633/1982), but it is included. Because of the surfactant, water resistance is also a problem, and a metallized film having good water resistance and hot water resistant interlayer adhesion strength has not been obtained.
（発明が解決しようとする問題点）
本発明者等は上記従来技術の問題点に鑑み、二軸配向さ
れた熱可塑性樹脂フィルムにおいて耐水性、耐熱水性に
優れた接着力、特に、金属等の蒸着層との層間接着力に
優れたフィルムを提供しようとするものである。(Problems to be Solved by the Invention) In view of the above-mentioned problems of the prior art, the present inventors have developed a biaxially oriented thermoplastic resin film with excellent adhesive strength and excellent water resistance and hot water resistance. The purpose is to provide a film that has excellent interlayer adhesion with the vapor deposited layer.
（問題点を解決するための手段）
すなわち本発明は熱可塑性樹脂よりなるフィルムの少な
くとも片面に、水不溶性でかつ水分散性を有する樹Ｒｒ
Ｎへ）の１種又は２種以］−及び疎水性化合物＋［３１
より選ばれた１種又は２種以にを重量比で（Ａ）／＋［
３１＝ １００１０．５〜１００／１００となるごとく
配合された樹脂組成物層が形成されてなるｒａｔを特徴
とする耐水接着性二輪配向フィルムである。(Means for Solving the Problems) That is, the present invention provides water-insoluble and water-dispersible resin Rr on at least one side of a film made of a thermoplastic resin.
to N)] - and hydrophobic compound + [31
The weight ratio of one or more selected from (A)/+[
This is a water-resistant adhesive two-wheel oriented film characterized by a rat in which a resin composition layer is formed with a ratio of 31=10010.5 to 100/100.
本発明における水不溶性でかつ水分散性を有する樹脂（
Ａ）としてはポリエステル樹脂、ビニル系樹脂、アクリ
ル系樹脂、アルキッド樹脂、ウレタン樹脂、ビニリデン
系樹脂、ジエン系樹脂、ポリオレフィン系共重合樹脂、
ポリアミド系樹脂、エポキシ系樹脂、アミン樹脂その他
の付加縮合型、ポリ縮合型、ポリ付加型等の縮合系及び
不飽和重合型、開環取合型等の重合系等の各種合成樹脂
類、繊維素樹脂、ゴム系樹脂、タンパク質系樹脂等の゛
ト合成及び天然系樹脂類等の各種の樹〃ｈが挙げられる
が、ポリエステル系、アクリル系、ポリウレタン系等か
ら選ばれたものが好ましく用いられる。The water-insoluble and water-dispersible resin (
A) includes polyester resin, vinyl resin, acrylic resin, alkyd resin, urethane resin, vinylidene resin, diene resin, polyolefin copolymer resin,
Various synthetic resins and fibers, including polyamide resins, epoxy resins, amine resins, and other condensation types such as addition condensation types, polycondensation types, and polyaddition types, and polymerization types such as unsaturated polymerization types and ring-opening combination types. Examples include various types of resins such as synthetic resins, rubber resins, protein resins, etc., and natural resins, but those selected from polyester, acrylic, polyurethane, etc. are preferably used. .
特に本発明でｄう水不溶性でかつ水分散性を示す樹脂組
成として、ポリエステル系の場合には全エステル形成性
ジカルボン酸成分のうチ、０．５〜１５モル％がスルホ
ン酸金属塩基含有ジカルボン酸であるようなジカルボン
酸類とグリコール類とから成る共重合ポリエステル類が
、アクリル系の場合には共重合成分の５０モル％以上が
アクリル酸又はメタアクリル酸のアルキルエステル類か
らなり、その他の共重合成分として遊離のカルボン酸、
スルホン酸又はその塩、或いはヒドロキシル基、グリシ
ジル基、アミン基、アミド基その他の官能性基をイｒし
たビニル系単量体等を有する共重合体であり、更に好ま
しくは界面活性剤等の乳化剤を実質的に含まないような
共重合体分散液が、更にポリウレタン系としてはそのポ
リオール成分がポリエステル系であり、かつ該ポリエス
テルにおける酸成分の５０モル％以上が芳香族カルボン
酸類から得られたごときポリエステル類とジイソシアネ
ート類から形成されたごときポリエステルウレタン共重
合体がより好ましく用い得る。In particular, in the case of a polyester-based resin composition that is water-insoluble and water-dispersible in the present invention, 0.5 to 15 mol% of the total ester-forming dicarboxylic acid component is a sulfonic acid metal base-containing dicarboxylic acid. If the copolymerized polyester consisting of dicarboxylic acids and glycols is an acrylic type, 50 mol% or more of the copolymerization component consists of an alkyl ester of acrylic acid or methacrylic acid, and other copolymerized polyesters are used. Free carboxylic acid as a polymerization component,
A copolymer containing sulfonic acid or a salt thereof, or a vinyl monomer containing a hydroxyl group, glycidyl group, amine group, amide group or other functional group, and more preferably an emulsifier such as a surfactant. A copolymer dispersion liquid that does not substantially contain , and furthermore, as a polyurethane type, the polyol component thereof is a polyester type, and 50 mol% or more of the acid component in the polyester is obtained from aromatic carboxylic acids. Polyester urethane copolymers such as those formed from polyesters and diisocyanates are more preferably used.
本発明でいう水不溶性とは、樹脂（△）を８０°Ｃの熱
水中で撹拌しても熱水中に樹脂が消散しないことを意味
し、具体的には樹脂を過剰の８０℃熱水中で２４時間撹
拌処理した後の重電減少が５重量％以ドのものである。Water-insoluble in the present invention means that even if the resin (△) is stirred in hot water at 80°C, the resin does not dissipate in the hot water. The weight loss after stirring in water for 24 hours is 5% by weight or more.
また水分散性とは機械的な撹拌や超音波等の混合、乳化
、分散等の処理により水に対して５ｍ融％以−Ｌの樹脂
が均−系を作り得るものを言う。またその分子ｔ！ｉ岐
の作製方法としては、すｉ電体成分を撹拌しつつ重合せ
しめて樹脂分散液とするいわゆる乳化重合法や、取合、
縮合等の操作により高分子とした樹脂を分散液とする方
法等、既知の各種の方法が用い得る。Furthermore, water dispersibility refers to the ability to form a homogeneous system of resin with a melting % of 5 m% or more in water by mechanical stirring, mixing using ultrasonic waves, emulsification, dispersion, etc. Also that molecule t! Methods for producing i-type include the so-called emulsion polymerization method in which the i-electrode component is polymerized while stirring to form a resin dispersion, and
Various known methods can be used, such as a method in which a resin made into a polymer by operations such as condensation is made into a dispersion liquid.
またこれらの樹脂水分散液を安定に得る手段として、乳
化剤を用いる方法や、少電の水溶性有機化合物を併用す
る方法等があり、いずれであっても良いが、本発明の主
旨である耐水性の点からは乳化剤は用いないか、出来る
だけ少晴が望ましい。In addition, as means for stably obtaining these resin aqueous dispersions, there are a method of using an emulsifier, a method of using a low-current water-soluble organic compound, etc., and any of these methods may be used, but the main purpose of the present invention is water resistance. From the viewpoint of properties, it is desirable not to use an emulsifier or to use as little light as possible.
水溶性有機化合物を併用する場合には、２０”ＣでｌΩ
の水に対する溶解度が２０ｇ以上のイｒ機化合物が好ま
しい。これらの方法以外に樹脂又はその’ｌ’−！１１
体を溶解し得る６機溶媒中に溶解せしめて樹脂溶液とな
した後、水と混合せしめ、分離或は分離する方法により
有機溶媒のみを除去する方法等もある。When water-soluble organic compounds are used together, 1Ω at 20”C
An organic compound having a solubility in water of 20 g or more is preferred. In addition to these methods, resin or its 'l'-! 11
There is also a method in which only the organic solvent is removed by dissolving the resin solution in a solvent capable of dissolving the resin, mixing it with water, and separating or separating the resin solution.
一方本発明における疎水性化合物（Ｉ３１とは、水に対
する親和性が少なく水不溶性樹脂（Ａｌと混合可能な化
合物をさすが、具体的には疎水性化合物ｆｉ＋それ自身
を単独で皮膜となした時の該皮膜表面の水による接触角
０の余弦（ｃｏｓＬ）が−１，０以１．０．３５以下の
値を示す化合物が効果的に用いられ−０，８５〜０．２
５の範囲の値を示すものがより好ましく用い得る。この
値が０．３５を越える場合には所期の疎水性の改善効果
を充分に得るｉｊＩが出来ない。下限としては−１，０
まで特に制限はないが、化合物の入手の容易さや、樹脂
ｆＡｌとの相溶性等の実用、ヒの観点から−０，８５程
度であれば充分な効果を期待し得る（但し０≦−〇≦−
π）。On the other hand, the hydrophobic compound (I31) in the present invention refers to a compound that has low affinity for water and can be mixed with a water-insoluble resin (Al, but specifically, when the hydrophobic compound fi + itself is formed into a film alone) A compound exhibiting a cosine of zero contact angle (cosL) of the film surface with water from -1.0 to 1.0.35 is effectively used.
Those exhibiting a value in the range of 5 can be more preferably used. If this value exceeds 0.35, ijI cannot sufficiently obtain the desired hydrophobicity improvement effect. The lower limit is -1,0
There is no particular limit to the above, but from the viewpoint of ease of obtaining the compound, compatibility with the resin fAl, etc., a sufficient effect can be expected if it is around -0.85 (however, 0≦-〇≦ −
π).
このような値を示す化合物の例としてはシリコン系、又
はフッ素系の重合体或は共重合体、パラフィン系化合物
、動植物及び鉱物油脂類或はそれらの変性体、ポリオレ
フィン系の重合体或は共重合体、その他の化合物が挙げ
られるが皮膜形成性、水への分散性或は水分散性樹脂Ｉ
ＡＩへの混合性、相溶性等の観点から選択されなければ
ならない。これらの観点からシリコン系またはフッ素系
の重合体がより好ましく、特に水不性樹脂仏）との相溶
性の点から市；４比で少なくとも２０％以−Ｌがポリエ
ステル部分から成るごときポリエステル変性シリコーン
化合物等が好適に用い得る。Examples of compounds exhibiting such values include silicone-based or fluorine-based polymers or copolymers, paraffin-based compounds, animal, vegetable, and mineral oils and fats or modified products thereof, and polyolefin-based polymers or copolymers. Examples include polymers and other compounds, but film-forming, water-dispersible or water-dispersible resins I
It must be selected from the viewpoints of miscibility and compatibility with AI. From these points of view, silicone-based or fluorine-based polymers are more preferable, and in particular, from the viewpoint of compatibility with water-insoluble resins, polyester-modified silicones in which at least 20% or more of L is composed of polyester moieties are preferred. Compounds etc. can be suitably used.
水不溶性でかつ水分散性を有する樹脂（Ａ）と疎水性化
合物（Ｂ）の配合比は、重量比でＴＡＩ／（８１＝ １
００１０．５〜１００／１００の範囲とする必要がある
。（Ａｌ ／ １８）が１００１０．５より大きい場合
には所期の耐水性を得る事が出来ず、１００／１００よ
り小さい場合には充分な接着力を得る事が困難になる。The blending ratio of the water-insoluble and water-dispersible resin (A) and the hydrophobic compound (B) is TAI/(81=1
It needs to be in the range of 0010.5 to 100/100. If (Al/18) is larger than 10010.5, the desired water resistance cannot be obtained, and if it is smaller than 100/100, it becomes difficult to obtain sufficient adhesive strength.
さらにＴＡ）／ｆＢｌ＝ １００ ／ ５〜１００１５
０の範囲がより好ましい。水不溶性でかつ水分散性を自
゛する樹脂（Ａｌ及び疎水性化合物ｆＢ）はそれぞれ１
種を配合しても良いし、２挿置りを組合せ配合しても良
い。特に樹脂（△）の場合、共重合ポリエステルとアク
リル系共重合体またはこれらとポリウレタン系樹脂等と
の併用利用は接着性の点において効果的である場合が多
い。Furthermore, TA)/fBl= 100/5~10015
A range of 0 is more preferable. Water-insoluble and water-dispersible resins (Al and hydrophobic compound fB) each have 1
Seeds may be added or a combination of two seeds may be added. Particularly in the case of resin (△), the combined use of a copolymerized polyester and an acrylic copolymer, or a combination of these and a polyurethane resin or the like is often effective in terms of adhesiveness.
これらの配合樹脂組成物中にシリカ、炭酸カルシウム、
カオリナイト、アルミナ、タルク、硫酸バリウムその他
各種の無機系粒子や、ベンゾグアナミン系樹脂やポリス
チレン系樹脂等の有機系の０．０１〜１０μ程度の不活
性粒子を添加することにより滑り性や耐ブロッキング性
の改良がはかれる場合がある。また必要により有機系、
無機系の制電剤その他の添加剤を混合する事は、本来の
目的である接着力の耐水性、耐熱水性を大きく損わない
限り、添加物、添加量について同等制限されるものでは
ない。Silica, calcium carbonate,
By adding various inorganic particles such as kaolinite, alumina, talc, barium sulfate, and organic inert particles of about 0.01 to 10 μm such as benzoguanamine resin and polystyrene resin, slipperiness and blocking resistance are improved. Improvements may be made. In addition, if necessary, organic
When mixing inorganic antistatic agents and other additives, there are no similar restrictions on the additives or the amount added, as long as the original purpose of adhesion, water resistance, and hot water resistance is not significantly impaired.
本発明における配合された樹脂組成物層をフィルム表面
に形成せしめる方法としては、前記水不溶性でかつ水分
散性を有する樹脂ｔＡ＋と疎水性化合物（Ｂ）の混合さ
れた樹脂組成物とフィルム用原料樹脂とを押出機の別々
の押出口から同時に共押出しする方法や樹脂ｆＡ＋と疎
水性化合物＋［ｌｌの混合された樹脂組成物の溶融シー
トをフィルムの上に押出し積層する方法、樹脂ＴＡ）と
疎水性化合物＋［３１の混合された樹脂組成物の水系分
散液をフィルムをコーティングする方法等があり、いず
れを採用してもよいが該樹脂組成物を少なくともその５
０重量％以−にが水よりなる媒体中に分散させた分散液
をロールコーティング等の塗布法によって形成させるの
が望ましく、特に熱可塑性樹脂が溶融押出しされた後の
未延伸フィルム、あるいは縦または横方向へ一軸に延伸
された後のフィルムに塗布を行ない、次いで二軸または
一軸方、向に延伸を行なった後熱処理を行なうことによ
り二軸配向されたコートフィルムを得る方法がコート被
膜の密着性、透明性及び経済性の見地から好ましい。特
に塗膜の乾燥性、作業性等を考慮した場合、−軸方向に
延伸した後塗布する方法が好ましく、縦方向に一軸延伸
された後中布し、更に横方向に延伸することにより二軸
配向フィルムを得る方法が特に好ましい。As a method for forming a blended resin composition layer on a film surface in the present invention, a resin composition in which the water-insoluble and water-dispersible resin tA+ and a hydrophobic compound (B) are mixed and a film raw material are used. A method of simultaneously coextruding resin and a resin from separate extrusion ports of an extruder, a method of extruding and laminating a molten sheet of a mixed resin composition of resin fA + and a hydrophobic compound + [ll on a film, resin TA) and There is a method of coating a film with an aqueous dispersion of a resin composition mixed with a hydrophobic compound + [31].
It is preferable to form a dispersion in a medium containing 0% by weight or less of water by a coating method such as roll coating. In particular, it is preferable to form an unstretched film after the thermoplastic resin has been melt-extruded, or a longitudinal or vertical film. A method for obtaining a biaxially oriented coated film is to coat the film after it has been uniaxially stretched in the transverse direction, then heat-treat the film after stretching in the biaxial or uniaxial direction. preferred from the viewpoints of performance, transparency and economy. In particular, when considering the drying properties and workability of the coating film, it is preferable to apply the coating after stretching it in the -axial direction. Particularly preferred are methods for obtaining oriented films.
塗布されるべき塗布晴は二軸延伸後のフィルム上に存在
する：１１として０．００５〜５ｇ／Ｉ１１’が好まし
く０．０１〜３ｇ／ｒｌが特に好ましい。塗布量が０．
００５ｇ／ｍ’未満の場合は所期の効果が得られず、５
ｇ／Ｉ／を越えると、プロ＋７キング、透明性紙Ｆ等の
弊害を生じやすい。また必要により塗布工程の前または
後に、コロナ処理その他による物理的、化学的な表面活
性化処理を行なっても良い。The coating film to be applied is present on the film after biaxial stretching: 11 is preferably 0.005 to 5 g/I11', particularly preferably 0.01 to 3 g/rl. Coating amount is 0.
If it is less than 0.005g/m', the desired effect will not be obtained, and the
If it exceeds g/I/, problems such as Pro+7 King and Transparent Paper F tend to occur. Further, if necessary, physical or chemical surface activation treatment such as corona treatment may be performed before or after the coating step.
また本発明において、該水性樹脂組成物分散液が塗布さ
れるべき基材として好ましいポリエステルフィルムは、
主たる成分がポリエチレンテレフタレートより成り、そ
の８０玉Ｍ％以］１がポリエチレンテレフタレートであ
るルが好ましい。ポリエステル成分として残り２０重量
％未満は、ジカルボン酸成分として芳香族、脂肪族、脂
環族のジカルボン酸が使用でき、芳香族ジカルボン酸と
してはイソフタル酸、オルソフタル酸、２，６−ナフタ
レンジカルボン酸等、また脂肪族および脂環族のジカル
ボン酸としてはコハク酸、アジピン酸、セバシン酸、シ
ュウ酸、１，３−シクロペンタンジカルボン酸、１．２
−シクロヘキサンジ力ルボ７＋’Ｌ １１３−シクロ
ヘキサンジカルボン酸、１１４−シクロヘキサンジカル
ボン酸等や、ｐ−ヒドロキシ安息香酸等のオキシ酸の一
部等と、グリコール成分として炭素数２〜８個の脂肪族
グリコールまたは炭素数６〜１２個の脂環族グリコール
であり、具体的にはエチレングリコール、１．２−プロ
ピレングリコール、１．３−プロパンジオール、１．４
−ブタンジオール、ネオペンチルグリコール、１．６−
ヘキサンジオール、１，２−シクロヘキサンジメタツー
ル、１，３−シクロヘキサンジメタツール、１．４−シ
クロヘキサンジメタツール、ｐ−キシリレングリコール
、ジエチレングリコ−Ｊし、トリエチレングリコールな
ど、またポリエーテルとしてポリエチレングリコール、
ポリプロピレングリコール、ポリテトラメチレングリコ
ールなどとから成るエステルが含まれていても良い。こ
れらの、ポリエチレンテレフタレート以外の成分は共重
合、重合体混合いずれの方法によって含まれても良い。Further, in the present invention, polyester films preferable as substrates to which the aqueous resin composition dispersion is applied include:
Preferably, the main component is polyethylene terephthalate, and 80% or more of polyethylene terephthalate is polyethylene terephthalate. For the remaining less than 20% by weight of the polyester component, aromatic, aliphatic, and alicyclic dicarboxylic acids can be used as the dicarboxylic acid component, and the aromatic dicarboxylic acids include isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, etc. , and aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, oxalic acid, 1,3-cyclopentanedicarboxylic acid, 1.2
-Cyclohexane dicarboxylic acid, 114-cyclohexane dicarboxylic acid, etc., a part of oxyacid such as p-hydroxybenzoic acid, etc., and aliphatic glycol having 2 to 8 carbon atoms as a glycol component. or alicyclic glycol having 6 to 12 carbon atoms, specifically ethylene glycol, 1.2-propylene glycol, 1.3-propanediol, 1.4
-butanediol, neopentyl glycol, 1.6-
Hexanediol, 1,2-cyclohexane dimetatool, 1,3-cyclohexane dimetatool, 1,4-cyclohexane dimetatool, p-xylylene glycol, diethylene glycol, triethylene glycol, etc., and as polyether polyethylene glycol,
It may also contain an ester consisting of polypropylene glycol, polytetramethylene glycol, or the like. These components other than polyethylene terephthalate may be included by either copolymerization or polymer mixing.
本発明のフィルムは接着力の耐水性、耐熱水性、耐熱性
に優れており、特にフィルムと蒸着層との境界面におけ
る層間接着力が高温熱水処理によって低下する事がない
。The film of the present invention has excellent adhesive strength in water resistance, hot water resistance, and heat resistance, and in particular, the interlayer adhesive strength at the interface between the film and the vapor-deposited layer does not deteriorate due to high-temperature hot water treatment.
ヒ記フィルムの表面に蒸着されるものとしては金、銀、
アルミニウム、亜鉛、錫、銅、ニッケル、鉄、コバルト
、クロム、マンガン、パラジウム、インジウム、チタン
等の単独又は２種以上の金属およびその酸化物が挙げら
れ、特にアルミニウムが多用され有効である。その他と
して酸化ケイ素化合物にも有効性が認められる。Items deposited on the surface of the film include gold, silver,
Examples include metals such as aluminum, zinc, tin, copper, nickel, iron, cobalt, chromium, manganese, palladium, indium, titanium, etc., and their oxides, and aluminum is particularly effective. In addition, silicon oxide compounds are also found to be effective.
Ｌ記のフィルムの蒸着面にポリエチレン、ポリプロピレ
ン、アイオノマー、エチレン・酢１’ｌ［＝ル共重合体
、エチレン舎エチルアクリレート共重合体、ポリエステ
ル、ポリアミド等のシートまたはフィルムを積層して使
用する事が出来る。A sheet or film of polyethylene, polypropylene, ionomer, ethylene/vinegar copolymer, ethylene ethyl acrylate copolymer, polyester, polyamide, etc. may be laminated on the vapor-deposited surface of the film described in L. I can do it.
（実施例）
以ド、実施例によって本発明を説明する。例中の部、％
はいずれも特にことわらない限りすべて市喰基準を意味
する。(Examples) Hereinafter, the present invention will be explained with reference to Examples. Example part, %
Unless otherwise specified, all mean Ichikui standards.
また例中の各特性評価は次の方法で行った。In addition, each characteristic evaluation in the example was performed by the following method.
１、ｃｏｓＯのａｌｌ定
疎水性化合物＋８＋又はその溶液か分散液をガラス板−
トに流延し、乾燥処理を行なった後、該皮膜表面におけ
る水ＭＮの接触角を、協和科学■製接触角計ＣＡ−Ａ型
によって測定し、該角度の余弦値（ｃｏｓＯ）を計算に
よって求めた。1. All constant hydrophobic compounds of cosO+8+ or their solutions or dispersions were placed on a glass plate.
After casting and drying, the contact angle of water MN on the surface of the film was measured using a contact angle meter model CA-A manufactured by Kyowa Kagaku, and the cosine value (cosO) of the angle was calculated. I asked for it.
２、接着力評価用サンプルの作製
試料フィルムの表面（塗布フィルムは塗布面）上に、常
法によりアルミニウムの蒸着処理を行ない蒸着フィルム
を得た。このアルミニウム蒸着フィルムの蒸着面に厚さ
６０ミクロンの未延伸ポリエチレン又はポリプロピレン
シートを通常のドライラミネート法により積層した後、
エージング処理を２４時間行ない、アルミニウム蒸着フ
ィルム積層体を得た。得られた蒸着フィルム積層体を、
１５、、幅の知冊状にカットし、９５℃の沸騰水又は１
２０℃の高圧水中で３０分間の浸漬処理を行った後、接
着力測定用サンプルとして供した。なお比較として該処
理なしについても同様のサンプルを作製した。2. Preparation of sample for evaluation of adhesive strength Aluminum was vapor-deposited on the surface of the sample film (the coated surface for the coated film) by a conventional method to obtain a vapor-deposited film. After laminating an unstretched polyethylene or polypropylene sheet with a thickness of 60 microns on the vapor-deposited surface of this aluminum vapor-deposited film by a normal dry lamination method,
The aging treatment was performed for 24 hours to obtain an aluminum vapor-deposited film laminate. The obtained vapor-deposited film laminate is
15. Cut into width pieces and boil in 95℃ water or 1.
After performing immersion treatment in high pressure water at 20° C. for 30 minutes, it was used as a sample for measuring adhesive strength. For comparison, a similar sample was also prepared without the treatment.
３、接着力のＩｉ？＋定
上記で作製した短冊状蒸着フィルム積層体を東洋ボール
ドウィン社製テンシロンを用い、通常のＴ型剥離を杼な
う方法、及び剥離界面に水滴をつけつつ行なう耐水剥離
法の２種について層間接着力の評価を行った。3. Adhesive force Ii? The strip-shaped vapor-deposited film laminate produced above was subjected to two types of interlayer separation using Tensilon manufactured by Toyo Baldwin Co., Ltd.: a conventional T-peel method and a water-resistant peeling method in which water droplets are applied to the peeling interface. We evaluated the adhesion.
４、フィルム透明性
配合された樹脂組成物層が形成されたフィルムの透明性
は、ブランクフィルムとの比較において、−［１視によ
り次のように判定した。4. Film Transparency The transparency of the film on which the blended resin composition layer was formed was determined as follows by -[1 observation] in comparison with a blank film.
○ ブランクと差なく、透明
Δ やや不透明
× 樹脂層が白濁又は、不均一で著しく不透明
５、蒸着層の光沢
蒸着フィルム積層体の１２０℃高温高圧水処理後のアル
ミニウム蒸着層の光沢変化を目視により次のように判定
した。○ Same as blank, transparent Δ Slightly opaque It was determined as follows.
Ｏ良好な金属光沢有
△ やや光沢がない
× 白化又は透明化
実施例１〜６
ポリエチレンテレフタレートを２９０°Ｃで溶融押出し
し、３０℃の冷却ロールで冷却して厚さ約１５０ミクロ
ン未延伸フィルムを得、この未延伸フィルムを周速の異
なる８５℃の−・対のロール間で縦方向に３．５倍延伸
した。次いで第１表に記載の樹脂組成物塗布液をそれぞ
れ固形分５％としロールコータ一方式で塗布し、７０℃
の熱風で乾燥、次いでテンターで９８℃で横方向に３．
５倍鉦伸し、さらに２１０℃で熱固定し厚さ１２ミクロ
ンの二軸延伸コーティングポリエステルフィルムとした
。最終的なコート塗布量は各々約０．０８ｇ／ｄであっ
た。得られたフィルムの評価結果を第３表に示す。O Good metallic luster △ Slightly lackluster × Whitening or transparency Examples 1 to 6 Polyethylene terephthalate was melt-extruded at 290°C and cooled with a cooling roll at 30°C to form an unstretched film with a thickness of about 150 microns. This unstretched film was then stretched 3.5 times in the longitudinal direction between a pair of rolls at different circumferential speeds of 85°C. Next, each of the resin composition coating liquids listed in Table 1 was coated with a solid content of 5% using a roll coater, and the coating solution was heated at 70°C.
Dry with hot air, then crosswise in a tenter at 98°C for 3.
It was stretched 5 times and further heat-set at 210°C to form a biaxially stretched coated polyester film with a thickness of 12 microns. Final coat coverage was approximately 0.08 g/d each. The evaluation results of the obtained films are shown in Table 3.
比較例１
樹脂組成物塗布液を塗布しない以外は実施例と同様にし
て二軸延伸ポリエステルフィルムを得た。Comparative Example 1 A biaxially stretched polyester film was obtained in the same manner as in Example except that the resin composition coating liquid was not applied.
比較例２〜９
樹脂組成物塗布液を第２表に記載したものとする以外は
実施例とまったく同様にして二軸延伸コーティングポリ
エステルフィルムを得た。得られたフィルムの評価を第
３表に示す。Comparative Examples 2 to 9 Biaxially stretched coated polyester films were obtained in exactly the same manner as in the examples except that the resin composition coating liquid was used as shown in Table 2. Table 3 shows the evaluation of the obtained film.
以−ド余白
（発明の効果）
以上実施例で示した通り、本発明のフィルムは耐水接着
力、特に金属等の蒸着層とフィルムとの層間接着力にお
ける耐熱水性が著しく優れている°１「が分る。Margin (Effects of the Invention) As shown in the examples above, the film of the present invention is extremely excellent in water-resistant adhesive strength, particularly in terms of interlayer adhesive strength between the film and a vapor-deposited layer of metal, etc. I understand.
また本発明に用いられる水不溶性でかつ水分散性の樹脂
ｆＡ）のみを用いても、疎水性化合物ｉＢｌを用いない
場合には、特に高温、高圧水による熱水処理後の耐水接
着力が著しく劣ることが分る（比較例２〜４）。Furthermore, even if only the water-insoluble and water-dispersible resin fA) used in the present invention is used, if the hydrophobic compound iBl is not used, the water-resistant adhesive strength will be significantly lower, especially after hot water treatment with high-temperature, high-pressure water. It can be seen that the results are inferior (Comparative Examples 2 to 4).
また本発明の疎水性化合物ＩＢＩを用いてもそれのみで
本発明の樹脂（Δ）と配合しない場合（比較例５）は初
期から充分な接着力が得られず、＋Ａｌ／ｌｅｌの配合
比が本発明の範囲より多すぎる、或は少なすぎる場合（
比較例６．７）はそれぞれ充分な耐熱水接ｌｔ力が得ら
れず、特に配合比（Ａｌ ／ ＋８１が１００／１００
より小さい場合には（比較例６）、フィルムの透明性も
不充分である。Furthermore, even if the hydrophobic compound IBI of the present invention is used alone and is not blended with the resin (Δ) of the present invention (Comparative Example 5), sufficient adhesive strength cannot be obtained from the initial stage, and the +Al/lel blending ratio is If the amount is too much or too little than the scope of the present invention (
In Comparative Examples 6 and 7), sufficient hot water contact strength could not be obtained, especially when the blending ratio (Al/+81 was 100/100).
If it is smaller (Comparative Example 6), the transparency of the film is also insufficient.
史に疎水性化合物ｆ［ｌｌのＣｏ５０が本発明の範囲よ
り人なるような場合（比較例８）は、（Ａｌ ／ ＋［
ｌｌ配合比等が発明の範囲内であっても充分な耐熱水接
着力を得るルが出来ない事、及び樹脂ｆＡ＋が水溶性で
あるような場合にも所期の耐水接Ｚｔ力が得られない１
丁が分る。In the case where the Co50 of the hydrophobic compound f[ll is higher than the range of the present invention (Comparative Example 8), (Al/+[
Even if the compounding ratio etc. are within the range of the invention, it is not possible to obtain sufficient hot water resistant adhesion strength, and even when the resin fA+ is water soluble, the desired water resistant Zt strength cannot be obtained. No 1
I understand the ding.
特許出願人 東洋紡績株式会社 手続補正書（自発） １． 事件の表示 昭和６２年特許願第１２４１９７号 ２ 発明の名称 耐水接む性二軸配向フィルム ３、 補正をする者 事件との関係 特許出願人 大阪市北区堂島浜二丁目２番８号 明細書の発明の詳細な説明の欄 ５、 補正の内容 （１） 明細書第１２頁第６行目 「水分性樹脂（Ａ）」を 「水分散性樹脂（Ａ）」と訂正する。Patent applicant: Toyobo Co., Ltd. Procedural amendment (voluntary) 1. Incident display 1986 Patent Application No. 124197 2 Name of the invention Water resistant biaxially oriented film 3. Person making the amendment Relationship to the case Patent applicant 2-2-8 Dojimahama, Kita-ku, Osaka Detailed description of the invention in the specification 5. Contents of amendment (1) Page 12, line 6 of the specification "Water-based resin (A)" Corrected to "water-dispersible resin (A)".
■ 同第１８頁第１６行目 「知冊伏にカットし、」を 「短冊状にカットし、」と訂正する。■ Page 18, line 16 "Cut to the book book" "Cut it into strips," I corrected.
以 上that's all
Claims (3)
に、水不溶性でかつ水分散性を有する樹脂（Ａ）の１種
又は２種以上及び疎水性化合物（Ｂ）より選ばれた１種
又は２種以上を重量比で（Ａ）／（Ｂ）１００／０．５
〜１００／１００となるごとく配合された樹脂組成物層
が形成されてなる事を特徴とする耐水接着性二軸配向フ
ィルム。(1) At least one side of the film made of thermoplastic resin is coated with one or more water-insoluble and water-dispersible resins (A) and one or two selected from hydrophobic compounds (B). The weight ratio of the above is (A)/(B) 100/0.5
A water-resistant adhesive biaxially oriented film comprising a resin composition layer having a ratio of 100/100 to 100/100.
ときの表面特性が下式を満足するごとき化合物である事
を特徴とする特許請求の範囲第１項記載のフィルム。 −１．０≦ｃｏｓθ≦０．３５ （θ：水による接触角、但し０≦θ≦π）(2) The film according to claim 1, wherein the hydrophobic compound (B) is a compound whose surface properties satisfy the following formula when formed into a single film. -1.0≦cosθ≦0.35 (θ: contact angle with water, however, 0≦θ≦π)
する特許請求の範囲第１項および第２項記載のフィルム
。(3) The film according to claims 1 and 2, wherein the thermoplastic resin is polyester-based.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12419787A JPS63288749A (en) | 1987-05-21 | 1987-05-21 | Water-resistant adhesive biaxially drawn film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12419787A JPS63288749A (en) | 1987-05-21 | 1987-05-21 | Water-resistant adhesive biaxially drawn film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63288749A true JPS63288749A (en) | 1988-11-25 |
Family
ID=14879386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12419787A Pending JPS63288749A (en) | 1987-05-21 | 1987-05-21 | Water-resistant adhesive biaxially drawn film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63288749A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100454111B1 (en) * | 1997-01-13 | 2005-01-15 | 주식회사 코오롱 | Preparation method of nylon film by primary coating solution comprising aqueous urethane resin and aqueous aziridine curing agent, and drying, drawing to at least one direction and heat treating the coated one |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58146065A (en) * | 1982-02-24 | 1983-08-31 | Toyobo Co Ltd | Transparent friction plate for cassette |
| JPS59121631A (en) * | 1982-12-28 | 1984-07-13 | Toray Ind Inc | Covered film |
| JPS6092829A (en) * | 1983-10-27 | 1985-05-24 | Toyobo Co Ltd | Manufacture of slippery and transparent film |
-
1987
- 1987-05-21 JP JP12419787A patent/JPS63288749A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58146065A (en) * | 1982-02-24 | 1983-08-31 | Toyobo Co Ltd | Transparent friction plate for cassette |
| JPS59121631A (en) * | 1982-12-28 | 1984-07-13 | Toray Ind Inc | Covered film |
| JPS6092829A (en) * | 1983-10-27 | 1985-05-24 | Toyobo Co Ltd | Manufacture of slippery and transparent film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100454111B1 (en) * | 1997-01-13 | 2005-01-15 | 주식회사 코오롱 | Preparation method of nylon film by primary coating solution comprising aqueous urethane resin and aqueous aziridine curing agent, and drying, drawing to at least one direction and heat treating the coated one |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10843447B2 (en) | Heat-sealable and peelable polyester film, use thereof and process for production thereof | |
| JP4092941B2 (en) | Antistatic polymer film | |
| EP0953440B1 (en) | Polyester film for imaging media | |
| EP2450187B1 (en) | Multilayer polyester film | |
| KR20060048529A (en) | Extrusion-coatable polyester film comprising poly(m-xyleneadipamide) | |
| JP2004224047A (en) | Transparent, biaxially oriented, coextruded polyester film and its manufacturing method | |
| CA1328140C (en) | Polyester film coated with metal adhesion promoting coating and having superior winding performance | |
| JP2605816B2 (en) | Evaporated polyester film | |
| JPH11348211A (en) | Laminated thermoplastic film | |
| JPH08258232A (en) | Easily bondable polyamide film | |
| JPS63288749A (en) | Water-resistant adhesive biaxially drawn film | |
| JP2792110B2 (en) | Evaporated polyester film | |
| JP2926889B2 (en) | Coated polyester film and vapor-deposited film using the same | |
| JPH06293875A (en) | Coating agent and easily adhesive polyester film coated therewith | |
| JP2570462B2 (en) | Coated polyester film and vapor deposited film using the same | |
| JPH0681714B2 (en) | Coated plastic film | |
| JP3064328B2 (en) | Coated polyester film and vapor deposited film using the same | |
| JP3973942B2 (en) | Laminate and water dispersion | |
| JP3717130B2 (en) | Polyester film coating agent and printed laminate | |
| JP2605817B2 (en) | Coated polyester film and vapor-deposited film using the same | |
| JP3040532B2 (en) | Aqueous dispersion of polyester and easily adhered polyester film coated with the same | |
| JP2586177B2 (en) | Coated polyester film and vapor deposited film using the same | |
| JP3097266B2 (en) | Print laminate | |
| JP2998294B2 (en) | Print laminate | |
| JPS63290730A (en) | Deposited film |