JPS63290743A - Multi-layer polypropylene film - Google Patents
Multi-layer polypropylene filmInfo
- Publication number
- JPS63290743A JPS63290743A JP12606387A JP12606387A JPS63290743A JP S63290743 A JPS63290743 A JP S63290743A JP 12606387 A JP12606387 A JP 12606387A JP 12606387 A JP12606387 A JP 12606387A JP S63290743 A JPS63290743 A JP S63290743A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- layer
- parts
- film
- polypropylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 70
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 56
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000004711 α-olefin Substances 0.000 claims abstract description 22
- 239000006259 organic additive Substances 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 14
- 238000003851 corona treatment Methods 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 abstract 6
- 238000013329 compounding Methods 0.000 abstract 3
- 230000032683 aging Effects 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 58
- 239000010408 film Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 16
- 238000007740 vapor deposition Methods 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000314 lubricant Substances 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229920001384 propylene homopolymer Polymers 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- GCAONVVVMAVFDE-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC GCAONVVVMAVFDE-CLFAGFIQSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 229930003427 Vitamin E Natural products 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 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
- 230000008901 benefit Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- FQQQPWVZDLGNAP-ZZEZOPTASA-N n-[(z)-octadec-9-enyl]docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC FQQQPWVZDLGNAP-ZZEZOPTASA-N 0.000 description 1
- CNYJHBNJPXGDGJ-UHFFFAOYSA-N n-octadecylbutanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCC CNYJHBNJPXGDGJ-UHFFFAOYSA-N 0.000 description 1
- SVCKESZOKLIWKX-UHFFFAOYSA-N n-octadecyldocosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)NCCCCCCCCCCCCCCCCCC SVCKESZOKLIWKX-UHFFFAOYSA-N 0.000 description 1
- DJWFNQUDPJTSAD-UHFFFAOYSA-N n-octadecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC DJWFNQUDPJTSAD-UHFFFAOYSA-N 0.000 description 1
- PCPVQTNQMJCULF-UHFFFAOYSA-N n-octadecyloctanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCC PCPVQTNQMJCULF-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は包装材料に適した多層ポリプロピレンフィルム
に関し、詳しくは高い蒸着強度、光輝性、接着性などの
すぐれた表面特性を有し、かっ剛性０強度、耐熱性など
ポリプロピレンの木質的［従来の技術および発明が解決
しようとする問題点］
従来からポリプロピレンフィルムは透明性１機械的強度
、耐熱性および寸法安定性にすぐれているため包装材料
に使用されている。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a multilayer polypropylene film suitable for packaging materials, and more specifically, it has excellent surface properties such as high vapor deposition strength, brightness, and adhesiveness, and is stiff and rigid. 0 Woody characteristics of polypropylene such as strength and heat resistance [Problems to be solved by conventional techniques and inventions] Polypropylene films have traditionally been used as packaging materials due to their excellent transparency, 1 mechanical strength, heat resistance, and dimensional stability. It is used.
さらにこのポリプロピレンフィルム表面に金属を蒸着さ
せた金属蒸着ポリプロピレンフィルムは金属と同等な光
沢を持ち、商品価値にすぐれること、ガスバリヤ−性の
よいこと、遮光性に優れていること等の特性を持つため
アルミ箔などに代って食品包装材料や建築材料として多
量に利用されている。そして通常この金属蒸着フィルム
の表面に印刷をしたりあるいは他基材をラミネートして
使用されている。Furthermore, this metal-deposited polypropylene film, in which metal is deposited on the surface of the polypropylene film, has the same gloss as metal, has excellent commercial value, has good gas barrier properties, and has excellent light-shielding properties. Therefore, it is used in large quantities as a food packaging material and building material instead of aluminum foil. The surface of this metallized film is usually printed or laminated with other substrates.
しかしながらポリプロピレンは、ＰＥＴ （ポリエチレ
ンテレフタラート）などと異なりポリマー自体が極性基
を有しないために金属蒸着性、他の樹脂との接着性、印
刷性などの二次加工性が良好ではなく、いまだ十分に実
用に供し得ない状況にある。However, unlike PET (polyethylene terephthalate), polypropylene itself does not have polar groups, so it does not have good secondary processability such as metal vapor deposition, adhesion with other resins, and printability, and is still insufficient. The situation is such that it cannot be put to practical use.
すなわち金属蒸着強度が弱く、また、蒸着後の金属表面
の濡れ指数（ＪＩＳ Ｋ ６７６８による）が経時的に
大巾に低下することである。この理由はポリオレフィン
に添加される滑剤、塩酸捕捉剤、酸化防止剤、帯電防止
剤などの添加剤が経時的に表面にブリードアウトするた
め蒸着強度が低下し、またフィルム成形後通常は巻物の
状態で放置されることによりブリードアウトした添加剤
が金属蒸着面に移行転写されて、表面に薄膜を形成する
ことにより濡れ指数が低下すると考えられている。That is, the metal vapor deposition strength is weak, and the wettability index (according to JIS K 6768) of the metal surface after vapor deposition decreases significantly over time. The reason for this is that additives such as lubricants, hydrochloric acid scavengers, antioxidants, and antistatic agents added to polyolefins bleed out onto the surface over time, reducing the strength of the vapor deposition. It is thought that the additive that bleeds out by being left standing is transferred to the metal-deposited surface, forming a thin film on the surface and lowering the wettability index.
これらの問題点を解決するために、種々の方法が提案さ
れている。すなわち、化学薬品により表面処理を行うア
ンカーコーティング処理方法、エチレン・α−オレフィ
ン共重合などの改質樹脂をブレンドする方法、コロナ放
電処理による表面活性化方法あるいは添加剤の総量を０
．２重量％以下とする方法（特開昭５６−１８７７３２
）などがある。Various methods have been proposed to solve these problems. In other words, an anchor coating treatment method in which the surface is treated with chemicals, a method of blending a modified resin such as ethylene/α-olefin copolymerization, a surface activation method using corona discharge treatment, or a method in which the total amount of additives is reduced to zero.
．． Method for reducing the amount to 2% by weight or less (Japanese Patent Application Laid-open No. 56-187732
)and so on.
アンカーコーティング処理方法は通常硫酸−クロム酸塩
などの薬品により表面をエツチングして接着力を向上さ
せる方法であるが、薬剤の消耗。The anchor coating treatment method usually involves etching the surface with chemicals such as sulfuric acid and chromate to improve adhesion, but the chemicals are consumed.
設備等のコストがかかり、また高速処理ができないなど
の経済的欠点がある。There are economic disadvantages such as high equipment costs and inability to perform high-speed processing.
改質樹脂をブレンドする方法はブレンド量を増やすと表
面光輝性が悪くなり、金属蒸着力も不十分であり、また
強度・剛性も低下する。In the method of blending modified resins, if the blending amount is increased, the surface brightness deteriorates, the metal vapor deposition ability is insufficient, and the strength and rigidity also decrease.
コロナ放電処理方法は処理が弱いと効果がなく、強いと
添加剤が経時的にブリードアウトし易く、処理直後の金
属蒸着力は良好であっても次第に蒸着力が低下する。The corona discharge treatment method is ineffective if the treatment is weak, and if the treatment is strong, additives tend to bleed out over time, and even if the metal vapor deposition power is good immediately after the treatment, the metal deposition power gradually decreases.
添加剤の総量を０．２重量％以下とする方法は金属蒸着
力の経時的低下は少ないが成形加工時にポリマーの分解
が生じフィルムの劣化を防ぐことができない他、滑性不
良による製膜性に劣るなどの欠点がある。A method in which the total amount of additives is 0.2% by weight or less does not reduce the metal deposition strength over time, but the polymer decomposes during the molding process, making it impossible to prevent film deterioration, and also reduces film formability due to poor lubricity. It has disadvantages such as being inferior to
［問題点を解決するための手段］
そこで本発明者らは、かかる欠点を解消するために鋭意
研究を重ねた結果、ポリプロピレンに改質剤として特定
の密度を有するエチレン・α−オレフィン共重合体、さ
らに有機系添加剤および無機系添加剤を特定割合で配合
した組成物を製膜した後、コロナ放電処理してなるポリ
プロピレン系フィルムが蒸着強度、光輝性等にすぐれた
ものであることを見出した。[Means for Solving the Problems] Therefore, as a result of extensive research in order to eliminate such drawbacks, the present inventors have developed an ethylene/α-olefin copolymer having a specific density as a modifier for polypropylene. Furthermore, they discovered that a polypropylene film obtained by forming a composition containing a specific proportion of organic additives and inorganic additives and then subjecting it to corona discharge treatment had excellent vapor deposition strength, brightness, etc. Ta.
しかしながら、ポリプロピレンの特徴９強度。However, polypropylene features 9 strength.
剛性を生かすためには、改質剤がより少ない方が好まし
い。また改質剤の添加によるコスト上昇もあり、全フィ
ルム中における改質剤の比率を低くすることが望まれる
。In order to take advantage of rigidity, it is preferable to use less modifier. In addition, there is also an increase in cost due to the addition of a modifier, so it is desirable to reduce the proportion of the modifier in the entire film.
そこで本発明者らはさらに研究を進め、上記組成物から
なる層に、さらに特定の組成を有する層を組合せてなる
多層フィルムによれば、蒸着面層側の添加剤量を少なく
して非蒸着層（中間層を含む）の有機系添加剤の配合量
をやや増やすことができ、その結果、熱安定性などにす
ぐれたフィルムが得られることを見出し、かかる知見に
基いて本発明を完成した。Therefore, the present inventors conducted further research, and found that a multilayer film consisting of a layer made of the above composition and a layer having a specific composition was created by reducing the amount of additives on the vapor deposition surface layer side. The inventors discovered that it is possible to slightly increase the amount of organic additives in the layers (including the intermediate layer), and as a result, a film with excellent thermal stability can be obtained, and based on this knowledge, the present invention was completed. .
すなわち本発明は第１に１工としてポリブロピレン系樹
脂９９〜６０重量％および密度０．８６〜０．９１ｇ／
ｃｍ３のエチレン・α−オレフィン共重合体１〜４０重
量％からなる樹脂成分１００重量部に対し、有機系添加
剤０．３重量部以下および無機系添加剤０．０１〜２重
量部を配合してなる組成物、層ＩＩとしてポリプロピレ
ン系樹脂１００重量部に対し、有機系添加剤０．３重量
部以下および無機系添加剤０．０１〜２重量部を配合し
てなる組成物を共押出成形して得られる、前記層Ｉの厚
みが１〜３０μ、前記層１１の厚みが５〜１５０μのフ
ィルムであって、前記層Ｉの表面をコロナ放電処理して
なる多層ポリプロピレンフィルムを提供するものであり
、第２に層Ｉとしてポリプロピレン系樹脂９９〜６０重
量％および密度０．８６〜０．９１８／ｃｍ３のエチレ
ン・α−オレフィン共重合体１〜４０重量％からなる樹
脂成分１００重量部に対し、有機系添加剤０．３重量部
以下および無機系添加剤０．０１〜２重量部を配合して
なる組成物、層ＩＩとしてポリプロピレン系樹脂１００
重量部に対し、有機系添加剤０，３重量部以下および無
機系添加剤０．０１〜２重量部を配合してなる組成物、
層ＩＩＩとしてポリプロピレン系樹脂９９〜５０重量％
および低結晶性ないし非晶性のα−オレフィン共重合体
１〜５０重量％からなる樹脂成分１００重量部に対し、
有機系添加剤０．３重量部以下および無機系添加剤０．
０１〜２重量部を配合してなる組成物を共押出成形して
得られる前記層Ｉの厚みが１〜３０μ、前記層ＩＩの厚
みが５〜１５０μ、前記層Ｉ１１の厚みが１〜３０μの
フィルムであって、前記層Ｉの表面をコロナ放電処理し
てなる多層ポリプロピレンフィルムを提供するものであ
る。That is, the present invention firstly uses a polypropylene resin of 99 to 60% by weight and a density of 0.86 to 0.91 g/
0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive are blended with 100 parts by weight of a resin component consisting of 1 to 40% by weight of an ethylene/α-olefin copolymer of cm3. Co-extrusion molding of a composition comprising 0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive to 100 parts by weight of a polypropylene resin as Layer II. The present invention provides a multilayer polypropylene film in which the layer I has a thickness of 1 to 30μ, the layer 11 has a thickness of 5 to 150μ, and the surface of the layer I is subjected to a corona discharge treatment. Second, Layer I contains 99 to 60% by weight of a polypropylene resin and 1 to 40% by weight of an ethylene/α-olefin copolymer with a density of 0.86 to 0.918/cm3, based on 100 parts by weight of the resin component. , a composition comprising 0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive, a polypropylene resin 100 as layer II;
A composition comprising 0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive based on the weight of the composition;
99-50% by weight of polypropylene resin as layer III
and 100 parts by weight of a resin component consisting of 1 to 50% by weight of a low-crystalline to amorphous α-olefin copolymer,
0.3 parts by weight or less of organic additives and 0.3 parts by weight of inorganic additives.
The thickness of the layer I obtained by co-extrusion molding a composition containing 01 to 2 parts by weight is 1 to 30 μm, the thickness of the layer II is 5 to 150 μm, and the thickness of the layer I11 is 1 to 30 μm. The present invention provides a multilayer polypropylene film in which the surface of layer I is subjected to corona discharge treatment.
すなわち本発明の第１は層Ｉと層ＩＩを組合せてなる多
層フィルムであり、本発明の第２は本発明の第１で得ら
れるフィルムにさらに層ＩＩＩを組合せてなる多層フィ
ルムである。That is, the first aspect of the present invention is a multilayer film formed by combining layer I and layer II, and the second aspect of the present invention is a multilayer film formed by further combining layer III with the film obtained in the first aspect of the present invention.
本発明の層Ｉに用いるポリプロピレン系樹脂は、結晶性
ポリプロピレンであり、プロピレンの単独重合体あるい
は、エチレン、ブテン−１，ヘキセン−１などのα−オ
レフィンを１０モル％以下、好ましくは１〜７モル％含
んだ共電Ｉ体を含む。The polypropylene resin used in Layer I of the present invention is crystalline polypropylene, and contains propylene homopolymer or α-olefin such as ethylene, butene-1, hexene-1, etc. in an amount of 10 mol% or less, preferably 1 to 7 mol%. Contains mol % of Kyoelectric I body.
この共重合体としては、ランダム共重合体、あるいは多
段重合で得られる単独重合体とのブレンド物、通常のブ
レンド物であってもよい、また、ポリプロピレン系樹脂
の密度は０．８９０〜０．９０５ｇ／ｃｍ”であり、メ
ルトインデックス（ＭＩ）は０．１〜３０ｇ７１０分、
好ましくは０．２〜２０ｇ７１０分である。This copolymer may be a random copolymer, a blend with a homopolymer obtained by multistage polymerization, or a normal blend.The density of the polypropylene resin is 0.890 to 0. 905g/cm", melt index (MI) is 0.1-30g710min,
Preferably it is 0.2 to 20g and 710 minutes.
また無水マレイン酸などの不飽和カルボン酸またはその
誘導体をグラフトした変性ポリオレフィンを加えること
もできる。It is also possible to add a modified polyolefin grafted with an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof.
次にエチレン・α−オレフィン共重合体は、たとえばバ
ナジウム化合物と有機アルミニウム化合物からなる重合
触媒を用いてエチレンとα−オレフィンとを重合して得
られるエチレン含有量８０〜９７モル％、好ましくは８
３〜９５モル％の共重合体である。α−オレフィンとし
ては通常炭素数３〜６のα−オレフィン、特にプロピレ
ン、ブテン−１が好ましい。この共重合体の密度は、０
．８６〜０．９１ｇ／ｃｍ３、好ましくは０．８７〜０
．９０ｇ／ｃａ＋’で、結晶化度７０％以下の低結晶性
ないし非晶性のものである。ここで密度が０．８６ｇ／
ｃｍ３未溝であると耐ブロッキング性、耐熱性に劣り、
一方密度が０．９１ｇ／ｃ＋ａ’を超えると、蒸着強度
に劣ったものとなるため好ましくない。Next, the ethylene/α-olefin copolymer has an ethylene content of 80 to 97 mol%, preferably 80 to 97 mol%, obtained by polymerizing ethylene and α-olefin using a polymerization catalyst consisting of a vanadium compound and an organoaluminum compound, for example.
It is a copolymer of 3 to 95 mol%. As the α-olefin, preferred are usually α-olefins having 3 to 6 carbon atoms, particularly propylene and 1-butene. The density of this copolymer is 0
．． 86-0.91g/cm3, preferably 0.87-0
．． It is low crystallinity or amorphous with a crystallinity of 70% or less and a weight of 90 g/ca+'. Here the density is 0.86g/
If cm3 is not grooved, blocking resistance and heat resistance will be poor.
On the other hand, if the density exceeds 0.91 g/c+a', the deposition strength will be poor, which is not preferable.
本発明においては層Ｉの樹脂成分として上記ポリプロピ
レン系樹脂とエチレン・α−オレフィン共重合体を用い
る。In the present invention, the above polypropylene resin and an ethylene/α-olefin copolymer are used as the resin components of layer I.
上記樹脂成分の配合割合はポリプロピレン系樹脂９９〜
６０重量％、好ましくは９５〜７０重量％に対し、エチ
レン・α−オレフィン共重合体は１〜４０重量％、好ま
しくは５〜３０重量％である。ここでポリプロピレン系
樹脂の配合割合が９９重量％を超えると蒸着強度が低下
し、一方６０重量％未満であると光輝性が低下するため
いずれも好ましくない。The blending ratio of the above resin components is polypropylene resin 99~
60% by weight, preferably 95-70% by weight, and 1-40% by weight, preferably 5-30% by weight of the ethylene/α-olefin copolymer. If the blending ratio of the polypropylene resin exceeds 99% by weight, the deposition strength will decrease, while if it is less than 60% by weight, the brightness will decrease, which is not preferable.
また、層Ｉに用いる有機系添加剤には滑剤として流動パ
ラフィン、塩素化ナフタリン、三フッ化塩化エチレン低
重合物などの炭化水素系滑剤：高級脂肪酸、脂肪酸アミ
ド、アルキレンビス脂肪酸アミドなどの脂肪酸系滑剤ニ
ブチルステアレート、ポリグリコールエステルなどの脂
肪酸エステル系滑剤；脂肪酸アルコール、ポリグリコー
ルなどのアルコール系滑剤なと種々の滑剤が挙げられる
。その内脂肪酸アミドとしてエルカ酸アミド。In addition, the organic additives used in Layer I include hydrocarbon lubricants such as liquid paraffin, chlorinated naphthalene, and trifluorochloroethylene low polymers; fatty acid lubricants such as higher fatty acids, fatty acid amides, and alkylene bis fatty acid amides. Lubricants Various lubricants include fatty acid ester-based lubricants such as nibyl stearate and polyglycol ester; alcohol-based lubricants such as fatty acid alcohol and polyglycol. Among them, erucic acid amide is a fatty acid amide.
ステアリン酸アミド、オレイン酸アミド、ベヘニン酸ア
ミド、Ｎ−ステアリル酪酸アミド、Ｎ−ステアリルカプ
リル酸アミド、Ｎ−ステアリルラウリン酸アミド、Ｎ−
ステアリルステアリン酸アミド、Ｎ−ステアリルベヘニ
ン酸アミド、Ｎ−オレイルオレイン酸アミド、Ｎ−オレ
イルベヘニン酸アミド、Ｎ−ブチルエルカ酸アミド、Ｎ
−オクチルエルカ酸アミドおよびＮ−ラウリルエルカ酸
アミド等が挙げられる。Stearic acid amide, oleic acid amide, behenic acid amide, N-stearylbutyric acid amide, N-stearylcaprylic acid amide, N-stearyllauric acid amide, N-
Stearyl stearic acid amide, N-stearyl behenic acid amide, N-oleyl oleic acid amide, N-oleyl behenic acid amide, N-butyl erucic acid amide, N
-octyl erucamide, N-lauryl erucamide, and the like.
また滑剤および遊離塩酸捕捉剤として、ステアリン酸カ
ルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウ
ムなどの金属石けんを加えることも有効である。It is also effective to add metal soaps such as calcium stearate, zinc stearate, and magnesium stearate as lubricants and free hydrochloric acid scavengers.
さらに帯電防止剤としてはカチオン系、アニオン系、非
イオン系および両性イオン系のいずれをも使用すること
ができる。具体的には第１級アミン塩、第３ｗＬアミン
、第４１１Ｌアンモニウム化合物、ピリジン誘導体等の
カチオン系のもの；硫酸化油、セッケン、硫酸化エステ
ル油、硫酸化アミド油、オレフィンの硫酸ダニステル塩
類、脂肪アルコール硫酸エステル塩、アルキル硫酸エス
テル塩、脂肪酸エチルスルホン酸塩、アルキルナフタレ
ンスルホン酸塩、アルキルベンゼンスルホン酸塩、コハ
ク酸エステルスルホン酸塩、リン酸エステル塩等のアニ
オン系のもの】多価アルコールの部分的脂肪酸エステル
、脂肪アルコールのエチレンオキサイド付加物、脂肪酸
のエチレンオキサイド付加物、多脂肪アミノまたは脂肪
酸アミドのエチレンオキサイド付加物、アルキルフェノ
ールのエチレンオキサイド付加物、アルキルナフトール
のエチレンオキサイド付加物、多価アルコールの部分的
脂肪酸エステルのエチレンオキサイド付加物、ポリエチ
レングリコール等の非イオン系のもの：カルボン酸誘導
体、イミダシリン話導体等の両性イオン系のものを例示
することができる。Further, as the antistatic agent, any of cationic, anionic, nonionic, and amphoteric antistatic agents can be used. Specifically, cationic ones such as primary amine salts, tertiary wL amines, 411L ammonium compounds, pyridine derivatives; sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfuric danister salts of olefins, Anionic products such as fatty alcohol sulfate ester salts, alkyl sulfate ester salts, fatty acid ethyl sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, succinate ester sulfonates, phosphate ester salts] Polyhydric alcohols Partial fatty acid esters, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of polyfatty aminos or fatty acid amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of alkylnaphthols, polyhydric alcohols Examples include ethylene oxide adducts of partial fatty acid esters, nonionic ones such as polyethylene glycol, and zwitterionic ones such as carboxylic acid derivatives and imidacillin conductors.
これらの中でも非イオン系のものが好ましく、特にポリ
オキシエチレンアルキルアミン、ポリオキシエチレンア
ルキルアミドまたはそれらの脂肪酸エステル、グリセリ
ン脂肪酸エステルが好まし。Among these, nonionic ones are preferred, and polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid esters thereof, and glycerin fatty acid esters are particularly preferred.
い。stomach.
また、酸化防止剤としては大別してフェノール系酸化防
止剤と、イオウ・リン系酸化防止剤が挙げられる。フェ
ノール系酸化防止剤としては１−Ｂｕ−フェノール、ス
チレン化フェノールなどのアルキルフェノール類；ビス
フェノールなどのアルキルジフェノール類；チオビスア
ルキルフェノール類などがあり、イオウ・リン系酸化防
止としてはＢ、Ｂ’−チオプロピオン酸エステル類；亜
リン酸エステル類などが例示される。さらに他の酸化防
止剤としては、ビタミンＥなどがある。Furthermore, antioxidants can be broadly classified into phenolic antioxidants and sulfur/phosphorous antioxidants. Phenolic antioxidants include alkylphenols such as 1-Bu-phenol and styrenated phenol; alkyldiphenols such as bisphenol; and thiobisalkylphenols; examples of sulfur and phosphorus antioxidants include B, B'- Examples include thiopropionate esters; phosphite esters. Further, other antioxidants include vitamin E and the like.
これら有機系添加剤の配合量は、上記樹脂成分１００皿
量部に対し、０．３重量部以下、好ましくは０．２重量
部以下である。特に有機系滑剤の場合には、０．１重量
部以下とすることが、蒸着強度の点から好ましい。The blending amount of these organic additives is 0.3 parts by weight or less, preferably 0.2 parts by weight or less, per 100 parts by weight of the resin component. Particularly in the case of organic lubricants, it is preferable to use 0.1 part by weight or less from the viewpoint of vapor deposition strength.
一方層■に用いる無機系添加剤としては天然シリカ、合
成シリカなとのシリカ類、ゼオライトＡ、ゼオライトＸ
、ゼオライトＹ、ゼオライトし１モルデナイトなどのゼ
オライト類及びハイドロタルサイト類無機添加剤が例示
される。これら添加剤のなかでも、ゼオライト、パイド
ロタルサイト類が好ましく、その平均粒子径は２０μ以
下のものが好ましい。On the other hand, inorganic additives used in layer (■) include natural silica, synthetic silica, zeolite A, and zeolite X.
Examples include zeolites such as , zeolite Y, zeolite 1 mordenite, and hydrotalcite inorganic additives. Among these additives, zeolites and pyrotalcites are preferred, and those with an average particle diameter of 20 μm or less are preferred.
これら無機系添加剤の配合量は上記樹脂成分１００重量
部に対し、０．０１〜２重量部、好ましくは０．０２〜
１．５１重量部の割合である。ここで無機系添加剤の配
合割合が０．０１重量部未満であると製膜性、蒸着性な
どが劣り、２重量部を超えると表面の荒れが大きくなり
好ましくない。The blending amount of these inorganic additives is 0.01 to 2 parts by weight, preferably 0.02 to 2 parts by weight, based on 100 parts by weight of the above resin component.
The proportion is 1.51 parts by weight. If the blending ratio of the inorganic additive is less than 0.01 parts by weight, film forming properties, vapor deposition properties, etc. will be poor, and if it exceeds 2 parts by weight, the surface will become rough, which is not preferred.
次に本発明の層ＩＩはポリプロピレン系樹脂に有機系お
よび無機系の添加剤を加えてなるものである。Layer II of the present invention is formed by adding organic and inorganic additives to a polypropylene resin.
ここで用いるポリプロピレン系樹脂、有機系および無機
系添加剤は層！で用いるものと木質的には同じものであ
る。The polypropylene resin, organic and inorganic additives used here are layer! The wood quality is the same as that used in .
しかし層ＩＩで用いるポリプロピレン系樹脂は、強度、
耐熱性などの点から、プロピレン単独重合体または、エ
チレンなどのα−オレフィンを５モル％以下共重合した
ランダム共重合体が好ま駿い。また有機系添加剤は、ポ
リプロピレン系樹脂１００重量部に対して、０．３重量
部以下配合される。層ＩＩにあっては、蒸着強度等に悪
影響を直接与えないため、酸化防止剤等の添加剤を比較
的十分に加えることができるので、フィルム成形を安定
して行なうことができる。However, the polypropylene resin used in layer II has
From the viewpoint of heat resistance, a propylene homopolymer or a random copolymer copolymerized with 5 mol % or less of an α-olefin such as ethylene is preferred. Further, the organic additive is blended in an amount of 0.3 parts by weight or less with respect to 100 parts by weight of the polypropylene resin. Since Layer II does not have a direct adverse effect on the vapor deposition strength, etc., additives such as antioxidants can be added in a relatively sufficient amount, so that film formation can be carried out stably.
ざらに層ＩＩには、無機系添加剤を０．０１〜２重量部
、層Ｉと同様に添加する。ここで層Ｉと層ＩＩで加える
添加剤は、同じでも異なってもよいが、眉間での添加剤
の移動を防止する点から類似のもの如き層Ｉと層ＩＩを
構成成分とするものである。In the same manner as in Layer I, 0.01 to 2 parts by weight of an inorganic additive is added to Rough Layer II. The additives added in layer I and layer II may be the same or different, but from the point of view of preventing the additive from moving between the eyebrows, layers I and II are similar components. .
次に本発明の第２の多層ポリプロピレンフィルムは、上
記本発明の第１、すなわち層重と層ＩＩを構成成分とす
る多層ポリプロピレンフィルムに、さらに層ＩＩＩを組
合せてなるものである。Next, the second multilayer polypropylene film of the present invention is obtained by further combining the first multilayer polypropylene film of the present invention, that is, the multilayer polypropylene film having the layer weight and layer II as constituent components, with layer III.
層ＩＩＩの成分は、ポリプロピレン系樹脂と非品性ない
し低結晶性α−オレフィン共重合体からなる樹脂成分に
、有機系および無機系添加剤を配合したものである。The component of layer III is a resin component consisting of a polypropylene resin and a non-quality to low crystalline α-olefin copolymer, and organic and inorganic additives added thereto.
ここで用いるポリプロピレン系樹脂は層Ｉで用いたポリ
プロピレン系樹脂と同様にプロピレンのホモポリマーで
もよいし、あるいはα−オレフィンを１０モル％以下加
えたものでもよいが、好ましくはプロピレン・エチレン
ランダム共重合体が好ましい。The polypropylene resin used here may be a propylene homopolymer like the polypropylene resin used in Layer I, or it may be a propylene homopolymer containing 10 mol% or less of α-olefin, but it is preferably a propylene/ethylene random copolymer. Combination is preferred.
また非晶性ないし低結晶性α−オレフィン共重合体とは
、エチレン、プロピレン、ブテン−１を主成分とする共
重合体であるが、１．４−ヘキサジエン、ジシクロペン
タジェン、５−メチル−２−ノルボルナン等を含んだ、
例えばエチレン・α−オレフィン・ジエン共重合体など
の三元共重合体でもよい、さらにこの共重合体は非晶性
ないし結晶化度３０％以下の低結晶性のものが望ましく
、その密度は０．８５〜０．９０ｇ／ｃｍ３である。こ
こで密度が０．８５ｇ／ｃ＋＋’未満であると耐ブロッ
キング性、耐熱性の点で十分でなく、０．９０ｇ／ｃｍ
３襟士を超えるとシール性などが低下し好ましくない。In addition, amorphous or low crystalline α-olefin copolymers are copolymers whose main components are ethylene, propylene, and butene-1, but include 1,4-hexadiene, dicyclopentadiene, 5-methyl -Contains 2-norbornane, etc.
For example, a terpolymer such as an ethylene/α-olefin/diene copolymer may be used. Furthermore, this copolymer is desirably amorphous or has a low crystallinity of 30% or less, and its density is 0. It is .85 to 0.90 g/cm3. If the density is less than 0.85 g/c++', the blocking resistance and heat resistance are insufficient, and the density is less than 0.90 g/cm.
If the thickness exceeds 3, the sealing performance etc. deteriorates, which is not preferable.
また、上記樹脂成分に配合する有機系添加剤および無機
系添加剤は、前記層ＩＩで説明したと同様のものが挙げ
られ、層！■で用いたと同じものを用いてもよく、或い
は異なるものを用いてもよい。Further, the organic additives and inorganic additives to be added to the resin component include the same ones as explained in the layer II, and the layer! The same material as used in (2) may be used, or a different material may be used.
有機系添加剤の配合割合は上記樹脂成分１００重量部に
対し、０．３重量部以下、好ましくは０．２重量部以下
である。また無機系添加剤の配合割合は上記樹脂成分１
００重量部に対し、０．０１〜２重量部、好ましくは０
．０２〜１．５重量部である。The blending ratio of the organic additive is 0.3 parts by weight or less, preferably 0.2 parts by weight or less, based on 100 parts by weight of the resin component. In addition, the blending ratio of inorganic additives is as follows:
0.01 to 2 parts by weight, preferably 0.00 parts by weight
．． 02 to 1.5 parts by weight.
なお、有機系添加剤は直接、蒸着面となる層Ｉのみでな
く、層ＩＩ 、層ＩＩＩにおいても少ないほどよい。こ
れは成形時、またはフィルム巻取状態で比較的薄い層の
Ｉ、ＩＩＩ層へ添加剤が容性するおそれがあるからであ
る。Note that it is better to use a smaller amount of organic additive not only in layer I, which is the direct vapor deposition surface, but also in layer II and layer III. This is because there is a possibility that additives may be absorbed into the relatively thin layers I and III during molding or when the film is wound.
本発明における多層フィルムは上記の如く配合した組成
物を共押出ししてなるものであり、Ｔ−ダイ法あるいは
インフレーション法により成形される。また成形条件と
しては２００〜３００℃で溶融混練後、７０℃以下のロ
ールなどを用いて冷却する方法が採用できる。The multilayer film of the present invention is formed by coextruding the composition blended as described above, and is molded by a T-die method or an inflation method. Further, as the molding conditions, a method of melting and kneading at 200 to 300°C and then cooling using a roll or the like at 70°C or lower can be adopted.
本発明の第１における層の膜厚は層Ｉが１〜３０μ、好
ましくは１〜１５μであり、１μより薄いと製膜性が困
難になるとともに、層ＩＩの添加剤の容性による影響が
大となり、３０μより厚いと、物性上およびコスト面か
ら問題となる。The thickness of the layer in the first aspect of the present invention is 1 to 30 μm for layer I, preferably 1 to 15 μm; if it is thinner than 1 μm, film formability becomes difficult, and the solubility of the additive in layer II may affect the film thickness. If it is thicker than 30 μm, it will cause problems in terms of physical properties and cost.
また、層ＩＩの膜厚は強度、剛性、耐熱性および製膜上
から５〜１５０ｇｍが好適である。Further, the thickness of layer II is preferably 5 to 150 gm in terms of strength, rigidity, heat resistance, and film formation.
さらに、本発明の第２における層１１層ＩＩの膜厚は上
記と同様であり、また層ＩＩＩの膜厚は１〜３０μ、好
ましくは１〜２０μである。１μより薄いと製膜性、ヒ
ートシール性、添加剤の容性−の点で好ましくなくなる
。Further, the thickness of the layer 11 layer II in the second aspect of the present invention is the same as above, and the thickness of the layer III is 1 to 30 μm, preferably 1 to 20 μm. If it is thinner than 1μ, it becomes unfavorable in terms of film formability, heat sealability, and additive compatibility.
本発明の多層ポリプロピレンフィルムは上記層Ｉ、ＩＩ
、あるいは層Ｉ、ｕ、ａｔ、ｌを積層製膜後、層Ｉの表
面をコロナ放電処理してなるものである。コロナ放電処
理条件は特に制限はないが、通常、消費電力３０〜２０
０１７ｍ”７分、好ましくは３５〜１５０Ｗ／＋”７分
であり、処理雰囲気は空気、窒素（酸素濃度５％以下）
あるいは炭酸ガスなどである。The multilayer polypropylene film of the present invention has the above-mentioned layers I and II.
Alternatively, after laminating layers I, u, at, and l, the surface of layer I is subjected to corona discharge treatment. There are no particular restrictions on the corona discharge treatment conditions, but usually the power consumption is 30 to 20
017m"7 minutes, preferably 35 to 150W/+"7 minutes, and the processing atmosphere is air, nitrogen (oxygen concentration 5% or less)
Or carbon dioxide, etc.
また、処理速度は１０〜２００ ｍ１分で行なえばよい
。Further, the processing speed may be 10 to 200 m/min.
本発明の多層ポリプロピレンフィルムは上記の如きもの
であるがこの様にしてコロナ放ｔｆｉ３１されたフィル
ム面に金属を蒸着させて金属蒸着多層ポリプロピレンフ
ィルムとしても良いし、あるいはその上に他基材フィル
ムを積層して使用しても良い。The multilayer polypropylene film of the present invention is as described above, but a metal may be vapor-deposited on the surface of the film subjected to corona emission in this manner to form a metal-deposited multilayer polypropylene film, or another base film may be formed on top of the metal-deposited multilayer polypropylene film. They may be used in a stacked manner.
ポリプロピレンフィルム面への金属蒸着の方法は、フィ
ルムを高真空（１０−’〜１０−’Ｔｏｒｒ、通常５
ｘ １０−’Ｔｏｒｒ）内に保ちその内へ蒸発させた金
属蒸気を導入してポリプロピレンフィルム表面に蒸着さ
せればよい。またグロー放電を利用して金属を飛ばして
蒸着させるスパッタリング法や放電によりイオン化され
加速されたアルゴンにより基体をエツチングし蒸着させ
るイオンブレーティング法などによってもよい。The method of metal vapor deposition on the surface of a polypropylene film is to place the film in a high vacuum (10-' to 10-' Torr, usually 5
x 10-'Torr) and introduce the evaporated metal vapor therein to deposit it on the surface of the polypropylene film. Alternatively, a sputtering method in which metal is evaporated by using glow discharge or an ion blating method in which the substrate is etched and deposited using argon ionized and accelerated by discharge may be used.
なお、蒸着させる金属はアルミニウム、チタン、クロム
、ニッケル、銅、銀、金、亜鉛、ゲルマニウム、スズ、
セレン等があげられるが、作業性１反射率、経済性等か
らアルミニウムが望ましい。この場合のアルミニウム蒸
着層は通常４００〜６００人（０，０４〜０．０６μ）
である。The metals to be vapor-deposited include aluminum, titanium, chromium, nickel, copper, silver, gold, zinc, germanium, tin,
Examples include selenium, but aluminum is preferable from the viewpoint of workability, reflectance, economy, etc. The aluminum vapor deposition layer in this case is usually 400-600 people (0.04-0.06μ)
It is.
［実施例］ 次に本発明を実施例により詳しく説明する。[Example] Next, the present invention will be explained in detail with reference to examples.
実施例１〜５および比較例１〜３ 第１表に示す各層樹脂配合組成物を（１）。Examples 1-5 and Comparative Examples 1-3 The resin blend composition for each layer shown in Table 1 was (1).
（ＩＩ ） 、 （ＩＩＩ ）層として、各々５０ｍ
ｍφ、 ６５ｍｍφ。(II) and (III) layers, each 50m
mφ, 65mmφ.
５０ｍｍφの押出機で溶融混練してマルチマニホールド
多層Ｔ−ダイ（ダイ巾８００ｍｍ）に供給し、ダイ温度
２５０℃で押出し、チルロール（４０℃）で冷却して総
膜厚２５μのフィルムを得た。このフィルムの１層表面
を４１１１７ｍ２７分の条件下コロナ放電処理を行ない
二層または三層フィルムを得た。これらフィルムのコロ
ナ放電処理面の濡れ指数、アルミニウムを真空蒸着した
場合の蒸着強度、光輝性。The mixture was melt-kneaded in a 50 mmφ extruder, supplied to a multi-manifold multilayer T-die (die width 800 mm), extruded at a die temperature of 250°C, and cooled with a chill roll (40°C) to obtain a film with a total thickness of 25 μm. The surface of one layer of this film was subjected to corona discharge treatment for 41,117 m27 minutes to obtain a two-layer or three-layer film. The wettability index of the corona discharge treated surface of these films, the deposition strength and brightness when aluminum is vacuum deposited.
シール性の評価結果を第１表に示す。The evaluation results of sealing performance are shown in Table 1.
比較例４
コロナ放電処理を行わなかったこと以外は実施例１〜４
および比較例１〜３と同様にしてフィルムを得、評価し
た。結果を第１表に示す。Comparative Example 4 Examples 1 to 4 except that corona discharge treatment was not performed
Films were obtained and evaluated in the same manner as in Comparative Examples 1 to 3. The results are shown in Table 1.
参考例
コロナ放電処理を濡れ指数３０６ｙｎｅ／ａｍの条件で
行ったこと以外は実施例１〜４および比較例１〜５３と
同様にしてフィルムを得、評価した。結果を第１表に示
す。Reference Example Films were obtained and evaluated in the same manner as Examples 1 to 4 and Comparative Examples 1 to 53, except that the corona discharge treatment was performed under the conditions of a wetting index of 306 yne/am. The results are shown in Table 1.
（注）
奉ｌ ポリプロピレン（ホモポリマー）［出光石油化学
■出光ポリプロＦ７０４ ＮＯ，ＭＩ ７ｇ／１０分。(Note) Polypropylene (homopolymer) [Idemitsu Petrochemical ■Idemitsu Polypro F704 NO, MI 7g/10 minutes.
密度０．９０ｇ／ｃｍ’ ］
＊２ エチレン−ブテン−１共重合体［ＭＩ ４ｇ／１
０分。Density 0.90g/cm' *2 Ethylene-butene-1 copolymer [MI 4g/1
0 minutes.
密度０．８８ｇ／ｃｍ’、 ｍｐ ７０℃、ブテン−１
含量１５重量％、ムーニー粘度Ｍ Ｌ １．４（１００
℃）１８コ＊３ エチレン−ブテン−１共重合体［ＭＩ
２ｇ／１０分。Density 0.88g/cm', mp 70℃, Butene-1
Content 15% by weight, Mooney viscosity M L 1.4 (100
°C) 18*3 Ethylene-butene-1 copolymer [MI
2g/10 minutes.
密度０．９２ｇ／ｃｍ’ ］
＊４ ポリプロピレン（ランダムポリマー）［出光石油
化学■出光ポリプロＦ７４０ ＮＬｌ、 ＭＩ ７ ｇ
／ｌ。Density 0.92g/cm'] *4 Polypropylene (random polymer) [Idemitsu Petrochemical ■Idemitsu Polypro F740 NLl, MI 7 g
/l.
分、密度０．９０ｇ／ｃｍ’ ］
＊５ ［ＭＩ ３．６ ｇ／ｌｏ 分、 密ｆｔ０．
８６ｇ／ｃｍ’ 、 ニア’ａヒレン含ｉ ２３ｉ量％
、ムーニー粘ｆｌｔ Ｍ Ｌ １− ａ（１００℃）２
０］
傘６ ＪＩＳ に６７６８に準拠
−蒸着フィルムへＯＰＰフィルムをドライラミネート（
接着剤は東洋モートン製ポリエステル系、塗布量２．５
ｇ／ｃ＋ｎ’、 ８０℃、 ５ｋｇ／ｃｍ”で圧着）し
、Ｔ型剥離強度を求めた。minute, density 0.90 g/cm'] *5 [MI 3.6 g/lo minute, density ft0.
86g/cm', Nia'a Hillen content 23i amount%
, Mooney viscous flt M L 1- a (100°C) 2
0] Umbrella 6 Compliant with JIS 6768 - Dry lamination of OPP film to vapor deposited film (
Adhesive is Toyo Morton polyester type, coating amount 2.5
g/c+n', pressure bonded at 80°C and 5 kg/cm", and the T-peel strength was determined.
傘８ アルミ蒸着面を蛍光灯下で官能評価［優◎。Umbrella 8: Sensory evaluation of aluminum vapor deposited surface under fluorescent light [Excellent ◎].
良Ｑ、可Δ、不可×］
中９ 非蒸着面同志のシール温度（２ｋｇ／ｃｍ２で１
秒間シールした際に、剥離強度３００ｇ／２５ｍａ＋ど
なるときのシール温度を示す。）
［発明の効果］
取上の如く、本発明の第１によれば、従来のポリプロピ
レン系フィルムに比べ金属蒸着強度が高く、またその強
度の経時変化が少く、かつ強度・剛性が良好な多層ポリ
プロピレンフィルムを得る事ができる。また光輝性にす
ぐれ、酸化防止剤等添加剤処決も容易となる。さらに本
発明の第２によればシール性にすぐれ、印刷性も改善さ
れ包装材料として極めて優れた物性を備えた多層ポリプ
ロピレンフィルムを得る事ができる。Good Q, Fair Δ, Bad ×] Medium 9 Sealing temperature between non-evaporated surfaces (1
It shows the sealing temperature at which the peel strength is 300 g/25 ma + roar when sealed for seconds. ) [Effects of the Invention] As mentioned above, according to the first aspect of the present invention, the multilayer film has higher metal deposition strength than conventional polypropylene films, has less change in strength over time, and has good strength and rigidity. Polypropylene film can be obtained. It also has excellent brightness and can be easily treated with additives such as antioxidants. Furthermore, according to the second aspect of the present invention, it is possible to obtain a multilayer polypropylene film that has excellent sealing properties, improved printability, and has extremely excellent physical properties as a packaging material.
Claims (2)
量％および密度０．８６〜０．９１ｇ／ｃｍ＾３のエチ
レン・α−オレフィン共重合体１〜４０重量％からなる
樹脂成分１００重量部に対し、有機系添加剤０．３重量
部以下および無機系添加剤０．０１〜２重量部を配合し
てなる組成物、層IIとしてポリプロピレン系樹脂１００
重量部に対し、有機系添加剤０．３重量部以下および無
機系添加剤０．０１〜２重量部を配合してなる組成物を
共押出成形して得られる、前記層 I の厚みが１〜３０
μ、前記層IIの厚みが５〜１５０μのフィルムであって
、前記層 I の表面をコロナ放電処理してなる多層ポリ
プロピレンフィルム。(1) Layer I, based on 100 parts by weight of a resin component consisting of 99 to 60% by weight of a polypropylene resin and 1 to 40% by weight of an ethylene/α-olefin copolymer with a density of 0.86 to 0.91 g/cm^3 , a composition containing 0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive, a polypropylene resin 100 as layer II.
The thickness of the layer I obtained by co-extrusion molding a composition formed by blending 0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive with respect to parts by weight. ~30
A multilayer polypropylene film in which the layer II has a thickness of 5 to 150 μ, and the surface of the layer I is subjected to a corona discharge treatment.
量％および密度０．８６〜０．９１ｇ／ｃｍ＾３のエチ
レン・α−オレフィン共重合体１〜４０重量％からなる
樹脂成分１００重量部に対し、有機系添加剤０．３重量
部以下および無機系添加剤０．０１〜２重量部を配合し
てなる組成物、層IIとしてポリプロピレン系樹脂１００
重量部に対し、有機系添加剤０．３重量部以下および無
機系添加剤０．０１〜２重量部を配合してなる組成物、
層IIIとしてポリプロピレン系樹脂９９〜５０重量％お
よび低結晶性ないし非晶性のα−オレフィン共重合体１
〜５０重量％からなる樹脂成分１００重量部に対し、有
機系添加剤０．３重量部以下および無機系添加剤０．０
１〜２重量部を配合してなる組成物を共押出成形して得
られる前記層 I の厚みが１〜３０μ、前記層IIの厚み
が５〜１５０μ、前記層IIIの厚みが１〜３０μのフィ
ルムであって、前記層 I の表面をコロナ放電処理して
なる多層ポリプロピレンフィルム。(2) Layer I, based on 100 parts by weight of a resin component consisting of 99 to 60% by weight of a polypropylene resin and 1 to 40% by weight of an ethylene/α-olefin copolymer with a density of 0.86 to 0.91 g/cm^3 , a composition containing 0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive, a polypropylene resin 100 as layer II.
A composition comprising 0.3 parts by weight or less of an organic additive and 0.01 to 2 parts by weight of an inorganic additive based on the weight of the composition;
Layer III: 99 to 50% by weight of polypropylene resin and low crystalline to amorphous α-olefin copolymer 1
Up to 0.3 parts by weight of organic additives and 0.0 parts by weight of inorganic additives per 100 parts by weight of the resin component consisting of ~50% by weight
The thickness of the layer I obtained by co-extrusion molding of a composition containing 1 to 2 parts by weight is 1 to 30μ, the thickness of the layer II is 5 to 150μ, and the thickness of the layer III is 1 to 30μ. A multilayer polypropylene film obtained by subjecting the surface of the layer I to a corona discharge treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62126063A JPH085173B2 (en) | 1987-05-25 | 1987-05-25 | Multi-layer polypropylene film for metal deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62126063A JPH085173B2 (en) | 1987-05-25 | 1987-05-25 | Multi-layer polypropylene film for metal deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63290743A true JPS63290743A (en) | 1988-11-28 |
| JPH085173B2 JPH085173B2 (en) | 1996-01-24 |
Family
ID=14925708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62126063A Expired - Lifetime JPH085173B2 (en) | 1987-05-25 | 1987-05-25 | Multi-layer polypropylene film for metal deposition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085173B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221661A (en) * | 1996-02-15 | 1997-08-26 | Mitsubishi Chem Corp | Antifogging agent and resin sheet treated with the same antifogging agent |
| JP2005186320A (en) * | 2003-12-24 | 2005-07-14 | Takemoto Oil & Fat Co Ltd | Manufacturing method of thermoplastic resin laminated film and thermoplastic resin laminated film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5294381A (en) * | 1976-02-04 | 1977-08-08 | Mitsui Petrochem Ind Ltd | Biaxially stretched polypropylene composite film |
| JPS6085948A (en) * | 1983-10-18 | 1985-05-15 | 出光石油化学株式会社 | Laminated material |
| JPS61253361A (en) * | 1985-04-15 | 1986-11-11 | Mitsubishi Petrochem Co Ltd | Manufacture of biaxially stretched polypropylene film having vapor-deposited metal |
-
1987
- 1987-05-25 JP JP62126063A patent/JPH085173B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5294381A (en) * | 1976-02-04 | 1977-08-08 | Mitsui Petrochem Ind Ltd | Biaxially stretched polypropylene composite film |
| JPS6085948A (en) * | 1983-10-18 | 1985-05-15 | 出光石油化学株式会社 | Laminated material |
| JPS61253361A (en) * | 1985-04-15 | 1986-11-11 | Mitsubishi Petrochem Co Ltd | Manufacture of biaxially stretched polypropylene film having vapor-deposited metal |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221661A (en) * | 1996-02-15 | 1997-08-26 | Mitsubishi Chem Corp | Antifogging agent and resin sheet treated with the same antifogging agent |
| JP2005186320A (en) * | 2003-12-24 | 2005-07-14 | Takemoto Oil & Fat Co Ltd | Manufacturing method of thermoplastic resin laminated film and thermoplastic resin laminated film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH085173B2 (en) | 1996-01-24 |
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