CN1241487A - Biaxially stretched multilayer film - Google Patents
Biaxially stretched multilayer film Download PDFInfo
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- CN1241487A CN1241487A CN99110953A CN99110953A CN1241487A CN 1241487 A CN1241487 A CN 1241487A CN 99110953 A CN99110953 A CN 99110953A CN 99110953 A CN99110953 A CN 99110953A CN 1241487 A CN1241487 A CN 1241487A
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- resin
- plural layers
- skin
- layers
- weight
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- Pending
Links
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000004806 packaging method and process Methods 0.000 claims abstract description 21
- 239000011342 resin composition Substances 0.000 claims abstract description 21
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 19
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 19
- -1 polypropylene Polymers 0.000 claims abstract description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 claims description 35
- 229920000178 Acrylic resin Polymers 0.000 claims description 35
- 210000001161 mammalian embryo Anatomy 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 28
- 238000012856 packing Methods 0.000 claims description 28
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 14
- 230000004888 barrier function Effects 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 238000003851 corona treatment Methods 0.000 claims description 8
- 235000013622 meat product Nutrition 0.000 claims description 8
- 239000004760 aramid Substances 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 abstract description 28
- 230000001954 sterilising effect Effects 0.000 abstract description 13
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 8
- 239000005001 laminate film Substances 0.000 abstract description 5
- 229920001155 polypropylene Polymers 0.000 abstract description 5
- 235000021067 refined food Nutrition 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 151
- 239000010408 film Substances 0.000 description 66
- 235000013580 sausages Nutrition 0.000 description 28
- 238000000034 method Methods 0.000 description 21
- 239000004698 Polyethylene Substances 0.000 description 20
- 229920002647 polyamide Polymers 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 239000004952 Polyamide Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 238000011049 filling Methods 0.000 description 14
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 13
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 13
- 235000013372 meat Nutrition 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 9
- 235000019690 meat sausages Nutrition 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- 229920000554 ionomer Polymers 0.000 description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 239000004840 adhesive resin Substances 0.000 description 7
- 229920006223 adhesive resin Polymers 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 244000144972 livestock Species 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 241000251468 Actinopterygii Species 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 229920000305 Nylon 6,10 Polymers 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 230000000249 desinfective effect Effects 0.000 description 5
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000007 Nylon MXD6 Polymers 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920003354 Modic® Polymers 0.000 description 3
- 229920000571 Nylon 11 Polymers 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 229920000572 Nylon 6/12 Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000021055 solid food Nutrition 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 244000247812 Amorphophallus rivieri Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 description 2
- 229920002752 Konjac Polymers 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 229920003620 Grilon® Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000000975 dye Substances 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
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Laminated Bodies (AREA)
Abstract
A biaxially stretched multilayer film suitable for packaging a processed food product is formed of a biaxially stretched laminate film of at least three layers including a pair of outer layers each comprising a thermoplastic resin, and an intermediate layer disposed between the outer layers. The intermediate layer comprises a polyamide resin composition comprising an aromatic diamine copolymer and an aromatic diamine polymer, and at least one of the outer layers comprises a polypropylene resin. The multilayer film shows a good balance among formability, heat-shrinkability, easy-sealability, gas-barrier characteristic, moisture-barrier characteristic and softness, and also good heat-resistance adapted to retort sterilization.
Description
What the present invention relates to biaxial stretching has outer field plural layers of the acrylic resin of containing, especially a kind of required characteristics (for example hear resistance, distillation sterilizing operation, be easy to sealing, formability, heat-shrinkable, gas barrier property, steam and flexibility block water) between the splendid packing film of balance.Herein, term " film " does not specially refer to especially little thickness but the thickness of finger beam scope, comprises probably the thickness that is used for " sheet material ".
Resin stretched plural layers are particularly suitable for as embryo clothing film, flow packing film, deep-draw packing film, or the like, be used for filling and packing fluid or semifluid food, for example sausage, and solid food, for example meat and the ham of process processing.
In recent years, there has been tangible technological innovation in the packaging for foodstuff field, every kind of food all needs best packaging material to be used for packing, to store and transportation or the like, in addition, and according to for example improving the requirement of producing and reducing cost, various packaging material also need automatic packaging machine is presented splendid adaptability.
In order to load and pack for example sausage of the tame livestock products processed comprising of fluid or semifluid food, the aquatic products of having processed are fish meat sausage for example, the agricultural products of having processed is colloidal-carbon hydrate or starch product (" konnyaku " and " wirou " and the soya-bean milk that comprise Japan) for example, and cooked food, meat and the ham for example processed with solid food, as embryo clothing film, mobile packing film or deep-draw packing film, people have used the single thin film and the plural layers of various synthetic resin continually.For example, resin combination film that comprises nylon and vistanex that has frequently been used and the plural layers that form by lamination nylon layer and polyolefin resin layer are arranged as embryo clothing film.
In these films, be extensive use of the plural layers that form by lamination nylon layer and polyethylene layer (below be abbreviated as " Ny/PE film "), because it has good heat seal and gas barrier property, but it also is attended by the flexibility of being on duty mutually.In addition, the Ny/PE film be suitable for symmetry or self-adhesion mould assembly sealing technology (wherein polyethylene layer surface self seal) and be unsuitable for asymmetric or so-called bottom sealing or envelope type sealing technology (wherein between nylon layer surface and polyethylene layer surface, forming seal bond).Therefore, the Ny/PE film is unsuitable for being equipped with the automatic filling and the packing machine of envelope type sealing mechanism.
Proposed several suggestions so that individual layer embryo clothing film to be provided about Amilan polyamide resin composition, every suggestion all can be satisfied various desired performances.For example, the embryo clothing film that a kind of mixture by nylon 6 and aromatic copolyamides of day patent application of the present disclosure (JP-A) 4-122732 suggestion (below be abbreviated as " nylon 6I/6T ") forms, the aromatic series copolyamide is formed by hexamethylene diamine and terephthalic acid (TPA) and isophthalic acid polycondensation.Yet be difficult to stably produce this embryo clothing film, because the raising of the air pressure in the bubble frequently causes the bubble explosion under extended state because the high internal stress of tubular parison causes in the inflation drawing process by blowing-up technology.In addition, when filling the sausage material with embryo clothing film, boil after the cooking and the cooling according to common process, the product of gained is easy to follow the wrinkling stable shaped and size that product maybe can not be provided of surface film.In addition, embryo clothing film is easy to present poor processing characteristics quite firmly in becoming shirred and/or filling process.
If the aromatic polyamide that forms from adipic acid and diamines methylbenzene of the nylon 6I/6T in the above-mentioned Amilan polyamide resin composition (below be abbreviated as " nylon MXD 6 ") replaces, then above-mentioned tendency and difficulty can become more remarkable.In addition, when the film (or sheet material) that forms by blowing when standing deep-draw from corresponding to the bottom corner portion of deep-draw mould to the tendency that failure is arranged aspect the even elongation of sidewall sections, so its to be applied to deep-draw be difficult.
Main purpose of the present invention provides a kind of biaxial stretching plural layers, it is in the required performance of packaging material, for example hear resistance, distillation sterilizing operation, be easy to sealing, formability, heat-shrinkable, gas barrier property, the balance that blocks water between steam and the flexibility is splendid.
Another purpose of the present invention provides and a kind ofly forms the embryo clothing by aforesaid biaxial stretching plural layers, and in the embryo clothing fill fluid or semifluid inclusion material and the packaging product that obtains.
According to the present invention, a kind of biaxial stretching plural layers that contain at least three layers of biaxial stretching laminate film are provided, it comprises a pair of skin that respectively contains thermoplastic resin, and be configured in intermediate layer between the skin, wherein Amilan polyamide resin composition is contained in the intermediate layer, it comprises aromatic diamine copolymer and aromatic diamine polymer, and at least one skin contains acrylic resin.
According to a further aspect in the invention, provide a kind of biaxial stretching plural layers to be used to pack the meat product of having processed, this film contains at least three layers biaxial stretching laminate film, these three layers comprise a pair of skin that respectively contains thermoplastic resin, and be configured in intermediate layer between the skin, wherein one of skin that will contact with the meat product of having processed contains the resin compound of the polyvinyl resin of the acrylic resin of 90-80% weight and 10-20% weight, and by sided corona treatment.
The aspect further according to the present invention, a kind of biaxial stretching plural layers are provided, comprise at least three layers biaxial stretching laminate film, these three layers comprise a pair of skin that respectively contains thermoplastic resin, and be configured in intermediate layer between the skin, wherein aromatic polyamide (being total to) polymer is contained in the intermediate layer of gas barrier resin, at least one of skin contains acrylic resin, adhesive phase is configured between intermediate layer and said at least one skin, and said adhesive phase contains acrylic resin and the polyvinyl resin mixture with weight ratio 80/20-20/80.At least one of the acrylic resin of said adhesive phase and polyvinyl resin have the functional group.
Further again aspect provides a kind of packaging product according to the present invention, and it contains the embryo clothing that aforesaid biaxial stretching plural layers are formed, and is included in fluid or semifluid material in this embryo clothing.
In some sense, the present invention is equivalent to a selection invention of the invention that the open WO-A98/29250 of international monopoly disclosed, this patent is said from kind and is expressed as single or multiple lift packing film or sheet material, it has the layer that at least one strata amide resin composition forms, wherein the layer of Amilan polyamide resin composition formation is the layer (A) that contains the Amilan polyamide resin composition formation of copolymer nylon (c), and copolymer nylon (c) is made up of with the ratio of 5% weight aliphatic nylon (being total to) polymers compositions (1) and aromatic nylon (being total to) polymers compositions (2) at least.
(acrylic resin)
The fundamental characteristics of biaxial stretching plural layers is that at least one pair of respectively contains acrylic resin for the skin of thermoplastic resin according to the present invention.
Herein, acrylic resin can comprise the propylene of Noblen (being polypropylene) and at least 90% weight and have the copolymer of another alkene of 4 carbon atoms (being ethene or butylene) at the most.This acrylic resin can use separately or to contain at least 50% weight in the mixture, the acrylic resin of preferred at least 60% weight and another thermoplastic resin composition's form are used to constitute at least one skin.
The preferred example of acrylic resin can comprise propylene-ethylene copolymers and propylene-ethylene-butene-1 copolymer, and it can preferably present 130-155 ℃, more preferably 130-140 ℃ melting point resin.
(another thermoplastic resin)
The preferred example of this another thermoplastic resin can comprise polyvinyl resin, includes Alathon (being polyethylene) and at least 75% weight, and preferred at least 90% weight ethene and another have the copolymer of the alkene of 8 carbon atoms at the most.The preferred example of this polyvinyl resin can comprise: Alathon, for example low density polyethylene (LDPE) (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE); And ethene-alpha-olefin copolymer, for example LLDPE (LLDPE), very low density polyethylene (VLDPE), also have the ethylene copolymer that polymerization obtains in the presence of metalloscene catalyst, comprise those resins (trade mark is called " Affinity " or " Elite ") that to have bought from Dow ChemicalCorp..The preferred density of using is at least 0.900g/cm
3Polyvinyl resin.
The preferred example of this another thermoplastic resin except above-mentioned polyvinyl resin can include the ethylene copolymer of polar group, for example ethylene vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA), and ionomer (IO) resin.
(skin)
Be lower than 50% weight if constitute the acrylic resin content that propylene content is lower than in 90% weight or the skin in the outer field acrylic resin, in skin, use the effect of acrylic resin, for example improve hear resistance and distillation sterilizing operation, will become not enough.
Skin can especially preferably contain 95-70% weight, more preferably the acrylic resin of 90-80% weight and 5-30% weight, the more preferably mixture of the polyvinyl resin of 10-20% weight.In conjunction with the Corona discharge Treatment that imposes on superficies, this is promptly with meat or through the meat product of processing such as the adhesion of ham and sausage, effective especially for providing skin to have significantly improved meat adherence.This Corona discharge Treatment is processed food in packing, is easy to present relatively poor meat adherence, and is for example effective especially under the situation of fish meat sausage.If acrylic resin content surpasses 95% weight, it is not enough that the Corona discharge Treatment effect is easy to become.On the other hand, if polyvinyl resin content is excessive, then is easy to reduce a little and distills sterilizing operation and be easy to become not enough with the common tensile property in Amilan polyamide resin composition intermediate layer.
(another skin)
Preferably the pair of outer layer resin combination that all contains acrylic resin or comprise at least 50% weight polyacrylamide resin is to improve envelope type sealing property and distillation sterilizing operation.Yet one of skin can be made up of the thermoplastic resin beyond the acrylic resin.The example of the resin of enumerating in the part that used for this purpose thermoplastic resin can be preferably selected from above-mentioned (another thermoplastic resin) also can preferably comprise mylar, for example PETG.
This another skin can preferably constitute and is arranged on and the inclusion material, for example the skin (so-called outer surface layer) on the outer opposite (so-called interior surface layers) of (half-) fluent material contact.Also (surface) layer contains 1000ppm at the most preferably in addition, and the graininess lubricant of preferred 200-800ppm for example has the silica granule of 10 μ m particle diameters at the most, thereby improves the slip of gained plural layers, and improved mobile packaging character is provided thus.
(intermediate layer)
The intermediate layer can preferably contain the Amilan polyamide resin composition that comprises aromatic diamine copolymer and aromatic diamine polymer with provide suitable at high temperature or the falling, pierce through or rupture strength of the gas barrier property in the distillation procedure process, stretch stability and packaging product.
(aromatic diamine)
Aromatic diamine provides aromatic diamine polymer and/or aromatic diamine copolymer, it preferably contains the diamines methylbenzene, especially has only a diamines methylbenzene, or at least 60% weight, diamines methylbenzene and 40% weight at the most between preferred at least 70% weight, the preferably mixture to the diamines methylbenzene of 30% weight at the most.
(aromatic diamine polymer)
The aromatic diamine polymer can be by the above-mentioned aromatic diamine of polycondensation and aromatic series or aliphatic dicarboxylic acid, the preferred aliphat dicarboxylic acids, the aliphatic dicarboxylic acid that more preferably has 6-12 carbon atom, for example adipic acid, decanedioic acid, suberic acid, heneicosanedioic acid, or dodecanedioic acid, the polyamide of formation.Its special case can comprise: homopolymers, for example poly-meta-xylene adipamide, poly-meta-xylene decanedioyl diamines and poly-meta-xylene suberoyl diamines; Meta-xylene/to methylbenzene adipamide copolymer, meta-xylene/to methylbenzene heptanedioyl diamine copolymer, meta-xylene/to methylbenzene nonanedioyl diamines/decanedioyl diamine copolymer.Among them, poly-meta-xylene adipamide (MXD6) is particularly preferred.Aromatic diamine polymer in the intermediate layer is especially effective for providing biaxial stretching plural layers of the present invention to have vapor barrier properties.
(aromatic diamine copolymer)
The aromatic diamine copolymer can contain the copolycondensation product, the polycondensation unit that wherein contains constitutes above-mentioned aromatic diamine polymer (for example meta-xylene adipamide) and at least a other polyamide, the preferred fat polyamide, for example nylon 6, nylon 11, nylon 12, nylon 66, nylon 69 and NYLON610, the polycondensation unit.This aromatic diamine copolymer can preferably contain the polycondensation unit of 4-40% weight aromatic diamine polymer.When 4% weight is following, make the resistance oxygen reduction of these product plural layers; When 40% weight is above, be easy to make plural layers to have excessive hardness, so just be easy to cause mouldability, heat-shrinkable and flexibility variation.The preferred example of aromatic diamine copolymer can comprise: nylon 6/12/MXD6 copolymer, NYLON610/MXD6 copolymer and nylon 66/610/MXD6 copolymer.
The aromatic diamine copolymer effectively reduces the crystalline rate of the crystalline polyamide resin combination of main composition aromatic diamine polymer, facilitates the hot-stretch operation like this.Therefore, the aromatic diamine copolymer helps to improve stretch stability, film forming and high frequency sealing.This aromatic diamine copolymer further has the function of improving product plural layers flexibility, improve the fillibility of sausage material etc. thus, and the improvement secondary operations, for example shirred, annular is processed, film cuts, the performance of flow automatically packing and deep-draw.The aromatic diamine copolymer also has improvement product plural layers gas barrier property function extremely to a certain degree.Fatty polyamide, as nylon 6, and aromatic polyamide, rather than the mixture of aromatic diamine copolymer can not provide good balance between above-mentioned performance.
The Amilan polyamide resin composition that constitutes the intermediate layer can preferably contain the aromatic diamine copolymer of the aromatic diamine polymer and the 1-50% weight, particularly 5-40% weight of 50-99% weight, particularly 60-95% weight.It is less that the aromatic diamine copolymer of less content causes postponing the effect of crystallization of Amilan polyamide resin composition.On the other hand, the aromatic diamine copolymer of big content is easy to cause the product plural layers soft excessively, causes film embryo clothing inclusion material, when for example the sausage material is filled, film is easy to be become film pressure elongation, thereby uniform product size can not be provided and cause the instability of shape of product.So just cause film embryo clothing size and dimension bad stability.
(other polyamide etc.)
Constitute the Amilan polyamide resin composition in intermediate layer, except above-mentioned aromatic diamine polymer and aromatic diamine copolymer, can contain all non-limiting component up to 30% weight, for example up to the fatty polyamide of 20% weight, up to the noncrystalline polyamide of 20% weight with up to the vistanex of 30% weight.
The example of fatty polyamide can comprise nylon 6, nylon 11, nylon 12, nylon 66, nylon 69, NYLON610, nylon 6/66 and nylon 6/12.
Noncrystalline or unsetting nylon is a kind ofly to comprise aromatic ring on its main chain and/or side chain, does not have crystallization or the polyamide of very rare crystallization is only arranged.More particularly, this example can comprise: dicarboxylic acids, for example terephthalic acid (TPA) and M-phthalic acid, with diamines, hexamethylene diamine for example, between polycondensation products; With their copolymer.Its special case can be the dicarboxylic acid mixture of M-phthalic acid of the terephthalic acid (TPA) of 10-50% weight and 90-50% weight and the copolyamide (representing with nylon 6I/6T sometimes) that the hexamethylene diamine polycondensation forms.
The non-limiting vistanex that mixes for example can comprise the homopolymers of ethene or alpha-olefin in the intermediate layer, for example high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), or polypropylene; The copolymer of ethene and alpha-olefin, for example LLDPE (LLDPE), very low density polyethylene (VLDPE), or the copolymer that polymerization obtains in the presence of metalloscene catalyst (for example resin of the trade mark " Affinity " or " Elite " by name that can buy from Dow Chemical Corp.); Ionomer resin, modified polyamide ionic bond resin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, or ethylene-methacrylic acid copolymer.These vistanexes can be used separately or as its two or multiple mixture used.
As this by sneaking into the non-limiting vistanex that mixes in the Amilan polyamide resin composition, from with the compatibility viewpoint of aromatic diamine polymers compositions, preferably use ethylene copolymer, for example ethylene-acrylic acid copolymer or ethylene-methacrylic acid copolymer, or modified polyamide ionomer resin.
The above modified polyamide ionomer resin refers to the resin that obtains by following technology, use metal, the ion of zinc, lithium, potassium, magnesium, calcium or sodium for example, the copolymer of ionization ethene and α, beta-unsaturated carboxylic acid forms ionomer, add polyamide and with the melt kneading modification under 200-350 ℃ high temperature of this ionomer.For the used polyamide of above-mentioned purpose for example can be nylon 6, nylon 66, nylon 6/66, nylon 6/10, nylon 6/12, nylon 11, nylon 12, or two or multiple mixture of these materials.Preferred nylon 6 or its copolymer of using in these materials.
Included vistanex can effectively reduce and passes the intermediate layer, thereby and the poisture-penetrability of passing the product plural layers, prevent thus packaging product in processes such as storage the inclusion material for example sausage see through the loss in weight of packing film.When using vistanex, the 10-30% weight that its general additional proportion is an Amilan polyamide resin composition.Be lower than 10% weight, it adds effect deficiency, and more than 30% weight, the stretching stability in intermediate layer is easy to variation and oxygen permeability and is easy to raise cause to cause in some cases because of oxidation and degenerates.
(Amilan polyamide resin composition)
The Amilan polyamide resin composition that constitutes the intermediate layer can be by preparing with the already known processes mixing said ingredients.For example, the mixture of pellet, particle or the powder by extruding each polymers compositions with extruder can form homogeneous compositions.This Amilan polyamide resin composition can further contain (in the scope that the film performance to the product plural layers has no adverse effect) various additives, for example plasticizer, stabilizing agent, lubricant, antioxidant, pigment or dyestuff arbitrarily.
(adhesive resin layer)
Plural layers according to the present invention contain above-mentioned at least pair of outer layer and intermediate layer and can produce by this simple coextrusion of three layers.Yet, also can better adhesive plural layers be arranged between each layer by producing at insertion adhesive resin layer between each layer.
The example of this adhesive resin can comprise: for example, comprise unsaturated acids by grafting, maleic acid for example, fumaric acid or acrylic acid, or the unsaturated acidic group modifier of its acid anhydrides or ester is to raw polymer, the for example homopolymers of alkene or copolymer, (comprise copolymer as polyvinyl resin with alpha-olefin, for example LLDPE and VLDPE), polypropylene, polybutene, copolymer between these resin monomers, ionomer resin, ethylene-acrylic acid copolymer, what obtain with ethylene-vinyl acetate copolymer is polymer-modified, and this polymer-modified and aforesaid olefin feedstock mixture of polymers.
The preferred especially adhesive resin layer that contains 20-80% weight polyacrylamide resin and 80-20% weight polyvinyl resin mixture that uses, these mixtures at least one of them by unsaturated acidic group modifier, for example maleic acid modification is because have only strong cohesive and enough lasting hear resistances just can keep out the distillation sterilization.If the content of (modification) acrylic resin is excessive, adhesive resin layer is peeled off or is peeled off at folded part when shirred between acrylic resin layer and polyamide layer at the folded part of embryo clothing with regard to being easy to.On the other hand, if the content of (modification) acrylic resin is excessive, be easy to when stretching, between acrylic resin layer and polyamide layer, occur peeling off in these layers, cause small crackle to cause the explosion of inflatable stretching bubble.
(other resin bed)
Plural layers according to the present invention can further contain other resin bed or additional resin bed except above-mentioned resin bed.For example can adjacent above-mentioned intermediate layer by or the ethylene-vinyl acetate copolymer (EVOH) or the nylon MXD 6 choke resin bed of saponification arbitrarily be not set by adhesive resin layer.
(film production)
Can use any explained hereafter that does not limit especially according to plural layers of the present invention, can be coextrusion or progressively laminated, for example, and according to T-die head technology or blowing-up technology.Generally can adopt blowing-up technology.The shape layer molten resin temperature can be: for constituting at least one outer field acrylic resin, general 160-220 ℃ preferred 180-200 ℃; For generally at the most 300 ℃ of the polyamides that constitutes the intermediate layer, preferred 240-280 ℃, further preferred 250-270 ℃.The non-stretched film still that obtains by T-die head technology can according to tenter frame process for example at the most 130 ℃ draft temperature (it generally is lower than the resin melt temperature of acrylic resin) by biaxial stretching synchronously or progressively.By the resulting tubular parison of blowing-up technology by the bubble inflation and in similar draft temperature gas enclosure and by biaxial stretching.At vertical and horizontal (MD and TD) draw ratio generally is 2.0-10.0 times, and preferred 2.2-8.0 times, more preferably 2.2-6.0 doubly.By stretching, can reach the degree of heat-shrinkage and the dimensional stability of suitable degree, for example anti-wrinkling.
(laminar structure)
By above-mentioned production technology, form biaxial stretching plural layers according to the present invention, as plural layers it comprise following indicate the component layers (comprising selectable layer) of thickness respectively thus provide 10-250 μ m, the gross thickness of preferred 15-200 μ m:
First skin (outer surface layer under the tubular state): 5-100 μ m, preferred 5-80 μ m,
The intermediate layer: 2-50 μ m, preferred 2-20 μ m,
Gas barrier layer (selectable): 1-20 μ m, preferred 2-10 μ m,
Second skin (interior surface layers under the tubular state): 5-100 μ m, preferred 5-80 μ m,
Adhesive resin layer (selectable): 0.5-30 μ m, preferred 1-20 μ m.
(performance)
At the meat product packaging field of processing, occurring wrinkle on the packaging product of for example sausage is disgusting from the viewpoint of commodity aesthetics.In order to prevent wrinkle, need boil cook or the sterilizing operation process in packing film is under the tension force of film thermal contraction.Oriented film according to the present invention when in 80 ℃ of hot water, soaking, each vertically (MD) and horizontal (TD) can present at least 5%, preferably at least 8%, more preferably at least 10% shrinkage (hot water shrinkage).
If plural layers according to the present invention have the hot water shrinkage below 5% in the time of 80 ℃, then fill with fluid or semifluid sausage material when this film embryo clothing, and subsequent boiling is cooked or just can break away from wrinkle on packaging product during heating disinfection.
As the measurement of film dimensions stability, can adopt 80 ℃ 10 second 1kg/mm
2Hot water creep elongation under the load.Can preferably be presented to according to oriented film of the present invention many 20%, preferred 18% hot water creep elongation at the most.If the hot water creep elongation is excessive, the size of packaging product just is easy to fluctuation after filling and cook sausage for example.In order to measure the hot water creep elongation, the sample thin film that the wide 100mm of 20mm is long immerses 80 ℃ 10 seconds of hot water, at 1kg/mm
2The percentage (%) of length elongation is measured in load down.
Membrane according to the invention can preferably be presented to many 20% haze value, therefore can easily see through packing film and see inclusion material, for example sausage.
Can preferably be presented to many 200cm according to plural layers of the present invention
3(NTP)/m
2Dayatm, more preferably 135cm at the most
3(NTP)/m
2The oxygen permeability of dayatm is at the environment measurement of 30 ℃ and 80%RH (relative humidity) and 70g/m at the most
2The rate of perviousness of day is at 40 ℃ and 90%RH environment measurement.These performances prevent to degenerate and because of the saturating wet loss in weight of inclusion material because of oxidation for container for long-term storage food, and for the local flavor that keeps the inclusion material all be effective.
Plural layers according to the present invention present splendid high frequency heat seal or weldability.Though the film to the various resin combinations that contain polyamide and vistanex has proposed a large amount of suggestions, then there is not any list of references for the high frequency heat seal of this film.As our result to various film heat sealer researchs, has only polyamide film, nylon 6 films for example, automatically fill and packing machine (for example " KAP " that be used for sausage product etc. that can buy from KurehaKagaku Kogyo K.K.) when standing high frequency heat seal when using, expect and can not present good heat sealer owing to partly occur leaking in heat seal.On the other hand, plural layers according to the present invention contain the intermediate layer of the skin and the Amilan polyamide resin composition of acrylic resin, and this film can not have the heat seal of the material of leakage continous-stable when the automatic filling of using this outfit high frequency heat seal system and packing machine carry out high frequency heat seal.Not only present this good high frequency heat seal but also also have good heat seal and ultrasonic sealing according to plural layers of the present invention.
Plural layers according to the present invention are suitable for use as embryo clothing film.Plural layers according to the present invention present good film mouldability and draftability in its film production process, also present the flexibility, hot water shrinkage, creep resistance, toughness, gas barrier property, dimensional stability of the suitable degree that matches and to the adaptability of automatic packaging machine, therefore it is particularly suitable for as filling and packing fluid, semifluid or solid food, comprise tame livestock products, for example sausage, ham and meat through processing through processing; Aquatic products, for example fish meat sausage; Agricultural products through processing, for example packaging material of carbohydrate pasty product (" konnyaku " and " wirou " and the soya-bean milk that comprise Japan) and cook food.
Contain the meat product of having processed in filling, for example before the inclusion material of sausage or ham, the superficies that preferably film contacted the inclusion material stand Corona discharge Treatment so that improved so-called " meat adherence " is provided, promptly with the adherence of meat product, thereby prevent to produce dirty juice between film and inclusion, this is not only for the outward appearance of improving packaging product and is in order to keep the quality of inclusion.
Corona discharge Treatment can use the corona discharge machine that is equipped with high frequency electric source to carry out, it contains high-frequency generator and high-tension transformer, film is sent on the treatment tube of silicone coating, use the alternation waveform, has the AC power of the 4KW at the most of the frequency of 18 kilovoltages and 5-120kHz at the most in the sinusoidal waveform of preferred voltage and electric current, make film between sparking electrode and treatment tube, be exposed to corona discharge, make processed film surface have at least 34 dynes per centimeter thus
2, more preferably at least 34 dynes per centimeter
2Surface tension.
That be not only applicable to symmetry according to plural layers of the present invention or self-adhesion mould assembly heat seal process and be applicable to the bottom heat seal or asymmetric technology (be so-called envelope type heat seal process, wherein pair of outer layer overlap in case be in contact with one another in its marginal portion and for mutually bonding and by heat seal).For example by bottom heat seal and suitably filling (half-) fluid inclusion material, subsequently by vertically holding the heat seal sealing so that packaged products is provided at two of embryo clothing, so just form and have flat layer width 260mm at the most, preferred 15-160mm, the tubular embryo clothing of heat seal width 0.1-15mm.
[embodiment]
Hereinafter, the present invention will be illustrated based on embodiment and Comparative Examples more specially.Some physical property described herein is based on the measured value of following method.
(1) oxygen permeability
" the MOCON OXTRAN-2/20 " that use can have been bought from Modern Control Co. measures under 30 ℃ and 80%RH condition according to ASTMD3985-81.
(2) poisture-penetrability
" PERMATRAN-W3/31 " that use can have been bought from Modern Control Co. measures under 40 ℃ and 90%RH condition.
(3) intermediate layer tack
Product film is cut into two sample strip, respectively is 15mm wide (TD) and 100mm long (MD), with vertical end of each sample strip with the cutting machine edge or between the outermost layer ∥ sandwich layer or between innermost layer ∥ sandwich layer, stand the part and peel off.Each tape all stands the measurement of T-shape peel strength, promptly each sample laminate film is measured outermost layer ∥ pin adhesion and sandwich layer ∥ innermost layer bonding strength with peel tip reflectively.
(4) shrinkage
Sample thin film is immersed the contraction % that measures subsequently for 3 seconds in MD and TD direction in 80 ℃ of hot water.
(5) stretch modulus
Product film is cut into two sample strip, respectively is 20mm wide (TD or MD) and 100mm long (MD or TD)." the TENSILON RTM-100 " that use can have been bought from Toyo Boldwin k.k. stands at the extension test of its vertical 10mm draw speed stress when measuring in 1% strain each sample strip as the stretch modulus in MD or TD direction.
(6) meat adherence (film peeling force)
Use test machine (" the FUDOH RHE0 METER " that can buy from Rheotech K.K) is used to measure the meat adherence with the sausage product of packing.Embryo clothing film perpendicular to length cutting 3cm loose and from the two ends of the loose otch of 3cm at vertical 2 lines of cutting of length direction.Then, the embryo clothing vertically peeling off about 2cm in advance, is then clamped released part.Then, with cylindric bar shaped bar sausage is run through its central axis to relative circumference from its circumference and bore a hole, in measuring process, keep the direction of delaminate of film always vertical simultaneously so that this sausage can rotate.This film is peeled off the length of about 3cm with the speed of 6cm/min with this understanding.The average peeling force of measurement in stripping process is to estimate the meat adherence.
(7) crystalline melt point (Tm)
Use differential scanning calorimetry (DSC) (" DSC-7 " that can buy from Perkin-Elmer Inc) to measure the crystalline melt point of resin material.The 5-10mg sample resins of once weighing, fusion and this time fusing point exceed 40 ℃ temperature and kept 2 minutes, the speed with 200 ℃/min is quickly cooled to 0 ℃ subsequently.With the speed heating of sample, in heating process, measure fusion peak dot temperature then as crystalline melt temperature with 20 ℃/min.
Embodiment 1
Have 5 plural layers of laminated structure layer by layer that comprise outermost layer/adhesive phase/sandwich layer/adhesive phase/innermost layer by the following resin raw material preparation that is used for each layer.
Outer ﹠amp; Innermost layer: 90% weight ethylene/propene/butene-1 (2/93/5 weight) copolymer (" SUMITOMONOBULENE FL851 ", Sumitomo Kagaku K.K makes, be abbreviated as " PP ", fusing point (Tm)=139 ℃, density (d)=0.90, melt index (MI)=6g/10min, Vicat softening point (Tv)=128 ℃) and the polyethylene (" Elete 5100 " of 10% weight metallocene catalyst, Dow ChemicalCo makes, and is abbreviated as " PE "; Tm=121 ℃, d=0.92, MI=0.85g/10min, Tv=107 ℃) mixture.
Sandwich layer: 95% weight nylon MXD 6 (" POLYAMIDE MXD6 # 6007 ", Mitsubishi KagakuK.K makes; Tm=240 ℃, Tg=75 ℃, d=1.22) and 5% weight nylon 66/610/MXD6 copolymer (" the GRILON BM-18SBH " that can buy from EMS-Chemie A.G.; Tm=181 ℃, Tg=57 ℃, d=1.12; Be abbreviated as " M-PA ") mixture.
Adhesive phase: 50% weight modified polypropylene resin (" the MODIC P504V " that can buy from Mitsubishi Kagaku K.K.; Be abbreviated as " M-PP "; Tm=140 ℃, d=0.89, MI=4g/10min, Tv=100 ℃) and 50% weight modification LLDPE (" MODICOM-101 " that Mitsubishi Kagaku K.K. makes is abbreviated as " M-PE "; Tm=120 ℃, d=0.93, MI=3.2g/10min, Tv=56 ℃) mixture.
Each resin material (had 40mm diameter die head size for each outermost layer, innermost layer and sandwich layer at 250 ℃ resin temperature by 4 extruders, for adhesive phase is the 30mm diameter) and an annular die head coextrusion, then with the quenching of 10 ℃ of water sprays, formation have comprise 4 kinds of resins 5 layer by layer laminated structure and thickness be 850mm, flat width is the parison of 70mm.
Then, this parison is heated to 150 ℃ surface temperature again and forms tubular film with 4.5/4.5 stretch rate doubly at MD/TD direction biaxial stretching by blowing-up technology with far-infrared heater, it has the layer thickness of 15/2/8/2/15 μ m, and gross thickness is 42 μ m.Then according to the measured film surface temperature of infra-red thermometer with this film 140 ℃ of heat treatments, obtain thus according to plural layers of the present invention.
Be summarized as follows by the resin (and thickness) of ground floor (outermost layer) to each layer of layer 5 (innermost layer):
Outermost layer AD (adhesive) sandwich layer AD innermost layer resin ratio PP+PE M-PP+M-PE MXD6+M-PA M-PP+M-PE PP+PE (weight) 90+10 50+50 95+5 50+50 90+10 thickness (μ m) 15 282 15
Gross thickness=42 μ m
Oxygen permeability, poisture-penetrability, intermediate layer cohesive, shrinkage and the stretch modulus of the plural layers of measuring according to said method are summarized in the table 1 of following appearance with those parameters of following examples and Comparative Examples.
Embodiment 2 and 3
Prepare in the mode identical that just to change the MXD6 and the weight rate between the M-PA that constitute sandwich layer according to plural layers of the present invention as follows with embodiment 1
MXD6+M-PA (embodiment 2) 90+10 (embodiment 3) 80+20
Embodiment 4
By the plural layers that have 5 layers of structure of PP/M-PP/MXD6 (95)+M-PA (5)/M-PP/PP with the similar technology preparation of embodiment 1, only be to use different surface resin layers (promptly, the mixture that replaces PP (90)+PE (10) with PP) with different adhesive phase resin (that is, replacing M-PP (50)+M-PE (50) binder combination) with M-PP.
Embodiment 5
By the plural layers that have 5 layers of structure of PP/M-PP (50)+M-PE (50)/MXD6/M-PP (50)+M-PE (50)/PP with the similar technology preparation of embodiment 1, only be to use different surface resin layers (promptly, the mixture that replaces PP (90)+PE (10) with PP) with different sandwich layer resin (that is, replacing MXD6 (95)+M-PA (5) mixture) with above MXD6.
Embodiment 1-2
Attempt to prepare the biaxial stretching plural layers of 5 layers of structure with PP/Ad/MXD6/AD/PP of same thickness ratio with the similar technology of embodiment 1, in embodiment 1, use the acrylic resin (M-PP of modification simultaneously, " MODIC P504V ", Mitsubishi Kagaku K.K) as the Ad adhesive), in embodiment 2, use the LLDPE (M-PE of modification, " MODIC OM 101 ", Mitsubishi Kagaku K.K) as Ad (adhesive).
In embodiment 1, can obtain plural layers, yet in embodiment 2, in the inflation drawing process, cause the bubble explosion, so just can not provide plural layers because peel off the part between the layer.
The performance of the film of embodiment 1 only is shown in following table 1.
Table 1 example or Comparative Examples thickness (μ m) 1) 2) 3) 4) 5)
Oxygen poisture-penetrability intermediate layer cohesive shrinkage (%) stretch modulus
Permeability (MD/TD) is (MD/TD) embodiment 1 42 30 11 57,/53 8/12 1.5/1.5 embodiment 2 42 31 10 68,/65 7/13 1.4/1.4 embodiment 3 42 32 8 70,/65 8/13 1.3/1.3 embodiment 4 42 30 10 35,/35 7/12 1.6/1.6 embodiment 5 42 28 10 40,/45 7/11 1.5/1.6 embodiment 1 42 28 10 17,/12 7/12 1.5/1.6 (MPa)
Embodiment 6
With the plural layers of real embodiment 3 by the bottom sealing as the embryo clothing and with automatic packaging machine (" KAP2000 " that can buy from Kureha-Kagaku Kogyo K.K.) through filling automatically with pack 100 bullet shapes of starchiness livestock meat sausage manufacture of materials and pack sausage product, they respectively have about 22mm diameter, long and about 55 grammes per square metres of 140mm.Then the sausage product of packing is stood to distill at 120 ℃ with the steam of 2kg/cm gauge pressure and disinfected 15 minutes.Disinfecting the sausage product of packing in the process in distillation does not have blasting phenomena (being that explosion (appearance) rate is 0%), and this sausage product presents after week in room temperature storage 2 not to be had decomposition and degenerate and only cause seldom 0.18% loss in weight.
Embodiment 7
The plural layers of embodiment 4 as the embryo clothing and through filling automatically and packing livestock meat sausage material, are distilled sterilization in the mode identical with embodiment 6 subsequently.As a result, it is 0% that the sausage product of packing presents blow-up rate in distillation in the disinfecting process, and this sausage product presents after 2 weeks in room temperature storage not to be had decomposition and degenerate and only cause 0.17% loss in weight.
Embodiment 8
The plural layers of embodiment 5 as the embryo clothing and through filling automatically and packing livestock meat sausage material, are distilled sterilization in the mode identical with embodiment 6 subsequently.As a result, it is 5% that the sausage product of packing presents blow-up rate in distillation in the disinfecting process, and this sausage product presents after 2 weeks in room temperature storage not to be had decomposition and degenerate and only cause 0.17% loss in weight.
Embodiment 3
The plural layers of embodiment 1 as the embryo clothing and through filling automatically and packing livestock meat sausage material, are distilled sterilization in the mode identical with embodiment 6 subsequently.As a result, to present blow-up rate in distillation in the disinfecting process be 40% to the sausage product of packing.
Embodiment 9
To present surface tension be 36 dynes per centimeter so that provide with the plural layers of embodiment 3 elder generation its surface that contacts with inclusion sausage material of Corona discharge Treatment
2Surface treated.The film of handling like this is used for filling and packing fish meat sausage material, distills sterilization in the mode identical subsequently with embodiment 6.Resulting fish meat sausage product presents 0% blow-up rate in the distillation disinfecting process, room temperature storage 2 after week this sausage meat do not decompose and degenerate and 0.15% low weight loses, also show good meat adherence (peeling rate at 6cm/min is represented by the wide film peeling force of 100g/3cm-).
As mentioned above, the invention provides a kind of biaxial stretching plural layers, its not only at formability, heat-shrinkable, to be easy between heat sealer, gas barrier property, moisture resistance and the flexibility balance splendid but also present splendid hear resistance and be suitable for the distillation sterilization.Especially, these plural layers are suitable for providing usefulness (half-) fluid food, for example flesh of fish, livestock meat and by these product processed, and the embryo clothing of filling provides a kind of outward appearance and intensity splendid packaging product thus.
Claims (14)
1. biaxial stretching plural layers comprise at least three layers biaxial stretching laminated film, and these three layers comprise a pair of skin that respectively contains thermoplastic resin, and an intermediate layer that is configured between the skin, wherein
Amilan polyamide resin composition is contained in the intermediate layer, and it comprises aromatic diamine copolymer and aromatic diamine polymer, and at least one skin contains acrylic resin.
2. according to the plural layers of claim 1, wherein said Amilan polyamide resin composition contains the aromatic diamine copolymer of 1-50% weight and the aromatic diamine polymer of 99-50% weight.
3. according to the plural layers of claim 1 or 2, wherein said aromatic diamine (being total to) polymer contains xylylene amine (being total to) polymer.
4. according to each plural layers of claim 1-3, wherein two skins all contain acrylic resin.
5. according to each plural layers of claim 1-3, wherein at least one skin contains the mixture of acrylic resin and polyvinyl resin.
6. according to the plural layers of claim 5, wherein at least one outer field said mixture contains the acrylic resin of 5-30% weight.
7. one kind is used to pack the biaxial stretching plural layers that pass through the meat product of processing, the laminated film that comprises at least three layers biaxial stretching, these three layers comprise a pair of respectively have contain the outer of thermoplastic resin and be arranged on intermediate layer between the skin, wherein the skin that will contact with the meat product through processing contain the resin compound of polyvinyl resin of the acrylic resin of 90-80% weight and 10-20% weight and its exposed surface by sided corona treatment.
8. biaxial stretching plural layers, the laminated film that comprises at least three layers biaxial stretching, these three layers comprise a pair of respectively have contain the outer of thermoplastic resin and be arranged on intermediate layer between the skin, wherein aromatic polyamide (being total to) polymer is contained in the intermediate layer of gas barrier resin, at least one skin contains acrylic resin, adhesive phase is arranged between intermediate layer and the said at least one skin, it is 80/20 to 20/80 acrylic resin and polyvinyl resin mixture that said adhesive phase contains weight ratio, and one of the acrylic resin of said at least adhesive phase and polyvinyl resin have the functional group.
9. according to each plural layers of claim 1-8, it is heat-shrinkable.
10. packaging product, comprise according to claim 1-9 each the film formed embryo clothing of biaxial stretching multi-layer thin and be included in fluid or semifluid material in this embryo clothing.
11. according to the packaging product of claim 10, wherein the embryo clothing forms by the bottom heat seal.
12. according to the packaging product of claim 11, wherein the embryo clothing has two vertically ends, their all sealed heat seals.
13. according to the packaging product of claim 12, wherein fluid or semifluid material are by the automatic splendid attire of packing machine and be packaged in the embryo clothing.
14. according to each packaging product of claim 11-13, wherein the embryo clothing has the wide flat layer width of 15-160mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110953A CN1241487A (en) | 1998-06-26 | 1999-06-25 | Biaxially stretched multilayer film |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP195102/98 | 1998-06-26 | ||
| CN99110953A CN1241487A (en) | 1998-06-26 | 1999-06-25 | Biaxially stretched multilayer film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1241487A true CN1241487A (en) | 2000-01-19 |
Family
ID=5274794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99110953A Pending CN1241487A (en) | 1998-06-26 | 1999-06-25 | Biaxially stretched multilayer film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1241487A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329185C (en) * | 2003-01-06 | 2007-08-01 | 东丽株式会社 | Laminated film and method for producing same |
| CN116056896A (en) * | 2020-09-11 | 2023-05-02 | 东洋制罐集团控股株式会社 | Packaging bag and multilayer film for packaging used to make the packaging bag |
-
1999
- 1999-06-25 CN CN99110953A patent/CN1241487A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329185C (en) * | 2003-01-06 | 2007-08-01 | 东丽株式会社 | Laminated film and method for producing same |
| CN116056896A (en) * | 2020-09-11 | 2023-05-02 | 东洋制罐集团控股株式会社 | Packaging bag and multilayer film for packaging used to make the packaging bag |
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