CN100448667C - Film for packaging - Google Patents
Film for packaging Download PDFInfo
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- CN100448667C CN100448667C CNB2004800089842A CN200480008984A CN100448667C CN 100448667 C CN100448667 C CN 100448667C CN B2004800089842 A CNB2004800089842 A CN B2004800089842A CN 200480008984 A CN200480008984 A CN 200480008984A CN 100448667 C CN100448667 C CN 100448667C
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- 10min
- film
- ethene
- mfr
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Links
- 238000004806 packaging method and process Methods 0.000 title claims description 75
- 239000004711 α-olefin Substances 0.000 claims abstract description 80
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 71
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 71
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 37
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 35
- 239000011342 resin composition Substances 0.000 claims abstract description 23
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 22
- 229920006280 packaging film Polymers 0.000 claims abstract description 4
- 239000012785 packaging film Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 63
- 230000008569 process Effects 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract 3
- 239000011229 interlayer Substances 0.000 abstract 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 210000000713 mesentery Anatomy 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920005678 polyethylene based resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- MSXXDBCLAKQJQT-UHFFFAOYSA-N 2-tert-butyl-6-methyl-4-[3-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCCOP2OC3=C(C=C(C=C3C=3C=C(C=C(C=3O2)C(C)(C)C)C(C)(C)C)C(C)(C)C)C(C)(C)C)=C1 MSXXDBCLAKQJQT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- VYGRRCKMMADGBB-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] phosphono hydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O VYGRRCKMMADGBB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [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
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229950007687 macrogol ester Drugs 0.000 description 1
- 210000004379 membrane Anatomy 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
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
Abstract
A packaging film composed of at least three layers, i.e., an inner layer, interlayer, and outer layer, wherein the interlayer is made of a polyethylene resin composition comprising (M-1) 20 to 75 wt.% ethylene/alpha-olefin copolymer having an MFR of 0.1 to 100 g/10 min and a density of 0.90 to 0.940 g/cm<3>, (M-2) 20 to 70 wt.% high-density polyethylene having an MFR of 0.001 to 50 g/10 min and a density of 0.942 to 0.97 g/cm<3>, and (M-3) 5 to 20 wt.% high-pressure-process low-density polyethylene having an MFR of 0.01 to 20 g/10 min . The packaging film is excellent in heat-sealing strength, gloss, modulus, and impact strength and is thin and tough.
Description
Technical field
The present invention relates to film for packaging.Relate to heat seal strength and gloss excellence and hard and soft property and impact strength excellence and thin and solid film for packaging in more detail.
Technical background
Toilet article packaging film for paper nappy, physiological articles etc. generally requires excellences such as heat seal strength and gloss.And; requirement can be protected content, easy aggregation and carry easily etc.; in addition; viewpoint from the environment of preserving our planet in recent years, minimizing rubbish; make every effort to make reduced thickness; therefore, with film, require its hard and soft property (spring rate) and impact strength excellence, thin and solid for toilet article packaging.
For example, open in the 2002-273843 communique the spy, compression packing polyethylene mesentery as tearing strength and impact strength excellence, put down in writing by outer, the three layers of compression packing that constitutes polyethylene mesentery of internal layer and intermediate layer, its skin and internal layer are to be that 0.1～10g/10min, density are 0.910～0.930g/cm by containing MFR
3The resin of ethene-alpha-olefin copolymer constitute, the intermediate layer is to be that 0.1～10g/10min, density are 0.925～0.945g/cm by containing MFR
3The resin of ethene-alpha-olefin copolymer constitute.
But, for the compression packing polyethylene mesentery of putting down in writing in the above-mentioned patent disclosure communique, also require to carry out the further improvement of heat seal strength and gloss, in order to reach thinner and solid,, also require further improvement for hard and soft property and impact strength.
Summary of the invention
The purpose of this invention is to provide a kind of heat seal strength and gloss excellence and hard and soft property (spring rate) and impact strength excellence, thin and solid film for packaging.
The inventor etc. scrutinize discovery in view of above-mentioned such actual conditions, use have internal layer at least, resin combination that specific character is satisfied in intermediate layer and outer field three layers, intermediate layer, can solve above-mentioned problem, finished the present invention thus.
That is, purport of the present invention provides a kind of film for packaging, it is characterized in that, has following at least internal layer, intermediate layer and outer field three layers, and the intermediate layer is between internal layer and skin, and each layer is made of following resin combination.
The intermediate layer is by containing:
(M-1) MFR is that 0.1～100g/10min, density are 0.90～0.940g/cm
3Ethene-alpha-olefin copolymer 20～75 weight %;
(M-2) MFR is that 0.001～50g/10min, density are 0.942～0.97g/cm
3High density polyethylene (HDPE) (M-2) 20～70 weight %; With
(M-3) MFR is the layer that the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 5～20 weight % of 0.01～20g/10min constitutes.(wherein, the total amount of above-mentioned copolymer (M-1), high density polyethylene (HDPE) (M-2) and high-pressure process low density polyethylene (LDPE) (M-3) is 100 weight %.)
Internal layer and skin are to be made of polyvinyl resin or resin combination, this polyvinyl resin or resin combination, and MFR is in the scope of 0.01～20g/10min, and density is at 0.90～0.95g/cm
3Scope in.Internal layer and outer field resin or resin combination are identical separately also can be different.
And internal layer is preferably by containing:
(I-1) MFR is that 0.1～100g/10min, density are 0.90～0.95g/cm
3Ethene-alpha-olefin copolymer 45～90 weight %; With
(I-2) MFR is the layer that the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 10～55 weight % of 0.01～20g/10min constitutes.(wherein, the total amount of above-mentioned copolymer (I-1) and high-pressure process low density polyethylene (LDPE) (I-2) is 100 weight %.)，
Skin is preferably by containing:
(O-1) MFR is that 0.1～100g/10min, density are 0.90～0.95g/cm
3Ethene-alpha-olefin copolymer 70～90 weight %; With
(O-2) MFR is the layer that the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 10～30 weight % of 0.01～20g/10min constitutes.(wherein, the total amount of above-mentioned copolymer (O-1) and high-pressure process low density polyethylene (LDPE) (O-2) is 100 weight %.)。
And, (M-2) composition in intermediate layer preferably by:
(LL-3) MFR is that 0.1～2g/10min, density are 0.88g/cm
3More than and discontented 0.93g/cm
3Ethene-alpha-olefin copolymer 20～80 weight %; With
(LL-4) MFR is that 2～100g/10min, density are 0.93～0.97g/cm
3Ethene-alpha-olefin copolymer 20～80 weight % constitute that (wherein, total amount (LL-3) and (LL-4) is 100 weight %.)。
The specific embodiment
The intermediate layer
The intermediate layer of film for packaging of the present invention is by containing:
(M-1) ethene-alpha-olefin copolymer 20～75 weight %;
(M-2) high density polyethylene (HDPE) 20～70 weight %; With
(M-3) layer of the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 5～20 weight % formation.Wherein, (M-1), (M-2) and total amount (M-3) are 100 weight %.(M-1) preferred 30～70 weight %, (M-2) preferred 20～65 weight %.(M-1) if in above-mentioned scope, then film-strength improves, and institute thinks preferred.(M-2) if in above-mentioned scope, then the spring rate of film and heat seal strength can both improve, and institute thinks preferred.(M-3) if in above-mentioned scope, then the heat seal strength of film improves, and institute thinks preferred.
(M-1)
The MFR of ethene-alpha-olefin copolymer (M-1) is 0.1～100g/10min, and density is 0.90～0.940g/cm
3
MFR is if in above-mentioned scope, and then the viewpoint from the intensity of extruding processing characteristics and film for packaging is preferred.In addition, density is preferred from the hard and soft property of film for packaging and the viewpoint of intensity then if in above-mentioned scope.
(M-2)
The MFR of the high density polyethylene (HDPE) (M-2) that the intermediate layer is used is 0.001～50g/10min, is preferably 0.03～10g/10min, more preferably 0.1～1g/10min.MFR is if more than 0.001g/10min, then extruding on good this aspect of processing characteristics to preferred, if below 2g/10min, is preferably on this aspect that has good stability of bubble in the intensity of film for packaging and when being shaped then.
The density of high density polyethylene (HDPE) (M-2) is 0.942～0.97g/cm
3, be preferably 0.945～0.970g/cm
3, more preferably greater than 0.945 and be 0.960g/cm
3Below.If density is at 0.942g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.97g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
(M-3)
The MFR of the high-pressure process low density polyethylene (LDPE) (M-3) that the intermediate layer of film for packaging of the present invention is used is 0.01～20g/10min, is preferably 0.1～5g/10min, more preferably 0.3～2g/10min.MFR is if more than 0.01g/10min, and then with the intermiscibility height of (M-1), institute thinks preferred, if below 20g/10min, then in the intensity of film for packaging and when being shaped on this aspect that has good stability of bubble for preferably.
The not special regulation of the density of high-pressure process low density polyethylene (LDPE) (M-3) is preferably 0.917～0.930g/cm
3, 0.919～0.925g/cm more preferably
3If density is at 0.917g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.93g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
(LL-3)
And above-mentioned (M-1) preferably constitutes by two kinds of ethene-alpha-olefin copolymers (LL-3) with (LL-4).When (M-1) composition is 100 weight %, being 20～80 weight % (LL-3), being preferably 50～70 weight %, (LL-4) is 20～80 weight %, is preferably 30～50 weight %.
The MFR of copolymer (LL-3) is 0.1～2g/10min, is preferably 0.3～1g/10min.MFR is if more than 0.1g/10min, then extruding on good this aspect of processing characteristics to preferred, if below 2g/10min, is preferably on this aspect that has good stability of bubble in the intensity of film for packaging and when being shaped then.
The density of copolymer (LL-3) is 0.88～0.93g/cm
3, be preferably 0.90～0.91g/cm
3, 0.903～0.907g/cm more preferably
3If density is at 0.88g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.93g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
(LL-4)
The MFR of ethene-alpha-olefin copolymer (LL-4) is 2～100g/10min, is preferably 20～80g/10min.MFR is if more than 2g/10min, then extruding on good this aspect of processing characteristics to preferred, if below 100g/10min, is preferably on this aspect that has good stability of bubble in the intensity of film for packaging and when being shaped then.
The density of copolymer (LL-4) is 0.93～0.97g/cm
3, be preferably 0.930～0.949g/cm
3If density is at 0.93g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.97g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
When ethene-alpha-olefin copolymer (M-1) by (LL-3) and (LL-4) constitutes, with respect to the intermediate layer, the content of ethene-alpha-olefin copolymer (LL-3) is 15～60 weight %, the content of ethene-alpha-olefin copolymer (LL-4) is 5～25 weight %, the content of high density polyethylene (HDPE) (M-2) is 20～70 weight %, and the content of high-pressure process low density polyethylene (LDPE) (M-3) is 5～20 weight %.And, as the content of ethene-alpha-olefin copolymer (LL-3), be preferably 15～50 weight %, as the content of high density polyethylene (HDPE) (M-2), be preferably 20～60 weight %.
(internal layer)
The internal layer of film for packaging of the present invention is made of polyethylene resin composition, and the MFR of this polyvinyl resin or resin combination is in the scope of 0.01～20g/10min, preferably in the scope of 0.1～10g/10min.Density is at 0.90～0.95g/cm
3Scope in, preferably at 0.91～0.93g/cm
3Scope in.As polyvinyl resin or resin combination, can enumerate straight chain shape or branch's polyethylene, high-pressure process low density polyethylene (LDPE) or by these compositions of forming.And, internal layer preferably by:
(I-1) MFR is that 0.1～100g/10min, density are 0.90～0.95g/cm
3Ethene-alpha-olefin copolymer 45～90 weight %; With
(I-2) MFR is the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 10～55 weight % composition of 0.01～20g/10min.Wherein, the total amount of above-mentioned copolymer (I-1) and high-pressure process low density polyethylene (LDPE) (I-2) is 100 weight %.(I-1) if in above-mentioned scope, then film-strength improves, for preferably.(I-2) if in above-mentioned scope, then the heat seal strength of film improves, for preferably.
(I-1)
The MFR of ethene-alpha-olefin copolymer (I-1) is 0.1～100g/10min, is preferably 0.5～50g/10min.MFR is if in above-mentioned scope, then in the intensity of film for packaging and extrude on good this aspect of processing characteristics to preferably.(I-1) density is 0.90～0.95g/cm
3, be preferably 0.91～0.94g/cm
3Density is if in above-mentioned scope, and then the hard and soft property of film for packaging and intensity improve, and institute thinks preferred.
Moreover ethene-alpha-olefin copolymer (I-1) is preferably formed by two kinds of ethene-alpha-olefin copolymers (LL-1) with (LL-2).(I-1) all be made as 100 weight % the time, (LL-1) be 20～80 weight %, (LL-2) be 20～80 weight %.Preferably (LL-1) is that 55～75 weight %, (LL-2) are 25～45 weight %.
(LL-1)
The MFR of copolymer (LL-1) is 0.1～10g/10min, is preferably 0.2～5g/10min, more preferably 0.4～1g/10min.MFR is if more than 0.1g/10min, then extruding on good this aspect of processing characteristics to preferred, if below 10g/10min, is preferably on this aspect that has good stability of bubble in intensity, the hear resistance of film for packaging and when being shaped then.
The density of copolymer (LL-1) is 0.88～0.93g/cm
3, be preferably 0.91～0.92g/cm
3, 0.913～0.918g/cm more preferably
3If density is at 0.88g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.93g/cm
3Below, then the heat sealability at film for packaging improves on this aspect to preferred.
(LL-2)
The MFR of ethene-alpha-olefin copolymer (LL-2) is 2～100g/10min, is preferably 2～80g/10min.MFR is preferred extruding on good this aspect of processing characteristics then if more than 2g/10min, if below 100g/10min, is preferred on good this aspect of the intensity of film for packaging then.
The density of copolymer (LL-2) is 0.93～0.97g/cm
3, be preferably 0.925～0.950g/cm
3, 0.935～0.945g/cm more preferably
3If density is at 0.93g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.97g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
(I-2)
The MFR of high-pressure process low density polyethylene (LDPE) (I-2) is 0.01～20g/10min, is preferably 0.3～5g/10min.If more than 0.01g/10min since with the intermiscibility height of (I-1), institute thinks preferred, if below 20g/10min, then when being shaped on this aspect that has good stability of bubble for preferably.
(I-2) density does not have special provision, is preferably 0.917～0.930g/cm
3, 0.910～0.925g/cm more preferably
3If density is at 0.917g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.930g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
(I-1) by ethene-alpha-olefin copolymer (LL-1) and (LL-2) when forming, all with respect to internal layer, (LL-1) content is 20～60 weight %, and content (LL-2) is 25～40 weight %, and the content of high-pressure process low density polyethylene (LDPE) (I-2) is 10～55 weight %.Wherein, the total amount of above-mentioned copolymer (LL-1), above-mentioned copolymer (LL-2) and high-pressure process low density polyethylene (LDPE) (I-2) is 100 weight %.
The content of the copolymer (LL-1) that internal layer is used is during less than 20 weight %, and the intensity of film for packaging reduces sometimes, and when surpassing 60 weight %, the load of extruding of the used polyethylene resin composition of internal layer increases sometimes, and the gloss of film for packaging reduces.
The content of copolymer (LL-2) is 25% weight when following, and the hard and soft property of film for packaging reduces sometimes, and when surpassing 40 weight %, the intensity of film for packaging reduces sometimes.
As the content of high-pressure process low density polyethylene (LDPE) (I-2), be preferably 15～60 weight %.The content of I-2 is during less than 10 weight %, and the gloss of film for packaging reduces sometimes, in addition, when the used polyethylene resin composition of internal layer is shaped, bubble instability sometimes, when surpassing 60 weight %, the intensity of film for packaging reduces sometimes.
(skin)
The skin of film for packaging of the present invention is made of polyethylene resin composition, and the MFR of this polyvinyl resin or resin combination is in the scope of 0.01～20g/10min, preferably in the scope of 0.1～10g/10min.Density is at 0.90～0.95g/cm
3Scope in, preferably at 0.91～0.93g/cm
3Scope in.As polyvinyl resin or resin combination, can list straight chain shape or branch's polyethylene, high-pressure process low density polyethylene (LDPE) or by these compositions that constitutes.And, skin preferably by:
(O-1) MFR is that 0.1～100g/10min, density are 0.90～0.95g/cm
3Ethene-alpha-olefin copolymer 70～90 weight %; With
(O-2) MFR is the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 10～30 weight % formation of 0.01～20g/10min.The total amount of above-mentioned copolymer (O-1) and hp-ldpe (O-2) is 100 weight %.(O-1) if in above-mentioned scope, then film-strength improves, and institute thinks preferred.(O-2) if in above-mentioned scope, then the heat seal strength of film improves, and institute thinks preferred.
(O-1)
The MFR of ethene-alpha-olefin copolymer (O-1) is 0.1～100g/10min, is preferably 0.5～50g/10min.MFR is if in above-mentioned scope, then in the intensity of film for packaging and extrude on good this aspect of processing characteristics to preferably.(O-1) density is 0.90～0.95g/cm
3, be preferably 0.91～0.94g/cm
3Density is if in above-mentioned scope, and then the hard and soft property of film for packaging and intensity improve, and institute thinks preferred.
(O-2)
The MFR of the high-pressure process low density polyethylene (LDPE) (O-2) that skin is used is 0.01～20g/10min, is preferably 0.3～5g/10min.If more than 0.01g/10min, then with the intermiscibility height of (O-1), institute thinks preferred, if below 20g/10min, then when being shaped on this aspect that has good stability of bubble for preferably.
(O-2) density does not have special provision, is preferably 0.917～0.930g/cm
3, 0.910～0.925g/cm more preferably
3If density is at 0.917g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.930g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
(LL-1)
And above-mentioned ethene-alpha-olefin copolymer (O-1) preferably constitutes by two kinds of ethene-alpha-olefin copolymers (LL-1) with (LL-2).When (O-1) all being made as 100 weight %, (LL-1) be that 20～80 weight %, (LL-2) they are 20～80 weight %.Preferably (LL-1) is 55～75 weight %, (LL-2) is 25～45 weight %.
The MFR of copolymer (LL-1) is 0.1～10g/10min, is preferably 0.2～5g/10min, more preferably 0.4～1g/10min.MFR is if more than 0.1g/10min, then extruding on good this aspect of processing characteristics to preferred, if below 10g/10min, is preferably on this aspect that has good stability of bubble in the intensity and the hear resistance of film for packaging and when being shaped then.
The density of copolymer (LL-1) is 0.88～0.93g/cm
3, be preferably 0.91～0.92g/cm
3, 0.913～0.918g/cm more preferably
3If density is at 0.88g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.93g/cm
3Below, then the heat sealability at film for packaging improves on this aspect to preferred.
(LL-2)
The MFR of copolymer (LL-2) is 2～100g/10min, is preferably 2～80g/10min.MFR is preferred extruding on good this aspect of processing characteristics then if more than 2g/10min, if below 100g/10min, is preferred on good this aspect of the intensity of film for packaging then.
The density of copolymer (LL-2) is 0.93～0.97g/cm
3, be preferably 0.925～0.950g/cm
3, 0.935～0.945g/cm more preferably
3If density is at 0.93g/cm
3More than, then be preferred on this aspect of hard and soft property raising of film for packaging, if at 0.97g/cm
3Below, then the intensity at film for packaging improves on this aspect to preferred.
When (O-1) by ethene-alpha-olefin copolymer (LL-1) and (LL-2) constituting, all with respect to skin, content (LL-1) is that the content of 20～60 weight %, (LL-2) is that the content of 25～40 weight %, high-pressure process low density polyethylene (LDPE) (O-2) is 10～55 weight %.Wherein, the total amount of above-mentioned copolymer (LL-1), above-mentioned copolymer (LL-2) and high-pressure process low density polyethylene (LDPE) (O-2) is 100 weight %.
During less than 20 weight %, the intensity of film for packaging reduces sometimes at the content of the used copolymer of skin (LL-1), and when surpassing 60 weight %, the used polyethylene resin composition of internal layer extrudes that load increases, the gloss of film for packaging reduces sometimes.
The content of copolymer (LL-2) is during less than 25 weight %, and the hard and soft property of film for packaging reduces sometimes, and when surpassing 40 weight %, the intensity of film for packaging reduces sometimes.
As the content of high-pressure process low density polyethylene (LDPE) (O-2), be preferably 15～60 weight %.The content of O-2 is during less than 10 weight %, and the gloss of film for packaging reduces sometimes, in addition, when the employed polyethylene resin composition of internal layer is shaped, bubble instability sometimes, when surpassing 60 weight %, the intensity of film for packaging reduces sometimes.
(copolymer)
Ethene-alpha-olefin copolymer that can use among the present invention (LL-1) and ethene-alpha-olefin copolymer (LL-3), being preferably and using metalloscene catalyst, make ethene and carbon number is the ethene-alpha-olefin copolymer that 4～12 alpha-olefin copolymer obtains.Ethene-alpha-olefin copolymer (LL-2) and ethene-alpha-olefin copolymer (LL-4) be with metalloscene catalyst or Ziegler-Natta catalyst, to make ethene and carbon number be the ethene-alpha-olefin copolymer that 4～12 alpha-olefin copolymer obtains.
Copolymer (LL-1) and copolymer (LL-2) thus also can be by making ethene and alpha-olefin copolymer make copolymer (LL-1) thus make ethene and alpha-olefin copolymer make the material that the such method of copolymer (LL-2) obtains afterwards, continuously.And used alpha-olefin both can identical, also can be different in the manufacturing of used alpha-olefin and copolymer (LL-2) in the manufacturing of copolymer (LL-1).In addition, copolymer (LL-1) and copolymer (LL-2) also can be to incite somebody to action the polymer (LL-1) of individually copolymerization manufacturing and the material that copolymer (LL-2) obtains with the extruder melting mixing respectively.
Copolymer (LL-3) and copolymer (LL-4) thus also can be by making ethene and alpha-olefin copolymer make copolymer (LL-3) thus make ethene and alpha-olefin copolymer make the material that the such method of copolymer (LL-4) obtains afterwards, continuously.And used alpha-olefin both can identical, also can be different in the manufacturing of used alpha-olefin and copolymer (LL-4) in the manufacturing of copolymer (LL-3).
In addition, copolymer (LL-3) and copolymer (LL-4) also can be to incite somebody to action the polymer (LL-3) of individually copolymerization manufacturing and the material that copolymer (LL-4) obtains with the extruder melting mixing respectively.
It as carbon number 4～12 alpha-olefin, for example can enumerate butene-1, amylene-1, hexene-1, heptene-1, octene-1, nonylene-1, decylene-1, laurylene-1,4-methyl-amylene-1,4-methyl-hexene-1 etc., be preferably hexene-1,4-methyl-amylene-1, octene-1.In addition, above-mentioned carbon number be 4～12 alpha-olefin both can use separately, also can at least two kinds and use.
Copolymer (LL-1), copolymer (LL-2), copolymer (LL-3) and copolymer (LL-4) as ethene-alpha-olefin copolymer, for example, can enumerate ethene-1-Butylene copolymer, ethene-4-methyl-pentene-1 copolymer, ethene-hexene-1 copolymer, ethylene-octene-1 copolymer, be preferably ethene-hexene-1 copolymer, ethene-4-methyl-pentene-1 copolymer, ethylene-octene-1 copolymer, more preferably ethene-hexene-1 copolymer.
Ethene-alpha-olefin copolymer used in the present invention [(LL-1)～(LL-4)] is to use metalloscene catalyst or Ziegler-Natta catalyst, utilizes solution polymerization process, slurry polymerization process, high-pressure ion polymerization, gaseous polymerization obtain ethene and above-mentioned alpha-olefine polymerizing.
(polymerization)
Ethene-alpha-olefin copolymer (LL-1) that the present invention is used and ethene-alpha-olefin copolymer (LL-3) are to use metalloscene catalyst and the polymer that obtains, as employed metalloscene catalyst, the catalyst that preferably contains transistion metal compound, this transistion metal compound has the base of the anion frame that is cyclopentadiene shape.The transistion metal compound that what is called has the base that is cyclopentadiene shape anion frame is meant Metallocenic compound, and for example, (in the formula, M is the 4th family or the lanthanide transition metal atom of the periodic table of elements with formula MLaX (n-a); L has the base that is cyclopentadiene shape anion frame or contains heteroatomic base, and at least one is the base with cyclopentadiene shape anion frame; A plurality of L can be crosslinked mutually; X is that halogen atom, hydrogen or carbon number are 1～20 alkyl; N represented the valence of plating atom, and a is the integer of 0＜a≤n) expression, can use separately, also can at least two kinds and use.
Moreover, above-mentioned Metallocenic compound, with organo-aluminum compounds such as triethyl aluminum, triisobutyl aluminium, aluminium methyl tetrahydrochysene mutter mutter compound and/or trityl four penta phenyl fluoride boron acid esters, N such as (Methylalumoxane) aluminium tetrahydrochysene, accelerine four penta phenyl fluoride boron acid esters isoiony compounds are used in combination.
In addition, above-mentioned metalloscene catalyst can be with above-mentioned Metallocenic compound, organo-aluminum compound and, mutter compound and/or ionic compound of aluminium tetrahydrochysene carry to hold or contain and be dipped in SiO
2, AI
2O
3Etc. the catalyst that forms in particulate inorganic polymer carrier or the particulate organic polymer carrier such as polyethylene, polystyrene.
As the ethene-alpha-olefin copolymer that obtains by the polymerization of using above-mentioned metalloscene catalyst, for example can enumerate the spy and open the ethene-alpha-olefin copolymer of putting down in writing in the flat 9-183816 communique.
The used ethene-alpha-olefin copolymer (LL-2) and the preparation method of ethene-alpha-olefin copolymer (LL-4) among the present invention can be enumerated the method for using above-mentioned metallocene.In addition, also can enumerate use Ziegler-Natta catalyst, in the presence of solvent or not and the method that under gas phase-solid phase, liquid phase-solid phase or homogeneous liquid phase, makes ethene and alpha-olefin carry out polymerization.Normally 30～300 ℃ of polymerization temperatures, polymerization pressure is normal pressure～3000kg/cm normally
2
High-pressure process low density polyethylene (LDPE) used in the present invention (I-2), (O-2) and manufacture method (M-3) be to use tank reactor or tube-type reactor, in the presence of free radical generating agent, polymerization pressure is 1400～3000kg/cm
2, polymerization temperature is the method that makes vinyl polymerization under 200～300 ℃ the condition.In addition, use hydrocarbon such as hydrogen, methane, ethane, can regulate melt index as molecular weight regulator.
The manufacture method of high density polyethylene (HDPE) used in the present invention (M-2) is to use Ziegler-Natta catalyst, be the method for 3～18 ethene-alpha-olefin polymerization making ethene and carbon number in the presence of the solvent or not and under gas phase-solid phase, liquid phase-solid phase or homogeneous liquid phase.Normally 30～300 ℃ of polymerization temperatures, polymerization pressure is normal pressure～3000kg/cm normally
2In addition, as high density polyethylene (HDPE), can be selected from commercially available product.
(manufacture method)
The manufacture method of the internal layer of film for packaging of the present invention, intermediate layer, outer employed polyethylene resin composition separately, can enumerate with the dry mixed method of each composition granulation of separately polyethylene resin composition or, the method for melting mixing.Dried mixing can be used various mixers such as Henschel mixer, barrel mixer, the various mixers that melting mixing can be used with single screw extrusion machine, double screw extruder, banbury mixers, hot-rolling.Also have,, for example can enumerate the following preferred manufacture method of institute as the manufacture method of polyethylene-based resin composition used among the present invention.
(1) use 1 polymerizer, be divided into the above reaction condition of two conditions, continuously with after ethene-alpha-olefin copolymer LL-1～4 and the high density polyethylene (HDPE) polymerization, the method for mixed high-voltage method low density polyethylene (LDPE) again.
(2) utilize multistage polymerization technique,, finally obtain polyethylene-based resin method for compositions of the present invention with a plurality of each compositions of polymerizer polymerization.
(3) utilize multistage polymerization, make any 2 compositions among each composition after, the method for mixing remaining 2 compositions again.
In ethene-alpha-olefin copolymer (LL-1) and ethene-alpha-olefin copolymer (LL-2), alpha-olefin can be identical alpha-olefin, also can be different separately alpha-olefins.Also have, in ethene-alpha-olefin copolymer (LL-3) and ethene-alpha-olefin copolymer (LL-4), alpha-olefin can be identical alpha-olefin, also can be different separately alpha-olefins.When mixing ethene-alpha-olefin copolymer (LL-1) and ethene-alpha-olefin copolymer (LL-2), perhaps, when mixing ethene-alpha-olefin copolymer (LL-3) and ethene-alpha-olefin copolymer (LL-4), as compounding process, in order to obtain excellent film for packaging such as outward appearance and intensity, from preventing resin generation projection and the viewpoint of disperseing equably, preferably adopt twin-screw to extrude the compounding process of mixing roll.
The internal layer of film for packaging of the present invention, intermediate layer, outer used polyethylene resin composition separately utilize film blowing manufacturing installation and T type casting film device etc., are configured as multilayer film, use as film for packaging.
In film for packaging of the present invention, internal layer, intermediate layer and outer separately thickness ratio, from obtaining the sufficient rigidity and the viewpoint of heat seal strength fully, normally 1/1/1～1/4/1, be preferably 1/1/1～1/3/1.Film for packaging of the present invention, all density of film preferably surpass 0.93.Density is if in above-mentioned scope, and then mechanical and physical property is good, and institute thinks preferred.
In the used polyethylene resin composition separately of internal layer, intermediate layer, the skin of film for packaging of the present invention, as required can the used resin resin in addition of blending the present invention.For example, in order to improve impact strength, can blending low-density elastomer etc. polyolefin-based resins.
Internal layer at film for packaging of the present invention, the intermediate layer, in the outer used polyethylene resin composition separately, can add as required with 2,6-di-t-butyl-P-cresols (BHT), four [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane (trade name: IRGANOX1010) or n-octadecane base-3-(4 '-hydroxyl-3,5 '-di-tert-butyl-phenyl) (trade name: IRGANOX1076) grade is a stabilizing agent for the phenol of representative to propionic ester, with two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphate and three (2, the 4-di-tert-butyl-phenyl) phosphate etc. is for the phosphate of representative is a stabilizing agent, with two functional-type stabilizing agents such as Sumilizer GP, higher fatty acid amides or high-grade aliphatic ester etc. are the lubricant of representative, with carbon number the glyceride or the sorbitan acid esters of 8～22 aliphatic acid, carbon number is the alkyl di alkanolamide of 8～22 aliphatic acid, the anti-live agent of macrogol ester etc., with fatty acid metal salts of calcium stearate etc. is the processability modifying agent of representative, the pigment of titanium oxide etc.
Additives such as the resin of low-density elastomer that cooperates according to various purposes etc., antioxidant, antiblocking agent, lubricant, processability modifying agent, melting mixing is in internal layer, intermediate layer and the outer employed polyethylene resin composition separately of film for packaging of the present invention in advance, also can do mixing respectively, in addition, do mixing after also can becoming at least a main batch of material.
On film for packaging of the present invention, in order to print, can suitably carry out surface treatments such as sided corona treatment, the heat sealability excellence of the treated side after the secondary operations of enforcement surface treatment etc. can access high intensity.
Film for packaging of the present invention is specially adapted to the film for packaging as the paper nappy of amenities and physiological articles etc.
(embodiment)
Below, utilize embodiment and comparative example to illustrate in greater detail the present invention, but mode of the present invention is not limited to these embodiment.Evaluation is carried out according to following method.
(1) density: the extrudate when MFR is measured (monofilament) is 120 ℃ of following heat treatments 2 hours, spends 1 hour at leisure behind the cool to room temperature, according to the method for stipulating among the JIS K7112, measures with density gradient column.
(2) according to melt index (MFR, unit: the g/10min) method of stipulating among the JIS K6760.Load heavily is 2.16kg, and temperature is 190 ℃.
(3) glossiness (unit: %)
According to the method for stipulating among the ASTM D1003.With 20 ° of outsides of measuring pipe of reflection angle.This is worth, and high glaze is good more more.
(4) tension test
Stamp out the dumbbell shape test film of the size of defined the JIS K6781 from film, distance between anchor clamps is 86mm, draw speed is 200mm/min, carry out tension test, obtain with the draw speed be that 500mm/min stretches, (the unit: MPa) and percentage elongation (unit: %) of the intensity when disrumpent feelings.
(5) spring rate (unit: MPa)
Stamp out the dumbbell shape test film of the size of defined the JIS K6781 from film, the distance between anchor clamps is 86mm, and draw speed is 200mm/min, carries out tension test, obtains the slope of pre-stress with respect to displacement, as spring rate.
(6) Elmendorf (Elmendorf) tearing strength (unit: kN/m)
Measure according to ASTM D1922.
(7) boomerang shape drop impact (unit: N)
Measure according to ASTM 1709A method.
(8) heat seal strength (unit: N/15mm)
Use the film that heat sealing machine seals at various temperatures or from sealed membrane product, gather the wide test film of 15mm, use cupping machine, the peel strength of the heat-sealing portion when obtaining the tensile load (200mm/min) that applies 180 °.
Table 1 represented employed ethene-alpha-olefin copolymer composition (A), utilize the low density polyethylene (LDPE) (B) that the high-pressure free radical polymerization obtains, the physical characteristic of high density polyethylene (HDPE) (C).
(table 1)
| MFR[g/10min] | Density [g/cm 3] | ||
| A1 | 0.5 | 0.904 | (the trade (brand) name: エ ボ リ ユ one) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system ethene-hexene-1 copolymer |
| A2 | 0.5 | 0.913 | (the trade (brand) name: エ ボ リ ユ one) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system ethene-hexene-1 copolymer |
| A3 | 5 | 0.940 | (the trade (brand) name: エ ボ リ ユ one) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system ethene-hexene-1 copolymer |
| 4A4 | 50 | 0.945 | (the trade (brand) name: エ ボ リ ユ one) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system ethene-hexene-1 copolymer |
| A5 | 60 | 0.930 | (the trade (brand) name: エ ボ リ ユ one) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system ethene-hexene-1 copolymer |
| A6 | 1 | 0.920 | Japan's Port リ ケ system (strain) system ethene-1-Butylene copolymer |
| B1 | 0.5 | 0.923 | (the trade (brand) name: ス ミ カ セ Application) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high-pressure process low density polyethylene (LDPE) |
| B2 | 0.6 | 0.922 | (the trade (brand) name: ス ミ カ セ Application) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high-pressure process low density polyethylene (LDPE) |
| B3 | 1.1 | 0.923 | (the trade (brand) name: ス ミ カ セ Application) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high-pressure process low density polyethylene (LDPE) |
| C1 | 0.1 | 0.956 | (the trade (brand) name: Ha イ ゼ Star Network ス) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high density polyethylene (HDPE) |
| C2 | 1 | 0.947 | (the trade (brand) name: Ha イ ゼ Star Network ス) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high density polyethylene (HDPE) |
| C3 | 5 | 0.960 | (the trade (brand) name: Ha イ ゼ Star Network ス) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high density polyethylene (HDPE) |
| C4 | 0.35 | 0.955 | (the trade (brand) name: Ha イ ゼ Star Network ス) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high density polyethylene (HDPE) |
| C5 | 0.03 | 0.947 | (the trade (brand) name: Ha イ ゼ Star Network ス) of Sumitomo Mitsui Port リ オ レ Off イ Application (strain) system high density polyethylene (HDPE) |
(embodiment 1～5)
Use 3 layer film blowing processing machines,
Extruder x3 platform, mould
-slit 2.0mm, barrel temperature are 190 ℃, and mold temperature is 200 ℃, and expansion ratio is 2.0, and hauling speed is 30m/min, the thickness structure ratio: internal layer/intermediate/outer layer=1/2/1, processing thickness is the film of 50 μ m.The composition of resulting film, physical characteristic and evaluation result are represented in table 2.
As intermediate layer (M-1) composition, used the mixture of A1/A3=65/35 (weight ratio).As internal layer (I-1) composition, in embodiment 1 and embodiment 5, used the mixture of A2/A4=60/40 (weight ratio), in embodiment 2～4, used the mixture of A2/A5=60/40 (weight ratio).As outer (O-1) composition, in embodiment 1,2 and 5, used the mixture of A2/A4=60/40 (weight ratio), in embodiment 3 and 4, used the mixture of A2/A5=60/40 (weight ratio).
In internal layer, with respect to internal layer 100 weight portions, interpolation is as alumina silicate 0.4 weight portion of antiblocking agent, as erucyl amide 0.2 weight portion of lubricant, in skin, with respect to outer 100 weight portions, add alumina silicate 0.2 weight portion, as erucyl amide 0.04 weight portion of lubricant as antiblocking agent.The density of each layer of film is that the density by each used polymer multiply by weight fraction and tries to achieve.The holostrome density of film is that the density with each layer multiply by thickness ratio and calculates.
(comparative example 1～4)
With the process equipment of embodiment 1, the thickness structure ratio is made as internal layer/intermediate/outer layer=1/1/1, obtain a kind three layers film constituting by three layers of all identical resin combination, change thickness, in addition, processing conditions is identical with embodiment 1.With respect to film 100 weight portions, add alumina silicate 0.4 weight portion, as erucyl amide 0.07 weight portion of lubricant as antiblocking agent.
Reach (O-1) composition as (M-1), (I-1), in comparative example 1 and 2, used the mixture of A2/A4=60/40 (weight ratio), in comparative example 3, used A6, in comparative example 4, used the mixture of A1/A3=65/35 (weight ratio).The composition of resulting film, physical characteristic and evaluation result are represented in table 3.
Each of film layer and holostrome density are to use the method identical with embodiment 1 to obtain.
Comparative example that the discontented unabridged version invention in intermediate layer is formed 1,2,4 is compared with embodiment, and heat seal strength is poor.In addition, the comparative example 3 that discontented equally unabridged version invention is formed is compared with embodiment, and gloss and tearing strength are poor.
(table 2)
| Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Internal layer is formed | Weight % | A2＝51 A4＝34 B1＝15 | A2＝51 A5＝34 B1＝15 | A2＝51 A5＝34 B1＝15 | A2＝26 A5＝17 B1＝57 | A2＝46 A4＝30 B1＝14 B4＝10 |
| (i-1) composition (i-1) density (i-1) MFR | (LL-1)/(LL-2) [kg/m3] [g/10min] | 60/40 920 2.5 | 60/40 920 2.6 | 60/40 920 2.6 | 60/40 920 2.6 | 60/40 936 2.5 |
| The internal layer gross density | [kg/m3] | 925 | 920 | 920 | 921 | 925 |
| Internal layer MFR | [g/10min] | 1.9 | 1.9 | 1.9 | 1.0 | 1.9 |
| The intermediate layer is formed | Weight % (notes) | A1＝42 A3＝23 B2＝15 C1＝20 | A1＝21 A3＝12 B2＝7 C1＝10 C2＝50 | A1＝21 A3＝12 B2＝7 C1＝10 C3＝50 W-MB＝5 | A1＝21 A3＝12 B2＝7 C1＝60 W-MB＝5 | A1＝19 A3＝10 C1＝9 B2＝7 C4＝55 W-MB＝5 |
| (M-1) composition (M-1) density (M-1) MFR | (LL-3)/(LL-4) [kg/m3] [g/10min] | 65/35 916 1.4 | 65/35 916 1.4 | 65/35 916 1.4 | 65/35 916 1.4 | 65/35 916 1.4 |
| Intermediate layer density | [kg/m3] | 926 | 937 | 943 | 941 | 938 |
| Intermediate layer MFR | [g/10min] | 0.9 | 1.0 | 2.1 | 0.33 | 0.5 |
| The outer composition | Weight % | A2＝51 A4＝34 B1＝15 | A2＝51 A4＝34 B1＝15 | A2＝51 A5＝34 B1＝15 | A2＝51 A5＝34 B1＝15 | A2＝46 A4＝30 B1＝14 B4＝10 |
| (O-1) composition (O-1) density (O-1) MFR | (LL-1)/(LL-2) [kg/m3] [g/10min] | 60/40 926 2.5 | 60/40 926 2.5 | 60/40 920 2.6 | 60/40 920 2.6 | 60/40 926 2.5 |
| Outer density | [kg/m3] | 925 | 925 | 920 | 920 | 925 |
| Outer MFR | [g/10min] | 1.9 | 1.9 | 1.9 | 1.9 | 1.9 |
| Holostrome density | [kg/m3] | 926 | 931 | 931 | 931 | 931 |
| Glossiness | ％ | 93 | 93 | 43 | 51 | 32 |
| Spring rate | MPa MD TD | 550 700 | 590 760 | 640 580 | 560 710 | 720 1000 |
| Tensile break strength | MPa MD TD | 48 51 | 48 47 | 42 40 | 39 40 | 49 20 |
| Tension failure point percentage elongation | ％ MD TD | 480 740 | 580 760 | 580 760 | 480 720 | 440 720 |
| Drawing crack intensity | kN/mMD TD | 27 270 | 38 230 | 43 280 | 28 290 | 19 340 |
| Boomerang shape drop impact | N | 3.0 | 2.1 | 2.0 | 1.7 | 1.2 |
| Heat seal strength | N/15mm130℃ N/15mm135℃ N/15mm140℃ | 12 15 16 | 14 15 15 | 15 15 15 | 15 17 17 | 17 20 19 |
(notes) W-MB: Chinese white 60 weight % concentration
Add up to the W-MB that has added 5 weight portions in 100 weight portions at polymer.
(table 3)
(notes) W-MB: Chinese white 60 weight % concentration
Add up to the W-MB that adds 5 weight portions in 100 weight portions at polymer.
Utilizability on the industry
According to the present invention, can obtain heat seal strength and glossiness excellent and hard and soft property and excellent, the thin and solid film for packaging of impact strength.
Claims (5)
1. film for packaging is characterized in that: have following internal layer, intermediate layer and outer three layers at least, the intermediate layer is between internal layer and skin, and they are made of following composition,
The intermediate layer is by containing
M-1:MFR is that 0.1～100g/10min, density are 0.90～0.940g/cm
3Ethene-alpha-olefin copolymer 20～75 weight %,
M-2:MFR is that 0.001～50g/10min, density are 0.942～0.97g/cm
3High density polyethylene (HDPE) 20～70 weight % and
M-3:MFR is the layer that the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 5～20 weight % of 0.01～20g/10min constitutes, wherein, the total amount of described copolymer M-1, high density polyethylene (HDPE) M-2 and high-pressure process low density polyethylene (LDPE) M-3 is 100 weight %;
Internal layer and skin are made of polyvinyl resin or resin combination respectively, this polyvinyl resin or resin combination, and MFR is in the scope of 0.01～20g/10nin, and density is at 0.90～0.95g/cm
3Scope in, internal layer and outer field resin or resin combination can be identical, also can be different.
2. film for packaging as claimed in claim 1 is characterized in that:
Described internal layer is by containing
I-1:MFR is that 0.1～100g/10min, density are 0.90～0.95g/cm
3Ethene-0-olefin copolymer 45～90 weight % and
I-2:MFR is that the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 10～55 weight % of 0.01～20g/10min constitutes, and wherein, the total amount of described copolymer I-1 and high-pressure process low density polyethylene (LDPE) I-2 is 100 weight %;
And described skin is by containing
O-1:MFR is that 0.1～100g/10min, density are 0.90～0.95g/cm
3Ethene-alpha-olefin copolymer 70～90 weight % and
O-2:MFR is that the polyethylene resin composition of high-pressure process low density polyethylene (LDPE) 10～30 weight % of 0.01～20g/10min constitutes, and wherein, the total amount of described copolymer O-1 and high-pressure process low density polyethylene (LDPE) O-2 is 100 weight %.
3. film for packaging as claimed in claim 1 is characterized in that:
The ethene-alpha-olefin copolymer composition M-1 in described intermediate layer is made of following LL-3 and LL-4,
LL-3:MFR is that 0.1～2g/10min, density are greater than 0.88g/cm
3Less than 0.93g/cm
3Ethene-alpha-olefin copolymer 20～80 weight %,
LL-4:MFR is that 2～100g/10min, density are 0.93～0.97g/cm
3Ethene-alpha-olefin copolymer 20～80 weight %,
Wherein, the total amount of LL-3 and LL-4 is 100 weight %.
4. film for packaging as claimed in claim 2 is characterized in that:
The ethene-alpha-olefin copolymer I-1 of described internal layer and described outer field ethene-alpha-olefin copolymer O-1 are made of following LL-1 and LL-2,
LL-1:MFR is that 0.1～10g/10min, density are greater than 0.88g/cm
3Less than 0.93g/cm
3Ethene-alpha-olefin copolymer 20～80 weight %,
LL-2:MFR is that 2～100g/10min, density are 0.93～0.97g/cm
3Ethene-alpha-olefin copolymer 20～80 weight %,
Wherein, the total amount of LL-1 and LL-2 is 100 weight %, and internal layer and outer field polymer composition can be the same or different.
5. a toilet article packaging film is characterized in that: be made of each described film for packaging in the claim 1～4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003099976 | 2003-04-03 | ||
| JP099976/2003 | 2003-04-03 |
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| CN1767947A CN1767947A (en) | 2006-05-03 |
| CN100448667C true CN100448667C (en) | 2009-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004800089842A Expired - Fee Related CN100448667C (en) | 2003-04-03 | 2004-04-01 | Film for packaging |
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| Country | Link |
|---|---|
| JP (1) | JP4359850B2 (en) |
| KR (1) | KR100825346B1 (en) |
| CN (1) | CN100448667C (en) |
| WO (1) | WO2004089626A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318577B (en) * | 2008-07-07 | 2011-08-17 | 苏州天加新材料有限公司 | Thermal contraction sheet film for bone and meat packaging |
| CN101787155B (en) * | 2010-03-16 | 2012-07-25 | 南阳金牛彩印集团有限公司 | Preparation method of stewing film for beverage packing |
| CN103112228B (en) * | 2011-11-16 | 2016-04-27 | 李军 | Polyamide multifunctional fresh-keeping film |
| JP6314510B2 (en) * | 2014-02-03 | 2018-04-25 | 日本ポリエチレン株式会社 | Method for producing packaging film |
| CN104098819A (en) * | 2014-05-17 | 2014-10-15 | 重庆四平塑料包装股份有限公司 | Sanitary napkin outside bag automatic packaging film |
| JP7380345B2 (en) | 2020-03-09 | 2023-11-15 | 日本ポリエチレン株式会社 | Sealant film for retort food |
| KR102559970B1 (en) * | 2020-12-30 | 2023-07-28 | 삼영화학공업주식회사 | Polyolefin based multilayer wrap film |
| KR102559983B1 (en) * | 2022-04-19 | 2023-07-28 | 삼영화학공업주식회사 | Multilayer polyolefin film having excellent adhesion properties, method for preparing the same, and wrap comprising the wrap film |
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| CN1051714A (en) * | 1990-10-16 | 1991-05-29 | 漳州师范学院 | The method of comprehensive utilization of papermaking and phosphate fertilizer waste liquid |
| JPH05220909A (en) * | 1992-02-14 | 1993-08-31 | Sekisui Chem Co Ltd | Heat-shrinkable laminated film |
| CN1084452A (en) * | 1992-09-18 | 1994-03-30 | 格雷斯公司 | Moisture-proofing film |
| CN1136996A (en) * | 1995-01-20 | 1996-12-04 | 大仓工业株式会社 | Heat-shrinkable polyolefin multilayer film |
| CN1191804A (en) * | 1997-01-30 | 1998-09-02 | 三井化学株式会社 | Multilayer film for packaging |
| CN1344206A (en) * | 1999-12-21 | 2002-04-10 | 巴赛尔技术有限公司 | Co-extruded, multilayer packaging film made from propylene polymer materials |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0924587A (en) * | 1995-07-12 | 1997-01-28 | Nippon Petrochem Co Ltd | Laminate, chuck bag, and compression storage bag |
| JP2000169598A (en) * | 1998-12-04 | 2000-06-20 | Daiya Plastic Kk | Packing film and its manufacture |
| JP4085589B2 (en) * | 2001-03-22 | 2008-05-14 | 住友化学株式会社 | Film for compression packaging |
-
2004
- 2004-04-01 KR KR20057018564A patent/KR100825346B1/en active IP Right Grant
- 2004-04-01 CN CNB2004800089842A patent/CN100448667C/en not_active Expired - Fee Related
- 2004-04-01 JP JP2005505242A patent/JP4359850B2/en not_active Expired - Lifetime
- 2004-04-01 WO PCT/JP2004/004775 patent/WO2004089626A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051714A (en) * | 1990-10-16 | 1991-05-29 | 漳州师范学院 | The method of comprehensive utilization of papermaking and phosphate fertilizer waste liquid |
| JPH05220909A (en) * | 1992-02-14 | 1993-08-31 | Sekisui Chem Co Ltd | Heat-shrinkable laminated film |
| CN1084452A (en) * | 1992-09-18 | 1994-03-30 | 格雷斯公司 | Moisture-proofing film |
| CN1136996A (en) * | 1995-01-20 | 1996-12-04 | 大仓工业株式会社 | Heat-shrinkable polyolefin multilayer film |
| CN1191804A (en) * | 1997-01-30 | 1998-09-02 | 三井化学株式会社 | Multilayer film for packaging |
| CN1344206A (en) * | 1999-12-21 | 2002-04-10 | 巴赛尔技术有限公司 | Co-extruded, multilayer packaging film made from propylene polymer materials |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100825346B1 (en) | 2008-04-28 |
| WO2004089626A1 (en) | 2004-10-21 |
| CN1767947A (en) | 2006-05-03 |
| KR20060059869A (en) | 2006-06-02 |
| JP4359850B2 (en) | 2009-11-11 |
| JPWO2004089626A1 (en) | 2006-07-06 |
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