CN107428968A - 聚乙烯系膜 - Google Patents
聚乙烯系膜 Download PDFInfo
- Publication number
- CN107428968A CN107428968A CN201680018586.1A CN201680018586A CN107428968A CN 107428968 A CN107428968 A CN 107428968A CN 201680018586 A CN201680018586 A CN 201680018586A CN 107428968 A CN107428968 A CN 107428968A
- Authority
- CN
- China
- Prior art keywords
- film
- polyethylene
- layers
- arithmetic average
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Polyethylene Polymers 0.000 title claims abstract description 67
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 46
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 46
- 210000000713 mesentery Anatomy 0.000 title claims abstract description 38
- 239000000565 sealant Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 39
- 238000007789 sealing Methods 0.000 claims description 27
- 229920005678 polyethylene based resin Polymers 0.000 claims description 26
- 229920005673 polypropylene based resin Polymers 0.000 claims description 20
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 229920000915 polyvinyl chloride Polymers 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 25
- 239000000314 lubricant Substances 0.000 description 23
- 239000004925 Acrylic resin Substances 0.000 description 17
- 229920000178 Acrylic resin Polymers 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000004743 Polypropylene Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 230000003746 surface roughness Effects 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000003475 lamination Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000004804 winding Methods 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000008393 encapsulating agent Substances 0.000 description 6
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000009820 dry lamination Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005630 polypropylene random copolymer Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- 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
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B29C48/911—Cooling
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- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/917—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means by applying pressurised gas to the surface of the flat article
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- 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
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
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Abstract
提供一种聚乙烯系膜,其在从膜卷状态卷出时的耐粘连性、与基材层压后的密封剂彼此的耐粘连性更良好,且兼具透明性和低温下也良好的热封性。一种聚乙烯系膜,其特征在于,在至少一个面中,膜的流向上的算术平均粗糙度(Ra(MD))与垂直于流向的方向的算术平均粗糙度(Ra(TD))的比值满足下述式(1)。(1)1.2≤Ra(TD)/Ra(MD)≤3.6。Ra(MD):在膜的流向上测定的算术平均粗糙度[μm];Ra(TD):在与膜的流向垂直的方向上测定的算术平均粗糙度[μm]。
Description
技术领域
本发明涉及聚乙烯系膜。更详细地,涉及耐粘连性、低温下的热封性优异、并且刚从卷中卷出后也显示出良好的滑动性的聚乙烯系膜。
背景技术
近年来,由于方便性、省资源、对环境的负荷降低等,应用了膜的包装或容器在广泛的领域中使用。膜与现有的成形容器、成形物相比,具有质量轻、容易废弃处理、成本低的优点。
一般而言,密封材料通常与低温热粘接性比密封材料差的双轴拉伸尼龙膜、双轴拉伸酯膜、双轴拉伸聚丙烯膜等基材层压后使用,但在层压加工后进行保存之后,有时在密封材料与基材之间发生粘连,难以进行用于制袋加工的层压膜的重绕,或者,有时在制袋加工时成为袋内表面的密封材料彼此发生粘连,从而难以填充食品。
出于改善上述情况的目的,已知的策略是散布淀粉等粉末,从而避免密封材料与基材的粘连、避免密封材料彼此的粘连。
但是,这样不仅会污染膜加工装置的周边,而且,还会产生使包装食品的外观显著恶化、或者附着于密封材料的粉末与食品一起直接混入到包装体内之类的卫生性等的问题。
为了解决上述问题而公开了:在具有热封性的聚乙烯系树脂膜中,热封性与耐粘连性呈现平衡的层叠聚乙烯系无拉伸膜(例如参照专利文献1等。)。
然而,寻求进一步改善将膜卷进行卷出时的聚乙烯系膜彼此的耐粘连性。
现有技术文献
专利文献
专利文献1:日本特许第4779822号公报
发明内容
发明要解决的课题
本发明以所述现有技术的课题为背景。即,本发明的目的是提供一种聚乙烯系膜,其在从膜卷状态卷出时的耐粘连性、与基材层压后的密封剂彼此的耐粘连性更良好,且兼具透明性和低温下也良好的热封性。
用于解决课题的方法
本发明人为了达成所述目的而进行了深入研究,结果完成了本发明。即,本发明具有以下的方式。
〔1〕算术平均粗糙度(Ra(TD)[μm])
一种聚乙烯系膜,其特征在于,在至少一个面中,膜的流向的算术平均倾斜角(Ra(MD)[μm])与垂直于流向的方向的算术平均粗糙度(Ra(TD)[μm])的值满足下述式(1)。
(1)1.2≤Ra(TD)/Ra(MD)≤3.6
Ra(MD):在膜的流向上测定的算术平均粗糙度[μm]
Ra(TD):在与膜的流向垂直的方向上测定的算术平均粗糙度[μm]
〔2〕一种聚乙烯系膜,其特征在于,其至少包含密封层(A层)、中间层(B层)、层压层(C层)这3层,A层的面的膜的流向的算术平均粗糙度(Ra(MD)[μm])与垂直于流向的方向的算术平均粗糙度(Ra(TD)[μm])的值满足下述式(1)。
(1)1.2≤Ra(TD)/Ra(MD)≤3.6
Ra(MD):在膜的流向上测定的算术平均粗糙度
Ra(TD):在与膜的流向垂直的方向上测定的算术平均粗糙度
〔3〕如上述〔1〕或〔2〕所述的聚乙烯系膜,其中,相对于构成层的树脂组合物整体,包含聚乙烯系树脂75~97重量%、聚丙烯系树脂25~3重量%,所述层具有满足上述式(1)的面。
〔4〕如上述〔3〕所述的聚乙烯系膜,其中,上述聚乙烯系树脂为直链状低密度聚乙烯。
〔5〕如上述〔3〕或〔4〕所述的聚乙烯系膜,其中,上述聚丙烯系树脂的按照ASTM D-1238(230℃、21.18N)测定的熔体流动速率(MFR)为0.6~3.0g/10分钟。
〔6〕如上述〔1〕~〔5〕中任一项所述的聚乙烯系膜,其在120℃下进行热封后的热封强度为25N/15mm以上。
〔7〕如上述〔1〕~〔6〕中任一项所述的聚乙烯系膜,其中,粘连强度为60mN/20mm以下。
本发明通过采取上述方式,从膜卷状态卷出时的粘连得到改善。这是因为:通过采取上述方式,将膜彼此重叠时的接触面积显著减少,该特征也表现在刚将聚乙烯系膜的卷卷出后的聚乙烯系膜的滑动性非常良好的特性。
发明的效果
本发明的聚乙烯系膜即使在以单独的形式卷绕时也不发生卷粘连,此外,即使在刚卷出后也显示出良好的滑动性,在低温下显示出良好的热封性。另外,即使在进行层压加工后,滑动性的恶化也少,填充时的开口性也良好,并且加工损耗也少。
附图说明
图1是示出本发明的评价方法所涉及的粘连强度的测定方法的图。
具体实施方式
以下,详细说明本发明。
本发明的膜的至少一面的由膜的流向的算术平均粗糙度(Ra(MD)[μm])与垂直于流向的方向的算术平均粗糙度(Ra(TD)[μm])计算的Ra(TD)/Ra(MD)的下限优选为1.2,更优选为1.3,进一步优选为1.4。Ra(TD)/Ra(MD)小于1.2时,有时在卷状态、制袋后发生粘连。
Ra(TD)/Ra(MD)的上限优选为3.0,更优选为2.7,进一步优选为2.5。Ra(TD)/Ra(MD)超过3.0时,有时透明性发生恶化。
Ra(MD):在膜的流向上测定的算术平均粗糙度
Ra(TD):在与膜的流向垂直的方向上测定的算术平均粗糙度。
算术平均粗糙度(Ra(MD)〔μm〕)和算术平均粗糙度(Ra(TD)[μm])的测定如下所述地进行。
首先,使用形状测定激光显微镜(Keyence公司制,型号为VK-9700),在膜的密封层(A层)侧的任意部位拍摄图像(倍率为50倍)。
接着,使用粗糙度分析软件(Keyence公司制,VK Analyzer),对该图像测定线粗糙度(线粗糙度)。
表面粗糙度(线粗糙度)基于JIS-B0601进行测定,截取使用λc=0.08mm,在MD方向上将分析长度设为200μm,在TD方向上将分析间隔设为3.3μm,测定n=60根。对于各个表面粗糙度(线粗糙度)曲线,按照JIS0601:2001方式,将测定间距设为0.01μm,算出算术平均粗糙度,平均后得到算术平均粗糙度Ra(MD)。
算术平均粗糙度(Ra(TD)[μm])也同样地,在TD方向上将分析长度设为200μm,在MD方向上将分析间隔设为3.3μm。
Ra(MD)的上限优选为0.9,更优选为0.7。Ra(MD)的下限优选为0.2,更优选为0.4。Ra(TD)的上限优选为1.4,更优选为1.2。Ra(TD)的下限优选为0.6,更优选为0.8。
本发明发现:通过设定为上述式(1)的范围,在膜表面形成如下的形状:在MD方向上整体存在洗衣板那样的脊状凹凸,并且,在某些地方进一步突出有突起的山。由此,将膜重叠时的接触面积显著减少,不仅能够防止粘连,而且滑动性变得良好。
此处提及的粘连是指:将膜从卷的状态重绕时,膜的背面与表面的接触部分不会顺利剥离的现象。
另外也发现:即使想要如现有方法那样地通过添加抗粘连剂和有机系润滑剂,在膜表面形成突起来减小接触面积,并在突起以外的部分用有机系润滑剂覆盖表面来易于滑动,在卷的状态下,由于膜的不存在抗粘连剂的部分的表面彼此发生密合,因此有机系润滑剂难以渗出至膜表面。
已知:即使想要如专利文献1公开的那样在聚乙烯系膜中添加某种程度的量的有机系润滑剂等来使膜的滑动性提高,在将膜以卷的状态保存的期间,渗出至膜表面的量也少,此外,在从卷中卷出膜时表层的有机系润滑剂进入内部,因此实质上在聚乙烯系膜的表面不存在充分的有机系润滑剂,其结果是无法满足滑动性。
可以认为,膜以卷的状态保存时,膜表面彼此发生密合,从而阻碍有机系润滑剂的渗出。而且,进行接触的面两者为相同的树脂组成时,该效果增大。本发明中,在密封层中添加有聚丙烯树脂,从而在卷的状态下进行接触的面彼此的树脂组成稍有不同。因此推测,表层彼此不易产生密合,因此,密封层内的有机系润滑剂易于留在密封层表层。
调节为上述(1)式的范围的方法如下所述。
例如,将熔体流动速率(MFR)不同的2种以上的原料树脂、例如聚乙烯系树脂和聚丙烯系树脂共混并使其熔融时,树脂相互微细分散,呈现均匀混合的状态。此时,各种树脂若为相容性高的树脂,则仿佛相互融合一般,若相容性差,则各种树脂完全分离,且各种树脂的粒径增大。
各种树脂的熔体流动速率(MFR)不同、且各自为特定范围的熔体流动速率(MFR)时,能够制作出微分散状态。
此外,例如在挤出机内呈现微分散状态的聚丙烯系树脂被由T型模头牵引至冷却辊上时的拉力所拉伸,从而在膜的流向(MD)的方向上形成有脊的细微凹凸。
本发明中已知,即使向聚乙烯系树脂中添加聚丙烯系树脂,也意外地不损害低温密封性,使滑动性提高。
作为所使用的聚乙烯系树脂,例如可举出选自乙烯·α-烯烃共聚物、高压法聚乙烯中的1种或者将2种以上混合而得的树脂。上述乙烯·α-烯烃共聚物为乙烯与碳数4~18的α-烯烃的共聚物,作为α-烯烃,可举出1-丁烯、1-己烯、4-甲基1-戊烯、1-辛烯、1-癸烯等。由这些聚乙烯系树脂得到的膜具有优异的热封强度,即使在刚密封后密封树脂在熔融状态下也具有密封强度,具有即使在填充内容物时承受压力冲击密封部也不发生剥离的性质(热粘性),在包装时即使内容物即液体、粘体物、粉末等附着于密封部,密封性也不易降低,具有能够安全地进行密合密封的性质(夹杂物密封性),具有耐冲击性,该聚乙烯系树脂可以在不损害这些特性的范围内与其它树脂、例如乙烯·乙酸乙烯酯共聚物、乙烯·丙烯酸酯共聚物等混合后使用。
其中,作为本发明中使用的聚乙烯系树脂,从制膜性、制膜品的物性和功能性等的观点出发,熔体流动速率(以下有时记为MFR)优选为2.5~4.5g/分钟左右。在此,MFR按照ASTM D1238进行测定。另外,该聚乙烯系树脂自身通过已知的方法合成。
本发明中,在配合中所使用的原料聚乙烯树脂的密度范围没有特别限定,但优选为900~970kg/m3,更优选为905~965kg/m3,进一步优选为910~960kg/m3。密度为900kg/m3以上的聚乙烯树脂本身的操作性良好。另外,密度为970kg/m3以下的聚乙烯树脂容易发生聚合。
在配合中所使用的聚乙烯树脂的分子量分布(Mw/Mn)优选为2.0~3.5。更优选为2.2~3.3,进一步优选为2.4~3.1。若使用分子量分布(Mw/Mn)为2.0以上的聚乙烯系树脂,则不易发生由熔融时的树脂的流动特性所致的颈缩等,制造膜时容易稳定生产,有助于降低膜的厚度不均等。另外,若使用分子量分布为3.5以下的聚乙烯树脂,则高分子量体所致的鱼眼的生成减少。
所使用的聚丙烯系树脂优选为聚丙烯系无规共聚物,更优选为大量(约85重量%以上)的丙烯与少量(约15重量%以下)的α-烯烃的无规共聚物(聚丙烯-α烯烃无规共聚物)。作为获得所述聚丙烯无规共聚物时的α-烯烃单体,可以使用乙烯、1-丁烯、1-戊烯、4-甲基1-戊烯、1-己烯、1-辛烯等,从生产率的方面考虑,特别优选使用乙烯、1-丁烯。另外,共聚中使用的α-烯烃为至少1种以上即可,可以根据需要混合2种以上后使用。
聚丙烯系树脂的密度的下限优选为870kg/cm3,更优选为885kg/cm3。若小于上述值,则聚丙烯完全不相容,有时膜发生白化。向密封层添加的聚丙烯系树脂的密度的上限优选为920kg/cm3,更优选为900kg/cm3。若为920kg/cm3以下,则聚丙烯与聚乙烯树脂完全不相容,密封层表层容易出现凹凸。
聚丙烯系树脂的熔体流动速率(MFR)的下限优选为0.6g/10分钟,更优选为1.0g/10分钟,进一步优选为1.2g/10分钟。若为0.6g/10分钟以上,则聚丙烯与聚乙烯树脂的相容性变得良好,膜不易发生白化。
聚丙烯系树脂的熔体流动速率的上限优选为3.0g/10分钟,更优选为2.0g/10分钟,进一步优选为1.7g/10分钟。若超过上述值,则有时聚丙烯与聚乙烯树脂完全相容,在密封层表层不出现凹凸。
聚丙烯系树脂的添加量相对于聚乙烯系树脂与聚丙烯树脂的混合物整体的下限优选为3重量%,更优选为8重量%,进一步优选为10重量%。若为3重量%以上,则不易发生粘连,刚卷出后的滑动性不易发生恶化。密封层的聚丙烯系树脂添加量的上限优选为25重量%,更优选为15重量%,若为25重量%以下,则低温密封性变得良好。
在日本特许第4411960号公报中,向聚丙烯树脂中加入了2.0重量%的高密度聚乙烯树脂,但若仅向作为基质的聚乙烯系树脂加入2重量%的聚丙烯系树脂,则如上所述密封层表层不会出现凹凸。
本发明中,可以含有抗粘连剂。抗粘连剂可以为1种,但配合2种以上的粒径、形状不同的无机粒子时,对于膜表面的凹凸而言,还形成复杂的突起,可以得到更高的防粘连效果。
本发明中,作为抗粘连剂,优选添加无机粒子。通过该对策,能够维持低温密封性、并赋予高度的防粘连效果。作为其原因,推测是:通过配合无机粒子而在膜表面形成突起,因此膜的接触面积减小,其结果是得到防粘连效果。
本发明中,作为抗粘连剂使用的无机粒子的组成、组合没有限定,可以使用二氧化硅、沸石、硅藻土、滑石等。优选混合二氧化硅和沸石后使用。此外,优选为表面呈无孔状且粒度分布窄的抗粘连剂。作为其原因,表面呈多孔状时,受吸附于无机粒子的水分的影响,有时膜产生发泡、外观变差。
出于将表面形状复杂化的目的,可以使各粒子的粒径不同,并使其分担作用。另外,若粒度分布广,则在膜的制造中,有时无机粒子堆积在T型模头的唇部,从而阻碍生产率。
抗粘连剂的粒径的下限优选为3μm。若为上述值以上,则容易改善粘连。
抗粘连剂的粒径的上限优选为20μm,更优选为16μm。若为上述值以下,则易于保持膜的透明性。
抗粘连剂的合计浓度的下限优选为0.1重量%,更优选为0.5重量%,进一步优选为0.8重量%。若为0.1重量%以上,则易于得到滑动性。
抗粘连剂的合计浓度的上限优选为5重量%,更优选为3重量%,进一步优选为2重量%。若为5重量%以下,则不会过度打滑,不易造成卷绕偏移。
满足上述式(1)的膜面的三维算术平均粗糙度SRa的下限优选为0.05μm,更优选为0.08μm,进一步优选为0.10μm。若为0.05μm以上,则在卷状态、制袋后不易发生粘连。
三维算术平均粗糙度SRa的上限优选为0.25μm,更优选为0.2μm。若为0.25μm以下,则增加表面粗糙度对耐粘连带来的效果变大。
本发明中,优选添加有机系润滑剂。层叠膜的滑动性、防粘连效果提高,且膜的处理性变好。作为其原因,可以认为:有机系润滑剂发生渗出并存在于膜表面,由此表现出润滑剂效果、脱模效果。此外,有机系润滑剂优选添加具有常温以上的熔点的润滑剂。有机系润滑剂可举出脂肪酸酰胺、脂肪酸酯。具体为油酸酰胺、芥酸酰胺、山嵛酸酰胺、亚乙基双油酸酰胺、六亚甲基双油酸酰胺、亚乙基双油酸酰胺等。它们可以单独使用,但通过并用2种以上,即使在严酷的环境下也能够维持滑动性、防粘连效果,因此优选。
密封层(A层)的有机系润滑剂的酰胺基浓度的下限优选为600重量ppm,更优选为800重量ppm。若为600重量ppm以上,则易于得到滑动性。有机系润滑剂的酰胺基浓度的上限优选为2000重量ppm,更优选为1500重量ppm。若为2000重量ppm以下,则不会过度打滑,不易造成卷绕偏移。
关于本发明的聚乙烯系膜,可以在不损害本发明目的的范围内,根据需要在任意的层中配合适量的热稳定剂、抗氧化剂、防静电剂、防雾剂、中和剂、润滑剂、成核剂、着色剂、其它添加剂和无机填充剂等。
优选在聚乙烯系树脂中配合抗氧化剂,可以并用酚系抗氧化剂、亚磷酸酯系抗氧化剂,或者,也可以单独使用在一个分子中具有酚系和亚磷酸酯系的骨架的抗氧化剂。
膜厚度的下限优选为10μm,更优选为30μm,进一步优选为35μm。若为10μm以上,则坚韧性不会过弱,易于进行加工。膜厚度的上限优选为100μm,更优选为50μm,进一步优选为40μm。若为100μm以下,则坚韧性不会过强,易于进行加工。
本发明的聚乙烯系膜的成形方法没有特别限定,例如可以使用吹塑方式、T型模头方式,为了提高透明性,由于容易施加拉力而优选为T型模头方式。吹塑方式中的冷却介质为空气,与其相对,T型模头方式使用冷却辊,因此,T型模头方式是对于提高冷却速度而言有利的制造方法。
熔融成形后的膜优选以卷的形式进行卷绕。卷绕长度没有特别限定,上限优选为8000m。若为8000m以下,则重量不会过于增加,容易操作。下限优选为100m。若为100m以下,则加工的效率不会降低。
(层叠膜)
本发明的聚乙烯系膜可以制成至少依次包含密封层(A层)、中间层(B层)、层压层(C层)的构成。最外层分别为A层、C层。此时,密封层(A层)的面需要满足下述式(1)。
(1)1.2≤Ra(TD)/Ra(MD)≤3.6
Ra(MD):在膜的流向上测定的算术平均粗糙度
Ra(TD):与膜的流向垂直地测定的算术平均粗糙度
本发明的膜的密封层(A层)中使用的树脂如下所述。
作为所使用的聚乙烯系树脂,例如可举出选自乙烯·α-烯烃共聚物、高压法聚乙烯中的1种或者将2种以上混合而得的树脂。上述乙烯·α-烯烃共聚物为乙烯与碳数4~18的α-烯烃的共聚物,作为α-烯烃,可举出1-丁烯、1-己烯、4-甲基1-戊烯、1-辛烯、1-癸烯等。由这些聚乙烯系树脂得到的膜具有优异的热封强度、热粘性、夹杂物密封性、耐冲击性,该聚乙烯系树脂可以在不损害这些特性的范围内与其它树脂、例如乙烯·乙酸乙烯酯共聚物、乙烯·丙烯酸酯共聚物等混合后使用。
其中,作为本发明中使用的聚乙烯系树脂,从制膜性、制膜品的物性和功能性等的观点出发,熔体流动速率(以下有时记为MFR)优选为2.5~4.5g/分钟左右。在此,MFR按照ASTM D-1238(230℃、21.18N)进行测定。另外,该聚乙烯系树脂自身通过已知的方法合成。
本发明中,在配合中所使用的原料聚乙烯树脂的密度范围更优选为905~965kg/m3,进一步优选为910~960kg/m3。密度小于900kg/m3的聚乙烯树脂本身的操作性变差。另外,密度大于970kg/m3的聚乙烯树脂因难以聚合而不易得到,是不合适的。
在配合中所使用的聚乙烯树脂的分子量分布(Mw/Mn)优选为2.0~3.5。更优选为2.2~3.3,进一步优选为2.4~3.1。若使用分子量分布(Mw/Mn)为2.0以上的聚乙烯系树脂,则不易发生由熔融时的树脂的流动特性所致的颈缩等,制造膜时容易稳定生产,有助于降低膜的厚度不均等。另外,若使用分子量分布为3.5以下的聚乙烯树脂,则高分子量体所致的鱼眼的生成减少。
所使用的聚丙烯系树脂优选为聚丙烯系无规共聚物,更优选为大量(约85重量%以上)的丙烯与少量(约15重量%以下)的α-烯烃的无规共聚物(聚丙烯-α烯烃无规共聚物)。作为得到所述聚丙烯无规共聚物时的α-烯烃单体,可以使用乙烯、1-丁烯、1-戊烯、4-甲基1-戊烯、1-己烯、1-辛烯等,从生产率的方面考虑,特别优选使用乙烯、1-丁烯。另外,共聚中使用的α-烯烃为至少1种以上即可,可以根据需要混合2种以上后使用。
聚丙烯系树脂的密度的下限优选为870kg/cm3,更优选为885kg/cm3。若为870kg/cm3以上,则聚丙烯易于与聚乙烯树脂相容,膜不易发生白化。向密封层添加的聚丙烯系树脂的密度的上限优选为920kg/cm3,更优选为900kg/cm3。若为920kg/cm3以下,则聚丙烯不易与聚乙烯树脂完全相容,易于在密封层表层表现出凹凸。
聚丙烯系树脂的熔体流动速率(MFR)的下限优选为0.6g/10分钟,更优选为1.0g/10分钟,进一步优选为1.2g/10分钟。若为0.6g/10分钟以上,则聚丙烯与聚乙烯树脂的相容性良好,膜不易发生白化。
聚丙烯系树脂的熔体流动速率的上限优选为3.0g/10分钟,更优选为2.0g/10分钟,进一步优选为1.7g/10分钟。若为3.0g/10分钟以下,则聚丙烯不易与聚乙烯树脂完全相容,易于在密封层表层表现出凹凸。
聚丙烯系树脂的添加量相对于其与聚乙烯系树脂的混合物整体的下限优选为3重量%,更优选为8重量%,进一步优选为10重量%。若为3重量%以上,则不易发生粘连,易于得到刚卷出后的滑动性。密封层的聚丙烯系树脂的添加量的上限优选为25重量%,更优选为15重量%,若为25重量%以下,则易于得到低温密封性。
本发明中,可以含有抗粘连剂。抗粘连剂可以为1种,但配合2种以上的粒径、形状不同的无机粒子时,对于膜表面的凹凸而言,还形成复杂的突起,可以得到更高的防粘连效果。
本发明中,作为抗粘连剂,优选添加无机粒子。通过该对策,能够维持低温密封性、并赋予高度的防粘连效果。作为其原因,推测是:通过配合无机粒子而在膜表面形成突起,因此膜的接触面积减小,其结果是得到防粘连效果。
本发明中,作为抗粘连剂使用的无机粒子的组成、组合没有限定,可以使用二氧化硅、沸石、硅藻土、滑石等。优选混合二氧化硅和沸石后使用。此外,优选为表面呈无孔状且粒度分布窄的抗粘连剂。其原因在于,表面呈无孔状时,水分不易吸附于无机粒子,膜不易发泡,从而可以保持外观。
出于将表面形状复杂化的目的,可以使各粒子的粒径不同,并使它们分担作用。另外,若粒度分布窄,则在膜的制造中,无机粒子不易堆积在T型模头的唇部,从而可以提高生产率。
抗粘连剂的粒径的下限优选为3μm。若为3μm以上,则容易降低粘连。
抗粘连剂的粒径的上限优选为20μm,更优选为16μm。若为20μm以下,则易于保持膜的透明性。
抗粘连剂的合计浓度的下限优选为0.1重量%,更优选为0.5重量%,进一步优选为0.8重量%。若为0.1重量%以上,则易于得到滑动性。
抗粘连剂的合计浓度的上限优选为5重量%,更优选为3重量%,进一步优选为2重量%。若为5重量%以下,则不会过度打滑,不易造成卷绕偏移。
作为中间层(B层)和层压层(C层)中使用的聚乙烯系树脂,例如可举出选自乙烯·α-烯烃共聚物、高压法聚乙烯中的1种或者将2种以上混合而得的树脂。上述乙烯·α-烯烃共聚物为乙烯与碳数4~18的α-烯烃的共聚物,作为α-烯烃,可举出1-丁烯、1-己烯、4-甲基1-戊烯、1-辛烯、1-癸烯等。由这些聚乙烯系树脂得到的膜具有优异的热封强度、热粘性、夹杂物密封性、耐冲击性,该聚乙烯系树脂可以在不损害这些特性的范围内与其它树脂、例如乙烯·乙酸乙烯酯共聚物、乙烯·丙烯酸酯共聚物等混合后使用。
层压层(C层)的作用在于,在与双轴拉伸酯膜等基材膜贴合时具有充分的粘接力。
中间层(B层)的作用在于,在将与基材层叠后的膜加工为袋状、且放入内容物后使用时,具有不影响操作的坚韧感和难破裂度。
本发明的膜的密封层(A层)相对于膜整体的厚度的比率的下限优选为10%,更优选为15%,进一步优选为18重量%。若为10%以上,则密封强度变得充分。
密封层比率的上限优选为40%,更优选为30%,进一步优选为25%。若为40%以下,则成本不会增高。
本发明的膜的层压层(C层)相对于膜整体的厚度的比率的下限优选为5%,更优选为16%。若为5%以上,则添加至密封层、中间层的抗粘连剂不会推顶层压层,在层压层与基材膜的贴合界面不易发生气泡。层压层比率的上限优选为50%,更优选为32%。若为50%以下,则膜的坚韧性不会过强,易于进行加工。
此时,上述膜的各层的聚乙烯树脂的平均密度优选为密封剂层(A层)≤基材层(B层)≤层压层(C层)。由于所配合的有机系润滑剂不易向密度高的层移动,因此对于维持层压后的滑动性而言是有效的。
本发明的膜的中间层(B层)的密度的下限优选为920kg/m3,更优选为925kg/m3,进一步优选为930kg/m3。若为920kg/m3以上,则坚韧性强,易于进行加工。
中间层(B层)的密度的上限优选为960kg/m3,更优选为940kg/m3,进一步优选为935kg/m3。
可以对本发明的膜的中间层(B层)使用上述有机系润滑剂,有机系润滑剂的下限优选为600重量ppm,更优选为800重量ppm。若为600重量ppm以上,则易于得到滑动性。
中间层的芥酸酰胺等有机系润滑剂的浓度的上限优选为2000重量ppm,更优选为1500重量ppm。若为2000重量ppm以上,则不会过度打滑,不易造成卷绕偏移。
可以向本发明的膜的中间层(B层)配合回收树脂10~30质量%。
本发明中,优选对上述聚乙烯系膜的层压层(C层)面进行电晕处理等活性射线处理。通过该对策,层压强度提高。
本发明的膜的层压层(C层)的润湿张力的下限优选为30N,更优选为40N。若为30N以上,则使其与双轴拉伸尼龙(ONy)膜、双轴拉伸聚对苯二甲酸乙二醇酯(PET)膜、双轴拉伸聚丙烯(OPP)膜等基材贴合时,易于得到充分的层压强度。
润湿张力的上限优选为55N,更优选为50N。若为55N以下,则有机系润滑剂向层压层(C层)表面的迁移量变大,易于维持层压粘接强度。
与在膜表面具有相同高度的突起的膜相比,在膜表面具有不同高度的突起的膜的耐粘连性更优异。此外,可以根据需要将上述无机粒子配合到层压层(C层)、中间层(B层)中。
(膜特性)
粘连强度的上限优选为60mN/20mm,更优选为50mN/20mm,进一步优选为40mN/20mm。若为60mN/20mm以下,则刚卷出后的滑动性易于变得良好。
本发明的聚乙烯系膜的雾度的下限优选为3%,更优选为5%,进一步优选为7%。若为3%以上,则不易发生粘连。
雾度的上限优选为15%,更优选为12%,进一步优选为10%。若为15%以下,则易于进行内容物的观察。
本发明的聚乙烯系膜的膜单独的密封强度的下限优选为5N/15mm,更优选为6N/15mm。若为5N/15mm以上,则在制袋后不易发生破袋。
膜单独的密封强度的上限优选为12N/15mm,更优选为10N/15mm。若为12N/15mm以下,则在制袋后易于将袋开封。
对本发明的聚乙烯系膜层压PET后的膜的热封开始温度的下限优选为90℃,更优选为100℃。若为90℃以上,则不易因密封以外的热而发生熔接。
热封开始温度的上限优选为120℃,更优选为115℃。若为120℃以下,则密封所需的热不大。
热封开始温度是指:将热封温度从80℃开始依次升高,至热封强度达到4.9N/15mm的最低温度。
与PET膜层压后的膜的120℃下的热封强度的下限优选为30N/15mm,更优选为35N/15mm。若为30N/15mm以上,则在制袋后不易发生袋破裂。
与PET膜层压后的膜的120℃下的热封强度的上限优选为60N/15mm,更优选为50N/15mm。若为60N/15mm以下,则在制袋后易于将袋开封。
本发明的聚乙烯系膜单独的静摩擦系数的下限优选为0.05,更优选为0.08,进一步优选为。若为0.05以上,则膜在卷绕时不会过度打滑,不易造成卷绕偏移。
单独的静摩擦系数的上限优选为0.20,更优选为0.15,进一步优选为0.10。若为0.20以下,则加工时的损失变少。
本发明的聚乙烯系膜在刚卷出后测定的静摩擦系数的下限优选为0.05,更优选为0.08。若为0.05以下,则膜在卷绕时不会过度打滑,不易造成卷绕偏移。
在刚卷出后测定的静摩擦系数的上限优选为0.25,更优选为0.18,进一步优选为0.10。若为0.25以下,则加工时的损失变少。
本发明的聚乙烯系膜的层压后的静摩擦系数的下限优选为0.05,更优选为0.08。若为0.05以上,则膜在卷绕时不会过度打滑,不易造成卷绕偏移。
层压后的静摩擦系数的上限优选为0.20,更优选为0.15。若为0.20以下,则在制袋后的开口性良好,加工时的损失少。
本发明的聚乙烯系膜的杨氏模量(MD)的下限优选为100MPa,更优选为200MPa。若为100MPa以上,则坚韧性不会过弱,易于进行加工。杨氏模量(MD)的上限优选为800MPa,更优选为600MPa。
本发明的聚乙烯系膜的杨氏模量(TD)的下限优选为100MPa,更优选为200MPa。若为100MPa以上,则坚韧性不会过弱,易于进行加工。
杨氏模量(TD)的上限优选为1000MPa,更优选为600MPa。
实施例
以下,通过实施例详细地说明本发明,但本发明并不限定于它们。此外,各实施例中得到的特性通过以下的方法进行测定、评价。
(1)树脂密度
按照JIS K7112:1999年来评价密度。
(2)熔体流动速率(MFR)
基于ASTM D-1238,在230℃、载荷21.18N下进行测定。
(3)算术平均粗糙度(Ra(MD)〔μm〕)和算术平均粗糙度(Ra(TD)[μm])
首先,使用形状测定激光显微镜(Keyence公司制,型号为VK-9700),在膜的密封层(A层)侧的任意部位拍摄图像(倍率为50倍)。
接着,对于该图像,使用粗糙度分析软件(Keyence公司制,VKAnalyzer)测定线粗糙度(线粗糙度)。
表面粗糙度(线粗糙度)基于JIS-B0601进行测定,截取使用λc=0.08mm,在MD方向上将分析长度设为200μm,在TD方向上将分析间隔设为3.3μm,测定n=60根。对于各个表面粗糙度(线粗糙度)曲线,按照JIS0601:2001方式,将测定间距设为0.01μm,算出算术平均粗糙度,平均后得到算术平均粗糙度Ra(MD)。
算术平均粗糙度(Ra(TD)[μm])也同样地,在TD方向上将分析长度设为200μm,在MD方向上将分析间隔设为3.3μm。
(4)膜的粘连强度
粘连强度的测定方法如下所述。将尺寸切成膜的流向为150mm且垂直于流向的方向为20mm的样品1与膜的层压层(C层)和密封层(A层)重合后,用长160mm、宽30mm的清洁玻璃板夹持,从上施加20kg的载荷后,在60℃的气氛下放置20小时。其后,取下载荷和玻璃板,在23度、65%Rh的气氛中放置1小时。如图1所示,将重合而得的膜沿着流向剥离30mm,向其间夹入φ5mm、长50mm的铝棒2。利用岛津制作所制造的AUTOGRAPH(AG-I)3,对贴付有铝棒的一侧以100mm/分钟进行拉伸,测定此时的载荷。
(5)自膜卷上卷出的卷出性(粘连的评价)
◎:能够毫无阻力地卷出
○:卷出时可听到膜彼此剥离的声音
×:卷出时有阻力
(6)膜的静摩擦系数
将膜的密封层(A层)侧彼此重合,使用万能拉伸试验机STM-T-50BP(东洋鲍德温公司制),按照JIS K7125进行测定。在以下的3种方法中,以MD方向为200mm、TD方向为80mm的大小切出样品,并进行测定。
(刚卷出后)
在从实施例、比较例中得到的卷状膜上卷出后经过30分钟的时刻测定静摩擦系数时,在将卷状的膜的表层5m以上拉出后的部分处获取样品。若使用最外层的膜,则保存时的膜彼此的密合弱,有时无法准确测定。
在获取上述样品后经过40分钟的时刻,在有机系润滑剂渗出至膜表面的状态下对密封层(A层)侧彼此进行测定。
(层压PET膜后)
将实施例、比较例中得到的干式层压膜的密封层(A层)侧彼此重合,并进行测定。
(7)三维表面粗糙度(SRa)
关于三维表面粗糙度SRa,使用接触式表面粗糙度(小坂研究所制,型号为ET4000A),从3cm×3cm见方的膜片任选地对测定面积为1mm×0.2mm的部位的表面粗糙度进行测定,求出三维表面粗糙度(SRa)。
(8)热封强度
热封条件和强度测定条件如下所述。即,将实施例、比较例中得到的层压膜的聚乙烯膜彼此重合,在0.1MPa的压力、密封条的宽度为10mm、热封温度为120℃的条件下热封1秒后,在23℃下放置冷却。从以120℃进行热封后的膜中沿着与热封条的方向垂直的方向切取宽度为15mm、长度为70mm的试验片,对于各试验片,测定以200mm/分钟的十字头速度剥离热封部时的剥离强度。
(9)热封开始温度
热封开始温度设定为下述温度:以上述(8)的方法进行热封强度的测定时,将热封温度从80℃开始依次升高,至热封强度达到4.9N/15mm的最低温度。
(10)雾度
通过雾度计NDH3000(日本电色工业公司制),按照JIS K7136进行测定。
(实施例1)
(密封膜的制作)
(密封层(A层)的聚乙烯系组合物)
对于90重量%的树脂密度为915kg/m3、MFR为3.5g/10分钟的聚乙烯树脂(陶氏化学公司制造的ELITE(注册商标)5220G),混合10重量%的树脂密度为890kg/m3、MFR为1.4g/10分钟的聚丙烯树脂(住友化学公司制,Noblen(注册商标)S131)。另外,作为抗粘连剂,将粒径为10μm的非晶性二氧化硅1.17重量%和粒径为4μm的沸石相对于上述树脂的合计量添加0.49重量%,并添加作为有机系润滑剂的芥酸酰胺1000ppm。添加剂分别以聚乙烯树脂的母料的形式进行混合。
(中间层(B层)的聚乙烯系组合物)
将树脂密度为930kg/m3的聚乙烯树脂(住友化学公司制,Sumikathene(注册商标)FV407)68重量%、树脂密度为962kg/m3的Prime Polymer公司制造的聚乙烯树脂(MORETEC(注册商标)0408G)12重量%、回收原料20重量%进行混合。添加作为有机系润滑剂的芥酸酰胺1000ppm。添加剂以聚乙烯树脂的母料的形式进行混合。
(层压层(C层)的聚乙烯系组合物)
将树脂密度为930kg/m3的聚乙烯树脂(住友化学公司制,SumikatheneFV407)80重量%和树脂密度为962kg/m3且分子量分布为2.8的聚乙烯树脂(Prime Polymer公司制,MORETEC 0408G)20重量%进行混合。
B层用聚乙烯系树脂组合物使用螺杆直径为90mm的三阶型单螺杆挤出机,A层用和C层用的聚乙烯系树脂组合物分别使用直径为45mm和直径为60mm的三阶型单螺杆挤出机,以依次为A层/B层/C层的方式导入至3层类型的T缝型模头,并以221℃的模头出口温度进行挤出,所述3层类型的T缝型模头的设定方式为:宽度为800mm,将预合模(preland)设为两个阶段,且以熔融树脂的流动达到均匀的方式将高低差部分的形状设为曲线状,从而使模头内的流动变得均匀。唇间隙设为1.6mm。将出自模头的熔融树脂片用38℃的冷却辊冷却,以A层/B层/C层的构成得到层厚度为8/23/6(μm)的聚乙烯系层叠膜。
另外,向上述挤出机中进行供给的供给用筒仓、料斗均进行氮气置换。利用冷却辊进行冷却时,用空气喷嘴将冷却辊上的膜的两端固定,用气刀将熔融树脂片的整个宽度向冷却辊按压,同时启用真空腔室来防止空气卷入到熔融树脂片与冷却辊之间。关于空气喷嘴,两端均沿膜的行进方向并列地设置。另外,气刀的风向相对于被挤出的片的行进方向呈40度。
另外,使真空腔室的抽吸口的方向与被挤出的片的行进方向一致。此外,模头周围用片包围,使得熔融树脂片不被风吹。对C层的表层实施电晕处理。以19m/分钟的制膜速度来实施。对于制膜得到的膜,修剪膜边,以卷的状态进行卷绕。将膜构成示于表1,将所得到的膜的物性结果示于表2。
(干式层压膜的制作)
使用将酯系干式层压用粘接剂(DIC Graphics公司制,LX500)32.4质量份、作为固化剂的(DIC Graphics公司制,KR90S)2.2质量份和乙酸乙酯65.4质量份混合而得到的酯系粘接剂,以使粘接剂的涂布量达到3.0g/m2的方式,对本发明所涉及的膜与基材膜(东洋纺公司制造的双轴拉伸聚酯膜,E5100,厚度为12μm)进行干式层压。将层叠而成的层压膜保持于40℃,进行3天熟化,得到干式层压膜。所得到的层压膜的物性结果示于表2。
(实施例2)
实施例1中,将密封层(A层)中的聚丙烯树脂与聚乙烯树脂的混合比设为聚丙烯树脂15重量%、聚乙烯树脂85重量%,除此以外,利用同样的方法得到密封膜。
(实施例3)
实施例1中,将密封层(A层)中的聚丙烯树脂与聚乙烯树脂的混合比设为聚丙烯树脂3重量%、聚乙烯树脂97重量%,除此以外,利用同样的方法得到密封膜。
(实施例4)
实施例1中,将向密封层(A层)中添加的芥酸酰胺的浓度设为800ppm,除此以外,利用同样的方法得到密封膜。
(实施例5)
实施例1中,将密封层(A层)/中间层(B层)/层压层(C层)的厚度设为6.5/18.5/5.0μm(合计为30μm),除此以外,利用同样的方法得到密封膜。
(实施例6)
实施例1中,将向密封层(A层)中添加的二氧化硅的浓度设为0.58重量%,除此以外,利用同样的方法得到密封膜。
(实施例7)
实施例1中,将向密封层(A层)中添加的沸石的浓度设为0.25重量%,除此以外,利用同样的方法得到密封膜。
(实施例8)
实施例1中,将密封层(A层)中的聚丙烯树脂与聚乙烯树脂的混合比设为聚丙烯树脂3重量%、聚乙烯树脂97重量%,不向密封层(A层)中添加二氧化硅,除此以外,利用同样的方法得到密封膜。
关于上述实施例1~8的膜,从膜卷中卷出时,粘连均被抑制,制袋加工而顺利地进行。另外,制袋后的开封性也良好,食品填充也顺利地进行。
(比较例1)
实施例1中,不添加密封层(A层)中的聚丙烯树脂,将聚乙烯树脂设为100重量%,除此以外,与实施例1同样地得到密封膜。但是,膜的凹凸变少,得不到刚卷出后的滑动性。
(比较例2)
实施例1中,将密封层(A)中的聚丙烯树脂与聚乙烯树脂的混合比设为聚丙烯树脂30重量%、聚乙烯树脂70重量%,除此以外,与实施例1同样地得到密封膜。但是,呈现密封强度恶化的结果。
(比较例3)
实施例1中,代替在密封层(A)中使用的聚丙烯树脂(住友化学公司制,NoblenS131),而使用将聚丙烯树脂(住友化学公司制,Noblen S131)以220℃熔融后再次颗粒化、并使其熔体流动速率(MFR)升高至3.2g/10分钟的聚丙烯树脂,除此以外,与实施例1同样地得到密封膜。
但是,聚丙烯树脂与聚乙烯树脂完全相容,膜的凹凸变小,得不到刚卷出后的滑动性。
(比较例4)
实施例1中,代替密封层(A)中使用的聚丙烯树脂(住友化学公司制,NoblenS131),而变更为聚丙烯树脂(住友化学公司制,Noblen D101,树脂密度为900kg/m3,MFR为0.5g/10分钟),除此以外,与实施例1同样地得到密封膜。
但是,聚丙烯树脂与聚乙烯树脂完全不相容,无法得到膜。
[表1]
[表2]
[表3]
[表4]
产业上的可利用性
由于从膜卷状态卷出时的粘连、与基材层压后的密封剂彼此的耐粘连性更良好,因此能够降低加工时的损失,能够在产业上做出显著贡献。
Claims (7)
1.一种聚乙烯系膜,其特征在于,在至少一个面中,膜的流向上的算术平均粗糙度Ra(MD)[μm]与垂直于流向的方向的算术平均粗糙度Ra(TD)[μm]的比值满足下述式(1),
(1) 1.2≤Ra(TD)/Ra(MD)≤3.6
Ra(MD):在膜的流向上测定的算术平均粗糙度、
Ra(TD):在与膜的流向垂直的方向上测定的算术平均粗糙度。
2.一种聚乙烯系膜,其特征在于,其至少包含密封层(A层)、中间层(B层)、层压层(C层)这3层,A层的面的膜的流向和垂直于流向的方向的算术平均粗糙度Ra[μm]的值满足下述式(1),
(1) 1.2≤Ra(TD)/Ra(MD)≤3.6
Ra(MD):在膜的流向上测定的算术平均粗糙度、
Ra(TD):在与膜的流向垂直的方向上测定的算术平均粗糙度。
3.如权利要求1或2所述的聚乙烯系膜,其中,具有满足所述式(1)的面的层包含聚乙烯系树脂75~97重量%、聚丙烯系树脂25~3重量。
4.如权利要求3所述的聚乙烯系膜,其中,所述聚乙烯系树脂为直链状低密度聚乙烯。
5.如权利要求3或4所述的聚乙烯系膜,其中,所述聚丙烯系树脂的按照ASTM D-1238以230℃、21.18N测定的熔体流动速率MFR为0.6~3.0g/10分钟。
6.如权利要求1~5中任一项所述的聚乙烯系膜,其进行120℃下的热封后的热封强度为25N/15mm以上。
7.如权利要求1~6中任一项所述的聚乙烯系膜,其中,粘连强度为60mN/20mm以下。
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