CN108032568B - It is a kind of high to be protected from light high-barrier liquid packaging film and its production method - Google Patents

It is a kind of high to be protected from light high-barrier liquid packaging film and its production method Download PDF

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CN108032568B
CN108032568B CN201711281861.1A CN201711281861A CN108032568B CN 108032568 B CN108032568 B CN 108032568B CN 201711281861 A CN201711281861 A CN 201711281861A CN 108032568 B CN108032568 B CN 108032568B
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layer
resin
composite
film
thickness
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CN108032568A (en
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张和平
汪学文
胡凯
韩铮
潘安定
章威
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Huangshan Novel Co Ltd
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Huangshan Novel Co Ltd
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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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • 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
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/082—Layered products comprising a layer of metal comprising metal 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 comprising vinyl resins; comprising acrylic resins
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/30—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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Abstract

High high-barrier liquid packaging film and its production method are protected from light the present invention relates to a kind of.Wherein the packaging film ecto-entad is followed successively by milky white delustring PE co-extrusion film layer, EAA squeezes out composite film, aluminium layer and EVOH co-extrusion film layer.The present invention obtains the liquid packaging film haveing excellent performance by the control of selection and thickness to each film layer formula.Not only production cost is low, equipment investment is few for packaging film of the present invention, simple process, but also has good light-shading effect, and barrier property is more than " Bai Libao " close to " Tetra Pak ", and the barrier property ratio " Tetra Pak " after rubbing is not bad.The waste recovery of the packaging membrane material is convenient, and packaging molding is unrestricted, can earnestly form, also thermoformable；The appearance for packing membrane material is in the milky white effect of delustring, and sense organ class is high.

Description

It is a kind of high to be protected from light high-barrier liquid packaging film and its production method
Technical field
The invention belongs to pack technology field of membrane materials, be specifically related to it is a kind of it is high be protected from light high-barrier liquid packaging film and its Production method.
Background technique
With the development of dairy industry, the packaging of dairy products is increasingly valued by people, the especially convenient liquid drunk State milk packaging mainly has " Tetra Pak " and " Bai Libao " two kinds of packagings at present in the market.The wherein membrane material of " Tetra Pak " packaging It is using the composite membrane of paper plastic-aluminum, the membrane material of " Bai Libao " packaging is using multi-layer co-extruded black and white film.The paper of " Tetra Pak " Aluminium plastic composite material, big using packaging facilities limitation, composite film material is at high cost, and waste recovery is difficult；It is black in " Tetra Pak " The addition of Masterbatch, there are food safety hazards.In view of the above-mentioned problems, the prior art proposes a kind of modeling modeling composite membrane, film Layer material-structure is: ink/three-layer co-extruded PE/ coating PVA/ glue/three-layer co-extruded VMPE, although the composite membrane production cost It is low, equipment investment is few, simple process, but has the disadvantage that the compactness of liquid PVA coating film forming is bad, it is anti-that PVA is easy dampness Barrier property should be reduced；Compound removing fastness is bad, has lamination in sterilization processing；Glue causes to obstruct to the destruction of aluminium layer Property is bad；The inadequate of fastness is removed, causes fervent intensity not high, there are packed products to have bale broken risk when transporting flowing.
Summary of the invention
High high-barrier liquid packaging film and its producer are protected from light in order to solve the above technical problem, the present invention provides a kind of Method.
In order to achieve the object of the present invention, the invention adopts the following technical scheme:
It is a kind of it is high be protected from light high-barrier liquid packaging film, the packaging film ecto-entad be followed successively by milky white delustring PE co-extrusion film layer, EAA squeezes out composite film, aluminium layer and EVOH co-extrusion film layer；
The milky white delustring PE co-extrusion film layer includes printing layer, middle layer and crowded cladding, the milky white delustring PE co-extrusion 82~88 μm of thicknesses of layers, wherein the printing layer is with a thickness of 24~26 μm, the intermediate layer thickness is 34~36 μm, described to squeeze Cladding is with a thickness of 24~26 μm；
The printing layer includes that mass ratio is (78~82): the high density polyethylene (HDPE) and metallocene PE of (18~22) Plastic body, the middle layer include that mass ratio is (63~67): (18~22): the linear polyethylene resin of (13~17), low close Polyvinyl resin and white master batch are spent, the crowded cladding includes that mass ratio is (28~32): the linear polyethylene of (68~72) Resin and ldpe resin；
The EVOH co-extrusion film layer include A composite layer, B outer layer, C adhesive layer, D middle layer, E adhesive layer, F outer layer with And G hot sealing layer, the EVOH co-extrusion thicknesses of layers is 51~57 μm, wherein the A composite layer, G hot sealing layer thickness are distinguished It is 12~14 μm, the B outer layer, F outer layer thickness are respectively 6~8 μm, and the C adhesive layer, E bondline thickness are respectively 3 ~5 μm, the D intermediate layer thickness is 5~7 μm；
The A composite layer includes that mass ratio is (48~52): (23~27): the metallocene linear polyethylene of (23~27), Linear polyethylene resin and ethylene methyl methacrylate copolymer resins, the B outer layer, F outer layer all include mass ratio For (73~77): the linear polyethylene resin and metallocene linear polyethylene of (23~27), the C adhesive layer, E adhesive layer are all Including binder resin, the D middle layer includes ETHYLENE-VINYL ALCOHOL COPOLYMER resin, and the G hot sealing layer includes that mass ratio is (48~52): (48~52): (1.0~2.0): the metallocene PE resin of (0.1~0.5), metallocene linear polyethylene tree Rouge, opening agent and processing aid；
The EAA squeeze out composite film include contacted with the crowded cladding compound the first composite layer and with the aluminium layer Contact the second compound composite layer, 7~9 μm of first composite bed thickness, 6~8 μm of second composite bed thickness；Described One composite layer includes metallocene PE resin, and second composite layer includes ethylene-methyl methacrylate-acrylic acid ternary polymerization Resin.
Further, described milky white 85 μm of delustring PE co-extrusion thicknesses of layers, wherein the printing layer is with a thickness of 25 μm, it is described in Interbed is with a thickness of 35 μm, and the crowded cladding is with a thickness of 25 μm；
The EVOH co-extrusion thicknesses of layers is 54 μm, wherein the A composite layer, G hot sealing layer thickness are respectively 13 μm, The B outer layer, F outer layer thickness are respectively 7 μm, and the C adhesive layer, E bondline thickness are respectively 4 μm, the D middle layer With a thickness of 6 μm；
8 μm of first composite bed thickness, 7 μm of second composite bed thickness.
Further, the printing layer includes the high density polyethylene (HDPE) and metallocene PE plasticity that mass ratio is 80:20 Body, the middle layer include that linear polyethylene resin, ldpe resin and white that mass ratio is 65:20:15 are female Grain, the crowded cladding include the linear polyethylene resin and ldpe resin that mass ratio is 30:70；
The A composite layer include mass ratio be the metallocene linear polyethylene of 50:25:25, linear polyethylene resin and Ethylene methyl methacrylate copolymer resins, the B outer layer, F outer layer all include the linear poly- second that mass ratio is 75:25 Olefine resin and metallocene linear polyethylene, the C adhesive layer, E adhesive layer all include binder resin, the D middle layer Including ETHYLENE-VINYL ALCOHOL COPOLYMER resin, the G hot sealing layer includes the metallocene PE tree that mass ratio is 50:50:1.5:0.3 Rouge, metallocene linear polyethylene resin, opening agent and processing aid.
Further, the printing layer medium high density polyethylene trade mark is HD3355F, metallocene PE in the printing layer The plastic body trade mark is PL1881G；The middle layer linear polyethylene resin grade is 5538G, low-density in the middle layer The polyvinyl resin trade mark is 150BW, and the white master batch trade mark is UF880 in the middle layer；The crowded cladding linear polyethylene Resin grade is 2045G, and the ldpe resin trade mark is 150BW in the crowded cladding；
The metallocene linear polyethylene trade mark is 2010MA, the A composite layer linear polyethylene resin in the A composite layer The trade mark is 2045G, and the ethylene methyl methacrylate copolymer resins trade mark is WH303 in the A composite layer；The B outer layer, F Secondary outer layer linear polyethylene resin grade is 2045G, and the metallocene linear polyethylene trade mark is in the B outer layer, F outer layer 2010MA；The binder resin trade mark is 41E687 in the C adhesive layer, E adhesive layer；Ethylene-vinyl alcohol is total in the D middle layer The poly resin trade mark is H171；Metallocene PE resin grade is 1881 in the G hot sealing layer, metallocene in the G hot sealing layer The linear polyethylene resin trade mark is 2010MA, and the G hot sealing layer split shed agent trade mark is AB-20LD, is processed in the G hot sealing layer The auxiliary agent trade mark is DS-A1058LD；
Metallocene PE resin grade in first composite layer is PT1450, the second in second composite layer Alkene-methacrylic acid-acrylic acid ter-polymer resin trade mark is AN4211-5C.
Further, the OD value of aluminium layer is 2.4~2.6.
A kind of height is protected from light the production method of high-barrier liquid packaging film, comprising the following steps:
Step 1, material contained in the printing layer, middle layer and crowded cladding is separately added by said components requirement The milky white delustring PE co-extrusion film layer is obtained by three-layer co-extruded molding mode out into coextrusion film blowing machine；
By institute in the A composite layer, B outer layer, C adhesive layer, D middle layer, E adhesive layer, F outer layer and G hot sealing layer The material contained by said components requirement be added separately in coextrusion film blowing machine to go out by seven-layer co-extrusion molding mode obtain it is described EVOH co-extrusion film layer；Then aluminize in the compound layer surface of A of the EVOH co-extrusion film layer by plasma technology and obtain institute State aluminium layer；
Step 2, material contained by first composite layer and the second composite layer is separately added by said components requirement The EAA extrusion composite film is obtained in compounding machine to squeezing out, and makes first composite layer and the milky white delustring PE total The crowded cladding extrusion of extruded film layer is compound, and the A composite layer of second composite layer and the EVOH co-extrusion film layer squeezes out compound；
Step 3, curing, cooling and shaping.
Further, the extrusion combined temp is 180~250 DEG C.
The beneficial effects of the present invention are:
(1) not only production cost is low, equipment investment is few, simple process for packaging film of the present invention, but also has and be protected from light well Effect, barrier property are more than " Bai Libao " close to " Tetra Pak ", and the barrier property ratio " Tetra Pak " after rubbing is not bad.The packaging film The waste recovery of material is convenient, and packaging molding is unrestricted, can earnestly form, also thermoformable；The appearance of packaging membrane material is in disappear The milky white effect of light, sense organ class are high.The specific performance parameter of packaging film of the present invention is as follows:
The milky white appearance of packaging film delustring: surface gloss is less than 8%, milky white effect；High-barrier: moisture-inhibiting is less than 1g/ (㎡ For 24 hours), oxygen flow is less than 1cm3/(㎡·24h·0.1MPa)；Moisture-inhibiting is less than 1g/ (㎡ for 24 hours after rubbing 10 times), oxygen flow is less than 5cm3/(㎡·24h·0.1MPa)；High photophobism: light transmittance is less than 0.5%；Compound fastness: peeling force is greater than 3.0N/15mm, It is not stratified that ethyl ester impregnates 30min；Molding easy to package: earnestly packaging molding；Foodsafety is high: internal layer PE does not add pigment colour It is female.Flexible relief printing plate table brush, upper film amount low compared to intaglio printing 30% can be used in the present invention.
(2) printing layer of the present invention select Thailand PTT company high density polyethylene (HDPE) (HDPE, trade mark HD3355F, Melt and refers to 1.1g/10min, density 0.951g/cm3) with metallocene PE plastic body (mLLDPE, the trade mark of DOW Chemical PL1881G melts and refers to 1g/10min, density 0.904g/cm3) be blended, the HDPE of high-crystallinity provides size big crystal grain area, low The mLLDPE of crystallinity provides size small amorphous area, so that it is microcosmic uneven to have the film surface of production, reaches and disappears Light effect.In addition the HDPE of high-crystallinity can also bring the barrier property and lower light transmittance of good steam.It is this microcosmic Uneven effect also improve film to the adhesive force and printing ink transfer effect of ink, keep printability more preferable.
(LLDPE, trade mark 5538G melt finger to the linear polyethylene resin for the DOW Chemical production that the middle layer is selected 1.3g/10min, density 0.941g/cm3), the crystallinity of medium density polyethylene resin is high, and pull-off force and elongation are high, processability Generally.Being mixed into the ldpe resin that Exxon produces, (LDPE, trade mark 150BW melt and refer to 3g/10min, density 0.933g/cm3), processability can be improved.Middle layer add DIC company production white master batch (trade mark UF880), it can be achieved that Uniform whiteness distribution.
(LLDPE, trade mark 2045G melt and refer to 1g/ the linear polyethylene resin that the crowded cladding is produced using DOW Chemical 10min, density 0.920g/cm3) with Exxon production ldpe resin (LDPE, trade mark 150BW, melt refer to 3g/ 10min, density 0.933g/cm3) be blended, processability is good, and LLDPE mechanical strength is high.
(3) A composite layer of the present invention selects the metallocene linear of the high strength of Exxon production poly- for aluminizing (mLLDPE, trade mark 2010MA melt and refer to 1g/10min, density 0.920g/cm ethylene3) with DOW Chemical production linear poly- second (LLDPE, trade mark 2045G melt and refer to 1g/10min, density 0.920g/cm olefine resin3) and Sumitomo Chemical production ethylene- (EMMA, trade mark WH303 melt and refer to 7g/10min, density 0.940g/cm methyl methacrylate copolymer resin3) be blended, MLLDPE and LLDPE provides mechanical strength, has a large amount of methyl methacrylate in EMMA molecular side chain, these polar groups Meeting is so that EMMA has good bonding force when vacuum aluminum-coated, with aluminium atom.
The B outer layer, F outer layer are used for the mechanical strength of enhanced film, the B outer layer, F outer layer ratio set Meter is according to optimal cost.
Bonding resin layer used in the C adhesive layer, E adhesive layer is to visit (the acid anhydrides grafting of firm resin by Du Pont's production Modified binder resin, trade mark 41E687 melt and refer to 1.7g/10min, density 0.91g/cm3), which has nonpolar alkene Hydrocarbon segment and polarity acid anhydrides segment, olefin segments and the polyvinyl resin compatibility in B times adjacent outer layer, F outer layer are good, melt Mutually winding is close after melting, and bond strength is high；The ETHYLENE-VINYL ALCOHOL COPOLYMER polarity tree of polarity acid anhydrides segment and D middle layer simultaneously Rouge chemically reacts, and forms the combination with hydrogen bond, covalent bond etc., so that secondary outer layer, adhesive layer, D middle layer firmly combine, Form a piece of not strippable high-barrier co-extrusion film.
The D middle layer be Kuraray production ETHYLENE-VINYL ALCOHOL COPOLYMER resin (EVOH, the trade mark are H171, Melt and refer to 1.8g/10min, density 1.19g/cm3,32%) vinyl alcohol molal weight is.EVOH resin has very high barrier to oxygen Property, but can be remarkably decreased after making moist, therefore design and hindering among wet good PE layer.
The G hot sealing layer select DOW Chemical low-temperature heat-sealing metallocene PE resin (mLLDPE, the trade mark 1881, Melt and refers to 1g/10min, density 0.904g/cm3) with Exxon production high strength metallocene linear polyethylene (mLLDPE, trade mark 2010MA melt and refer to 1g/10min, density 0.92g/cm3) be blended, make film that there is very low heat-sealing temperature With very high heat seal strength.
(4) EAA of the present invention squeezes out in composite film that contact compound first with milky white delustring PE co-extrusion film layer compound (mLLDPE, trade mark PT1450 melt and refer to 7.5g/ the low melting point metallocene PE resin that layer is produced using DOW Chemical 10min, density 0.902g/cm3), ethylene-metering system that the second compound composite layer selects Du Pont's production is contacted with aluminium layer (EAA, the trade mark are that AN4211-5C melts finger 32g/10min, density 0.93g/ to acid-acrylic ternary copolymer resin-firm resin cm3).The mLLDPE that first composite layer uses can be squeezed again with low temperature, while have good binding strength with crowded cladding, be squeezed Multiple thermoplastic resin can mutually be melted with crowded cladding and be wound again, reach not peelable.The firm resin EAA of Du Pont is special With the bonding in extrusion coated technique to non-stretching aluminizer, it can be squeezed again with low temperature, avoid non-stretching film high-temp. that aluminium layer tortoise occurs Joined EMMA resin in the A composite layer for the EVOH co-extrusion film layer split, and aluminized so that the second composite layer, aluminium layer and The combination chemically reacted between the A composite layer three of EVOH co-extrusion film layer, peeling force can reach 5N/15mm or more.
(5) present invention is aluminized using plasma technology in the compound layer surface of the A, and effect can eliminate milky white disappear The small-molecule substance of light PE co-extrusion film surface, and further the face of aluminizing of coarse milky white delustring PE co-extrusion film layer adheres to aluminium layer Fastness is more preferable, and aluminium layer distribution is finer and close, improves barrier property and aluminium layer and eliminates the combination jail of milky white delustring PE co-extrusion film layer Degree and depth.
Detailed description of the invention
Fig. 1 is packaging film structure schematic diagram of the present invention.
Attached meaning marked in the figure is as follows:
1- ink layer
The milky white delustring PE co-extrusion film layer of 2-
3-EAA squeezes out composite film
4- aluminium layer
5-EVOH co-extrusion film layer
Specific embodiment
More specific detail is made to technical solution of the present invention below with reference to embodiment:
The height is protected from light the production method of high-barrier liquid packaging film, comprising the following steps:
Step 1, milky white delustring PE co-extrusion film layer, production EVOH co-extrusion film layer are produced and EVOH co-extrusion film layer is plated Aluminium:
The production of milky white delustring PE co-extrusion film layer: by material contained in the printing layer, middle layer and crowded cladding point It is not added in coextrusion film blowing machine and the milky white delustring PE co-extrusion film layer is obtained by three-layer co-extruded molding mode out；The cream The working process parameter of white delustring PE co-extrusion film layer is as shown in table 1 below:
Table 1
The production of EVOH co-extrusion film layer: by the A composite layer, B outer layer, C adhesive layer, D middle layer, E adhesive layer, F times Material contained in outer layer and G hot sealing layer, which is added separately in coextrusion film blowing machine to go out molding mode by seven-layer co-extrusion, to be obtained The EVOH co-extrusion film layer；The working process parameter of the EVOH co-extrusion film layer is as shown in table 2 below:
Table 2
Aluminize to EVOH co-extrusion film layer: by plasma technology the EVOH co-extrusion film layer the compound layer surface of A Aluminize and obtains the aluminium layer；The OD value of the aluminium layer is 2.4~2.6.Specific aluminum plating process can refer to the prior art.
Step 2, material contained by first composite layer and the second composite layer is added separately to squeeze out in compounding machine It obtains the EAA and squeezes out composite film, and make the crowded cladding of first composite layer Yu the milky white delustring PE co-extrusion film layer Squeeze out compound, the A composite layer of second composite layer and the EVOH co-extrusion film layer squeezes out compound；The extrusion combined temp is 180~250 DEG C.
Step 3, curing, cooling and shaping obtain packaging film product.
3 embodiments are set forth below for illustrating the production method and product characteristic of packaging film of the present invention.
The production of milky white delustring PE co-extrusion film layer is carried out according to the formula of the following table 3 respectively in the embodiment:
Table 3
The production of EVOH co-extrusion film layer is carried out according to the formula of the following table 4 respectively in the embodiment:
Table 4
EAA squeezes out composite film and carries out according to the formula of the following table 5 in the embodiment:
Table 5
The packaging film particular product performance parameters produced according to above method are as shown in table 6 below:
Table 6
It can be seen that the present invention, which packs film properties, is completely superior to existing modeling modeling composite membrane, the present invention is more suitable for ox The packaging film of the liquid such as milk.

Claims (7)

1. high high-barrier liquid packaging film is protected from light a kind of, it is characterised in that: the packaging film ecto-entad is followed successively by milky white delustring PE Co-extrusion film layer, EAA squeeze out composite film, aluminium layer and EVOH co-extrusion film layer；
The milky white delustring PE co-extrusion film layer includes printing layer, middle layer and crowded cladding, the milky white delustring PE co-extrusion film layer 82~88 μm of thickness, wherein the printing layer is with a thickness of 24~26 μm, the intermediate layer thickness is 34~36 μm, the crowded cladding With a thickness of 24~26 μm；
The printing layer includes that mass ratio is (78~82): the high density polyethylene (HDPE) and metallocene PE plasticity of (18~22) Body, the middle layer include that mass ratio is (63~67): (18~22): the linear polyethylene resin of (13~17), low-density are poly- Vinyl and white master batch, the crowded cladding include that mass ratio is (28~32): the linear polyethylene resin of (68~72) And ldpe resin；
The EVOH co-extrusion film layer includes A composite layer, B outer layer, C adhesive layer, D middle layer, E adhesive layer, F outer layer and G Hot sealing layer, the EVOH co-extrusion thicknesses of layers is 51~57 μm, wherein the A composite layer, G hot sealing layer thickness are respectively 12 ~14 μm, the B outer layer, F outer layer thickness are respectively 6~8 μm, and the C adhesive layer, E bondline thickness are respectively 3~5 μ M, the D intermediate layer thickness are 5~7 μm；
The A composite layer includes that mass ratio is (48~52): (23~27): the metallocene linear polyethylene of (23~27), linear Polyvinyl resin and ethylene methyl methacrylate copolymer resins, the B outer layer, F outer layer are all including mass ratio (73~77): the linear polyethylene resin and metallocene linear polyethylene of (23~27), the C adhesive layer, E adhesive layer all wrap Binder resin is included, the D middle layer includes ETHYLENE-VINYL ALCOHOL COPOLYMER resin, and the G hot sealing layer includes that mass ratio is (48 ~52): (48~52): (1.0~2.0): the metallocene PE resin of (0.1~0.5), metallocene linear polyethylene resin, Opening agent and processing aid；
It includes contacting the first compound composite layer with the crowded cladding and contacting with the aluminium layer that the EAA, which squeezes out composite film, The second compound composite layer, 7~9 μm of first composite bed thickness, 6~8 μm of second composite bed thickness；Described first is multiple Closing layer includes metallocene PE resin, and second composite layer includes ethylene-methyl methacrylate-acrylic ternary copolymer tree Rouge.
2. height as described in claim 1 is protected from light high-barrier liquid packaging film, it is characterised in that: the milky white delustring PE co-extrusion film 85 μm of thickness degree, wherein the printing layer is with a thickness of 25 μm, the intermediate layer thickness is 35 μm, and the crowded cladding is with a thickness of 25 μ m；
The EVOH co-extrusion thicknesses of layers is 54 μm, wherein the A composite layer, G hot sealing layer thickness are respectively 13 μm, it is described B outer layer, F outer layer thickness are respectively 7 μm, and the C adhesive layer, E bondline thickness are respectively 4 μm, the D intermediate layer thickness It is 6 μm；
8 μm of first composite bed thickness, 7 μm of second composite bed thickness.
3. height as described in claim 1 is protected from light high-barrier liquid packaging film, it is characterised in that: the printing layer includes mass ratio For the high density polyethylene (HDPE) and metallocene PE plastic body of 80:20, the middle layer includes that mass ratio is 65:20:15 Linear polyethylene resin, ldpe resin and white master batch, the crowded cladding include that mass ratio is the linear of 30:70 Polyvinyl resin and ldpe resin；
The A composite layer includes metallocene linear polyethylene, linear polyethylene resin and the ethylene-that mass ratio is 50:25:25 Methyl methacrylate copolymer resin, the B outer layer, F outer layer all include the linear polyethylene resin that mass ratio is 75:25 And metallocene linear polyethylene, the C adhesive layer, E adhesive layer all include binder resin, and the D middle layer includes second Alkene-vinyl alcohol copolymer resin, the G hot sealing layer include that mass ratio is the metallocene PE resin of 50:50:1.5:0.3, cyclopentadienyl Metal linear polyvinyl resin, opening agent and processing aid.
4. height as described in claim 1 is protected from light high-barrier liquid packaging film, it is characterised in that: the printing layer middle-high density is poly- The ethylene trade mark is HD3355F, and the metallocene PE plastic body trade mark is PL1881G in the printing layer；The middle layer middle line Property the polyvinyl resin trade mark be 5538G, the ldpe resin trade mark is 150BW in the middle layer, in the middle layer The white master batch trade mark is UF880；The crowded cladding linear polyethylene resin grade is 2045G, low-density in the crowded cladding The polyvinyl resin trade mark is 150BW；
The metallocene linear polyethylene trade mark is 2010MA, the A composite layer linear polyethylene resin grade in the A composite layer For 2045G, the ethylene methyl methacrylate copolymer resins trade mark is WH303 in the A composite layer；The B outer layer, F times it is outer Layer linear polyethylene resin grade is 2045G, and the metallocene linear polyethylene trade mark is in the B outer layer, F outer layer 2010MA；The binder resin trade mark is 41E687 in the C adhesive layer, E adhesive layer；Ethylene-vinyl alcohol is total in the D middle layer The poly resin trade mark is H171；Metallocene PE resin grade is 1881 in the G hot sealing layer, metallocene in the G hot sealing layer The linear polyethylene resin trade mark is 2010MA, and the G hot sealing layer split shed agent trade mark is AB-20LD, is processed in the G hot sealing layer The auxiliary agent trade mark is DS-A1058LD；
Metallocene PE resin grade in first composite layer is PT1450, ethylene-first in second composite layer Base acrylic acid-acrylic acid ter-polymer resin grade is AN4211-5C.
5. height as described in claim 1 is protected from light high-barrier liquid packaging film, it is characterised in that: the OD value of the aluminium layer is 2.4 ~2.6.
6. a kind of height as claimed in any one of claims 1 to 5 is protected from light the production method of high-barrier liquid packaging film, feature exists In the following steps are included:
Step 1, material contained in the printing layer, middle layer and crowded cladding is added separately to altogether by said components requirement The milky white delustring PE co-extrusion film layer is obtained by three-layer co-extruded molding mode out in extrusion film machine；
It will be contained in the A composite layer, B outer layer, C adhesive layer, D middle layer, E adhesive layer, F outer layer and G hot sealing layer Material is added separately in coextrusion film blowing machine to go out molding mode by seven-layer co-extrusion by said components requirement obtains the EVOH Co-extrusion film layer；Then aluminize in the compound layer surface of A of the EVOH co-extrusion film layer by plasma technology and obtain the aluminium Layer；
Step 2, material contained by first composite layer and the second composite layer is added separately to squeeze by said components requirement The EAA is obtained in compounding machine out and squeezes out composite film, and makes first composite layer and the milky white delustring PE co-extrusion film The crowded cladding extrusion of layer is compound, and the A composite layer of second composite layer and the EVOH co-extrusion film layer squeezes out compound；
Step 3, curing, cooling and shaping.
7. the production method that height as claimed in claim 6 is protected from light high-barrier liquid packaging film, it is characterised in that: described to squeeze out again Closing temperature is 180~250 DEG C.
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