CN108032568A - A kind of high lucifuge high-barrier liquid packaging film and its production method - Google Patents

A kind of high lucifuge high-barrier liquid packaging film and its production method Download PDF

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Publication number
CN108032568A
CN108032568A CN201711281861.1A CN201711281861A CN108032568A CN 108032568 A CN108032568 A CN 108032568A CN 201711281861 A CN201711281861 A CN 201711281861A CN 108032568 A CN108032568 A CN 108032568A
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layer
resin
film
layers
composite
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CN108032568B (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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a kind of high lucifuge high-barrier liquid packaging film and its production method.Wherein the packaging film ecto-entad is followed successively by milky white delustring PE co-extrusions film layer, EAA extrusions composite film, aluminium lamination and EVOH co-extrusion film layers.The present invention obtains the liquid packaging film of excellent performance by the selection and the control of thickness to each film layer formula.Not only production cost is low, equipment investment is few for packaging film of the present invention, technique is simple, but also has good light-shading effect, its barrier exceedes " Bai Libao " close to " Tetra Pak ", and the barrier ratio " Tetra Pak " after rubbing is not bad.The waste recovery of the packaging membrane material is convenient, and packaging shaping is unrestricted, can earnestly be molded, also thermoformable；The appearance of packaging membrane material is in the milky white effect of delustring, and sense organ class is high.

Description

A kind of high lucifuge 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 a kind of high lucifuge high-barrier liquid packaging film and its Production method.
Background technology
With the development of dairy industry, the packaging of dairy products is increasingly valued by people, the particularly convenient liquid drunk State milk is packed, and in the market mainly has " Tetra Pak " and " Bai Libao " two kinds of packagings at present.The wherein membrane material of " Tetra Pak " packaging It is the composite membrane using paper plastic-aluminum, the membrane material of " Bai Libao " packaging is to use 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 of 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, its film Layer material-structure be：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, technique is simple, but there are shortcoming：The compactness of liquid PVA coating film formings is bad, and PVA easily makes moist instead Barrier should be reduced；Compound stripping fastness is bad, has lamination in sterilization processing；Destruction of the glue to aluminium lamination causes to obstruct Property is bad；The inadequate of fastness is peeled off, causes fervent intensity not high, has bale broken risk when transporting and flowing there are packed products.
The content of the invention
In order to solve the above technical problem, the present invention provides a kind of high lucifuge high-barrier liquid packaging film and its producer Method.
In order to achieve the object of the present invention, present invention employs following technical scheme：
A kind of high lucifuge high-barrier liquid packaging film, the packaging film ecto-entad be followed successively by milky white delustring PE co-extrusions film layer, EAA extrusions composite film, aluminium lamination and EVOH co-extrusion film layers；
The milky white delustring PE co-extrusions film layer includes printing layer, intermediate layer and crowded cladding, the milky white delustring PE co-extrusions 82~88 μm of thicknesses of layers, wherein the printing layer thickness is 24~26 μm, the intermediate layer thickness is 34~36 μm, described to squeeze Cladding thickness is 24~26 μm；
The printing layer is (78~82) including mass ratio:The high density polyethylene (HDPE) and metallocene PE of (18~22) Plastic body, the intermediate layer are (63~67) including mass ratio:(18~22):It is the linear polyethylene resin of (13~17), low close It is (28~32) including mass ratio to spend polyvinyl resin and white master batch, the crowded cladding:The linear polyethylene of (68~72) Resin and ldpe resin；
The EVOH co-extrusions film layer include A composite beds, B outer layer, C adhesive layers, D intermediate layers, E adhesive layers, F outer layer with And G hot sealing layers, the EVOH co-extrusions thicknesses of layers are 51~57 μm, wherein the A composite beds, G heat-sealing layer thickness difference For 12~14 μm, the B outer layer, F outer layer thickness are respectively 6~8 μm, and the C adhesive layers, E bondline thickness are respectively 3 ~5 μm, the D intermediate layer thickness is 5~7 μm；
The A composite beds are (48~52) including mass ratio:(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 layers, E adhesive layers are all Including binder resin, the D intermediate layers include ETHYLENE-VINYL ALCOHOL COPOLYMER resin, and the G hot sealing layers are including mass ratio (48~52):(48~52):(1.0~2.0):The metallocene PE resin of (0.1~0.5), metallocene linear polyethylene tree Fat, opening agent and processing aid；
EAA extrusion composite film include contacting with the crowded cladding the first compound composite bed and with the aluminium lamination Contact the second compound composite bed, 7~9 μm of first composite bed thickness, 6~8 μm of second composite bed thickness；Described One composite bed includes metallocene PE resin, and second composite bed includes ethylene-methyl methacrylate-acrylic acid ternary polymerization Resin.
Further, milky white 85 μm of the delustring PE co-extrusions thicknesses of layers, wherein the printing layer thickness is 25 μm, in described Between layer thickness be 35 μm, the crowded cladding thickness be 25 μm；
The EVOH co-extrusions thicknesses of layers is 54 μm, wherein the A composite beds, G heat-sealing layer thickness are respectively 13 μm, The B outer layer, F outer layer thickness are respectively 7 μm, and the C adhesive layers, E bondline thickness are respectively 4 μm, the D intermediate layers Thickness is 6 μm；
8 μm of first composite bed thickness, 7 μm of second composite bed thickness.
Further, it is 80 that the printing layer, which includes mass ratio,:20 high density polyethylene (HDPE) and metallocene PE plasticity Body, it is 65 that the intermediate layer, which includes mass ratio,:20:15 linear polyethylene resin, ldpe resin and white mother Grain, it is 30 that the crowded cladding, which includes mass ratio,:70 linear polyethylene resin and ldpe resin；
It is 50 that the A composite beds, which include mass ratio,:25:25 metallocene linear polyethylene, linear polyethylene resin and Ethylene methyl methacrylate copolymer resins, it is 75 that the B outer layer, F outer layer, which all include mass ratio,:25 linear poly- second Olefine resin and metallocene linear polyethylene, the C adhesive layers, E adhesive layers all include binder resin, the D intermediate layers Including ETHYLENE-VINYL ALCOHOL COPOLYMER resin, it is 50 that the G hot sealing layers, which include mass ratio,:50:1.5:0.3 metallocene PE tree Fat, 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 intermediate layer linear polyethylene resin grade is 5538G, low-density in the intermediate layer The polyvinyl resin trade mark is 150BW, and the white master batch trade mark is UF880 in the intermediate 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 in the A composite beds, the A composite beds linear polyethylene resin The trade mark is 2045G, and the ethylene methyl methacrylate copolymer resins trade mark is WH303 in the A composite beds；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 layers, E adhesive layers；Ethene-vinyl alcohol is common in the D intermediate layers The poly resin trade mark is H171；Metallocene PE resin grade is 1881 in the G hot sealing layers, metallocene in the G hot sealing layers The linear polyethylene resin trade mark is 2010MA, and the G hot sealing layers split shed agent trade mark is AB-20LD, is processed in the G hot sealing layers The auxiliary agent trade mark is DS-A1058LD；
Metallocene PE resin grade in first composite bed is PT1450, the second in second composite bed Alkene-methacrylic acid-acrylic acid ter-polymer resin trade mark is AN4211-5C.
Further, the OD values of aluminium lamination are 2.4~2.6.
A kind of production method of the high lucifuge high-barrier liquid packaging film, comprises the following steps：
Step 1, material contained in the printing layer, intermediate layer and crowded cladding is separately added into by said components requirement Into coextrusion film blowing machine by it is three-layer co-extruded go out molding mode obtain the milky white delustring PE co-extrusion film layers；
By institute in the A composite beds, B outer layer, C adhesive layers, D intermediate layers, E adhesive layers, F outer layer and G hot sealing layers The material contained by said components requirement be added separately in coextrusion film blowing machine by seven-layer co-extrusion go out molding mode obtain it is described EVOH co-extrusion film layers；Then in the compound layer surfaces of A of the EVOH co-extrusions film layer aluminize by plasma technology and obtain institute State aluminium lamination；
Step 2, the material contained by first composite bed and the second composite bed is separately added into by said components requirement The EAA extrusions composite film is obtained into extrusion compounding machine, and first composite bed is total to the milky white delustring PE The crowded cladding extrusion of extruded film layer is compound, and second composite bed and the A composite beds extrusion of the EVOH co-extrusions film layer are 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, technique is simple for packaging film of the present invention, but also has good lucifuge Effect, its barrier exceed " Bai Libao " close to " Tetra Pak ", and the barrier ratio " Tetra Pak " after rubbing is not bad.The packaging film The waste recovery of material is convenient, and packaging shaping is unrestricted, can earnestly be molded, 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/ (㎡ 24h), oxygen flow is less than 1cm3/(㎡·24h·0.1MPa)；Moisture-inhibiting is less than 1g/ (㎡ 24h 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 more than 3.0N/15mm, Ethyl ester immersion 30min is not stratified；Shaping easy to package：Earnestly packaging shaping；Foodsafety is high：Internal layer PE does not add pigment colour It is female.The present invention can use flexible relief printing plate table brush, upper film amount low compared to intaglio printing 30%.
(2) printing layer of the present invention select PTT companies of Thailand high density polyethylene (HDPE) (HDPE, trade mark HD3355F, Melt and refer 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) blending, the HDPE of high-crystallinity provides size big crystal grain area, low The mLLDPE of crystallinity provides size small amorphous area, so that the film surface of production has microcosmic uneven, reaches and disappears Light effect.In addition the HDPE of high-crystallinity can also bring the barrier of good steam and relatively low light transmittance.It is this microcosmic Uneven effect also improve adhesive force and printing ink transfer effect of the film to ink, make printability more preferable.
(LLDPE, trade mark 5538G, melts finger to the linear polyethylene resin for the DOW Chemical production that the intermediate 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.Be mixed into Exxon production ldpe resin (LDPE, trade mark 150BW, melt refer to 3g/10min, density 0.933g/cm3), processability can be improved.Intermediate layer add DIC companies 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) blending, processability is good, and LLDPE mechanical strengths are high.
(3) A composite beds of the present invention are used to aluminize, and select the metallocene linear of the high strength of Exxon production to gather (mLLDPE, trade mark 2010MA, melt and refer to 1g/10min, density 0.920g/cm ethene3) 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 ethene- (EMMA, trade mark WH303, melt and refer to 7g/10min, density 0.940g/cm methyl methacrylate copolymer resin3) blending, MLLDPE and LLDPE provides mechanical strength, has substantial amounts of methyl methacrylate in EMMA molecular side chains, these polar groups EMMA can be caused when vacuum aluminum-coated, to have good bonding force with aluminium atom.
The B outer layer, F outer layer are used for the mechanical strength of enhanced film, and the B outer layer, the ratio of F outer layer are set Meter is according to optimal cost.
Bonding resin layer used in the C adhesive layers, E adhesive layers is that (acid anhydrides is grafted by the firm resin of visiing of Du Pont's production Modified binder resin, trade mark 41E687, melts and refers 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；Polarity acid anhydrides segment and the ETHYLENE-VINYL ALCOHOL COPOLYMER polarity tree in D intermediate layers at the same time Fat chemically reacts, and forms the combination with hydrogen bond, covalent bond etc. so that and secondary outer layer, adhesive layer, D intermediate layers firmly combine, Form a piece of not strippable high-barrier co-extrusion film.
The D intermediate layers 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 resins have oxygen very high barrier Property, but can be remarkably decreased after making moist, therefore design and hindering among wet good PE layers.
The G hot sealing layers select DOW Chemical low-temperature heat-sealing metallocene PE resin (mLLDPE, the trade mark 1881, Melt and refer 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) blending, make film that there is very low heat-sealing temperature Very high heat seal strength.
(4) to contact compound first with milky white delustring PE co-extrusion film layers in EAA of the present invention extrusion composite film 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), ethene-metering system that the second compound composite bed selects Du Pont's production is contacted with aluminium lamination (EAA, the trade mark melt and refer to 32g/10min, density 0.93g/ acid-acrylic ternary copolymer resin-firm resin for AN4211-5C cm3).The mLLDPE that first composite bed 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 wound again, reach not peelable.The firm resin EAA of Du Pont is special It with the bonding in extrusion coated technique to non-stretching aluminizer, can be squeezed with low temperature again, avoid non-stretching film high-temp. that aluminium lamination tortoise occurs Split, and EMMA resins added in the A composite beds for the EVOH co-extrusion film layers aluminized so that the second composite bed, aluminium lamination and The combination chemically reacted between the A composite bed threes of EVOH co-extrusion film layers, peeling force can reach more than 5N/15mm.
(5) present invention is aluminized using plasma technology in the compound layer surfaces of the A, its effect can eliminate milky white disappear The small-molecule substance of light PE co-extrusion film surfaces, and further the face of aluminizing of coarse milky white delustring PE co-extrusion film layers adheres to aluminium lamination Fastness is more preferable, and aluminium lamination distribution is finer and close, improves barrier and aluminium lamination and eliminates the combination jail of milky white delustring PE co-extrusion film layers Degree and depth.
Brief description of the drawings
Fig. 1 is packaging film structure schematic diagram of the present invention.
The implication marked in attached drawing is as follows：
1- ink layers
The milky white delustring PE co-extrusion film layers of 2-
3-EAA extrudes composite film
4- aluminium laminations
5-EVOH co-extrusion film layers
Embodiment
More specific detail is made to technical solution of the present invention with reference to embodiment：
The production method of the high lucifuge high-barrier liquid packaging film, comprises the following steps：
Step 1, milky white delustring PE co-extrusions film layer, production EVOH co-extrusions film layer are produced and EVOH co-extrusion film layers are plated Aluminium：
The production of milky white delustring PE co-extrusion film layers：By material point contained in the printing layer, intermediate layer and crowded cladding Be not added in coextrusion film blowing machine by it is three-layer co-extruded go out molding mode obtain the milky white delustring PE co-extrusion film layers；The breast The working process parameter of white delustring PE co-extrusion film layers is as shown in table 1 below：
Table 1
The production of EVOH co-extrusion film layers：By the A composite beds, B outer layer, C adhesive layers, D intermediate layers, E adhesive layers, F times Contained material, which is added separately in coextrusion film blowing machine to go out molding mode by seven-layer co-extrusion, in outer layer and G hot sealing layers obtains The EVOH co-extrusions film layer；The working process parameter of the EVOH co-extrusions film layer is as shown in table 2 below：
Table 2
Aluminize to EVOH co-extrusion film layers：By plasma technology the EVOH co-extrusions film layer the compound layer surfaces of A Aluminize and obtain the aluminium lamination；The OD values of the aluminium lamination are 2.4~2.6.Specific aluminum plating process may be referred to the prior art.
Step 2, the material contained by first composite bed and the second composite bed is added separately in extrusion compounding machine The EAA extrusions composite film is obtained, and causes first composite bed and the crowded cladding of the milky white delustring PE co-extrusion film layers Extrude compound, the A composite beds extrusion of second composite bed and the EVOH co-extrusions film layer is compound；It is described extrusion combined temp be 180~250 DEG C.
Step 3, curing, cooling and shaping obtain packaging film product.
Production method and product performance that 3 embodiments are used to illustrate packaging film of the present invention is set forth below.
The production of milky white delustring PE co-extrusion film layers is carried out according to the formula of table 3 below respectively in the embodiment：
Table 3
The production of EVOH co-extrusion film layers is carried out according to the formula of table 4 below respectively in the embodiment：
Table 4
EAA extrudes composite film and is carried out according to the formula of table 5 below 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 from the above that present invention packaging film properties are 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. A kind of 1. high lucifuge high-barrier liquid packaging film, it is characterised in that：The packaging film ecto-entad is followed successively by milky white delustring PE Co-extrusion film layer, EAA extrusions composite film, aluminium lamination and EVOH co-extrusion film layers；
    The milky white delustring PE co-extrusions film layer includes printing layer, intermediate layer and crowded cladding, the milky white delustring PE co-extrusion film layers 82~88 μm of thickness, wherein the printing layer thickness is 24~26 μm, the intermediate layer thickness is 34~36 μm, the crowded cladding Thickness is 24~26 μm；
    The printing layer is (78~82) including mass ratio:The high density polyethylene (HDPE) and metallocene PE plasticity of (18~22) Body, the intermediate layer are (63~67) including mass ratio:(18~22):The linear polyethylene resin of (13~17), low-density are gathered Vinyl and white master batch, the crowded cladding are (28~32) including mass ratio:The linear polyethylene resin of (68~72) And ldpe resin；
    The EVOH co-extrusions film layer includes A composite beds, B outer layer, C adhesive layers, D intermediate layers, E adhesive layers, F outer layer and G Hot sealing layer, the EVOH co-extrusions thicknesses of layers are 51~57 μm, wherein the A composite beds, G heat-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 layers, E bondline thickness are respectively 3~5 μ M, the D intermediate layer thickness are 5~7 μm；
    The A composite beds are (48~52) including mass ratio:(23~27):It is 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 layers, E adhesive layers all wrap Binder resin is included, the D intermediate layers include ETHYLENE-VINYL ALCOHOL COPOLYMER resin, and it is (48 that the G hot sealing layers, which include mass ratio, ~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；
    The EAA extrusions composite film includes contacting the first compound composite bed with the crowded cladding and contacting with the aluminium lamination The second compound composite bed, 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 bed includes ethylene-methyl methacrylate-acrylic ternary copolymer tree Fat.
  2. 2. high lucifuge high-barrier liquid packaging film as claimed in claim 1, it is characterised in that：The milky white delustring PE co-extrusion films 85 μm of layer thickness, wherein the printing layer thickness is 25 μm, the intermediate layer thickness is 35 μm, and the crowded cladding thickness is 25 μ m；
    The EVOH co-extrusions thicknesses of layers is 54 μm, wherein the A composite beds, G heat-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 layers, E bondline thickness are respectively 4 μm, the D intermediate layer thickness For 6 μm；
    8 μm of first composite bed thickness, 7 μm of second composite bed thickness.
  3. 3. high lucifuge high-barrier liquid packaging film as claimed in claim 1, it is characterised in that：The printing layer includes mass ratio For 80:20 high density polyethylene (HDPE) and metallocene PE plastic body, it is 65 that the intermediate layer, which includes mass ratio,:20:15 Linear polyethylene resin, ldpe resin and white master batch, it is 30 that the crowded cladding, which includes mass ratio,:70 it is linear Polyvinyl resin and ldpe resin；
    It is 50 that the A composite beds, which include mass ratio,:25:25 metallocene linear polyethylene, linear polyethylene resin and ethene- Methyl methacrylate copolymer resin, it is 75 that the B outer layer, F outer layer, which all include mass ratio,:25 linear polyethylene resin And metallocene linear polyethylene, the C adhesive layers, E adhesive layers all include binder resin, the D intermediate layers include second Alkene-vinyl alcohol copolymer resin, it is 50 that the G hot sealing layers, which include mass ratio,:50:1.5:0.3 metallocene PE resin, cyclopentadienyl Metal linear polyvinyl resin, opening agent and processing aid.
  4. 4. high lucifuge high-barrier liquid packaging film as claimed in claim 1, it is characterised in that：The printing layer middle-high density gathers The ethene trade mark is HD3355F, and the metallocene PE plastic body trade mark is PL1881G in the printing layer；The intermediate layer center line The property polyvinyl resin trade mark is 5538G, and the ldpe resin trade mark is 150BW in the intermediate layer, in the intermediate 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 in the A composite beds, the A composite beds linear polyethylene resin grade For 2045G, the ethylene methyl methacrylate copolymer resins trade mark is WH303 in the A composite beds；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 layers, E adhesive layers；Ethene-vinyl alcohol is common in the D intermediate layers The poly resin trade mark is H171；Metallocene PE resin grade is 1881 in the G hot sealing layers, metallocene in the G hot sealing layers The linear polyethylene resin trade mark is 2010MA, and the G hot sealing layers split shed agent trade mark is AB-20LD, is processed in the G hot sealing layers The auxiliary agent trade mark is DS-A1058LD；
    Metallocene PE resin grade in first composite bed is PT1450, ethene-first in second composite bed Base acrylic acid-acrylic acid ter-polymer resin grade is AN4211-5C.
  5. 5. high lucifuge high-barrier liquid packaging film as claimed in claim 1, it is characterised in that：The OD values of the aluminium lamination are 2.4 ~2.6.
  6. It is 6. a kind of as the production method of the high lucifuge high-barrier liquid packaging film of Claims 1 to 5 any one of them, its feature exist In comprising the following steps：
    Step 1, material contained in the printing layer, intermediate layer and crowded cladding is added separately to altogether by said components requirement In extrusion film machine by it is three-layer co-extruded go out molding mode obtain the milky white delustring PE co-extrusion film layers；
    Will be contained in the A composite beds, B outer layer, C adhesive layers, D intermediate layers, E adhesive layers, F outer layer and G hot sealing layers 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 in the compound layer surfaces of A of the EVOH co-extrusions film layer aluminize by plasma technology and obtain the aluminium Layer；
    Step 2, the material contained by first composite bed and the second composite bed is added separately to squeeze by said components requirement Go out in compounding machine to obtain the EAA extrusions composite film, and cause first composite bed and the milky white delustring PE co-extrusion films The crowded cladding extrusion of layer is compound, and second composite bed and the A composite beds extrusion of the EVOH co-extrusions film layer are compound；
    Step 3, curing, cooling and shaping.
  7. 7. the production method of high lucifuge high-barrier liquid packaging film as claimed in claim 6, it is characterised in that：The extrusion is multiple It is 180~250 DEG C to close temperature.
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CN109130413A (en) * 2018-08-02 2019-01-04 黄山永新股份有限公司 A kind of compound grade high glaze aluminium plating polyethylene blown film and its production method
CN109177398A (en) * 2018-09-11 2019-01-11 上海福助工业有限公司 Three layers of Coloured film with delustring sense
CN109616005A (en) * 2018-11-15 2019-04-12 永新股份（黄山）包装有限公司 A kind of milky white PE label film and its production method
CN113815281A (en) * 2021-08-05 2021-12-21 黄山永新股份有限公司 High-barrier co-extrusion film and production method and application thereof
CN115464957A (en) * 2022-08-16 2022-12-13 黄山永新股份有限公司 Special extinction effect composite packaging material and preparation method thereof

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CN1880182A (en) * 2006-04-03 2006-12-20 浙江比例包装股份有限公司 High barrier aluminum-plating composite film for packing liquid dairy product
CN101380837A (en) * 2008-10-27 2009-03-11 南京金中达新材料有限公司 Aluminized non-stretching polypropylene film with enhanced aluminium layer peeling strength and preparation method thereof
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CN1752121A (en) * 2005-06-12 2006-03-29 浙江比例包装股份有限公司 Production method of polyethylene modified material capable of cladding aluminium
CN1760087A (en) * 2005-11-04 2006-04-19 大连富利达塑料制品有限公司 Composite packaging film including five layers being extruded out capable of obstructing liquid highly
CN1880182A (en) * 2006-04-03 2006-12-20 浙江比例包装股份有限公司 High barrier aluminum-plating composite film for packing liquid dairy product
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CN113815281A (en) * 2021-08-05 2021-12-21 黄山永新股份有限公司 High-barrier co-extrusion film and production method and application thereof
CN115464957A (en) * 2022-08-16 2022-12-13 黄山永新股份有限公司 Special extinction effect composite packaging material and preparation method thereof
CN115464957B (en) * 2022-08-16 2023-12-19 黄山永新股份有限公司 Special extinction effect composite packaging material and preparation method thereof

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