CN104149437B - A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof - Google Patents
A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof Download PDFInfo
- Publication number
- CN104149437B CN104149437B CN201310177343.0A CN201310177343A CN104149437B CN 104149437 B CN104149437 B CN 104149437B CN 201310177343 A CN201310177343 A CN 201310177343A CN 104149437 B CN104149437 B CN 104149437B
- Authority
- CN
- China
- Prior art keywords
- layer
- multilayer complex
- complex films
- multiplying power
- films according
- 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.)
- Active
Links
Abstract
The present invention provides a kind of multilayer complex films, it includes AXBXC Rotating fields, wherein, A layer and C layer in described Rotating fields include identical or different acrylic polymer independently of one another, B layer includes ethylene-based polymer, acrylic polymer or its combination, and X is adhesive layer, and described A layer is simple tension or biaxial tension, described C layer is simple tension or biaxial tension, and the draw ratio of A layer or stretching ratio different from the draw ratio of C layer or stretching ratio.The present invention also provides for the preparation method of above-mentioned multilayer complex films, its purposes and the goods comprising this multilayer complex films.The acrylic polymer of the present invention-ethylene-based polymer multilayer complex films has the performances such as high-stiffness, high transparent, low temperature resistant, high-tear strength.
Description
Technical field
The present invention relates to a kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method and application thereof, the invention still further relates to the goods comprising described composite membrane, belong to field of compound material.
Background technology
Biaxially oriented polypropylene (BOPP) thin film effectively utilizes the characteristics such as its excellent light weight, the transparency, mechanical strength, nontoxic, moistureproof, breathability is low, rigidity, for the wide spectrum being representative with packaging material.For example, be widely used for the packaging of the products such as food, medicine, daily light industry, medicated cigarette and lamination compound.A kind of purposes of BOPP thin film is to fit in paper surface, such as books, packing carton etc., plays effect that is moistureproof and that increase surface gloss.
BOPP thin film is generally the coextrusion structure of 3-5 layer, and step drawing production technology is mainly made up of following operation: dispensing batch mixing, extruder extrusion, extruded by T-shaped die head sheet, sheet chilling, sheet by heating roller preheating, sheet longitudinal stretching, thermal finalization, preheat again, cross directional stretch, thermal finalization, cooling, sided corona treatment, rolling, cut and put in storage.CN101160209A(Oji Paper) disclosed in a kind of Biaxially stretched multilayer polypropylene film, the two sides of the bidirectional stretching polypropylene film substrate layer that its propylene polymer composition adding inorganic compound powder in by acrylic polymer obtains, possessing the surface layer containing acrylic polymer and back layer, the acrylic polymer in described substrate layer can be identical or different with the acrylic polymer in surface/back layer.It by adding inorganic compound powder in substrate layer, obtain uniform hidden power and whiteness excellent, almost without the thin film that preferred thickness is 25-55 μm of concave-convex surface.Described thin film obtains by the following method: by itself known method co-extrusion modling, the acrylic polymer forming substrate layer is obtained multi-layer sheet, adopts the simultaneously bi-directionally biaxially oriented film forming method such as pulling method or sequentially biaxial tension method to be stretched to face multiplying power (longitudinal × horizontal) 45～65 times and obtain.To adopt sequentially biaxial tension method, can pass through at the temperature of longitudinally 70～140 ° of C with after the scope stretching of 4.5～7.5 times, then, under the temperature range of laterally 120～190 ° of C under 7～12 times and after face multiplying power (longitudinally × laterally) is stretched to 45～65 times, obtain at the temperature range heat fixation of 110～180 ° of C.
BOPP thin film has many desirable performances, such as high tensile, high-stiffness, the high grade of transparency etc..But, the life cycle of BOPP thin film is short, is generally some months to a year, and some physical properties such as resistance to low temperature, fall strength of briquette, tearing strength etc. is poor, is not suitable for the leaflet of life-time service, packaging material etc..It addition, the thickness of existing bidirectional stretching polypropylene film is generally less than 50 μm, its deflection can not meet high-end demand, therefore constrains its some ranges of application.
The density polyethylene film with high stretched has been used for plastics package field.Describing more such thin film in British Patent No. 1287527, they are biaxially stretched the degree more than 6.5 times on machine direction (MD) and horizontal (TD) both direction.U.S. Patent No. 4680207 relates to the twin shaft imbalance oriented film of linear low density polyethylene, and it stretches less than 6 times in the direction of the machine, and orientation is less than 3 times and less than stretching in the direction of the machine in the horizontal.
At present, industrial quarters, in the application that some are high to physical property requirements, generally uses biaxial stretching polyester (BOPET) thin film or biaxial tension nylon (BOPA) thin film.But BOPET film and BOPA thin film ratio are great, cost is high, and solvent resistance is poor.
Therefore, industrial quarters needs a kind of high transparent with traditional B OPP film and high-stiffness but has again the novel thin film of resistance to low temperature, high-tear strength simultaneously.
Summary of the invention
The present invention is for overcoming the deficiencies in the prior art, it is provided that a kind of acrylic polymer-ethylene-based polymer multilayer complex films, has the performances such as high-stiffness, high transparent, low temperature resistant and high-tear strength.
The preparation method that it is a further object to provide above-mentioned multilayer complex films.
It is also another object of the present invention to provide the purposes of above-mentioned multilayer complex films.
It is also another object of the present invention to provide the goods including above-mentioned multilayer complex films.
The present invention is achieved through the following technical solutions:
A kind of multilayer complex films, it includes AXBXC Rotating fields, wherein, A layer and C layer in described Rotating fields include identical or different acrylic polymer independently of one another, B layer includes ethylene-based polymer, acrylic polymer or its combination, X is adhesive layer, and described A layer and C layer include one of following combination:
(1) described A layer is simple tension, and described C layer is biaxial tension；
(2) described A layer is biaxial tension, and described C layer is simple tension；
(3) A layer and C layer are biaxial tension；Or
(4) A layer and C layer are simple tension；
Wherein, the draw ratio of A layer or stretching ratio are different from the draw ratio of C layer or stretching ratio.
According to the present invention, for scheme (1).The transverse direction of described A layer is stretched, and described the horizontal and vertical of C layer is all stretched；Or the longitudinal direction of described A layer is stretched, and described the horizontal and vertical of C layer is all stretched.It is highly preferred that the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described C layer；Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described C layer.
According to the present invention, for scheme (2).Described the horizontal and vertical of A layer is stretched, and the transverse direction of described C layer is stretched；Or described the horizontal and vertical of A layer is stretched, and the longitudinal direction of described C layer is stretched.It is highly preferred that the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described C layer；Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described C layer.
According to the present invention, for scheme (3).The vertically and horizontally draw ratio of described A layer is different from the vertically and horizontally draw ratio of described C layer；Preferably, the longitudinal stretching multiplying power of described A layer is more than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described C layer is more than longitudinal stretching multiplying power；It is highly preferred that the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of described A layer and described C layer is inversely proportional to, namely the longitudinal stretching of described A layer is equal to the cross directional stretch of described C layer and the ratio of longitudinal stretching with the ratio of cross directional stretch.It is highly preferred that the longitudinal stretching multiplying power of described A layer is same or like with the cross directional stretch multiplying power of described C layer, and the cross directional stretch multiplying power of described A layer is same or like with the longitudinal stretching multiplying power of described C layer；It is more preferred still that the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described C layer, and the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described C layer.
According to the present invention, for scheme (4).The stretching ratio of described A layer is different from the stretching ratio of described C layer；Preferably, the stretching ratio of described A layer is more than the stretching ratio of described C layer, or the stretching ratio of described A layer is less than the stretching ratio of described C layer.
According to the present invention, for scheme (4).Preferably, the transverse direction of described A layer is stretched, and the longitudinal direction of described C layer is stretched；Or the longitudinal direction of described A layer is stretched, and the transverse direction of described C layer is stretched.It is highly preferred that the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described C layer；Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described C layer.
According to the present invention, the B layer in described multilayer complex films does not stretch.
According to the present invention, A layer or C layer in described multilayer complex films are single layer structure or multi-layer co-extruded structure.
According to the present invention, the B layer in described multilayer complex films is single layer structure or multi-layer co-extruded structure.
According to the present invention, described A layer, the multi-layer co-extruded structure of B layer or C layer is at least 2 layers, for instance for 2-15 layer, it is preferable that 3-11 layer, more preferably 5-9 layer, even more preferably from 6-8 layer.
According to the present invention, the material of the binding agent in any one X layer described is identical or different, is selected from: chlorinated polypropylene, polyurethane, acrylic resin, epoxy resin or its mixture.
According to the present invention, described chlorinated polypropylene adopts solwution method, suspension method or solid phase method polypropylene chlorination to be prepared.The mass content of chlorine is 20%-70%, and fusing point is less than 150 ° of C.
According to the present invention, described polyurethane is solvent-borne type, water-dispersion type or no-solvent type one-component or Multi-component Polyurethane adhesive.
According to the present invention, the adhesive that described acrylic resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent contains acrylic acid or acrylates.
According to the present invention, described epoxy resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent epoxy type adhesive.
According to the present invention, the thickness of described multilayer complex films is 50-150 μm, it is preferable that 60-120 μm, more preferably 70-100 μm, even more preferably from 80-90 μm.
According to the present invention, in described multilayer complex films, the thickness of A layer or C layer is 5-65 μm, it is preferable that 10-55 μm, more preferably 20-40 μm.
According to the present invention, in described multilayer complex films, the thickness of each X layer is 0.5-10 μm, it is preferred to 1-6 μm, more preferably 2-5 μm.
According to the present invention, in described multilayer complex films, the summation of all X layer thicknesses is less than the 30% of this composite film thickness, it is preferable that less than 20%, more preferably no more than 15%, even more preferably from less than 10%.
According to the present invention, the B layer thickness in described multilayer complex films is 5-30 μm, it is preferable that 10-20 μm, and A layer and C layer thickness differ less than 20%, it is preferable that less than 15%, more preferably no more than 10%.
According to the present invention, in described multilayer complex films, the tensile strength of A layer is 1.5:1.0 to 7.0:1.0 at horizontal and vertical ratio, it is preferable that 2.0:1.0 to 5.0:1.0.
According to the present invention, in described multilayer complex films, the tensile strength of C layer is 1.0:1.5 to 1.0:7.0 at horizontal and vertical ratio, it is preferable that 1.0:2.0 to 1.0:5.0.
According to the present invention, for biaxial tension, the cross directional stretch multiplying power of the A layer in described multilayer complex films is 7-12.5 times, and longitudinal stretching multiplying power is 1-6 times, it is preferable that cross directional stretch multiplying power is 8-10 times, and longitudinal stretching multiplying power is 2-4 times.
According to the present invention, for biaxial tension, the cross directional stretch multiplying power of the C layer in described multilayer complex films is 1-6 times, and longitudinal stretching multiplying power is 7-12.5 times, it is preferable that cross directional stretch multiplying power is 2-4 times, and longitudinal stretching multiplying power is 8-10 times.
According to the present invention, for simple tension, the stretching ratio laterally or longitudinally of the A layer in described multilayer complex films is 1-12.5 times, it is preferable that cross directional stretch multiplying power is 7-12.5 times or longitudinal stretching multiplying power is 1-6 times；The vertical or horizontal stretching ratio of C layer is 1-12.5 times, it is preferable that longitudinal stretching multiplying power is 7-12.5 times or cross directional stretch multiplying power is 1-6 times.
According to the present invention, test value ratio horizontal and vertical in the tensile strength of described multilayer complex films, deflection and tear-resistant intensity is 0.7:1.0 to 1.0:1.3.
The vertically and horizontally hot strength of described multilayer complex films is more than 100MPa, it is preferable that more than 120MPa, more preferably greater than 140MPa.
According to the present invention, described acrylic polymer is preferably Noblen or propylene copolymer, it is typically isotaxy homopolymer, or is with different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, has the atactic propene copolymer of a small amount of comonomer and the polypropylene blend of ethylene copolymer-modified isotactic polypropylene.Comonomer is ethylene or higher alpha-olefin, such as ethylene, butylene, hexene or octene etc..
According to the present invention, the fusing point of described acrylic polymer is 148 to 170 ° of C, it is preferable that 150-167 ° of C；More preferably 155 ° of C-165 ° of C；Molecular weight distribution (GPC test) is 2-16, it is preferred to 4-10；Melt index is 0.5-10g/10min, it is preferable that 1-8g/10min.
According to the present invention, described ethylene-based polymer is preferably high density polyethylene (HDPE), high-pressure process low-density polyethylene or low-pressure process linear low density polyethylene.The density of high density polyethylene (HDPE) is about 0.941g/cm3Or it is higher, it is preferable that about 0.948g/cm3To about 0.968g/cm3, more preferably from about 0.952g/cm3To about 0.962g/cm3；About 130 ° of C to about 148 ° C of fusing point；Melt index (is measured) as 0.2-50g/10min according to ASTMD1238, it is preferable that 1-45g/10min, more preferably 2-40g/10min.The density of Low Density Polyethylene is about 0.912g/cm3To about 0.94g/cm3, it is preferable that 0.915g/cm3To 0.928g/cm3；Melt index (is measured) as 0.2-50g/10min according to ASTMD1238, it is preferable that 1-45g/10min, more preferably 2-40g/10min.Linear low density polyethylene is ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm3To 0.950g/cm3, preferred 0.905g/cm3To 0.940g/cm3, more preferably 0.910g/cm3To 0.928g/cm3The density of scope.Ethylene-based polymer can also is that terpolymer, such as ethylene/butene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymers have 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm3To 0.950g/cm3, preferred 0.905g/cm3To 0.940g/cm3, more preferably 0.910g/cm3To 0.928g/cm3The density of scope.
According to the present invention, A layer, B layer or C layer also can add another resin, such as Petropols or hydrogenated petroleum resin, to change the performances such as such as heat sealer, breathability, deflection and intensity, it is preferred to C5-C9Petropols or C5-C9Hydrogenated petroleum resin.Its addition is the 1-30% weight of each layer gross weight, it is preferable that 2-20% weight, more preferably 3-15% weight, even more preferably from 4-10% weight.
The preparation method that the present invention also provides for described multilayer complex films, it comprises the following steps:
(1) preparation of A layer and C layer
Being extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, then carry out simple tension under the temperature environment of 130-185 ° of C or biaxial tension processes A layer and C layer, wherein the draw ratio of A layer or stretching ratio are different from C layer；
(2) preparation of B layer
Extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, be processed into B layer；
(3) using rolling method, with X layer for adhesive, A layer, B layer and C layer are carried out gluing, wherein the outermost two-layer of composite membrane carries out single spreading, and middle each layer carries out one or two sides gluing, and after gluing, each layer is dried under 40-80 ° of C；
(4) the A layer of gluing, B layer and C layer are carried out lamination compound, obtain described composite membrane.
According to the present invention, A layer and/or the two-sided of C layer of step (1) gained both pass through sided corona treatment so that it is initial surface tension reaches more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.It is further preferred that surface tension reaches more than 38 dynes per centimeter.
Film prepared by the present invention can be used for needing high-stiffness, tear-resistant bill, marketable securities, leaflet and packaging material.
The present invention also provides for the application of the multilayer complex films described in a kind of aforementioned any one, and it is for bill, marketable securities, leaflet and packaging material.
The present invention also provides for a kind of goods, and it is prepared by the face coat of the multilayer complex films described in aforementioned any one and printing, and described goods include leaflet (such as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.
Beneficial effects of the present invention:
Acrylic polymer prepared by the present invention-ethylene-based polymer multilayer complex films, having the combination property of excellence, its tensile strength, deflection and tear-resistant intensity are all significantly high, and its vertical and horizontal performance has good balance, and having the good transparency, concrete performance is referring to table 1.
The performance of table 1 composite membrane of the present invention
Describe in detail
[composition of A layer, B layer and C layer]
It is preferably Noblen or propylene copolymer or polypropene composition according to the acrylic polymer in the present invention, described A layer or B layer or C layer；It is typically isotaxy homopolymer, or is with different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, has the atactic propene copolymer of a small amount of comonomer and the polypropylene blend of ethylene copolymer-modified isotactic polypropylene.Comonomer is ethylene or higher alpha-olefin, such as ethylene, butylene, hexene or octene etc..The content of comonomer is preferably 0.2wt% to 2.0wt%, more preferably 0.35wt% to 0.85wt%.These acrylic polymers of the present invention can be the mixture containing one kind or two or more polymer, for instance the Noblen that molecular weight is different, or the compositions of propylene and a small amount of alpha-olefin random copolymer.The acrylic polymer of the present invention, is generally the vistanex according to polyacrylic title manufacture, sale, it is common that density is 0.890～0.930g/cm3, MFR(ASTMD1238, load 2160g, 230 ° of C of temperature) be 0.5～60g/10min, be preferably 0.5～20g/10min, more preferably 0.5-15g/10min, be still more preferably the Noblen of 1～5g/10min.
According to the present invention, the fusing point of described acrylic polymer is 148 to 170 ° of C, it is preferable that 150-167 ° of C, more preferably 155 ° of C-165 ° of C；Molecular weight distribution (GPC test) is 2-16, it is preferred to 4-10；Melt index is 0.5-10g/10min, it is preferable that 1-8g/10min.The Noblen that industrial BOPP thin film is conventional has: the T38F of Lanzhou Petrochemical and Daqing petrochemical；The T36F of Dalian petrochemical industry；This kind of Noblen is tested melt index (MI) according to ASTMD-1238 and be can be about 0.2-20g/10min, it is preferable that 0.5-15g/10min, and fusing point can be about between 155 ° of C-165 ° of C.
According to the present invention, the ethylene-based polymer in described B layer is preferably high density polyethylene (HDPE) (HDPE), Low Density Polyethylene (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE not or has a small amount of comonomer, and comonomer is propylene or higher alpha-olefin, such as butylene, hexene or octene etc., and has about 0.941g/cm3Or higher (such as about 0.948g/cm3To about 0.968g/cm3, it is preferable that about 0.952g/cm3To about 0.962g/cm3) density, the fusing point of such as about 130 ° of C to about 148 ° of C and 0.2-50g/10min, it is preferable that 1-45g/10min, the more preferably melt index (measuring according to ASTMD1238) of 2-40g/10min.LDPE has at 0.912g/cm3To 0.94g/cm3(such as 0.915g/cm3To 0.928g/cm3) the density of scope and the preferred 1-45g/10min of 0.2-50g/10min(, more preferably 2-40g/10min) melt index (measuring according to ASTMD1238).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm3To 0.950g/cm3, preferred 0.905g/cm3To 0.940g/cm3, more preferably 0.910g/cm3To 0.928g/cm3The density of scope.In addition ethylene-based polymer can also is that terpolymer, such as ethylene/butene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymers have 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm3To 0.950g/cm3, preferred 0.905g/cm3To 0.940g/cm3, more preferably 0.910g/cm3To 0.928g/cm3The density of scope.
The polymer of described A layer and C layer also can be mixed into part ethylene-based polymer, for instance high density polyethylene (HDPE) (HDPE), Low Density Polyethylene (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE not or has a small amount of comonomer, and comonomer is propylene or higher alpha-olefin, such as ethylene, butylene, hexene or octene etc., and has about 0.941g/cm3Or higher (such as about 0.948g/cm3To about 0.968g/cm3, it is preferable that about 0.952g/cm3To about 0.962g/cm3) density, the fusing point of such as about 130 ° of C to about 148 ° of C and 0.2-50g/10min, it is preferable that 1-45g/10min, the more preferably melt index (measuring according to ASTMD1238) of 2-40g/10min.LDPE has at 0.912g/cm3To 0.94g/cm3(such as 0.915g/cm3To 0.928g/cm3) the density of scope and the preferred 1-45g/10min of 0.2-50g/10min(, more preferably 2-40g/10min) melt index (measuring according to ASTMD1238).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm3To 0.950g/cm3, preferred 0.905g/cm3To 0.940g/cm3, more preferably 0.910g/cm3To 0.928g/cm3The density of scope.In addition ethylene-based polymer can also is that terpolymer, such as ethylene/butene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymers have 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm3To 0.950g/cm3, preferred 0.905g/cm3To 0.940g/cm3, more preferably 0.910g/cm3To 0.928g/cm3The density of scope.
Deflection of the present invention refers to that Paper or cardboard supports resistant to bending strength character.Deflection is directly proportional to EI/W value, wherein the quality of W, E and I respectively Paper or cardboard, elastic modelling quantity and the moment of inertia.Wherein, the deflection of cardboard or claim flexural rigidity, refer to applying certain load from the fixture 5cm place sample to vertically clipping, observing from sample camber 3.81mm width, sample, to moment of flexure 15 ° required, represents with g cm.Paper sheet stiffness is a critically important index, directly affects the size (another influence factor is d ie cutting press) of folding line deflection, thus affecting finished product molding.Deflection is little, and finished product is prone to conquassation, warpage；Deflection is big, and finished product is difficult to molding.
In order to improve the deflection of the multilayer complex films of the present invention further, and the such as performance such as heat sealer, breathability and intensity, it is possible in A layer, B layer or C layer, add another resin, such as Petropols, hydrogenated petroleum resin etc., it is preferable that C5-C9Petropols or C5-C9Hydrogenated petroleum resin.Its addition is the 1-30% weight of each layer gross weight, it is preferable that 2-20% weight, more preferably 3-15% weight, even more preferably from 4-10% weight.
In the polymer of described A layer, B layer and C layer, all right master batch form adds the additive of about 0.01～5.0 mass %.Described additive is preferably 0.01～3.0 mass %, more preferably 0.05～1.0 mass %.
Described additive has: antiblocking agent, slipping agent (i.e. lubricant or slipping agent), antistatic additive, nucleator, heat-resisting stabilizing agent, weathering stabilizers, UV absorbent, anti-turbid dose, pigment, the known various additives that generally can add in polyolefin such as dyestuff.
As described antiblocking agent, antiblocking agent well known in the art can be used, such as Silicon stone, Talcum, Muscovitum, zeolite, or the inorganic compound particles such as the metal-oxide that metal alkoxide sintering is obtained；Or the organic compound such as polymethyl methacrylate, melamine resin, melamine urea resin, polyester resin.Wherein, Silicon stone, polymethyl methacrylate are particularly preferably used from resistance to blocking aspect.
As described lubricant, the such as amide based compound such as stearmide, erucyl amide, oleamide etc. can be used.
As described antistatic additive, can use such as the ethylene oxide adduct of betanin derivative, quaternary amine based compound, alkyldiethanolamine fatty acid ester, fatty acid glyceride, tristerin etc..
As described nucleator, such as Sorbitol system, organophosphate metal salt system, metal salt of organic carboxylic acid system, rosin series nucleator etc. can be used.
As described heat-resisting stabilizing agent, such as 2,6-di-tert-butyl-4-methy phenols (BHT) etc. can be used.
The polymer of described A layer, B layer or C layer also can add delustring masterbatch to produce Extinctive thin film, or addition pearly-lustre masterbatch produces pearly-lustre thin film.
Single or double as required, can be implemented the surface treatment such as sided corona treatment, flame treatment by the laminate stretch acrylic polymer-ethylene-based polymer thin film of the present invention.Additionally, according to purposes, for giving heat sealability, can overleaf on layer independent lamination contain the thin film of the low melting point polymers such as random copolymer or the random copolymer of alpha-olefin of propylene and ethylene or carbon number more than 4, polybutene, the ethene-vinyl acetate copolymer of high-pressure process low-density polyethylene, linear low density polyethylene (LLDPE), crystallinity or low-crystalline ethylene and the alpha-olefin of carbon number 3～10, or lamination contains their thin film of compositions.It addition, in order to improve the cementability with other material, the binding agents such as oriented film surface imines, carbamate can be fixed process, it is also possible to the maleic anhydride modified polyolefin of lamination.
[composition of X layer]
According to the present invention, the material of the binding agent in any one X layer described is identical or different, is selected from: chlorinated polypropylene, polyurethane, acrylic resin, epoxy resin or its mixture.
The chlorinated polypropylene of the present invention adopts solwution method, suspension method or solid phase method polypropylene chlorination to be prepared.The mass content of chlorine is 20%-70%, and fusing point is less than 150 ° of C.
According to the present invention, described polyurethane is solvent-borne type, water-dispersion type or no-solvent type one-component or Multi-component Polyurethane adhesive.
According to the present invention, the adhesive that described acrylic resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent contains acrylic acid or acrylates.
According to the present invention, described epoxy resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent epoxy type adhesive.
The polyurethane resin of the present invention is selected from generally as known polyester-polyurethane, polyether-polyurethane or the polyurethane polyureas carbamide resin etc. manufactured containing the dry lamination of polyurethane, waterborne dry-type lamination, solventless liminating, electronic beam solidified laminating adhesive of film adhesive.This polyurethane resin can be water-dispersion type or solvent type any one, but easily dimmable from the degree of cross linking of polyurethane resin cover layer, and from the working environment aspect of production scene, it is preferred to water dispersant type polyaminoester resin.
As water dispersant type polyaminoester resin, it is preferred to introduce carboxylate (-COONa etc.), sulfonate (-SO to main chain or the side chain of polyurethane resin3Na etc.) etc. the self-emulsifying type polyurethane resin of hydrophilic group.In solvent type situation, isocyanate-based resin is used for cross-linking agent, form the polyurethane with three dimensional structure, but the situation that water-dispersion type becomes linear polyurethane or polyurethane polyureas carbamide resin is in the majority, therefore relative to polyurethane resin, the cross-linking agent such as the melamine series resin of about 3～10 mass %, epoxy system resin, imines system resin can be added, it is possible to add the acid catalyst of about 0.5～1 mass %, promote curing reaction further.This cross-linking agent is possible not only to improve the resistance to water of easy-adhesion overlay film, solvent resistance, it is also possible to improve cementability.
It addition, when using water dispersant type polyaminoester resin, time in composition containing the surfactant such as defoamer or emulsifying agent, it is possible to make the surface of Biaxially stretched multilayer propylene polymer thin film turn white, cause bad order.It addition, in the polyurethane resin of the present invention, for instance, in order to prevent the purposes such as adhesion, as required, it is also possible to add inorganic particles or organic fine particles etc..
On the one or both sides of acrylic polymer-ethylene-based polymer thin film, when covering (lamination) polyurethane resin (X), can pass through gravure coater such as the aqueous solution of polyurethane resin or dispersion liquid Kohler coater, direct gravure coater, intaglio offset coating machine, electric arc gravure coater, reverse rotating gravure and nozzle modes；The reverse roll coating machines such as its top feed reverse roll coating machine, bottom feed reverse roll coating machine and nozzle material-feeding reverse roll coating machine, the coating machine of 5 rollers, lip are coated with machine, bar coater, inverse itself known coating machine various such as rod coater, die head formula coating machine, are 0.1～20g/m according to making the amount of contained compositions in polyurethane resin aqueous solution2, preferred 0.3～2g/m2After being coated, dry more than 10 seconds at the temperature of 50～140 ° of C and obtain.
[preparation method of multilayer complex films]
According to the present invention, adopt simple tension or biaxial tension, namely in stretching-machine, at certain temperature and speed, a direction (vertical or horizontal) or carry out stretching in vertical both direction (longitudinally, laterally) and make thin film.The so-called direction longitudinally referred to along thin film extrusion processing, the so-called direction laterally referring to vertical thin-film extrusion processing.Vertically and horizontally draw ratio refers to the ratio of longitudinal stretching multiplying power and cross directional stretch multiplying power.
The preparation method that the present invention provides described multilayer complex films, it comprises the following steps:
(1) preparation of A layer and C tunic
Prepared by the method adopting simple tension or biaxial tension, for biaxial tension, it is possible to adopts substep sequentially biaxial tension method, also can adopt synchro-draw method.
Described drawing process includes plain film method and periosteum method.For biaxial tension, the technical process of described plain film method includes synchro-draw process, comprises the steps:
Synchro-draw → the traction of dispensing → extrusion → chilling → vertically and horizontally and optional surface treatment → rolling → Ageing Treatment → cut → product.
The technical process of described plain film method also includes step drawing process, comprises the steps:
Dispensing → extrusion → chilling → longitudinal stretching → cross directional stretch → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.
According to the present invention, described longitudinal stretching includes preheating, micro-stretching and sizing.
According to the present invention, described cross directional stretch includes preheating, stretches greatly, shapes and cooling.
According to the present invention, described chilling refers to that use coolant cools down, it is preferable that coolant is cooling water.The effect of described chilling is to make crystallization refine, thus improving transparency and deflection.
According to the present invention, described extrusion includes monolayer extrusion or multi-layer co-extruded.Described extrusion employing melt extrudes.
According to the present invention, described dispensing includes the requirement according to formula and carries out dispensing, it is possible to pass through electronic measurement.
The technical process of described periosteum method includes synchro-draw process, comprises the steps:
Synchro-draw → the collapser of → chilling → mother's film → dewater → baker Far-infrared Heating → vertically and horizontally flattens → cut open limit → heat treatment → cooling → rolling → Ageing Treatment that dispensing → extrusion (includes monolayer extrusion or multilayered molten extrusion) → cut → product.
The technical process of described periosteum method also includes step drawing process, comprises the steps:
Dispensing → extrusion (includes monolayer extrusion or multilayered molten extrusion), and → chilling → mother's film → dewater → baker Far-infrared Heating → longitudinal stretching → cross directional stretch → collapser flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.
According to the present invention, described chilling refers to that use coolant cools down, it is preferable that coolant is cooling water.The effect of described chilling is to make crystallization refine, thus improving transparency and deflection.
When described plain film method is plain film substep biaxial tension, specifically include following steps:
A () carries out dispensing by the requirement of formula, add in the hopper above the extruder of single or multiple lift co-extrusion, and plastics enter the rack-style flat die of single or multiple lift coextru-lamination after passing through external heat and the screw rod rotational shear plasticizing of extruder barrel.Going out the lamellar melt after die head and be attached on chilling roller by air knife, lamellar melt supercooled is become sheet, then as the rotation of chilling roller, sheet enters tank and carries out further two-sided cooling.The thickness of sheet can be controlled by the rotating speed of the extrusion capacity of extruder and chilling roller.Wherein, the control temperature of extruder is 150-260 ° of C, it is preferable that 180-250 ° of C；Die head temperature is generally 190-240 ° of C, and chilling roll temperature is 15-30 ° of C, it is preferable that 20-25 ° of C.
B a number of pre-hot-rolling that () sheet enters back in vertically and horizontally tensioning system carries out two-sided preheating, and pre-heat roller temperature general control is at 90-150 ° of C, it is preferable that 100-120 ° of C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, carrying out longitudinal stretching by draw roll, draft temperature controls at 90-150 ° of C, it is preferable that 100-120 ° of C, and drawing process can a step, it is also possible to twice stretching or stretch for three times.Longitudinal stretching multiplying power is set according to the requirement of A layer and C tunic.Thin film after stretching carries out heat treatment by setting roller, and described setting temperature is 100-140 ° of C, it is preferred to 110-120 ° of C, to eliminate the internal stress of thin film, reduces longitudinal shrinkage factor.
C the thin film after () longitudinal stretching enters cross directional stretch system, first carry out preheating section preheating, and pre-heat roller temperature general control is at 100-160 ° of C, it is preferable that 110-140 ° of C, more preferably 115-130 ° of C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, then pass through the track expanding spoke and carry out cross directional stretch, the general 130-180 ° of C of control temperature of stretching-machine, it is preferable that 140-160 ° of C, then carries out thermal finalization process, setting temperature is 60-120 ° of C, it is preferable that 70-110 ° of C.Cross directional stretch multiplying power is set according to the requirement of A layer and C tunic.
(d) go out cross directional stretch system after thin film cooled down by chill roll, followed by trimming, be sided corona treatment with that, be finally by rolling.
E () leaves the big wound membrane after equipment after the Ageing Treatment depositing several days, just can cut, and makes A layer and the C layer film of Rack.
When described plain film method is the stretching of plain film synchronous bidirectional, plain film synchro-draw preparation method is similar with plain film step drawing preparation method, difference is only in that in synchro-draw process, and longitudinal stretching and cross directional stretch are synchronously performed, namely longitudinal stretching and cross directional stretch complete a system inter-sync, and longitudinal stretching and cross directional stretch is asynchronous carries out in step drawing.Thus concrete operating condition is similar with step drawing.At present, synchro-draw machine has two kinds of forms in the world, and one is mechanical type, and one is linear electric machine formula.
When described periosteum method is synchronous bidirectional stretching, it is similar with plain film method synchronous bidirectional stretching preparation method that periosteum method synchronous bidirectional stretches preparation method, and its longitudinal stretching and cross directional stretch are also synchronously performed.Being different in that, the die head of periosteum method is circular, and it is all that the form steeping pipe completes that whole thin film is formed.Main production parameter: extruder temperature is 180-240 ° of C, die head temperature is 190-230 ° of C, and cooling water temperature is 11-18 ° of C, oven drying temperature: 330-450 ° of C, and draft temperature is 140 ° of C.Vertically and horizontally draw ratio then requirement according to the draw ratio of each tunic carries out.
When described periosteum method is substep biaxial tension, periosteum method substep biaxial tension preparation method is similar with plain film method substep biaxial tension preparation method, and its longitudinal stretching and cross directional stretch are also synchronously performed.Being different in that, the die head of periosteum method is circular, and it is all that the form steeping pipe completes that whole thin film is formed.Main production parameter: extruder temperature is 180-240 ° of C, die head temperature is 190-230 ° of C, and cooling water temperature is 11-18 ° of C, oven drying temperature: 330-450 ° of C, and draft temperature is 140 ° of C.Vertically and horizontally draw ratio then requirement according to the draw ratio of each tunic carries out.
For simple tension, the technical process of described plain film method comprises the steps:
Dispensing → extrusion → chilling → vertical or horizontal stretching → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.
The technical process of described periosteum method comprises the steps:
Dispensing → extrusion (includes monolayer extrusion or multilayered molten extrusion), and → chilling → mother's film → dewater → baker Far-infrared Heating → vertical or horizontal stretching → collapser flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.
Concrete step is similar with above-mentioned biaxial tension method.
(2) preparation of B tunic
Extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, then process B layer；
(3) gluing
Using rolling method, with X for adhesive, A layer, B layer and C layer are carried out gluing, wherein the outermost two-layer of composite membrane carries out single spreading, and middle each layer carries out one or two sides gluing.
According to the present invention, described gluing carries out at normal temperatures.After gluing, each layer of composite membrane is dried under 40-80 ° of C.
(4) lamination
The A layer of gluing, B layer and C layer are carried out lamination compound, obtains described composite membrane.
According to the present invention, described lamination compound is undertaken by hot pressing, and described laminating temperature is 40-100 ° of C, it is preferable that 60-80 ° of C.
According to the present invention, the A layer of step (1) gained, B layer and/or the two-sided of C layer both pass through sided corona treatment so that it is initial surface tension reaches more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.It is further preferred that surface tension reaches more than 38 dynes per centimeter.
[purposes of multilayer complex films]
Film prepared by the present invention can be used for needing high-stiffness, tear-resistant bill, marketable securities, leaflet and packaging material.
The present invention also provides for the application of the multilayer complex films described in a kind of aforementioned any one, and it is for bill, marketable securities, leaflet and packaging material.
The present invention also provides for a kind of goods, and it is prepared by the face coat of the multilayer complex films of aforementioned any one and printing, and described goods include leaflet (such as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.
Accompanying drawing explanation
Fig. 1 is the structural representation of the composite membrane of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below in conjunction with embodiment, the present invention being described, but skilled in the art realises that, described embodiment is not limiting the scope of the invention, any make on basis of the present invention improvement, change all within protection scope of the present invention.
Embodiment 1:AXBXC type structure, layer thickness profile: 33 μm/2 μm/10 μm/2 μm/33 μm
A layer and C layer are all with the polypropylene copolymer containing ethylene, and ethylene contents is 0.35wt%, and molecular distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
B layer uses high density polyethylene (HDPE), and density is 0.955g/cm3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer passes through plain film method simple tension processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinally drawing high multiplying power is 1 times.
C layer passes through plain film method simple tension processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinally drawing high multiplying power is 9 times.
B layer processes film forming by conventional method.
A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, through being compounded to form composite membrane.Wherein A layer thickness is 33 μm, and B layer is 10 μm, and C layer thickness is 33 μm, and the thickness of X is 2 μm, and overall film thickness is 80 μm.
The performance test results of the film of preparation is listed in table 2.
Embodiment 2:AXBXC type structure, layer thickness profile: 38 μm/2 μm/30 μm/2 μm/38 μm
A layer and C layer are all with the polypropylene copolymer containing ethylene, and ethylene contents is 0.35wt%, and molecular distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.B layer is high density polyethylene (HDPE), and density is 0.955g/cm3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer passes through plain film method simple tension processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinally drawing high multiplying power is 1 times.
C layer passes through plain film method simple tension processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinally drawing high multiplying power is 9 times.
B layer processes film forming by conventional method.
A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, through being compounded to form composite membrane.Wherein A layer thickness is 38 μm, and B layer is 30 μm, and C layer thickness is 38 μm, and the thickness of X is 2 μm, and overall film thickness is 110 μm.
The performance test results of the film of preparation is listed in table 2.
Embodiment 3:AXBXC type structure, layer thickness profile: 23 μm/2 μm/10 μm/2 μm/23 μm
A layer is polypropylene homopolymer, and molecular distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.C layer is the polypropylene copolymer containing ethylene, and ethylene contents is 0.35wt%, and molecular distribution is 5.5, and melt index is 2.8g/10min.
B layer is Low Density Polyethylene, and density is 0.916g/cm3, melt index is 2.8g/10min.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinally drawing high multiplying power is 5 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinally drawing high multiplying power is 8 times.
B layer processes film forming by conventional method.
A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, then adopt the acid of roll coating model painting polypropylene, through being compounded to form composite membrane.Wherein A layer thickness is 23 μm, and B layer is 10 μm, and C layer thickness is 23 μm, and the thickness of X is 2 μm, and overall film thickness is 60 μm.
The performance test results of the film of preparation is listed in table 2 as follows.
Embodiment 4:AXBXC type structure, layer thickness profile: 43 μm/2 μm/20 μm/2 μm/43 μm
A layer is polypropylene homopolymer, and molecular distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.C layer is the polypropylene copolymer containing ethylene, and ethylene contents is 0.35wt%, and molecular distribution is 5.5, and melt index is 2.8g/10min.
B layer is linear low density polyethylene, and density is 0.915g/cm3, melt index is 2.8g/10min.
A layer and C are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
B layer processes film forming by conventional method.
A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, through being compounded to form composite membrane.Wherein A layer thickness is 43 μm, and B layer is 20 μm, and C layer thickness is 43 μm, and the thickness of X is 2 μm, and overall film thickness is 110 μm.
The performance test results of the film of preparation is listed in table 2.
The results of property of the multilayer complex films of table 2 embodiment 1-4
Claims (28)
1. a multilayer complex films, it includes AXBXC Rotating fields, wherein, A layer and C layer in described Rotating fields include identical or different acrylic polymer independently of one another, B layer includes ethylene-based polymer, acrylic polymer or its combination, X is adhesive layer, and described A layer and C layer include one of following combination:
(1) described A layer is simple tension, and described C layer is biaxial tension；
(2) described A layer is biaxial tension, and described C layer is simple tension；
(3) A layer and C layer are biaxial tension；Or
(4) A layer and C layer are simple tension；
Wherein, the draw ratio of A layer or stretching ratio are different from the draw ratio of C layer or stretching ratio；
For scheme (1), the transverse direction of described A layer is stretched, and described the horizontal and vertical of C layer is all stretched；Or the longitudinal direction of described A layer is stretched, and described the horizontal and vertical of C layer is all stretched；
For scheme (2), described the horizontal and vertical of A layer is stretched, and the transverse direction of described C layer is stretched；Or described the horizontal and vertical of A layer is stretched, and the longitudinal direction of described C layer is stretched；
For scheme (3), the vertically and horizontally draw ratio of described A layer is different from the vertically and horizontally draw ratio of described C layer；
For scheme (4), the stretching ratio of described A layer is different from the stretching ratio of described C layer；Wherein, the transverse direction of described A layer being stretched, and the longitudinal direction of described C layer is stretched, the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described C layer；Or the longitudinal direction of described A layer being stretched, and the transverse direction of described C layer is stretched, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described C layer.
2. multilayer complex films according to claim 1, it is characterised in that in scheme (1), the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described C layer；Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described C layer；
In scheme (2), the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described C layer；Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described C layer.
3. multilayer complex films according to claim 1, it is characterised in that for scheme (3), the longitudinal stretching multiplying power of described A layer is more than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described C layer is more than longitudinal stretching multiplying power.
4. multilayer complex films according to claim 3, it is characterized in that, for scheme (3), the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of described A layer and described C layer is inversely proportional to, and namely the longitudinal stretching of described A layer is equal to the cross directional stretch of described C layer and the ratio of longitudinal stretching with the ratio of cross directional stretch.
5. multilayer complex films according to claim 4, it is characterized in that, for scheme (3), the longitudinal stretching multiplying power of described A layer is same or like with the cross directional stretch multiplying power of described C layer, and the cross directional stretch multiplying power of described A layer is same or like with the longitudinal stretching multiplying power of described C layer.
6. multilayer complex films according to claim 5, it is characterized in that, for scheme (3), the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described C layer, and the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described C layer.
7. multilayer complex films according to claim 1, it is characterised in that A layer in described multilayer complex films or B layer or C layer are single layer structure or multi-layer co-extruded structure.
8. multilayer complex films according to claim 7, it is characterised in that the multi-layer co-extruded structure of described A layer, B layer or C layer is at least 2 layers.
9. multilayer complex films according to claim 8, it is characterised in that the multi-layer co-extruded structure of described A layer, B layer or C layer is 2-15 layer.
10. multilayer complex films according to claim 9, it is characterised in that the multi-layer co-extruded structure of described A layer, B layer or C layer is 3-11 layer.
11. multilayer complex films according to claim 10, it is characterised in that the multi-layer co-extruded structure of described A layer, B layer or C layer is 5-9 layer.
12. multilayer complex films according to claim 11, it is characterised in that the multi-layer co-extruded structure of described A layer, B layer or C layer is 6-8 layer.
13. multilayer complex films according to claim 1, it is characterized in that, the acrylic polymer of described A layer or B layer or C layer is Noblen or propylene copolymer, for isotaxy homopolymer, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the atactic propene copolymer of a small amount of comonomer and the polypropylene blend of ethylene copolymer-modified isotactic polypropylene；Comonomer is ethylene, butylene, hexene or octene.
14. multilayer complex films according to claim 1, it is characterised in that the fusing point of the acrylic polymer of described A layer or B layer or C layer is 148-170 DEG C；Molecular weight distribution is 2-16, and described molecular weight distribution GPC tests；Melt index is 0.5-10g/10min.
15. multilayer complex films according to claim 14, it is characterised in that the fusing point of the acrylic polymer of described A layer or B layer or C layer is 150-167 DEG C；Molecular weight distribution is 4-10；Melt index is 1-8g/10min.
16. multilayer complex films according to claim 15, it is characterised in that the fusing point of the acrylic polymer of described A layer or B layer or C layer is 155 DEG C-165 DEG C.
17. multilayer complex films according to claim 1, it is characterised in that the ethylene-based polymer of described B layer is high density polyethylene (HDPE), high-pressure process low-density polyethylene or low-pressure process linear low density polyethylene.
18. multilayer complex films according to claim 17, it is characterised in that the fusing point of the ethylene-based polymer of described B layer is 130-150 DEG C；Melt index is 0.2-50g/10min.
19. multilayer complex films according to claim 18, it is characterised in that the fusing point of the ethylene-based polymer of described B layer is 135-148 DEG C；Melt index is 1-45g/10min.
20. multilayer complex films according to claim 19, it is characterised in that the melt index of the ethylene-based polymer of described B layer is 2-40g/10min.
21. multilayer complex films according to claim 1, it is characterised in that add another resin in A layer, B layer or C layer, selected from Petropols or hydrogenated petroleum resin；Its addition is 1-30 weight %.
22. multilayer complex films according to claim 21, it is characterised in that described Petropols or hydrogenated petroleum resin are C5-C9Petropols or C5-C9Hydrogenated petroleum resin.
23. the multilayer complex films according to claim 21 or 22, it is characterised in that the addition of described resin is 2-20 weight %.
24. multilayer complex films according to claim 23, it is characterised in that the addition of described resin is 3-15 weight %.
25. multilayer complex films according to claim 24, it is characterised in that the addition of described resin is 4-10 weight %.
26. a preparation method for the multilayer complex films any one of claim 1 to 25, it comprises the following steps:
(1) preparation of A layer and C layer
Being extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, then carry out simple tension under the temperature environment of 130-185 DEG C or biaxial tension processes A layer and C layer, wherein the draw ratio of A layer or stretching ratio are different from C layer；
(2) preparation of B layer
Extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, then process B layer；
(3) using rolling method, with X layer for adhesive, A layer, B layer and C layer are carried out gluing, wherein the outermost two-layer of composite membrane carries out single spreading, and middle each layer carries out double spread, and after gluing, each layer is dried at 40-80 DEG C；
(4) the A layer of gluing, B layer and C layer are carried out lamination compound, obtain described composite membrane.
27. an application for the multilayer complex films any one of claim 1 to 25, it is for bill, marketable securities, Front cover of book and periodical, picture album and packaging material.
28. goods, it is prepared by the multilayer complex films face coat any one of claim 1 to 25 and printing, and described goods include Front cover of book and periodical, picture album, bill, marketable securities and packaging material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310177343.0A CN104149437B (en) | 2013-05-13 | 2013-05-13 | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310177343.0A CN104149437B (en) | 2013-05-13 | 2013-05-13 | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104149437A CN104149437A (en) | 2014-11-19 |
| CN104149437B true CN104149437B (en) | 2016-07-06 |
Family
ID=51875144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310177343.0A Active CN104149437B (en) | 2013-05-13 | 2013-05-13 | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104149437B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111605210A (en) * | 2020-06-01 | 2020-09-01 | 汕头市利农印刷有限公司 | Method for manufacturing multilayer polyethylene packaging material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329981A (en) * | 2001-05-02 | 2002-01-09 | 海南现代企业股份有限公司 | Bidirectionally extensible polypropylene film for cigarettes and its preparing process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4070329B2 (en) * | 1998-10-27 | 2008-04-02 | 株式会社ユポ・コーポレーション | Support and thermal transfer image receptor |
-
2013
- 2013-05-13 CN CN201310177343.0A patent/CN104149437B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329981A (en) * | 2001-05-02 | 2002-01-09 | 海南现代企业股份有限公司 | Bidirectionally extensible polypropylene film for cigarettes and its preparing process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104149437A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104149434B (en) | A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof containing composite tie layer | |
| CN103059763B (en) | Bidirectional stretching polypropylene film for hot binding compounding, and its preparation method | |
| US20140004336A1 (en) | Polyolefin laminate film for cardboard lamination | |
| US20100221528A1 (en) | Extrusion coated article | |
| CN102762373B (en) | Matt polyolefin film having release properties | |
| CN103847199B (en) | A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN107031156B (en) | A kind of multilayer complex films and its preparation method and application having XAYBX structure | |
| CN105774168B (en) | A kind of acrylic polymer ethylene-based polymer multilayer complex films, its preparation method, purposes and its product | |
| CN104149437B (en) | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN104149438B (en) | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN109572124B (en) | Bottomless coating composite film and preparation method thereof | |
| CN103847198B (en) | A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN103847172B (en) | A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN104149435B (en) | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN104149460B (en) | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN104149457B (en) | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN104149436B (en) | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN104149440B (en) | A kind of acrylic polymer-ethylene-based polymer multilayer complex films containing composite tie layer, its preparation method, purposes and goods thereof | |
| CN104149442B (en) | A kind of acrylic polymer containing composite tie layer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof | |
| CN104149461A (en) | Propylene polymer-ethylene polymer multilayer composite membrane containing composite bonding layers as well as preparation method, application and products thereof | |
| CN104149439B (en) | A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof containing composite tie layer | |
| CN104149459A (en) | Propylene polymer- ethene polymer multi-layer composite membrane containing composite binder layers, preparation method therefor, applications thereof and product thereof | |
| MXPA02010159A (en) | Biaxiallly oriented polyolefins with a reduced blocking tendency with respect to cold sealing products. | |
| CN104149458A (en) | Propylene polymer- ethene polymer multi-layer composite membrane, preparation method therefor, applications thereof and product thereof | |
| CN104149443B (en) | A kind of acrylic polymer containing composite tie layer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Dakui Inventor after: Huang Xusheng Inventor after: Zhan Yueqiang Inventor after: Yun Xiaobing Inventor before: Chen Dakui Inventor before: Huang Xusheng Inventor before: Zhan Yueqiang Inventor before: Gu Hanjin Inventor before: Yun Xiaobing |
|
| CB03 | Change of inventor or designer information |