CN104149435B - 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 PDF

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CN104149435B
CN104149435B CN201310176738.9A CN201310176738A CN104149435B CN 104149435 B CN104149435 B CN 104149435B CN 201310176738 A CN201310176738 A CN 201310176738A CN 104149435 B CN104149435 B CN 104149435B
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layer
multiplying power
multilayer complex
complex films
cross directional
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CN104149435A (en
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陈大魁
黄旭生
詹越强
谷汉进
云小兵
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ZHEJIANG ZHONGCHENG PACKING MATERIAL CO Ltd
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ZHEJIANG ZHONGCHENG PACKING MATERIAL CO Ltd
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Abstract

The present invention provides a kind of multilayer complex films, it includes n AXB Rotating fields each other by the X Rotating fields being composited, n is be more than or equal to 2, each A is identical or different, and each B is identical or different, and each X is identical or different, A layer in described Rotating fields includes identical or different acrylic polymer independently of one another, B layer includes identical or different ethylene-based polymer independently of one another, and X is adhesive layer, described A layer be simple tension or biaxial tension.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

A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof
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, to 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 its some ranges of application are constrained.
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 performance 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 a further object 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 n AXB Rotating fields each other by the X Rotating fields being composited, n is be more than or equal to 2, each A is identical or different, and each B is identical or different, and each X is identical or different, A layer in described Rotating fields includes identical or different acrylic polymer independently of one another, B layer includes identical or different ethylene-based polymer independently of one another, and X is adhesive layer, described A layer be simple tension or biaxial tension.
According to the present invention, in described multilayer complex films, n AXB Rotating fields is by X order compound, namely according to the order compound of AXBXAXB.
According to the present invention, in described multilayer complex films, n AXB Rotating fields replaces compound by X, namely according to the order compound of AXBXBXA.
According to the present invention, in described multilayer complex films, n AXB Rotating fields is by the unordered compound of X.
According to the present invention, described Rotating fields also includes one layer of A layer, is compound in the outer layer of outermost B layer by X, it is preferable that its structure is (AXBX)nA, n are be more than or equal to 2;Or the outer layer of outermost A layer it is compound in by X, it is preferable that its structure is A (XAXB)n, n is be more than or equal to 2.
According to the present invention, described Rotating fields also includes one layer of B layer, is compound in the outer layer of outermost B layer by X, it is preferable that its structure is (AXBX)nB, n are be more than or equal to 2;Or the outer layer of outermost A layer it is compound in by X, it is preferable that its structure is B (XAXB)n, n is be more than or equal to 2.
According to the present invention, the A layer in above-mentioned multilayer complex films is single layer structure or multi-layer co-extruded structure.
According to the present invention, the B layer in above-mentioned multilayer complex films is single layer structure or multi-layer co-extruded structure.
According to the present invention, the multi-layer co-extruded structure of described A layer or B 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, described B layer be do not stretch or simple tension or biaxial tension.
In accordance with the present invention it is preferred that, when described B layer is biaxial tension, its cross directional stretch multiplying power is same or like with longitudinal stretching multiplying power, and the cross directional stretch multiplying power of A layer is same or like with longitudinal stretching multiplying power.
In accordance with the present invention it is preferred that, when described B layer is not stretch, cross directional stretch multiplying power and the longitudinal stretching multiplying power of described A layer are same or like.
In accordance with the present invention it is preferred that, when described B layer be do not stretch and when n is even number, described A layer combines in pairs, and the longitudinal stretching multiplying power of one of them A layer is more than cross directional stretch multiplying power, and the longitudinal stretching multiplying power of another A layer is less than cross directional stretch multiplying power;It is highly preferred that the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of one A layer and another A layer is inversely proportional to, namely the longitudinal stretching of one A layer is equal to the cross directional stretch of another A 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 one A layer is same or like with the cross directional stretch multiplying power of another A layer, and the cross directional stretch multiplying power of one A layer is same or like with the longitudinal stretching multiplying power of another A layer;It is more preferred still that the longitudinal stretching multiplying power of one A layer is identical with the cross directional stretch multiplying power of another A layer, and the cross directional stretch multiplying power of one A layer is identical with the longitudinal stretching multiplying power of another A layer.
According to the present invention, preferably, when described B layer be do not stretch and when n is odd number, described A layer after combining in pairs remaining A layer individually combine, in wherein paired two-layer, the longitudinal stretching multiplying power of an A layer is more than cross directional stretch multiplying power, the longitudinal stretching multiplying power of another A layer is less than cross directional stretch multiplying power, and cross directional stretch multiplying power and the longitudinal stretching multiplying power of the A layer individually combined are same or like;More preferably, in wherein paired two-layer, the vertically and horizontally draw ratio of an A layer and the vertically and horizontally draw ratio of another A layer are inversely proportional to, namely the longitudinal stretching of one A layer is equal to the cross directional stretch of another A layer and the ratio of longitudinal stretching with the ratio of cross directional stretch, and cross directional stretch multiplying power and the longitudinal stretching multiplying power of the A layer individually combined are same or like;More preferably, in wherein paired two-layer, the longitudinal stretching multiplying power of an A layer and the cross directional stretch multiplying power of another A layer are same or like, and the cross directional stretch multiplying power of one A layer is same or like with the longitudinal stretching multiplying power of another A layer, cross directional stretch multiplying power and the longitudinal stretching multiplying power of the A layer individually combined are same or like;Even more preferably from ground, in wherein paired two-layer, the longitudinal stretching multiplying power of an A layer and the cross directional stretch multiplying power of another A layer are identical, and the cross directional stretch multiplying power of one A layer is identical with the longitudinal stretching multiplying power of another A layer, cross directional stretch multiplying power and the longitudinal stretching multiplying power of the A layer individually combined are same or like.
According to the present invention, when n is even number, between B layer, include one of following combination between two:
(1 ') two B layers are simple tension, and stretching ratio is identical, it is preferable that the cross directional stretch multiplying power of a B layer is identical with the longitudinal stretching multiplying power of another B layer;
(2 ') B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension is identical with a stretching ratio (cross directional stretch multiplying power or longitudinal stretching multiplying power) of biaxial tension;Or
(3 ') two B layers are biaxial tension, and the draw ratio of the two is identical.
When n is odd number, between B layer, include one of following combination between two:
(1 ') two B layers are simple tension, and stretching ratio is identical;
(2 ') B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension is identical with a stretching ratio (cross directional stretch multiplying power or longitudinal stretching multiplying power) of biaxial tension;Or
(3 ') two B layers are biaxial tension, and the draw ratio of the two is identical;
The draw ratio of remaining B layer or stretching ratio are then identical or different with the draw ratio of the above-mentioned layer of B between two or stretching ratio.
According to the present invention, under above-mentioned B layer restrictive condition, it is preferable that the draw ratio of A layer or stretching ratio are different from the draw ratio of B layer or stretching ratio.Preferably, the draw ratio of each A layer or stretching ratio are different.Preferably, the draw ratio of each B layer or stretching ratio are different.Preferably, described A layer and B layer include one of following combination:
(1) described A layer is simple tension, and described B layer is simple tension;
(2) described A layer is simple tension, and described B layer is biaxial tension;
(3) described A layer is biaxial tension, and described B layer is simple tension;
(4) described A layer is biaxial tension, and described B layer is biaxial tension.
According to the present invention, for scheme (1).Including following scheme:
The transverse direction of described A layer is stretched, the transverse direction of described B layer is stretched;Or
The transverse direction of described A layer is stretched, the longitudinal direction of described B layer is stretched;Or
The longitudinal direction of described A layer is stretched, the transverse direction of described B layer is stretched;Or
The longitudinal direction of described A layer is stretched, the longitudinal direction of described B 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 B layer;Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer.
According to the present invention, for scheme (2).Including following scheme:
The transverse direction of described A layer is stretched, described the horizontal and vertical of B layer is stretched;Or
The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B 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 B layer;Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer.
According to the present invention, for scheme (3).Including following scheme:
Described the horizontal and vertical of A layer is all stretched, the transverse direction of described B layer is stretched;Or
Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B 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 B layer;Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer.
According to the present invention, for scheme (4).Including following scheme:
Described the horizontal and vertical of A layer is all stretched, described the horizontal and vertical of B 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 B layer;Or, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B 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 each A layer or B 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 preferable that 1-6 μm, more preferably 2-5 μm.
According to the present invention, in above-mentioned 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, 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 B 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 B layer in described multilayer complex films is 1-12.5 times, and longitudinal stretching multiplying power is 1-12.5 times, it is preferable that cross directional stretch multiplying power is 2-10 times, and longitudinal stretching multiplying power is 2-10 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, the acrylic polymer of described A layer 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 the acrylic polymer of described A layer 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, the ethylene-based polymer of described B layer 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 or B 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 above-mentioned multilayer complex films, it comprises the following steps:
(1) preparation of A layer
Extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, then under the temperature environment of 130-185 ° of C, carry out simple tension or biaxial tension processes A layer;
(2) preparation of B layer
Extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, optional do not stretch or simple tension or biaxial tension process B layer;
(3) using rolling method, with X layer for adhesive, each A layer and B 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 and B layer are carried out lamination compound, obtain described composite membrane.
According to the present invention, A layer and/or the two-sided of B layer of step (1) and (2) gained both pass through sided corona treatment so that it is initial surface tension reaches more than 44 dyne.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 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.
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 and B layer]
According to the present invention, described A layer mainly includes acrylic polymer.Described acrylic polymer is preferably Noblen or propylene copolymer or polypropene composition;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, and 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 according to ASTMD-1238 test melt index (MI) can be about 0.2-20g/10min, it is preferable that 0.5-15g/10min, fusing point can be about between 155 ° of C-165 ° of C.
The polymer of described A 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 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.
According to the present invention, described B layer mainly includes ethylene-based polymer, and described ethylene-based polymer 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.
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 or B 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 and B 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 and B 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, electric wire curing type 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 propylene 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 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 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 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 the A 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
Employing does not stretch or prepared by the method for simple tension or biaxial tension, if simple tension or biaxial tension, identical with step (1).
(3) using rolling method, with X for adhesive, each A layer and B 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 and B 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, A layer and/or the two-sided of B layer of step (1) and step (2) 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.
[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 embodiment 1 preparation, and it is AXBXAXB structure.
Fig. 2 is the structural representation of the composite membrane of embodiment 1 preparation, and it is AXBXBXA structure.
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:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 19 μm/2 μm/19 μm/2 μm/19 μm/2 μm/19 μm.
A layer all uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 96.2%.
B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer and B layer all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.
Said two A layer is each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 times, and thickness is 19 μm.
Said two B layer is each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 times, and thickness is 19 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, structure is AXBXAXB structure or AXBXBXA structure, wherein, the thickness of X layer is 2 μm, and overall film thickness is 82 μm.The mechanical property of thin film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure is listed in table 2.
Embodiment 2:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 28 μm/2 μm/28 μm/2 μm/28 μm/2 μm/28 μm.
A layer all uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
Said two A layer is each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 12.5 times, and longitudinal stretching multiplying power is 12.5 times, and thickness is 28 μm.
Said two B layer is each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 12.5 times, and longitudinal stretching multiplying power is 12.5 times, and thickness is 28 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating chlorinated polypropylene, and then through being compounded to form composite membrane, structure is AXBXAXB structure or AXBXBXA structure, and overall film thickness is 118 μm.The mechanical property of thin film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure is listed in table 2.
Embodiment 3:AXBXAXBXA structure,
Layer thickness profile: 9 μm/1 μm/14 μm/1 μm/9 μm/1 μm/14 μm/1 μm/9 μm.
A layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is Low Density Polyethylene, and density is 0.916g/cm3, melt index is 2.8g/10min.
A layer and B layer all add Petropols respectively, and Petropols addition is 30% weight of each layer gross weight.
Described three A layers are each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 6 times, and thickness is 9 μm.
Said two B layer is each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 6 times, and thickness is 14 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating polyurethane, and then through being compounded to form composite membrane, structure is AXBXAXBXA, and wherein, the thickness of X layer is 1 μm, and overall film thickness is 59 μm.Test data such as table 2 of thin film.
Embodiment 4:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 17 μm/2 μm/17 μm/2 μm/17 μm/2 μm/17 μm
A layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is Low Density Polyethylene, and density is 0.916g/cm3, melt index is 2.8g/10min.
Said two A layer is processed each through plain film method stretch processes, and wherein longitudinal stretching multiplying power and cross directional stretch multiplying power are 8 times, and thickness is 17 μm.
Said two B layer is processed each through plain film method stretch processes, and wherein cross directional stretch multiplying power and longitudinal stretching multiplying power are 8 times, and thickness is 17 μm.
A layer and B layer are respectively through sided corona treatment, initial surface tension is 40 dynes per centimeter, then adopt roll coating model coating polyurethane, it is compounded to form composite membrane then through hot pressing, structure is AXBXAXB structure or AXBXBXA structure, and wherein, the thickness of X layer is 2 μm, overall film thickness is 74 μm, and wherein the performance test data of the film of AXBXAXB structure is listed in table 3.
Embodiment 5:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 28 μm/2 μm/28 μm/2 μm/28 μm/2 μm/28 μm.
A layer is Noblen, and molecular weight distribution is 5.5, and melt index is 2.9g/10min, and isotacticity is 96.2%.B layer is Low Density Polyethylene, and density is 0.916g/cm3, melt index is 2.8g/10min.
A layer and B layer all add Petropols respectively, and Petropols addition is 1% weight of each layer gross weight.
Said two A layer is each through the substep stretch processes processing of periosteum method, and wherein cross directional stretch multiplying power is 7 times, and longitudinal stretching multiplying power is 7 times, and thickness is 14 μm.
Said two B layer is each through the substep stretch processes processing of periosteum method, and wherein cross directional stretch multiplying power is 7 times, and longitudinal stretching multiplying power is 7 times, and thickness is 9 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 42 dynes per centimeter, then adopt the acid of roll coating model painting polypropylene, then through being compounded to form composite membrane, structure is AXBXAXB structure or AXBXBXA structure, wherein, the thickness of X layer is 2 μm, and overall film thickness is 118 μm.Wherein the performance test data of the film of AXBXAXB structure is listed in table 3.
Embodiment 6:BXAXBXAXB product structure,
Layer thickness profile: 9 μm/1 μm/14 μm/1 μm/9 μm/1 μm/14 μm/1 μm/9 μm.
A layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is linear low density polyethylene (LLDPE), and density is 0.915g/cm3, melt index is 2.8g/10min.
A layer and B layer all add hydrogenated petroleum resin respectively, and hydrogenated petroleum resin addition is 20% weight of each layer gross weight.
Said two A layer is each through the substep stretch processes processing of periosteum method, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times, and thickness is 14 μm.
Described three B layers are each through the substep stretch processes processing of periosteum method, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times, and thickness is 9 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating polyurethane, then through being compounded to form composite membrane, structure is BXAXBXAXB, wherein, the thickness of X layer is 1 μm, and overall film thickness is 59 μm, and the performance test data of film is listed in table 3.
Embodiment 7:
A layer uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
B layer uses linear low density polyethylene (LLDPE) to process, and density is 0.915g/cm3, melt index is 2.8g/10min.
A layer and B layer all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.
Described four A layers are each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 times, and thickness is 10 μm.
Described four B layers are each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 times, and thickness is 10 μm.
A layer and B layer are respectively through sided corona treatment, initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating chlorinated polypropylene, it is compounded to form composite membrane then through 4 AXB Rotating fields, wherein, the thickness of X layer is 1 μm, and structure is AXBXAXBXAXBXAXB structure (sequential organization) or AXBXBXAXAXBXBXA structure (alternating structure) or AXBXBXAXBXAXBXA structure (disordered structure), and overall film thickness is 87 μm.The mechanical property of thin film prepared by several Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXBXAXBXAXB structure is listed in table 4.
Embodiment 8:
A layer all uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
Described four A layers are each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 1.1 times, and longitudinal stretching multiplying power is 1.1 times, and thickness is 12 μm.
Described four B layers are each through the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 1.1 times, and longitudinal stretching multiplying power is 1.1 times, and thickness is 12 μm.
A layer and B layer are respectively through sided corona treatment, initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating chlorinated polypropylene, it is compounded to form composite membrane then through 4 AXB Rotating fields, wherein, the thickness of X layer is 1 μm, and structure is AXBXAXBXAXBXAXB structure (sequential organization) or AXBXBXAXAXBXBXA structure (alternating structure) or AXBXBXAXBXAXBXA structure (disordered structure), and overall film thickness is 103 μm.The mechanical property of thin film prepared by several Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXBXAXBXAXB structure is listed in table 4.
Embodiment 9:AXBXAXB structure
Layer thickness profile: 19 μm/2 μm/15 μm/2 μm/19 μm/2 μm/15 μm, or AXBXBXA structure, layer thickness profile: 19 μm/2 μm/15 μm/2 μm/15 μm/2 μm/19 μm
A layer all uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 96.2%.
B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer and B layer all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.
One A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 5 times, and thickness is 19 μm.
Another A layer described is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 9 times, and thickness is 19 μm.
Said two B layer is processed into, each through conventional method, the film that thickness is 15 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, structure is AXBXAXB structure or AXBXBXA structure, wherein, the thickness of X layer is 2 μm, and overall film thickness is 74 μm.The mechanical property of thin film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure is listed in table 4.
Embodiment 10:AXBXAXB structure, layer thickness profile: 28 μm/2 μm/25 μm/2 μm/28 μm/2 μm/25 μm, or AXBXBXA structure, layer thickness profile: 28 μm/2 μm/25 μm/2 μm/25 μm/2 μm/28 μm
A layer all uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
B layer all uses Low Density Polyethylene to process, and density is 0.916g/cm3, melt index is 2.8g/10min.
One A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 12.5 times, and longitudinal stretching multiplying power is 1.1 times, and thickness is 28 μm.
Another A layer described passes through plain film method simple tension processes, and wherein cross directional stretch multiplying power is 1.1 times, and longitudinal stretching multiplying power is 12.5 times, and thickness is 28 μm.
Said two B layer is processed into, each through conventional method, the film that thickness is 25 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating chlorinated polypropylene, and then through being compounded to form composite membrane, structure is AXBXAXB structure or AXBXBXA structure, and overall film thickness is 112 μm.The mechanical property of thin film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure is listed in table 4.
Embodiment 11:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 19 μm/2 μm/19 μm/2 μm/19 μm/2 μm/19 μm.
A layer all uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 96.2%.
B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer and B layer all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.
One A layer is by the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 5 times, and thickness is 19 μm.
Another A layer described is by the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 9 times, and thickness is 19 μm.
Said two B layer is processed into, by conventional method, the film that thickness is 19 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, structure is AXBXAXB structure or AXBXBXA structure, wherein, the thickness of X layer is 2 μm, and overall film thickness is 82 μm.The mechanical property of thin film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure is listed in table 5.
Embodiment 12:AXBXAXBXA structure,
Layer thickness profile: 9 μm/1 μm/14 μm/1 μm/9 μm/1 μm/14 μm/1 μm/9 μm.
A layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is Low Density Polyethylene, and density is 0.916g/cm3, melt index is 2.8g/10min.
A layer and B layer all add Petropols respectively, and Petropols addition is 30% weight of each layer gross weight.
Two, described outside A layer is each through the substep stretch processes processing of plain film method, and the cross directional stretch multiplying power of one of them A layer is 6 times, and longitudinal stretching multiplying power is 3 times, and thickness is 9 μm;The cross directional stretch multiplying power of another A layer is 3 times, and longitudinal stretching multiplying power is 6 times, and thickness is 9 μm.
One A layer at described center is by the substep stretch processes processing of plain film method, and wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 6 times, and thickness is 9 μm.
Said two B layer is processed into, by conventional method, the film that thickness is 14 μm.
A layer and B layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then adopt roll coating model coating polyurethane, and then through being compounded to form composite membrane, structure is AXBXAXBXA, and wherein, the thickness of X layer is 1 μm, and overall film thickness is 59 μm.Test data such as table 5 of thin film.
Embodiment 13:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 17 μm/2 μm/17 μm/2 μm/17 μm/2 μm/17 μm
A layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is Low Density Polyethylene, and density is 0.916g/cm3, melt index is 2.8g/10min.
One A layer is by the processing of plain film method stretch processes, and wherein longitudinal stretching multiplying power is 11 times, and cross directional stretch multiplying power is 4, and thickness is 17 μm.
Another A layer described is by the processing of plain film method stretch processes, and wherein longitudinal stretching multiplying power is 4 times, and cross directional stretch multiplying power is 11, and thickness is 17 μm.
Said two B layer is processed into, by conventional method, the film that thickness is 17 μm.
A layer and B layer are respectively through sided corona treatment, initial surface tension is 40 dynes per centimeter, then adopt roll coating model coating polyurethane, it is compounded to form composite membrane then through hot pressing, structure is AXBXAXB structure or AXBXBXA structure, and wherein, the thickness of X layer is 2 μm, overall film thickness is 74 μm, and wherein the performance test data of the film of AXBXAXB structure is listed in table 5.
The results of property of table 2 multilayer complex films
The results of property of table 3 multilayer complex films
The results of property of table 4 multilayer complex films
The results of property of table 5 multilayer complex films

Claims (27)

1. a multilayer complex films, it includes n AXB Rotating fields each other by the X Rotating fields being composited, n is be more than or equal to 2, each A is identical or different, and each B is identical or different, and each X is identical or different, A layer in described Rotating fields includes identical or different acrylic polymer independently of one another, B layer includes identical or different ethylene-based polymer independently of one another, and X is adhesive layer, described A layer be simple tension or biaxial tension;
Described B layer be do not stretch or simple tension or biaxial tension;
And,
I (), when described B layer is not stretch, the cross directional stretch multiplying power of described A layer is identical with longitudinal stretching multiplying power;Or,
(ii) when described B layer be do not stretch and when n is even number, described A layer combines in pairs, and the longitudinal stretching multiplying power of one of them A layer is more than cross directional stretch multiplying power, and the longitudinal stretching multiplying power of another A layer is less than cross directional stretch multiplying power;Or,
(iii) when described B layer be do not stretch and when n is odd number, described A layer after combining in pairs remaining A layer individually combine, in wherein paired two-layer, the longitudinal stretching multiplying power of an A layer is more than cross directional stretch multiplying power, the longitudinal stretching multiplying power of another A layer is less than cross directional stretch multiplying power, and individually the cross directional stretch multiplying power of the A layer of combination is identical with longitudinal stretching multiplying power;
(iv) when described B layer is simple tension or biaxial tension, the draw ratio of A layer or stretching ratio are different from the draw ratio of B layer or stretching ratio.
2. multilayer complex films according to claim 1, it is characterised in that
When n is even number, between B layer, include one of following combination between two:
(1 ') two B layers are simple tension, and stretching ratio is identical;
(2 ') B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension is identical with biaxial tension stretching ratio, and a stretching ratio of described biaxial tension refers to cross directional stretch multiplying power or longitudinal stretching multiplying power;Or
(3 ') two B layers are biaxial tension, and the draw ratio of the two is identical;
When n is odd number, between B layer, include one of following combination between two:
(1 ") two B layers are simple tension, and stretching ratio is identical;
(2 ") B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension is identical with in the cross directional stretch multiplying power of biaxial tension or longitudinal stretching multiplying power;Or
(3 ") two B layers are biaxial tension, and the draw ratio of the two is identical;
The draw ratio of remaining B layer or stretching ratio are then identical or different with the draw ratio of the above-mentioned layer of B between two or stretching ratio.
3. multilayer complex films according to claim 1, it is characterized in that, (ii) in, the vertically and horizontally draw ratio of one A layer and the vertically and horizontally draw ratio of another A layer are inversely proportional to, and namely the longitudinal stretching of one A layer is equal to the cross directional stretch of another A layer and the ratio of longitudinal stretching with the ratio of cross directional stretch.
4. multilayer complex films according to claim 1, it is characterized in that, (iii) in, in paired two-layer, the vertically and horizontally draw ratio of an A layer and the vertically and horizontally draw ratio of another A layer are inversely proportional to, namely the longitudinal stretching of one A layer is equal to the cross directional stretch of another A layer and the ratio of longitudinal stretching with the ratio of cross directional stretch, and individually the cross directional stretch multiplying power of the A layer of combination is identical with longitudinal stretching multiplying power.
5. multilayer complex films according to claim 1, it is characterised in that in (iv), described A layer and B layer include one of following combination:
(1) described A layer is simple tension, and described B layer is simple tension;
(2) described A layer is simple tension, and described B layer is biaxial tension;
(3) described A layer is biaxial tension, and described B layer is simple tension;
(4) described A layer is biaxial tension, and described B layer is biaxial tension;
For scheme (1), including following scheme:
The transverse direction of described A layer is stretched, the transverse direction of described B layer is stretched;Or
The transverse direction of described A layer is stretched, the longitudinal direction of described B layer is stretched;Or
The longitudinal direction of described A layer is stretched, the transverse direction of described B layer is stretched;Or
The longitudinal direction of described A layer is stretched, the longitudinal direction of described B layer is stretched;
For scheme (2), including following scheme:
The transverse direction of described A layer is stretched, described the horizontal and vertical of B layer is stretched;Or
The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B layer is stretched;
For scheme (3), including following scheme:
Described the horizontal and vertical of A layer is all stretched, the transverse direction of described B layer is stretched;Or
Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B layer is stretched;
For scheme (4), including following scheme:
Described the horizontal and vertical of A layer is all stretched, described the horizontal and vertical of B layer is stretched.
6. multilayer complex films according to claim 5, it is characterised in that for scheme (1), the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer;Or, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer.
7. multilayer complex films according to claim 5, it is characterised in that for scheme (2), the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer;Or, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer.
8. multilayer complex films according to claim 5, it is characterised in that for scheme (3), the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer;Or, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer.
9. multilayer complex films according to claim 5, it is characterised in that for scheme (4), the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer;Or, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer.
10. multilayer complex films according to claim 1, it is characterised in that in described multilayer complex films, n AXB Rotating fields is by X order compound, namely according to the order compound of AXBXAXB;Or, in described multilayer complex films, n AXB Rotating fields replaces compound by X, namely according to the order compound of AXBXBXA;Or, in described multilayer complex films, n AXB Rotating fields is by the unordered compound of X.
11. multilayer complex films according to claim 1, it is characterised in that described Rotating fields also includes one layer of A layer, it is compound in the outer layer of outermost B layer by X;Or the outer layer of outermost A layer it is compound in by X;Or, described Rotating fields also includes one layer of B layer, is compound in the outer layer of outermost B layer by X;Or the outer layer of outermost A layer it is compound in by X.
12. multilayer complex films according to claim 11, it is characterised in that described Rotating fields also includes one layer of A layer, being compound in the outer layer of outermost B layer by X, its structure is (AXBX)nA, n are be more than or equal to 2;Or the outer layer of outermost A layer it is compound in by X, its structure is A (XAXB)n, n is be more than or equal to 2;Or, described Rotating fields also includes one layer of B layer, is compound in the outer layer of outermost B layer by X, and its structure is (AXBX)nB, n are be more than or equal to 2;Or the outer layer of outermost A layer it is compound in by X, its structure is B (XAXB)n, n is be more than or equal to 2.
13. multilayer complex films according to claim 1, it is characterised in that the acrylic polymer of described A layer is Noblen or propylene copolymer, described Noblen is isotaxy homopolymer;Or the acrylic polymer of described A layer 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;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.
14. multilayer complex films according to claim 13, it is characterised in that described comonomer is ethylene, butylene, hexene or octene.
15. multilayer complex films according to claim 13, it is characterised in that the fusing point of the acrylic polymer of described A layer is 148 to 170 DEG C;Molecular weight distribution is 2-16, and described molecular weight distribution GPC tests;Melt index is 0.5-10g/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 is 150-167 DEG C;Molecular weight distribution is 4-10;Melt index is 1-8g/10min.
17. multilayer complex films according to claim 16, it is characterised in that the fusing point of the acrylic polymer of described A layer is 155 DEG C-165 DEG C.
18. multilayer complex films according to claim 1, it is characterised in that add another resin in A layer or B layer, selected from Petropols or hydrogenated petroleum resin;Its addition is the 1-30% weight of each layer gross weight.
19. multilayer complex films according to claim 18, it is characterised in that described Petropols or hydrogenated petroleum resin are C5-C9Petropols or C5-C9Hydrogenated petroleum resin.
20. the multilayer complex films according to claim 18 or 19, it is characterised in that the addition of described resin is the 2-20% weight of each layer gross weight.
21. multilayer complex films according to claim 20, it is characterised in that the addition of described resin is the 3-15% weight of each layer gross weight.
22. multilayer complex films according to claim 21, it is characterised in that the addition of described resin is the 4-10% weight of each layer gross weight.
23. multilayer complex films according to claim 2, it is characterised in that in (1 '), two B layers are simple tension, one B layer is cross directional stretch, and a B layer is longitudinal stretching, and the cross directional stretch multiplying power of a B layer is identical with the longitudinal stretching multiplying power of another B layer.
24. a preparation method for the multilayer complex films any one of claim 1 to 23, it comprises the following steps:
(1) preparation of A layer
Extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, then under the temperature environment of 130-185 DEG C, carry out simple tension or biaxial tension processes A layer;
(2) preparation of B layer
Extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, optional do not stretch or or simple tension or biaxial tension process B layer;
(3) using rolling method, with X layer for adhesive, each A layer and B 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 at 40-80 DEG C;
(4) the A layer of gluing and B layer are carried out lamination compound, obtain described composite membrane.
25. an application for the multilayer complex films any one of claim 1 to 23, it is for bill, marketable securities, leaflet and packaging material.
26. goods, it is prepared by face coat and the printing of the multilayer complex films any one of claim 1 to 23, and described goods include leaflet, bill, marketable securities and packaging material.
27. goods according to claim 26, it is characterised in that described leaflet is selected from Front cover of book and periodical or picture album.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
EP1142701A1 (en) * 1998-10-27 2001-10-10 Yupo Corporation Support and thermal transfer image receptor
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
CN1522201A (en) * 2001-05-02 2004-08-18 美国杜邦泰津胶片合伙人有限公司 Multilayer polymeric films

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1142701A1 (en) * 1998-10-27 2001-10-10 Yupo Corporation Support and thermal transfer image receptor
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
CN1522201A (en) * 2001-05-02 2004-08-18 美国杜邦泰津胶片合伙人有限公司 Multilayer polymeric films

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Inventor after: Chen Dakui

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