CN103847172B - A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof - Google Patents
A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof Download PDFInfo
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- CN103847172B CN103847172B CN201210525458.XA CN201210525458A CN103847172B CN 103847172 B CN103847172 B CN 103847172B CN 201210525458 A CN201210525458 A CN 201210525458A CN 103847172 B CN103847172 B CN 103847172B
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Landscapes
- Laminated Bodies (AREA)
Abstract
The invention provides a kind of multilayer complex films, it comprises n AXB Rotating fields each other by Rotating fields that X is composited, n is 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 and B layer comprise identical or different acrylic polymer independently of one another, X is adhesive layer, and described A layer is simple tension or biaxial tension, and described B layer is simple tension or biaxial tension.The present invention also provides the preparation method of above-mentioned multilayer complex films, its purposes and comprises the goods of this multilayer complex films.Acrylic polymer multilayer complex films of the present invention 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 multilayer complex films, its preparation method, purposes and comprise the goods of this composite membrane, belong to field of compound material.
Background technology
The characteristics such as Biaxially oriented polypropylene (BOPP) film effectively utilizes its excellent light weight, the transparency, mechanical strength, nontoxic, moistureproof, gas permeability is low, rigidity, for taking packaging material as the wide spectrum of representative.Such as be widely used in packaging and the lamination compound of the products such as food, medicine, daily light industry, cigarette.A kind of purposes of BOPP film fits in paper surface, and as books, packing carton etc., play a part moistureproof and increase surface gloss.
BOPP film is generally the coextrusion structure of 3-5 layer, and step drawing production technology forms primarily of following operation: batching batch mixing, extruder are extruded, extruded by T-shaped die head sheet, sheet chilling, sheet by warm-up mill preheating, sheet longitudinal stretching, thermal finalization, again preheating, cross directional stretch, thermal finalization, cooling, sided corona treatment, rolling, cut and put in storage.A kind of Biaxially stretched multilayer polypropylene film is disclosed in CN101160209A (Oji Paper), 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, possess the superficial layer containing acrylic polymer and back layer, the acrylic polymer in the acrylic polymer in described substrate layer and surface/back layer can be identical or different.It by adding inorganic compound powder in substrate layer, obtain even hidden power and whiteness excellent, the preferred thickness that almost do not have concave-convex surface is the film of 25-55 μm.Described film obtains by the following method: the acrylic polymer forming substrate layer is obtained multi-layer sheet by itself known method co-extrusion modling, adopts the biaxially oriented film such as biaxial tension method or biaxial tension method in turn forming method be simultaneously stretched to face multiplying power (longitudinal × horizontal) 45 ~ 65 times and obtain.To adopt biaxial tension method in turn, after stretching with the scope of 4.5 ~ 7.5 times at the temperature of longitudinal 70 ~ 140 DEG C, then after face multiplying power (longitudinally × laterally) 45 ~ 65 times stretches, to obtain at the temperature range heat fixations of 110 ~ 180 DEG C under 7 ~ 12 times under the horizontal temperature range of 120 ~ 190 DEG C.
BOPP film has many desirable performances, as high tensile, and high-stiffness, the high grade of transparency etc.But the life cycle of BOPP film is short, be generally some months by 1 year, some physical properties are as poor in resistance to low temperature, fall strength of briquette, tearing strength etc., are not suitable for the printed matter of Long-Time Service, packaging material etc.In addition, the thickness of existing bidirectional stretching polypropylene film is generally less than 50 μm, and its deflection can not meet high-end demand, therefore constrains its some ranges of application.
At present, industrial quarters, in the application that some are high to physical property requirements, generally uses biaxial stretching polyester (BOPET) film or biaxial tension nylon (BOPA) film.But BOPET film and BOPA film are than great, and cost is high, and solvent resistance is poor.
Therefore, industrial quarters need a kind of there is traditional B OPP film high transparent and high-stiffness but there is the novel thin film of resistance to low temperature, high-tear strength simultaneously.
Summary of the invention
The present invention, for overcoming the deficiencies in the prior art, provides a kind of acrylic polymer multilayer complex films, has the performances such as high-stiffness, high transparent, low temperature resistant and high-tear strength.
Another object of the present invention is to provide the preparation method of above-mentioned multilayer complex films.
Another object of the present invention is to provide the purposes of above-mentioned multilayer complex films.
Another object of the present invention is to provide the goods comprising above-mentioned multilayer complex films.
The present invention is achieved through the following technical solutions:
A kind of multilayer complex films, it comprises n AXB Rotating fields each other by Rotating fields that X is composited, n is 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 and B layer comprise identical or different acrylic polymer independently of one another, X is adhesive layer, and described A layer is simple tension or biaxial tension, and described B layer is 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, in described multilayer complex films, the acrylic polymer of A layer is identical with the acrylic polymer of B layer.
According to the present invention, described Rotating fields also comprises one deck A layer, is compound in the skin of outermost B layer by X, and preferably its structure is (AXBX)
na, n are more than or equal to 2; Or the skin of outermost A layer is compound in by X, preferably its structure is A (XAXB)
n, n is more than or equal to 2.
According to the present invention, described Rotating fields also comprises one deck B layer, is compound in the skin of outermost B layer by X, and preferably its structure is (AXBX)
nb, n are more than or equal to 2; Or the skin of outermost A layer is compound in by X, preferably its structure is B (XAXB)
n, n is more than or equal to 2.
According to the present invention, the A layer in described multilayer complex films is 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, the multi-layer co-extruded structure of described A layer or B layer is at least 2 layers, such as, be 2-15 layer, preferred 3-11 layer, more preferably 5-9 layer, also more preferably 6-8 layer.
According to the present invention, preferably, the draw ratio of the draw ratio of A layer or stretching ratio and B layer or stretching ratio different.Preferably, the draw ratio of each A layer or stretching ratio different.Preferably, the draw ratio of each B layer or stretching ratio different.Preferably, described A layer and B layer comprise one of following combination:
(1) described A layer is simple tension, and described B layer is biaxial tension;
(2) described A layer is biaxial tension, and described B layer is simple tension;
(3) A layer and B layer are biaxial tension; Or
(4) A layer and B layer are simple tension.
According to the present invention, for scheme (1).The transverse direction of described A layer is stretched, and described the horizontal and vertical of B layer is all stretched; Or the longitudinal direction of described A layer is stretched, and described the horizontal and vertical of B layer is all stretched.More preferably, 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).Described the horizontal and vertical of A layer is stretched, and the transverse direction of described B layer is stretched; Or described the horizontal and vertical of A layer is stretched, and the longitudinal direction of described B layer is stretched.More preferably, 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).Different to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer; Preferably, the longitudinal stretching multiplying power of described A layer is greater than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described B layer is greater than longitudinal stretching multiplying power; More preferably, being inversely proportional to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer, namely the described longitudinal stretching of A layer and the ratio of cross directional stretch equal the described cross directional stretch of B layer and the ratio of longitudinal stretching.More preferably, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described B layer; Also more preferably, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer.
According to the present invention, for scheme (4).The stretching ratio of described A layer is different from the stretching ratio of described B layer; Preferably, the stretching ratio of described A layer is greater than the stretching ratio of described B layer, or the stretching ratio of described A layer is less than the stretching ratio of described B 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 B layer is stretched; Or the longitudinal direction of described A layer is stretched, and the transverse direction of described B layer is stretched.More preferably, 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: be 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 obtained.The mass content of chlorine is 20%-70%, and fusing point is less than 150 DEG 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 contain 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, preferred 60-120 μm, more preferably 70-100 μm, also more preferably 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, preferred 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, preferred 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 no more than 30% of this composite film thickness, preferably more than 20%, more preferably no more than 15%, also 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, preferred 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, preferred 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, and preferred 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 1-6 times, and longitudinal stretching multiplying power is 7-12.5 times, and preferred 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 transverse direction of the A layer in described multilayer complex films or the stretching ratio of longitudinal direction be 1-12.5 doubly, preferred cross directional stretch multiplying power be 7-12.5 doubly or longitudinal stretching multiplying power be 1-6 doubly; The vertical or horizontal stretching ratio of B layer be 1-12.5 doubly, preferred longitudinal stretching multiplying power be 7-12.5 doubly or cross directional stretch multiplying power be 1-6 doubly.
According to the present invention, in the tensile strength of described multilayer complex films, deflection and tear-resistant intensity, horizontal and vertical test value ratio is 0.7:1.0 to 1.0:1.3.
The vertical transverse tensile strength of described multilayer complex films is greater than 100MPa, is preferably greater than 120MPa, more preferably greater than 140MPa.
According to the present invention, the acrylic polymer of described A layer or B layer is preferably Noblen or propylene copolymer, typically be isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the polypropylene blend of the atactic propene copolymer of a small amount of comonomer and ethylene copolymer-modified isotactic polypropylene.Comonomer is ethene or higher alpha-olefin, as ethene, butylene, hexene or octene etc.
According to the present invention, the fusing point of the acrylic polymer of described A layer or B layer is 148 to 170 DEG C, preferred 150-167 DEG C; More preferably 155 DEG C-165 DEG C; Molecular weight distribution (GPC test) is 2-16, is preferably 4-10; Melt index is 0.5-10g/10min, preferred 1-8g/10min.
According to the present invention, in A layer or B layer, also can add another resin again, as Petropols or hydrogenated petroleum resin, to change the performances such as such as heat sealer, gas permeability, deflection and intensity, be preferably C
5-C
9petropols or C
5-C
9hydrogenated petroleum resin.Its addition is the 1-30 % by weight of each layer gross weight, preferred 2--20 % by weight, more preferably 3-15 % by weight, also more preferably 4-10 % by weight.
The present invention also provides the preparation method of described multilayer complex films, and it comprises the following steps:
(1) preparation of A layer and B layer
To be extruded by individual layer 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 and B layer;
(2) use rolling method, with X layer for adhesive, carry out gluing to each A layer and B layer, wherein the outermost of composite membrane is two-layer 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;
(3) the A layer of gluing and B layer are carried out lamination compound, obtain described composite membrane.
According to the present invention, the A layer of step (1) gained and/or the two-sided all through sided corona treatment of B layer, make its initial surface tension reach more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, 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, printed matter and packaging material.
The present invention also provides the application of the multilayer complex films described in a kind of aforementioned any one, and it is for bill, marketable securities, printed matter and packaging material.
The present invention also provides a kind of goods, and its face coat by the multilayer complex films of aforementioned any one and printing obtain, and described goods comprise printed matter (as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.
Beneficial effect of the present invention:
Acrylic polymer multilayer complex films prepared by the present invention, have excellent combination property, its tensile strength, deflection and tear-resistant intensity are all very high, and its vertical and horizontal performance has good balance, and have the good transparency, concrete performance is see 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 and B layer mainly comprise acrylic polymer.Described acrylic polymer is preferably Noblen or propylene copolymer or polypropene composition; Typically be isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the polypropylene blend of the atactic propene copolymer of a small amount of comonomer and ethylene copolymer-modified isotactic polypropylene.Comonomer is ethene or higher alpha-olefin, as ethene, butylene, hexene or octene etc.The content of comonomer is preferably 0.2wt% to 2.0wt%, is more preferably 0.35wt% to 0.85wt%.These acrylic polymers of the present invention can be the mixtures containing one kind or two or more polymer, the Noblen that such as molecular weight is different, or the composition of propylene and a small amount of alpha-olefin random copolymer.Acrylic polymer of the present invention, is generally the vistanex according to polyacrylic title manufacture, sale, and normally density is 0.890 ~ 0.930g/cm
3, MFR (ASTMD1238, load 2160g, temperature 230 DEG C) be 0.5 ~ 60g/10min, be preferably 0.5 ~ 20g/10min, more preferably 0.5-15g/10min, be also more preferably the Noblen of 1 ~ 5g/10min.
According to the present invention, the fusing point of described acrylic polymer is 148 to 170 DEG C, preferred 150-167 DEG C; More preferably 155 DEG C-165 DEG C; Molecular weight distribution (GPC test) is 2-16, is preferably 4-10; Melt index is 0.5-10g/10min, preferred 1-8g/10min.The Noblen that industrial BOPP 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, preferred 0.5-15g/10min, fusing point can be between about 155 DEG C-165 DEG C.
Also part ethylene-based polymer can be mixed into, such as high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE) in the polymer of described A layer and B layer.Wherein, not or have a small amount of comonomer, comonomer is not propylene or higher alpha-olefin to HDPE, as ethene, butylene, hexene or octene etc., and has about 0.941g/cm
3or higher (such as about 0.948g/cm
3to about 0.968g/cm
3, preferably about 0.952g/cm
3to about 0.962g/cm
3) density, the fusing point of such as about 130 DEG C to about 148 DEG C and 0.2-50g/10min, preferred 1-45g/10min, the more preferably melt index (measuring according to ASTMD1238) of 2-40g/10min.LDPE has at 0.912g/cm
3to 0.94g/cm
3(such as 0.915g/cm
3to 0.928g/cm
3) the density of scope and the melt index (measuring according to ASTMD1238) of 0.2-50g/10min (preferred 1-45g/10min, more preferably 2-40g/10min).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has the melt index (measuring according to ASTMD1238) of 0.2-50g/10min (such as 1-10g/10min) and at 0.857g/cm
3to 0.950g/cm
3, preferred 0.905g/cm
3to 0.940g/cm
3, more preferably 0.910g/cm
3to 0.928g/cm
3the density of scope.In addition ethylene-based polymer can also be terpolymer, as ethylene/butene/hexene copolymer, and ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer; These copolymers have the melt index (measuring according to ASTMD1238) of 0.2-50g/10min (such as 1-10g/10min) and at 0.857g/cm
3to 0.950g/cm
3, preferred 0.905g/cm
3to 0.940g/cm
3, more preferably 0.910g/cm
3to 0.928g/cm
3the 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, and wherein W, E and I are respectively the quality of Paper or cardboard, elastic modelling quantity and the moment of inertia.Wherein, the deflection of cardboard or claim flexural rigidity, referring to applying certain load apart from fixture 5cm place to the sample vertically clipped, observing from sample camber 3.81mm width, and the moment of flexure needed for sample to 15 °, represents with gcm.Paper sheet stiffness is a very important index, directly affect the size (another influence factor is d ie cutting press) of folding line deflection, thus it is shaping to affect finished product.Deflection is little, and finished product is easy to conquassation, warpage; Deflection is large, and finished product is difficult to shaping.In order to improve the deflection of multilayer complex films of the present invention further, and the performance such as such as heat sealer, gas permeability and intensity, another resin can be added in A layer or B layer, as Petropols, hydrogenated petroleum resin etc., preferred C
5-C
9petropols or C
5-C
9hydrogenated petroleum resin.Its addition is the 1-30 % by weight of each layer gross weight, preferred 2-20 % by weight, more preferably 3-15 % by weight, also more preferably 4-10 % by weight.
Master batch form the additive of about 0.01 ~ 5.0 quality % can also be added in the polymer of described A layer and B layer.Described additive is preferably 0.01 ~ 3.0 quality %, more preferably 0.05 ~ 1.0 quality %.
Described additive has: antiblocking agent, slipping agent (i.e. lubricant or slipping agent), antistatic additive, nucleator, heat-resisting stabilizing agent, weathering stabilizers, ultra-violet absorber, anti-turbid dose, pigment, the known various additives that usually can add in polyolefin such as dyestuff.
As described antiblocking agent, antiblocking agent well known in the art can be used, as silica, talcum, mica, zeolite, or metal alkoxide be sintered the inorganic compound particles such as the metal oxide that obtains; Or the organic compound such as polymethyl methacrylate, melamine resin, melamine urea resin, mylar.Wherein, silica, polymethyl methacrylate is particularly preferably used from resistance to blocking aspect.
As described lubricant, the acid amides based compounds etc. such as such as stearmide, erucyl amide, oleamide can be used.
As described antistatic additive, the ethylene oxide adduct, quaternary amine based compound, alkyldiethanolamine fatty acid ester, fatty acid glyceride, tristerin etc. as betanin derivative can be used.
As described nucleator, such as D-sorbite 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.
Also can add delustring masterbatch in the polymer of described A layer and B layer to produce Extinctive thin film, or add pearly-lustre masterbatch to produce pearly-lustre film.
Laminate stretch propylene polymer thin film of the present invention as required, can implement the surface treatment such as sided corona treatment, flame treatment to single or double.In addition, according to purposes, for giving heat sealability, can overleaf on layer independent lamination contain the film of high-pressure process low-density polyethylene, linear low density polyethylene (LLDPE), crystallinity or the random copolymer of alpha-olefin of low-crystalline ethene and carbon number 3 ~ 10 or the low melting point polymer such as random copolymer, polybutene, ethene-vinyl acetate copolymer of the alpha-olefin of propylene and ethene or carbon number more than 4, or lamination contains the film of their composition.In addition, in order to improve the cementability with other material, process can be fixed to adhesives such as oriented film surface imines, carbamates, also can 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.
Chlorinated polypropylene of the present invention adopts solwution method, suspension method or solid phase method polypropylene chlorination to be obtained.The mass content of chlorine is 20%-70%, and fusing point is less than 150 DEG 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 contain 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.
Polyurethane resin of the present invention can be selected from generally as polyester-polyurethane, polyether-polyurethane or polyurethane polyureas carbamide resin etc. that the known dry lamination containing polyurethane of film adhesive, waterborne dry-type lamination, solventless liminating, electric wire curing type laminating adhesive manufacture.This polyurethane resin can be water-dispersion type or solvent type any one, but easily to regulate from the tectal degree of cross linking of polyurethane resin, and from the operating environment aspect of production scene, be preferably water dispersant type polyaminoester resin.
As water dispersant type polyaminoester resin, be preferably and introduce carboxylate (-COONa etc.), sulfonate (-SO to the main chain of polyurethane resin or side chain
3na etc.) etc. the self-emulsifying type polyurethane resin of hydrophilic group.In solvent type situation, isocyanate-based resin is used for crosslinking 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 crosslinking agents such as the melamine series resin of about 3 ~ 10 quality %, epoxy system resin, imines system resin can be added, also can add the acid catalyst of about 0.5 ~ 1 quality %, promote curing reaction further.This crosslinking agent not only can improve resistance to water, the solvent resistance of easy-adhesion overlay film, can also improve cementability.
In addition, when using water dispersant type polyaminoester resin, time in composition containing the surfactant such as defoamer or emulsifying agent, likely making the surface of Biaxially stretched multilayer propylene polymer thin film turn white, causing bad order.In addition, in polyurethane resin of the present invention, such as, in order to prevent the objects such as adhesion, as required, inorganic particles or organic fine particles etc. can also be added.
On the one or both sides of propylene polymer thin film, when covering (lamination) polyurethane resin (X), by by gravure coater such as the aqueous solution of polyurethane resin or dispersion liquid Kohler coaters, directly gravure coater, intaglio offset coating machine, electric arc gravure coater, reverse rotating gravure and nozzle mode; Its top feed is the inverse roll-coater such as against roll-coater, bottom feed against roll-coater and nozzle material-feeding against roll-coater, 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 composition in the polyurethane resin aqueous solution
2, preferred 0.3 ~ 2g/m
2after being coated with, at the temperature of 50 ~ 140 DEG C dry more than 10 seconds 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 film.What is called longitudinally refers to the direction of extruding processing along film, and what is called laterally refers to that vertical thin-film extrudes the direction of processing.The ratio of longitudinal stretching multiplying power and cross directional stretch multiplying power is referred in length and breadth to draw ratio.
The invention provides the preparation method of described multilayer complex films, it comprises the following steps:
(1) preparation of A layer, B tunic
Adopt the method preparation of simple tension or biaxial tension, for biaxial tension, substep biaxial tension method in turn can be adopted, also can adopt synchro-draw method.
Described drawing process comprises plain film method and periosteum method.For biaxial tension, the technical process of described plain film method comprises synchro-draw process, comprises the steps:
Prepare burden → extrude → chilling → is in length and breadth to synchro-draw → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.
The technical process of described plain film method also comprises step drawing process, comprises the steps:
Prepare burden → extrude → chilling → longitudinal stretching → cross directional stretch → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.
According to the present invention, described longitudinal stretching comprises preheating, micro-stretching and sizing.
According to the present invention, described cross directional stretch comprises preheating, stretches greatly, sizing and cooling.
According to the present invention, described chilling refers to and uses cooling fluid to cool, and preferred cooling fluid is cooling water.The effect of described chilling is to make crystallization refinement, thus improves transparency and deflection.
According to the present invention, described in extrude and comprise individual layer and to extrude or multi-layer co-extruded.Describedly extrude employing and melt extrude.
According to the present invention, described batching comprises prepares burden according to the requirement of formula, can pass through electronic measurement.
The technical process of described periosteum method comprises synchro-draw process, comprises the steps:
Limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product is flattened → cutd open to (comprise individual layer extrude or multilayered molten the is extruded) → chilling → female film → dewater → baker Far-infrared Heating → in length and breadth of preparing burden → extrude to synchro-draw → collapser.
The technical process of described periosteum method also comprises step drawing process, comprises the steps:
(comprise individual layer extrude or multilayered molten is extruded) → chilling → female film → dewater → baker Far-infrared Heating → longitudinal stretching → cross directional stretch → collapser of preparing burden → extrude flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.
According to the present invention, described chilling refers to and uses cooling fluid to cool, and preferred cooling fluid is cooling water.The effect of described chilling is to make crystallization refinement, thus improves transparency and deflection.
When described plain film method is the biaxial tension of plain film substep, specifically comprise the steps:
A () is prepared burden by the requirement of formula, in the hopper above the extruder adding single or multiple lift co-extrusion, plastics, by after the external heat of extruder barrel and screw rod rotational shear plasticizing, enter the rack-style flat die of single or multiple lift coextru-lamination.Going out the sheet melt after die head is attached on chilling roller by air knife, and sheet melt supercooled is become sheet, and then along with the rotation of chilling roller, sheet enters tank and carries out further two-sided cooling.The thickness of sheet controls by the extrusion capacity of extruder and the rotating speed of chilling roller.Wherein, the control temperature of extruder is 150-260 DEG C, preferred 180-250 DEG C; Die head temperature is generally 190-240 DEG C, and chilling roll temperature is 15-30 DEG C, preferred 20-25 DEG C.
B () sheet enters and carries out two-sided preheating to the preheat roll of the some in tensioning system in length and breadth, preheat roll temperature general control at 90-150 DEG C, preferred 100-120 DEG C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, carry out longitudinal stretching by draw roll, draft temperature controls at 90-150 DEG C, preferred 100-120 DEG C, and drawing process can a step, also can twice stretching or stretch for three times.Longitudinal stretching multiplying power sets according to the requirement of A layer and B tunic.Film after stretching is heat-treated by setting roller, and described setting temperature is 100-140 DEG C, is preferably 110-120 DEG C, to eliminate the internal stress of film, reduces longitudinal shrinkage factor.
C the film after () longitudinal stretching enters cross directional stretch system, first carry out preheating section preheating, preheat roll temperature general control at 100-160 DEG C, preferred 110-140 DEG C, more preferably 115-130 DEG C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, the track then by expanding spoke carries out cross directional stretch, the general 130-180 DEG C of control temperature of stretching-machine, preferred 140-160 DEG C, then carries out thermal finalization process, setting temperature is 60-120 DEG C, preferred 70-110 DEG C.Cross directional stretch multiplying power sets according to the requirement of A layer and B tunic.
Film d () goes out cross directional stretch system after is cooled by chill roll, is then trimming, is sided corona treatment with that, is finally carry out rolling.
E () leaves the large volume film after equipment after the Ageing Treatment depositing several days, just can cut, make A layer and the B layer film of Rack.
When described plain film method is the stretching of plain film synchronous bidirectional, plain film synchro-draw preparation method and plain film step drawing preparation method similar, difference is only that in synchro-draw process, longitudinal stretching and cross directional stretch synchronously carry out, namely longitudinal stretching and cross directional stretch complete a system inter-sync, and in step drawing, longitudinal stretching is asynchronous with cross directional stretch carries out.Thus concrete operating condition and step drawing similar.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 be synchronous bidirectional stretch time, periosteum method synchronous bidirectional stretching preparation method and plain film method synchronous bidirectional stretching preparation method similar, its longitudinal stretching and cross directional stretch also synchronously carry out.Difference is, the die head of periosteum method is circular, and whole film-shaped Chengdu is that the form of steeping pipe completes.Main production parameter: extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, and cooling water temperature is 11-18 DEG C, oven drying temperature: 330-450 DEG C, and draft temperature is 140 DEG C.Then carry out according to the requirement of the draw ratio of each tunic to draw ratio in length and breadth.
When described periosteum method is substep biaxial tension, periosteum method substep biaxial tension preparation method and plain film method step by step biaxial tension preparation method are similar, and its longitudinal stretching and cross directional stretch also synchronously carry out.Difference is, the die head of periosteum method is circular, and whole film-shaped Chengdu is that the form of steeping pipe completes.Main production parameter: extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, and cooling water temperature is 11-18 DEG C, oven drying temperature: 330-450 DEG C, and draft temperature is 140 DEG C.Then carry out according to the requirement of the draw ratio of each tunic to draw ratio in length and breadth.
For simple tension, the technical process of described plain film method comprises the steps:
Prepare burden → extrude → 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:
(comprise individual layer extrude or multilayered molten is extruded) → chilling → female film → dewater → baker Far-infrared Heating → vertical or horizontal stretching → collapser of preparing burden → extrude flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.
Concrete step and above-mentioned biaxial tension method are similar.
(2) gluing
Use rolling method, take X as adhesive, carry out gluing to each A layer and B layer, wherein the outermost of composite membrane is two-layer 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 at 40-80 DEG C.
(3) 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 DEG C, preferred 60-80 DEG C.
According to the present invention, the A layer of step (1) gained and/or the two-sided all through sided corona treatment of B layer, make its initial surface tension reach more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, 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, printed matter and packaging material.
The present invention also provides the application of the multilayer complex films described in a kind of aforementioned any one, and it is for bill, marketable securities, printed matter and packaging material.
The present invention also provides a kind of goods, and its face coat by the multilayer complex films of aforementioned any one and printing obtain, and described goods comprise printed matter (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 composite membrane prepared by embodiment 1, and it is AXBXAXB structure.
Fig. 2 is the structural representation of composite membrane prepared by embodiment 1, and it is AXBXBXA structure.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described, but those skilled in the art understand, 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 and B layer all use the propylene copolymer containing ethene 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%.
A layer and B layer all add Petropols respectively, and Petropols addition is 10 % by weight of each layer gross weight.
A layer is by the processing of plain film method substep 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.
B layer is by the processing of plain film method substep 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.
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, again 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 film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure lists 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 and B layer all use the propylene copolymer containing ethene 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%.
A layer is by the processing of plain film method substep 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.
B layer is by the processing of plain film method substep stretch 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.
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 are AXBXAXB structure or AXBXBXA structure, and overall film thickness is 118 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure lists 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 the propylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 96.4%.
A layer and B layer all add Petropols respectively, and Petropols addition is 30 % by weight of each layer gross weight.
A layer is by the processing of plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 3 times, and thickness is 9 μm.
B layer is by the processing of plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 3 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, then through being compounded to form composite membrane, structure are AXBXAXBXA, and wherein, the thickness of X layer is 1 μm, and overall film thickness is 59 μm.The test data of film is as table 2.
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 the propylene copolymer containing ethene, and ethylene contents is 0.25wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.Isotacticity is 96.0%.
A layer is by plain film method simple tension processes, and wherein longitudinal stretching multiplying power is 11 times, and thickness is 17 μm.
B layer is by plain film method simple tension processes, and wherein cross directional stretch multiplying power is 11 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, composite membrane is compounded to form again 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 lists 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 the propylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.3, and melt index is 2.9g/10min, and isotacticity is 95.9%.
A layer and B layer all add Petropols respectively, and Petropols addition is 1 % by weight of each layer gross weight.
A layer is by the processing of periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinal stretching multiplying power is 4 times, and thickness is 14 μm.
B layer is by the processing of periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 4 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, again 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 lists in table 3.
Embodiment 6:B ' XAXBXAXB 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 the propylene copolymer containing ethene, 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 ' is the propylene copolymer containing ethene, and ethylene contents is 0.30wt%, and molecular weight distribution is 5.2, and melt index is 3.1g/10min, and isotacticity is 95.6%
A layer and B layer all add hydrogenated petroleum resin respectively, and hydrogenated petroleum resin addition is 20 % by weight of each layer gross weight.
A layer is by the processing of periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times, and thickness is 14 μm.
B layer is by the processing of periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times, and thickness is 9 μm.
B ' layer is by periosteum method substep simple tension processes, and wherein cross directional stretch multiplying power is 5 times of thickness is 9 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 polyurethane, again through being compounded to form composite membrane, structure is B ' XAXBXAXB, and wherein, the thickness of X layer is 1 μm, overall film thickness is 59 μm, and the performance test data of film lists in table 3.
Embodiment 7:
A layer and B layer all use the propylene copolymer containing ethene 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%.
A layer and B layer all add Petropols respectively, and Petropols addition is 10 % by weight of each layer gross weight.
A layer is by the processing of plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.
B layer is by the processing of plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 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, composite membrane is compounded to form again 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 film prepared by several Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXBXAXBXAXB structure lists in table 4.
Embodiment 8:
A layer and B layer all use the propylene copolymer containing ethene 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%.
A layer is by the processing of plain film method substep 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 12 μm.
B layer is by the processing of plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 1.1 times, and longitudinal stretching multiplying power is 12.5 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, composite membrane is compounded to form again 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 film prepared by several Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXBXAXBXAXB structure lists in table 4.
Embodiment 9:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 19 μm/2 μm/15 μm/2 μm/19 μm/2 μm/15 μm.
A layer and B layer all use the propylene copolymer containing ethene 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%.
A layer and B layer all add Petropols respectively, and Petropols addition is 10 % by weight of each layer gross weight.
A layer is by plain film method simple tension processes, and wherein cross directional stretch multiplying power is 9 times, and thickness is 19 μm.
B layer is by the processing of plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 9 times, and 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, again 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 film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure lists in table 4.
Embodiment 10:AXBXAXB structure or AXBXBXA structure,
Layer thickness profile: 28 μm/2 μm/25 μm/2 μm/28 μm/2 μm/25 μm.
A layer and B layer all use the propylene copolymer containing ethene 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%.
A layer is by plain film method simple tension processes, and wherein cross directional stretch multiplying power is 12.5 times, and thickness is 28 μm.
B layer is by the processing of plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 1.1 times, and longitudinal stretching multiplying power is 12.5 times, and 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, then through being compounded to form composite membrane, structure are AXBXAXB structure or AXBXBXA structure, and overall film thickness is 112 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AXBXAXB structure lists in table 4.
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
Claims (68)
1. a multilayer complex films, it comprises n AXB Rotating fields each other by Rotating fields that X is composited, n is 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 and B layer comprise identical or different acrylic polymer independently of one another, X is adhesive layer, and described A layer is simple tension or biaxial tension, and described B layer is simple tension or biaxial tension;
Wherein, the draw ratio of the draw ratio of A layer or stretching ratio and B layer or stretching ratio different;
Described A layer and B layer comprise one of following combination:
(1) described A layer is simple tension, and described B layer is biaxial tension;
(2) described A layer is biaxial tension, and described B layer is simple tension;
(3) A layer and B layer are biaxial tension; Or
(4) A layer and B layer are simple tension;
For scheme (1), stretch to the transverse direction of described A layer, and all stretch to described the horizontal and vertical of B layer, the cross directional stretch multiplying power of described A layer is different from the cross directional stretch multiplying power of B layer; Or stretch to the longitudinal direction of described A layer, and all stretch to the horizontal and vertical of described B layer, the longitudinal stretching multiplying power of described A layer is different from the longitudinal stretching multiplying power of B layer;
For scheme (2), stretch to described the horizontal and vertical of A layer, and stretch to the transverse direction of described B layer, the cross directional stretch multiplying power of described B layer is different from the cross directional stretch multiplying power of A layer; Or stretch to described the horizontal and vertical of A layer, and stretch to the longitudinal direction of described B layer, the longitudinal stretching multiplying power of described B layer is different from the longitudinal stretching multiplying power of A layer;
For scheme (3), different to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer;
For scheme (4), the stretching ratio of described A layer is different from the stretching ratio of described B layer, wherein, stretches to the transverse direction of described A layer, and the longitudinal direction of described B layer is stretched, the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer; Or stretch to the longitudinal direction of described A layer, and stretch to the transverse direction of described B layer, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer.
2. composite membrane according to claim 1, is characterized in that, in described multilayer complex films, n AXB Rotating fields is by X order compound, namely according to the order compound of AXBXAXB.
3. composite membrane according to claim 1, is characterized in that, in described multilayer complex films, n AXB Rotating fields replaces compound by X, namely according to the order compound of AXBXBXA.
4. composite membrane according to claim 1, is characterized in that, in described multilayer complex films, n AXB Rotating fields is by the unordered compound of X.
5. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, in described multilayer complex films, the acrylic polymer of A layer is identical with the acrylic polymer of B layer.
6. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, described Rotating fields also comprises one deck A layer, is compound in the skin of outermost B layer by X; Or the skin of outermost A layer is compound in by X.
7. composite membrane according to claim 6, is characterized in that, described Rotating fields also comprises one deck A layer, is compound in the skin of outermost B layer by X, and its structure is (AXBX)
na, n are more than or equal to 2; Or the skin of outermost A layer is compound in by X, its structure is A (XAXB)
n, n is more than or equal to 2.
8. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, described Rotating fields also comprises one deck B layer, is compound in the skin of outermost B layer by X; Or the skin of outermost A layer is compound in by X.
9. composite membrane according to claim 8, is characterized in that, described Rotating fields also comprises one deck B layer, is compound in the skin of outermost B layer by X, and its structure is (AXBX)
nb, n are more than or equal to 2; Or the skin of outermost A layer is compound in by X, its structure is B (XAXB)
n, n is more than or equal to 2.
10. composite membrane according to claim 1, is characterized in that, the A layer in described multilayer complex films is single layer structure or multi-layer co-extruded structure.
11. composite membranes according to claim 1, is characterized in that, the B layer in described multilayer complex films is single layer structure or multi-layer co-extruded structure.
12. according to the composite membrane of claim 10 or 11, and it is characterized in that, the multi-layer co-extruded structure of described A layer or B layer is at least 2 layers.
13. composite membranes according to claim 12, is characterized in that, the multi-layer co-extruded structure of described A layer or B layer be 2 ?15 layers.
14. composite membranes according to claim 13, is characterized in that, the multi-layer co-extruded structure of described A layer or B layer 3 ?11 layers.
15. composite membranes according to claim 14, is characterized in that, the multi-layer co-extruded structure of described A layer or B layer be 5 ?9 layers.
16. composite membranes according to claim 15, is characterized in that, the multi-layer co-extruded structure of described A layer or B layer be 6 ?8 layers.
17. composite membranes according to claim 1, is characterized 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.
18. composite membranes according to claim 1, is characterized 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.
19. composite membranes according to claim 1, is characterized in that, for scheme (3), the longitudinal stretching multiplying power of described A layer is greater than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described B layer is greater than longitudinal stretching multiplying power.
20. composite membranes according to claim 19, it is characterized in that, being inversely proportional to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer, namely the described longitudinal stretching of A layer and the ratio of cross directional stretch equal the described cross directional stretch of B layer and the ratio of longitudinal stretching.
21. composite membranes according to claim 20, is characterized in that, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer.
22. composite membranes according to claim 21, is characterized in that, the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer.
23. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, 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.
24. composite membranes according to claim 23, is characterized in that, described chlorinated polypropylene adopts solwution method, suspension method or solid phase method polypropylene chlorination to be obtained; The mass content of the chlorine of described chlorinated polypropylene be 20% ?70%, fusing point is less than 150 DEG C;
Described polyurethane is solvent-borne type, water-dispersion type or no-solvent type one-component or Multi-component Polyurethane adhesive;
The adhesive that described acrylic resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent contain acrylic acid or acrylates;
Described epoxy resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent epoxy type adhesive.
25. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, the thickness of described multilayer complex films be 50 ?150 μm.
26. composite membranes according to claim 25, is characterized in that, the thickness of described multilayer complex films be 60 ?120 μm.
27. composite membranes according to claim 26, is characterized in that, the thickness of described multilayer complex films be 70 ?100 μm.
28. composite membranes according to claim 27, is characterized in that, the thickness of described multilayer complex films be 80 ?90 μm.
29. composite membranes according to claim 25, is characterized in that, in described multilayer complex films the thickness of each A layer or B layer be 5 ?65 μm.
30. composite membranes according to claim 29, is characterized in that, in described multilayer complex films the thickness of each A layer or B layer be 10 ?55 μm.
31. composite membranes according to claim 30, is characterized in that, in described multilayer complex films the thickness of each A layer or B layer be 20 ?40 μm.
32. composite membranes according to claim 25, is characterized in that, in described multilayer complex films the thickness of each X layer be 0.5 ?10 μm.
33., according to the composite membrane of claim 32, is characterized in that, in described multilayer complex films the thickness of each X layer be 1 ?6 μm.
34., according to the composite membrane of claim 33, is characterized in that, in described multilayer complex films the thickness of each X layer be 2 ?5 μm.
35. according to the composite membrane of claim 32, and it is characterized in that, in described multilayer complex films, the summation of all X layer thicknesses is no more than 30% of this composite film thickness.
36. according to the composite membrane of claim 35, and it is characterized in that, in described multilayer complex films, the summation of all X layer thicknesses is no more than 20% of this composite film thickness.
37. according to the composite membrane of claim 36, and it is characterized in that, in described multilayer complex films, the summation of all X layer thicknesses is no more than 15% of this composite film thickness.
38. according to the composite membrane of claim 37, and it is characterized in that, in described multilayer complex films, the summation of all X layer thicknesses is no more than 10% of this composite film thickness.
39. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, 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.
40. according to the composite membrane of claim 39, and it is characterized in that, in described multilayer complex films, the tensile strength of A layer is 2.0:1.0 to 5.0:1.0 at horizontal and vertical ratio.
41. according to the composite membrane of claim 39, and it is characterized in that, 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.
42. according to the composite membrane of claim 41, and it is characterized in that, in described multilayer complex films, the tensile strength of B layer is 1.0:2.0 to 1.0:5.0 at horizontal and vertical ratio.
43. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, for biaxial tension, the cross directional stretch multiplying power of the A layer in described multilayer complex films be 7 ?12.5 times, longitudinal stretching multiplying power be 1 ?6 times.
44., according to the composite membrane of claim 43, is characterized in that, for biaxial tension, the cross directional stretch multiplying power of the A layer in described multilayer complex films be 8 ?10 times, longitudinal stretching multiplying power be 2 ?4 times.
45. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, for biaxial tension, the cross directional stretch multiplying power of the B layer in described multilayer complex films be 1 ?6 times, longitudinal stretching multiplying power be 7 ?12.5 times.
46., according to the composite membrane of claim 45, is characterized in that, for biaxial tension, the cross directional stretch multiplying power of the B layer in described multilayer complex films be 2 ?4 times, longitudinal stretching multiplying power be 8 ?10 times.
47. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, for simple tension, the transverse direction of the A layer in described multilayer complex films or the stretching ratio of longitudinal direction be 1 ?12.5 times; The vertical or horizontal stretching ratio of B layer be 1 ?12.5 times.
48., according to the composite membrane of claim 47, is characterized in that, for simple tension, the cross directional stretch multiplying power of the A layer in described multilayer complex films be 7 ?12.5 times or longitudinal stretching multiplying power be 1 ?6 times; The longitudinal stretching multiplying power of B layer be 7 ?12.5 times or cross directional stretch multiplying power be 1 ?6 times.
49. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, in the tensile strength of described multilayer complex films, deflection and tear-resistant intensity, horizontal and vertical test value ratio is 0.7:1.0 to 1.0:1.3.
50. according to the composite membrane of any one of claim 1 ?4, and it is characterized in that, the vertical transverse tensile strength of described multilayer complex films is greater than 100MPa.
51. according to the composite membrane of claim 50, and it is characterized in that, the vertical transverse tensile strength of described multilayer complex films is greater than 120MPa.
52. according to the composite membrane of claim 51, and it is characterized in that, the vertical transverse tensile strength of described multilayer complex films is greater than 140MPa.
53. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, the acrylic polymer of described A layer or B layer is Noblen or propylene copolymer, and comonomer is ethene, butylene, hexene or octene.
54. according to the composite membrane of claim 53, it is characterized in that, the acrylic polymer of described A layer or B layer is isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the polypropylene blend of the atactic propene copolymer of a small amount of comonomer and ethylene copolymer-modified isotactic polypropylene; Comonomer is ethene, butylene, hexene or octene.
55. according to the composite membrane of claim 53, and it is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer is 148 to 170 DEG C; Molecular weight distribution (GPC test) be 2 ?16; Melt index be 0.5 ?10g/10min.
56., according to the composite membrane of claim 55, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer be 150 ?167 DEG C; Molecular weight distribution (GPC test) be 4 ?10; Melt index be 1 ?8g/10min.
57., according to the composite membrane of claim 56, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer be 155 DEG C ?165 DEG C.
58. according to claim 1 ?the composite membrane of 4 any one, it is characterized in that, in A layer or B layer, also can add another resin again, be selected from Petropols or hydrogenated petroleum resin.
59. according to the composite membrane of claim 58, and it is characterized in that, described resin is C
5?C
9petropols or C
5?C
9hydrogenated petroleum resin.
60., according to the composite membrane of claim 58, is characterized in that, the addition of described resin be each layer gross weight 1 ?30 % by weight.
61., according to the composite membrane of claim 60, is characterized in that, the addition of described resin be each layer gross weight 2 ??20 % by weight.
62., according to the composite membrane of claim 61, is characterized in that, the addition of described resin be each layer gross weight 3 ?15 % by weight.
63., according to the composite membrane of claim 62, is characterized in that, the addition of described resin be each layer gross weight 4 ?10 % by weight.
The preparation method of the multilayer complex films of 64. 1 kinds of any one of claim 1 ?63, it comprises the following steps:
(1) preparation of A layer and B layer
To be extruded by individual layer or multi-layer co-extruded, prepare polyolefin sheets, then 130 ?carry out simple tension under the temperature environment of 185 DEG C or biaxial tension processes A layer and B layer;
(2) use rolling method, with X layer for adhesive, carry out gluing to each A layer and B layer, wherein the outermost of composite membrane is two-layer carries out single spreading, and middle each layer carries out one or two sides gluing, after gluing, each layer 40 ?dry at 80 DEG C;
(3) the A layer of gluing and B layer are carried out lamination compound, obtain described composite membrane.
65. according to the method for claim 64, and it is characterized in that, the A layer of step (1) gained and/or the two-sided all through sided corona treatment of B layer, make its initial surface tension reach more than 44 dynes per centimeter; The surface tension of gained composite membrane is more than 36 dynes per centimeter.
66. according to the method for claim 65, and it is characterized in that, the surface tension of gained composite membrane reaches more than 38 dynes per centimeter.
The application of the multilayer complex films of 67. 1 kinds of any one of claim 1 ?63, it is for bill, marketable securities, Front cover of book and periodical, picture album and packaging material.
68. 1 kinds of goods, its face coat by the multilayer complex films of any one of claim 1 ?63 and printing obtain, and described goods comprise Front cover of book and periodical, picture album, bill, marketable securities and packaging material.
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| GB9201880D0 (en) * | 1992-01-29 | 1992-03-18 | Rasmussen O B | Laminated films |
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| CN1136997A (en) * | 1995-03-02 | 1996-12-04 | 三井石油化学工业株式会社 | Polypropylene composite film |
| 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 | biaxially oriented polypropylene cigarette shrink film and manufacturing method thereof |
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