CN104149457B - A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof - Google Patents
A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof Download PDFInfo
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- CN104149457B CN104149457B CN201310177859.5A CN201310177859A CN104149457B CN 104149457 B CN104149457 B CN 104149457B CN 201310177859 A CN201310177859 A CN 201310177859A CN 104149457 B CN104149457 B CN 104149457B
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Abstract
The invention provides a kind of multilayer complex films, it comprises n AXBXCXD 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, each B is identical or different, each C is identical or different, each D is identical or different, each X is identical or different, two-layer containing identical or different acrylic polymer in A layer in described AXBXCXD Rotating fields, B layer, C layer and D layer, two-layer containing identical or different ethylene-based polymer in addition, X is adhesive layer, and described A layer, B layer, C layer and D layer are biaxial tensiones.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 of the present invention-ethylene-based polymer multilayer complex films has the performances such as high-stiffness, high transparent, low temperature resistant, high-tear strength.
Description
Technical field
The present invention relates to a kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method and application thereof, the invention still further relates to the goods comprising described composite membrane, belong to field of compound material.
Background technology
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.CN101160209A(Oji Paper) in disclose 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, 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 ° of C, then under the temperature range of horizontal 120 ~ 190 ° of C under 7 ~ 12 times and after face multiplying power (longitudinally × laterally) is stretched to 45 ~ 65 times, 110 ~ 180 ° of C temperature range heat fixation and obtain.
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.
The density polyethylene film with high stretched has been used to plastics package field.In No. 1287527th, BP, describe some such films, they are biaxially stretched the degree being greater than 6.5 times on machine direction (MD) and horizontal (TD) both direction.No. 4680207th, United States Patent (USP) relates to the uneven oriented film of twin shaft of LLDPE, and it stretches in the direction of the machine and is no more than 6 times, the orientation stretching that is no more than 3 times and is less than 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) 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-ethylene-based 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 AXBXCXD 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, each B is identical or different, each C is identical or different, each D is identical or different, each X is identical or different, two-layer containing identical or different acrylic polymer in A layer in described AXBXCXD Rotating fields, B layer, C layer and D layer, two-layer in addition containing identical or different ethylene-based polymer, X is adhesive layer, and described A layer, B layer, C layer and D layer are biaxial tension and comprise one of following combination:
(1) described two-layer being inversely proportional to draw ratio in length and breadth containing acrylic polymer, described two-layer being inversely proportional to draw ratio in length and breadth containing ethylene-based polymer;
(2) described two-layer being inversely proportional to draw ratio in length and breadth containing acrylic polymer, is describedly 1 and two-layer stretching ratio is identical to draw ratio in length and breadth containing the two-layer of ethylene-based polymer;
(3) be describedly 1 and two-layer stretching ratio is identical, described two-layer being inversely proportional to draw ratio in length and breadth containing ethylene-based polymer to draw ratio in length and breadth containing the two-layer of acrylic polymer;
(4) be describedly 1 and two-layer stretching ratio is identical to draw ratio in length and breadth containing the two-layer of acrylic polymer, be describedly 1 and two-layer stretching ratio is identical to draw ratio in length and breadth containing the two-layer of ethylene-based polymer.
According to the present invention, described two-layer being inversely proportional to draw ratio in length and breadth represents that the longitudinal stretching multiplying power of wherein one deck and the ratio of cross directional stretch multiplying power equal the cross directional stretch multiplying power of another layer and the ratio of longitudinal stretching multiplying power, and two-layer is that 1 expression cross directional stretch multiplying power equals longitudinal stretching multiplying power to draw ratio in length and breadth.
According to the present invention, for scheme (1).Preferably, the longitudinal stretching multiplying power of described two-layer middle one deck be inversely proportional to draw ratio is in length and breadth identical or close with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical or close with the longitudinal stretching multiplying power of another layer; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck be inversely proportional to draw ratio is in length and breadth identical with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical with the longitudinal stretching multiplying power of another layer.In addition, preferably, the longitudinal stretching multiplying power of described two-layer middle one deck containing acrylic polymer is identical or close with the cross directional stretch multiplying power of described two-layer middle one deck containing ethylene-based polymer, and its cross directional stretch multiplying power is identical or close with the longitudinal stretching multiplying power of described two-layer middle one deck containing ethylene-based polymer; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck containing acrylic polymer is identical with the cross directional stretch multiplying power of described two-layer middle one deck containing ethylene-based polymer, and its cross directional stretch multiplying power is identical with the longitudinal stretching multiplying power of described two-layer middle one deck containing ethylene-based polymer.
According to the present invention, for scheme (2).Preferably, the longitudinal stretching multiplying power of described two-layer middle one deck be inversely proportional to draw ratio is in length and breadth identical or close with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical or close with the longitudinal stretching multiplying power of another layer; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck be inversely proportional to draw ratio is in length and breadth identical with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical with the longitudinal stretching multiplying power of another layer.In addition, preferably, the described two-layer stretching ratio containing ethylene-based polymer is identical or close with the cross directional stretch multiplying power of described two-layer middle one deck containing acrylic polymer, or the described two-layer stretching ratio containing ethylene-based polymer is identical or close with the longitudinal stretching multiplying power of described two-layer middle one deck containing acrylic polymer; Also more preferably, the described two-layer stretching ratio containing ethylene-based polymer is identical with the cross directional stretch multiplying power of described two-layer middle one deck containing acrylic polymer, or the described two-layer stretching ratio containing ethylene-based polymer is identical with the longitudinal stretching multiplying power of described two-layer middle one deck containing acrylic polymer.
According to the present invention, for scheme (3).Preferably, the longitudinal stretching multiplying power of described two-layer middle one deck be inversely proportional to draw ratio is in length and breadth identical or close with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical or close with the longitudinal stretching multiplying power of another layer; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck be inversely proportional to draw ratio is in length and breadth identical with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical with the longitudinal stretching multiplying power of another layer.In addition, preferably, the described two-layer stretching ratio containing acrylic polymer is identical or close with the cross directional stretch multiplying power of described two-layer middle one deck containing ethylene-based polymer, or the described two-layer stretching ratio containing acrylic polymer is identical or close with the longitudinal stretching multiplying power of described two-layer middle one deck containing ethylene-based polymer; Also more preferably, the described two-layer stretching ratio containing acrylic polymer is identical with the cross directional stretch multiplying power of described two-layer middle one deck containing ethylene-based polymer, or the described two-layer stretching ratio containing acrylic polymer is identical with the longitudinal stretching multiplying power of described two-layer middle one deck containing ethylene-based polymer.
According to the present invention, for scheme (4).Preferably, the described two-layer stretching ratio containing acrylic polymer is identical or close with the described two-layer stretching ratio containing ethylene-based polymer; More preferably, the described two-layer stretching ratio containing acrylic polymer is identical with the described two-layer stretching ratio containing ethylene-based polymer.
According to the present invention, in described multilayer complex films, n AXBXCXD Rotating fields is by X order compound, namely according to the order compound of AXBXCXDXAXBXCXD.
According to the present invention, in described multilayer complex films, n AXBXCXD Rotating fields replaces compound by X, namely according to the order compound of AXBXCXDXDXCXBXA.
According to the present invention, in described multilayer complex films, n AXBXCXD Rotating fields is by the unordered compound of X.
According to the present invention, the A layer in described multilayer complex films, B layer, C layer or D layer are single layer structure or multi-layer co-extruded structure.
According to the present invention, the multi-layer co-extruded structure of described A layer, B layer, C layer or D 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, 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 obtained.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 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 A layer, B layer, C layer or D 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, is preferably 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, described thickness two-layer arbitrarily difference is no more than 20%, preferably more than 15%, more preferably no more than 10%.
According to the present invention, in described multilayer complex films containing same polymer two-layer in the tensile strength of one deck be 1.5:1.0 to 7.0:1.0 at horizontal and vertical ratio, preferred 2.0:1.0 to 5.0:1.0; The tensile strength of another 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, in described multilayer complex films containing same polymer two-layer in the cross directional stretch multiplying power of one deck be 7-12.5 doubly, longitudinal stretching multiplying power be 1-6 doubly, preferred cross directional stretch multiplying power be 8-10 doubly, longitudinal stretching multiplying power be 2-4 doubly; The cross directional stretch multiplying power of another layer 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, 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, described acrylic polymer 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 described acrylic polymer is 148 to 170 ° of C, preferred 150-167 ° C; More preferably 155 ° of C-165 ° of 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, described ethylene-based polymer is preferably high density polyethylene (HDPE), high-pressure process low-density polyethylene or low-pressure process LLDPE.The density of high density polyethylene (HDPE) is about 0.941g/cm
3or higher, preferably about 0.948g/cm
3to about 0.968g/cm
3, more preferably from about 0.952g/cm
3to about 0.962g/cm
3; Fusing point about 130 ° of C to about 148 ° of C; Melt index (measuring according to ASTMD1238) is 0.2-50g/10min, preferred 1-45g/10min, more preferably 2-40g/10min.The density of low density polyethylene (LDPE) is about 0.912g/cm
3to about 0.94g/cm
3, preferred 0.915g/cm
3to 0.928g/cm
3; Melt index (measuring according to ASTMD1238) is 0.2-50g/10min, preferred 1-45g/10min, more preferably 2-40g/10min.LLDPE is ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and there is 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) 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.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 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) 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.
According to the present invention, in A layer, B layer, C layer or D 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% weight of each layer gross weight, preferred 2-20% weight, more preferably 3-15% weight, also more preferably 4-10% 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, B layer, C layer and D layer
To be extruded by individual layer or multi-layer co-extruded, prepare polyolefin sheets, under the temperature environment of 130-185 ° of C, then carry out biaxial tension process A layer, B layer, C layer and D layer, the cross directional stretch multiplying power of each layer and longitudinal stretching multiplying power are according to the restriction setting in above-mentioned multilayer complex films;
(2) use rolling method, with X layer for adhesive, carry out gluing to each A layer, B layer, C layer and D 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 under 40-80 ° of C;
(3) the A layer of gluing, B layer, C layer and D layer are carried out lamination compound, obtain described composite membrane.
According to the present invention, the A layer of step (1) gained and/or B layer and/or C layer and/or D layer two-sided all through sided corona treatment, makes 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 described in 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 prepared by the present invention-ethylene-based polymer multilayer complex films, 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, B layer, C layer and D layer]
According to the present invention, the acrylic polymer in described A layer or B layer or C layer or D layer 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 ° of 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 ° of C, preferred 150-167 ° C, more preferably 155 ° of C-165 ° of 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 is tested melt index (MI) according to ASTMD-1238 and be can be about 0.2-20g/10min, preferred 0.5-15g/10min, and fusing point can be between about 155 ° of C-165 ° of C.
According to the present invention, the ethylene-based polymer in described A layer or B layer or C layer or D layer is preferably high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, not or have a small amount of comonomer, comonomer is not propylene or higher alpha-olefin to HDPE, as 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, such as about 130 ° of C to the fusing point of about 148 ° of 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 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/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 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) 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.
If the polymer acrylic polymer of described A layer, B layer, C layer or D layer then wherein also can be mixed into part ethylene-based polymer, such as high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).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, such as about 130 ° of C to the fusing point of about 148 ° of 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 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/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 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) 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, B layer, C layer or D 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% weight of each layer gross weight, preferred 2-20% weight, more preferably 3-15% weight, also more preferably 4-10% weight.
Master batch form the additive of about 0.01 ~ 5.0 quality % can also be added in the polymer of described A layer, B layer, C layer or D 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, B layer, C layer or D layer to produce Extinctive thin film, or add pearly-lustre masterbatch to produce pearly-lustre film.
Laminate stretch acrylic polymer-ethylene-based polymer 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 ° 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 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, electronic beam solidified 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 acrylic polymer-ethylene-based polymer 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 ° of C dry more than 10 seconds and obtain.
[preparation method of multilayer complex films]
According to the present invention, adopt biaxial tension, namely in stretching-machine, at certain temperature and speed, vertical both direction (longitudinally, laterally) carries out stretching and makes 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 layer, C layer and D tunic
Adopt the method preparation of 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 ° of C, preferred 180-250 ° C; Die head temperature is generally 190-240 ° of C, and chilling roll temperature is 15-30 ° of C, preferred 20-25 ° 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 is at 90-150 ° of C, preferred 100-120 ° 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 ° of C, preferred 100-120 ° 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, B layer, C layer and D tunic.Film after stretching is heat-treated by setting roller, and described setting temperature is 100-140 ° of C, is preferably 110-120 ° of 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, and preheat roll temperature general control is at 100-160 ° of C, preferred 110-140 ° C, more preferably 115-130 ° of 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 of the control temperature ° C of stretching-machine, preferred 140-160 ° C, then carries out thermal finalization process, setting temperature is 60-120 ° of C, preferred 70-110 ° C.Cross directional stretch multiplying power sets according to the requirement of A layer, B layer, C layer and D 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 the A layer of Rack, B layer, C layer and D layer film.
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 ° of C, die head temperature is 190-230 ° of C, and cooling water temperature is 11-18 ° of C, oven drying temperature: 330-450 ° C, and draft temperature is 140 ° of 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 ° of C, die head temperature is 190-230 ° of C, and cooling water temperature is 11-18 ° of C, oven drying temperature: 330-450 ° C, and draft temperature is 140 ° of C.Then carry out according to the requirement of the draw ratio of each tunic to draw ratio in length and breadth.
(2) gluing
Use rolling method, take X as adhesive, carry out gluing to A layer, B layer, C layer and D 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 under 40-80 ° of C.
(3) lamination
The A layer of gluing, B layer, C layer and D 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, preferred 60-80 ° C.
According to the present invention, the A layer of step (1) gained, B layer, C layer and/or D layer two-sided all through sided corona treatment, makes 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 the embodiment of the present invention 1, and it is AXBXCXDXAXBXCXD structure.
Fig. 2 is the structural representation of composite membrane prepared by the embodiment of the present invention 1, and it is AXBXCXDXDXCXBXA 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:AXBXCXDXAXBXCXD structure,
Layer thickness profile:
33μm/2μm/10μm/2μm/33μm/2μm/10μm/2μm/33μm/2μm/10μm/2μm/33μm/2μm/10μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
33μm/2μm/10μm/2μm/33μm/2μm/10μm/2μm/10μm/2μm/33μm/2μm/10μm/2μm/33μm
A layer and C layer are all that ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6% with the polypropylene copolymer containing ethene.
B layer and D layer use high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
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 1 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinal stretching multiplying power is 9 times.
B 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 1 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinal stretching multiplying power is 9 times.
A layer, B layer, C layer and D layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt roll coating model coating chlorinated polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 33 μm, and B layer is 10 μm, and C layer thickness is 33 μm, and D layer is 10 μm, and the thickness of X is 2 μm, and overall film thickness is 186 μm.
The performance test results of the film of preparation lists in table 2.
Embodiment 2:AXBXCXDXAXBXCXD structure, layer thickness profile:
38μm/2μm/30μm/2μm/38μm/2μm/30μm/2μm/38μm/2μm/30μm/2μm/38μm/2μm/30μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
38μm/2μm/30μm/2μm/38μm/2μm/30μm/2μm/30μm/2μm/38μm/2μm/30μm/2μm/38μm
A layer and C layer are all that ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6% with the polypropylene copolymer containing ethene.
B layer and D layer are high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer, B layer, C layer and D layer all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times.
B layer 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 5 times.
D layer 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 5 times.
A layer, B layer, C layer and D layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt roll coating model coating chlorinated polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 38 μm, and B layer is 30 μm, and C layer thickness is 38 μm, and D layer is 30 μm, and the thickness of X is 2 μm, and overall film thickness is 286 μm.
The performance test results of the film of preparation lists in table 2.
Embodiment 3:AXBXCXDXAXBXCXD structure, layer thickness profile:
23μm/2μm/10μm/2μm/23μm/2μm/10μm/2μm23μm/2μm/10μm/2μm/23μm/2μm/10μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
23μm/2μm/10μm/2μm/23μm/2μm/10μm/2μm10μm/2μm/23μm/2μm/10μm/2μm/23μm
A layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.C layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.
B layer and D layer are the polypropylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt the acid of roll coating model painting polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 23 μm, and B layer is 10 μm, and C layer thickness is 23 μm, and D layer is 10 μm, and the thickness of X is 2 μm, and overall film thickness is 146 μm.
The performance test results of the film of preparation lists in table 2 as follows.
Embodiment 4:AXBXCXDXAXBXCXD structure, layer thickness profile:
43μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/43μm/2μm/20μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
43μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/43μm
A layer is polypropylene homopolymer, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.C layer is the polypropylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.
B layer is LLDPE, and density is 0.915g/cm
3, melt index is 2.8g/10min.
D layer is LLDPE, and density is 0.915g/cm
3, melt index is 2.8g/10min.
A layer, B layer, C layer and D layer all add Petropols respectively, and Petropols addition is 30% weight of each layer gross weight.
A layer and C are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
B layer and D layer are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
A layer, B layer, C layer and D layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt roll coating model coating chlorinated polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 43 μm, and B layer is 20 μm, and C layer thickness is 43 μm, and D layer is 20 μm, and the thickness of X is 2 μm, and overall film thickness is 266 μm.
The performance test results of the film of preparation lists in table 2.
Embodiment 5:AXBXCXDXAXBXCXD structure, layer thickness profile:
33μm/2μm/33μm/2μm/10μm/2μm/10μm/2μm/33μm/2μm/33μm/2μm/10μm/2μm/10μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
33μm/2μm/33μm/2μm/10μm/2μm/10μm/2μm/10μm/2μm/10μm/2μm/33μm/2μm/33μm
A layer and B layer are all that ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6% with the polypropylene copolymer containing ethene.
C layer and D layer use high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 2 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 2 times, and longitudinal stretching multiplying power is 8 times.
C 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 1 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinal stretching multiplying power is 9 times.
A layer, B layer, C layer and D layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt roll coating model coating chlorinated polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 33 μm, and B layer is 33 μm, and C layer thickness is 10 μm, and D layer is 10 μm, and the thickness of X is 2 μm, and overall film thickness is 186 μm.
The performance test results of the film of preparation lists in table 3.
Embodiment 6:AXBXCXDXAXBXCXD structure, layer thickness profile:
38μm/2μm/38μm/2μm/30μm/2μm/30μm/2μm/38μm/2μm/38μm/2μm/30μm/2μm/30μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
38μm/2μm/38μm/2μm/30μm/2μm/30μm/2μm/30μm/2μm/30μm/2μm/38μm/2μm/38μm
A layer and B layer are all that ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6% with the polypropylene copolymer containing ethene.
C layer and D layer are high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, and melt index is 3.8g/10min.
A layer, B layer, C layer and D layer all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 10 times, and longitudinal stretching multiplying power is 5 times.
B layer 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 10 times.
C layer 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 5 times.
D layer 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 5 times.
A layer, B layer, C layer and D layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt roll coating model coating chlorinated polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 38 μm, and B layer is 38 μm, and C layer thickness is 30 μm, and D layer is 30 μm, and the thickness of X is 2 μm, and overall film thickness is 286 μm.
The performance test results of the film of preparation lists in table 2.
Embodiment 7:AXBXCXDXAXBXCXD structure, layer thickness profile:
23μm/2μm/10μm/2μm/23μm/2μm/10μm/2μm23μm/2μm/10μm/2μm/23μm/2μm/10μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
23μm/2μm/10μm/2μm/23μm/2μm/10μm/2μm10μm/2μm/23μm/2μm/10μm/2μm/23μm
A layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.B layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.
C layer and D layer are the polypropylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt the acid of roll coating model painting polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 23 μm, and B layer is 10 μm, and C layer thickness is 23 μm, and D layer is 10 μm, and the thickness of X is 2 μm, and overall film thickness is 146 μm.
The performance test results of the film of preparation lists in table 3 as follows.
Embodiment 8:AXBXCXDXAXBXCXD structure, layer thickness profile:
43μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/43μm/2μm/
20μm
Or AXBXCXDXDXCXBXA structure, layer thickness profile:
43μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/20μm/2μm/43μm/2μm/20μm/2μm/43μm
A layer is polypropylene homopolymer, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is the polypropylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.
C layer is LLDPE, and density is 0.915g/cm
3, melt index is 2.8g/10min.
D layer is LLDPE, and density is 0.915g/cm
3, melt index is 2.8g/10min.
A layer, B layer, C layer and D layer all add Petropols respectively, and Petropols addition is 30% weight of each layer gross weight.
A layer and B are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
C layer and D layer are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
A layer, B layer, C layer and D layer are respectively through sided corona treatment, and initial surface tension is 45 dyne, and then adopt roll coating model coating chlorinated polypropylene, be compounded to form composite membrane in process, structure is AXBXCXDXAXBXCXD or AXBXCXDXDXCXBXA.Wherein A layer thickness is 43 μm, and B layer is 20 μm, and C layer thickness is 43 μm, and D layer is 20 μm, and the thickness of X is 2 μm, and overall film thickness is 266 μm.
The performance test results of the film of preparation lists in table 3.
The results of property of the multilayer complex films of table 2 embodiment 1-4
The results of property of the multilayer complex films of table 3 embodiment 5-8
Claims (30)
1. a multilayer complex films, it comprises n AXBXCXD 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, each B is identical or different, each C is identical or different, each D is identical or different, each X is identical or different, two-layer containing identical or different acrylic polymer in A layer in described AXBXCXD Rotating fields, B layer, C layer and D layer, two-layer in addition containing identical or different ethylene-based polymer, X is adhesive layer, and described A layer, B layer, C layer and D layer are biaxial tension and comprise one of following combination:
(1) described two-layer being inversely proportional to draw ratio in length and breadth containing acrylic polymer, described two-layer being inversely proportional to draw ratio in length and breadth containing ethylene-based polymer;
(2) described two-layer being inversely proportional to draw ratio in length and breadth containing acrylic polymer, is describedly 1 and two-layer stretching ratio is identical to draw ratio in length and breadth containing the two-layer of ethylene-based polymer;
(3) be describedly 1 and two-layer stretching ratio is identical, described two-layer being inversely proportional to draw ratio in length and breadth containing ethylene-based polymer to draw ratio in length and breadth containing the two-layer of acrylic polymer;
(4) be describedly 1 and two-layer stretching ratio is identical to draw ratio in length and breadth containing the two-layer of acrylic polymer, be describedly 1 and two-layer stretching ratio is identical to draw ratio in length and breadth containing the two-layer of ethylene-based polymer;
Wherein, in combination (4), the A layer in described multilayer complex films or B layer or C layer or D layer are multi-layer co-extruded structure.
2. multilayer complex films according to claim 1, is characterized in that, in described multilayer complex films, n AXBXCXD Rotating fields is by X order compound, namely according to the order compound of AXBXCXDXAXBXCXD; Or n AXBXCXD Rotating fields replaces compound by X in described multilayer complex films, namely according to the order compound of AXBXCXDXDXCXBXA; Or n AXBXCXD Rotating fields is by the unordered compound of X in described multilayer complex films.
3. multilayer complex films according to claim 1 and 2, is characterized in that, in combination (1) ~ (3), the A layer in described multilayer complex films or B layer or C layer or D layer are single layer structure or multi-layer co-extruded structure.
4. multilayer complex films according to claim 3, is characterized in that, described A layer, and the multi-layer co-extruded structure of B layer or C layer or D layer is at least 2 layers.
5. multilayer complex films according to claim 4, is characterized in that, described A layer, and the multi-layer co-extruded structure of B layer or C layer or D layer is 2-15 layer.
6. multilayer complex films according to claim 5, is characterized in that, described A layer, and the multi-layer co-extruded structure of B layer or C layer or D layer is 3-11 layer.
7. multilayer complex films according to claim 6, is characterized in that, described A layer, and the multi-layer co-extruded structure of B layer or C layer or D layer is 5-9 layer.
8. multilayer complex films according to claim 7, is characterized in that, described A layer, and the multi-layer co-extruded structure of B layer or C layer or D layer is 6-8 layer.
9. multilayer complex films according to claim 1 and 2, it is characterized in that, the acrylic polymer of described A layer or B layer or C layer or D layer is Noblen or propylene copolymer, for 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 ɑ-alkene.
10. multilayer complex films according to claim 9, is characterized in that, described comonomer is ethene, butylene, hexene or octene.
11. multilayer complex films according to claim 1 and 2, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer or C layer or D layer is 148-170 DEG C; Molecular weight distribution is 2-16, tests with GPC; Melt index is 0.5-10g/10min.
12. multilayer complex films according to claim 11, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer or C layer or D layer is 150-167 DEG C.
13. multilayer complex films according to claim 12, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer or C layer or D layer is 155 DEG C-165 DEG C.
14. multilayer complex films according to claim 11, is characterized in that, the molecular weight distribution of the acrylic polymer of described A layer or B layer or C layer or D layer is 4-10.
15. multilayer complex films according to claim 11, is characterized in that, the melt index of the acrylic polymer of described A layer or B layer or C layer or D layer is 1-8g/10min.
16. multilayer complex films according to claim 1 and 2, is characterized in that, the ethylene-based polymer of described A layer, B layer or C layer or D layer is high density polyethylene (HDPE), high-pressure process low-density polyethylene or low-pressure process LLDPE.
17. multilayer complex films according to claim 16, is characterized in that, the fusing point of the ethylene-based polymer of described A layer, B layer or C layer or D layer is 130-150 DEG C; Melt index is 0.2-50g/10min.
18. multilayer complex films according to claim 17, is characterized in that, the fusing point of the ethylene-based polymer of described A layer, B layer or C layer or D layer is 135-148 DEG C.
19. multilayer complex films according to claim 17, is characterized in that, the melt index of the ethylene-based polymer of described A layer, B layer or C layer or D layer is 1-45g/10min.
20. multilayer complex films according to claim 19, is characterized in that, the melt index of the ethylene-based polymer of described A layer, B layer or C layer or D layer is 2-40g/10min.
21. multilayer complex films according to claim 1 and 2, is characterized in that, add another resin again, be selected from Petropols in A layer, B layer or C layer or D layer; Its addition is 1-30 % by weight.
22. multilayer complex films according to claim 21, is characterized in that, described Petropols are C
5-C
9petropols.
23. multilayer complex films according to claim 21, is characterized in that, described Petropols are hydrogenated petroleum resin.
24. multilayer complex films according to claim 23, is characterized in that, described hydrogenated petroleum resin is C
5-C
9hydrogenated petroleum resin.
25. multilayer complex films according to claim 21, is characterized in that, the addition of described resin is 2-20 % by weight.
26. multilayer complex films according to claim 25, is characterized in that, the addition of described resin is 3-15 % by weight.
27. multilayer complex films according to claim 26, is characterized in that, the addition of described resin is 4-10 % by weight.
The preparation method of the multilayer complex films any one of 28. 1 kinds of claims 1 to 27, it comprises the following steps:
(1) preparation of A layer, B layer, C layer and D layer
To be extruded by individual layer or multi-layer co-extruded, prepare polyolefin sheets, under the temperature environment of 130-185 DEG C, then carry out biaxial tension process A layer, B layer, C layer and D layer, the cross directional stretch multiplying power of each layer and longitudinal stretching multiplying power are according to the restriction setting in above-mentioned multilayer complex films;
(2) use rolling method, with X layer for adhesive, carry out gluing to A layer, B layer, C layer and D 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, B layer, C layer and D layer are carried out lamination compound, obtain described composite membrane.
The application of the multilayer complex films any one of 29. 1 kinds of claims 1 to 27, it is for bill, marketable securities, Front cover of book and periodical, picture album and packaging material.
30. 1 kinds of goods, it is obtained by the multilayer complex films face coat any one of claim 1 to 27 and printing, and described goods comprise Front cover of book and periodical, picture album, bill, marketable securities and packaging material.
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| CN1251808A (en) * | 1998-09-28 | 2000-05-03 | 可乐丽股份有限公司 | Multi-layer films |
| CN101044019A (en) * | 2004-10-22 | 2007-09-26 | 陶氏环球技术公司 | Improved microlayer structures and methods |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1251808A (en) * | 1998-09-28 | 2000-05-03 | 可乐丽股份有限公司 | Multi-layer films |
| CN101044019A (en) * | 2004-10-22 | 2007-09-26 | 陶氏环球技术公司 | Improved microlayer structures and methods |
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