CN105619984B - A kind of acrylic polymer-ethylene-based polymer multilayer complex films, preparation method, purposes and its product - Google Patents

A kind of acrylic polymer-ethylene-based polymer multilayer complex films, preparation method, purposes and its product Download PDF

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CN105619984B
CN105619984B CN201610139313.4A CN201610139313A CN105619984B CN 105619984 B CN105619984 B CN 105619984B CN 201610139313 A CN201610139313 A CN 201610139313A CN 105619984 B CN105619984 B CN 105619984B
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layers
multilayer complex
multiplying power
complex films
layer
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CN105619984A (en
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陈大魁
黄旭生
詹越强
谷汉进
云小兵
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ZHEJIANG ZHONGCHENG PACKING MATERIAL CO Ltd
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ZHEJIANG ZHONGCHENG PACKING MATERIAL CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant

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  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of multilayer complex films comprising AXBXC layer structure, wherein the A layers in the layer structure include acrylic polymer, C layers include with A layers of identical or different acrylic polymer, B layers include ethylene-based polymer；Alternatively, A layers include ethylene-based polymer, C layer comprising with A layers of identical or different ethylene-based polymer, B layers include acrylic polymer；X is adhesive layer；A layers described, B layers and C layers is biaxial tension and A layers and C layer of the vertically and horizontally draw ratio is similar and different, and B layers of the cross directional stretch multiplying power is identical with longitudinal stretching multiplying power.The present invention also provides the preparation method of above-mentioned multilayer complex films, its purposes and include the product of the multilayer complex films.The acrylic polymer ethylene-based polymer multilayer complex films of the present invention have the performances such as high-stiffness, high transparency, low temperature resistant, high-tear strength.

Description

A kind of acrylic polymer-ethylene-based polymer multilayer complex films, preparation method, Purposes and its product
Technical field
The present invention relates to a kind of acrylic polymer-ethylene-based polymer multilayer complex films, preparation method and its application, The invention further relates to the products for including the composite membrane, belong to field of compound material.
Background technology
Biaxially oriented polypropylene (BOPP) film efficiently uses its excellent light, transparent, mechanical strength, nontoxic, anti- Tide, gas permeability be low, the characteristics such as rigid, is used for using packaging material as the wide range of areas of representative.For example be widely used for food, medicine, The packaging of the products such as daily light industry, cigarette and lamination are compound.A kind of purposes of BOPP film is to fit in paper surface, such as book This, packing carton etc. plays a part of moisture-proof and increases surface gloss.
BOPP film is generally 3-5 layers of coextrusion structure, and step drawing production technology is mainly made of following process：Match Expect that batch mixing, extruder are squeezed out, preheated by heating roller by T-shaped mould head extrusion sheet, sheet chilling, sheet, sheet is longitudinally drawn Stretch, thermal finalization, preheat again, cross directional stretch, thermal finalization, cooling, sided corona treatment, winding, cutting and storage.CN101160209A A kind of Biaxially stretched multilayer polypropylene film is disclosed in (Oji Paper), is added in by acrylic polymer The two sides for the bidirectional stretching polypropylene film substrate layer that propylene polymer composition made of inorganic compound powder obtains, tool Standby superficial layer and back layer containing acrylic polymer, acrylic polymer in the substrate layer in surface/back layer Acrylic polymer can be identical or different.It obtains uniform hidden power by adding inorganic compound powder in substrate layer With whiteness it is excellent, be 25-55 μm of film almost without the preferred thickness of concave-convex surface.The film is by the following method It obtains：The acrylic polymer for forming substrate layer is obtained into multi-layer sheet by itself well known method co-extrusion modling, It is (longitudinal × horizontal that face multiplying power is stretched to using simultaneously bi-directionally pulling method or sequentially the biaxially oriented films forming method such as biaxial tension method To) 45~65 times and obtain.By using for sequentially biaxial tension method, can by a temperature of 70~140 DEG C longitudinal with 4.5 After~7.5 times of range stretches, then under laterally 120~190 DEG C of temperature range under 7~12 times and face multiplying power is (longitudinal × laterally) be stretched to 45~65 times after, obtained in 110~180 DEG C of temperature range heat fixation.
There are many ideal performance, such as high tensile, high-stiffness, high grades of transparency etc. for BOPP film.However, BOPP film Service life it is short, generally some months to 1 year, some physical properties such as resistance to low temperature, fall strength of briquette, tearing strength etc. It is poor, be not suitable for printed matter, packaging material for being used for a long time etc..In addition, the thickness of existing bidirectional stretching polypropylene film Generally less than 50 μm, deflection cannot meet the needs of high-end, therefore constrain its some application ranges.
The density polyethylene film with high of stretching has been used for plastics package field.It is introduced in British Patent No. 1287527 Some such films, they are biaxially stretched on machine direction (MD) and laterally (TD) both direction more than 6.5 times Degree.The twin shaft imbalance oriented film that U.S. Patent No. 4680207 is related to linear low density polyethylene, it is in processing side It is pulled up and is no more than 6 times, be orientated in the horizontal no more than 3 times and less than stretching in the direction of the machine.
Currently, industrial quarters in some applications high to physical property requirements, generally uses biaxial stretching polyester (BOPET) Film or biaxial tension nylon (BOPA) film.But BOPET film and BOPA film ratios are great, and of high cost, solvent resistance is poor.
Therefore, industrial quarters needs a kind of high transparency with traditional BOPP film and high-stiffness but simultaneously again with resistance to low The novel thin film of warm nature energy, high-tear strength.
Invention content
The present invention in order to overcome the deficiencies of the prior art, provides a kind of acrylic polymer-ethylene-based polymer MULTILAYER COMPOSITE Film has the performances such as high-stiffness, high transparency, low temperature resistant and high-tear strength.
It is a further object to provide the preparation methods of above-mentioned multilayer complex films.
It is also another object of the present invention to provide the purposes of above-mentioned multilayer complex films.
It is also another object of the present invention to provide the products for including above-mentioned multilayer complex films.
The present invention is achieved through the following technical solutions：
A kind of multilayer complex films comprising AXBXC layers of structure, wherein X is adhesive layer；A layers, B in the layer structure Layer and the C layers of polymer for including are one of following combinations：
(a) A layers include acrylic polymer, C layer comprising with A layers of identical or different acrylic polymer, B layers include second Alkene based polymer；
(b) A layers include ethylene-based polymer, C layer comprising with A layers of identical or different ethylene-based polymer, B layers include third Alkene based polymer；
Also, A layers described, B layers and C layers is biaxial tension and includes one of following combination：
(1) described A layers, B layer of the cross directional stretch multiplying power and longitudinal stretching multiplying power different with C layers of transverse and longitudinal draw ratio It is identical；
(2) described A layers, B layer of the cross directional stretch multiplying power and longitudinal stretching multiplying power identical with C layers of vertically and horizontally draw ratio It is identical.
According to the present invention, for scheme (1).Described A layers of vertically and horizontally draw ratio and described C layers of vertically and horizontally draw ratio are not Together；Preferably, described A layers of longitudinal stretching multiplying power is more than cross directional stretch multiplying power, and C layers of the cross directional stretch multiplying power is more than vertical To stretching ratio；It is highly preferred that described A layers of vertically and horizontally draw ratio is inversely proportional with described C layers of vertically and horizontally draw ratio, i.e., it is described A layers of longitudinal stretching is equal to the ratio of C layers of the cross directional stretch and longitudinal stretching with ratio stretching in the transverse direction.It is highly preferred that Described A layers of longitudinal stretching multiplying power and C layers of the cross directional stretch multiplying power are same or similar, and A layers of the cross directional stretch times Rate and described C layers of longitudinal stretching multiplying power are same or similar；It is more preferred still that described A layers of longitudinal stretching multiplying power with it is C layers described Cross directional stretch multiplying power it is identical, and A layers of the cross directional stretch multiplying power is identical as described C layers of longitudinal stretching multiplying power.In addition, excellent Selection of land, B layers of the stretching ratio is identical as described A layers of a stretching ratio, i.e., described B layers of the stretching ratio and the A The cross directional stretch multiplying power of layer is identical or identical as described A layers of longitudinal stretching multiplying power.
According to the present invention, for scheme (2).Described A layers of vertically and horizontally draw ratio and described C layers of vertically and horizontally draw ratio phase Together；Preferably, described A layers of longitudinal stretching multiplying power is equal to cross directional stretch multiplying power, and described C layers of longitudinal stretching multiplying power is equal to laterally Stretching ratio and identical as A layers.Furthermore it is preferred that B layers of the stretching ratio is identical as described A layers of a stretching ratio, I.e. described B layers of the stretching ratio is identical as A layers of the cross directional stretch multiplying power, or the longitudinal stretching multiplying power phase with described A layers Together；It is highly preferred that described A layers of longitudinal stretching multiplying power is equal to cross directional stretch multiplying power, described C layers of longitudinal stretching multiplying power is equal to cross To stretching ratio and identical as A layers, B layers of the cross directional stretch multiplying power is equal to longitudinal stretching multiplying power and identical as A layers.
According to the present invention, A layers in the multilayer complex films or C layers are single layer structure or multi-layer co-extruded structure.
According to the present invention, the B layers in the multilayer complex films are single layer structure or multi-layer co-extruded structure.
A layers described according to the present invention, B layers or C layers of multi-layer co-extruded structure is at least 2 layers, for example, 2-15 layers, excellent Select 3-11 layers, it is 5-9 layers more preferable, even more preferably from 6-8 layers.
According to the present invention, the material identical or difference of the binder in described any one X layers are selected from：Chlorination poly- third Alkene, polyurethane, acrylic resin, or mixtures thereof epoxy resin.
According to the present invention, polypropylene chlorination is made using solwution method, suspension method or solid phase method for the chlorinated polypropylene. The mass content of chlorine is 20%-70%, and fusing point is less than 150 DEG C.
According to the present invention, the polyurethane is that either no-solvent type one-component or multicomponent are poly- for solvent type, water-dispersion type Urethane adhesive.
According to the present invention, the acrylic resin is solvent type, water-dispersion type either no-solvent type one-component or multigroup Divide the adhesive containing acrylic acid or acrylates.
According to the present invention, the epoxy resin is solvent type, water-dispersion type either no-solvent type one-component or multicomponent Epoxy type adhesive.
According to the present invention, the thickness of the multilayer complex films is 50-150 μm, preferably 60-120 μm, more preferable 70-100 μ M, even more preferably from 80-90 μm.
According to the present invention, in the multilayer complex films A layers or C layers of thickness be 5-65 μm, preferably 10-55 μm, more preferably 20-40μm。
According to the present invention, in the multilayer complex films each X layers of thickness be 0.5-10 μm, preferably 1-6 μm, more It is preferred that 2-5 μm.
According to the present invention, the summation of all X layer thickness is no more than the 30% of the composite film thickness in the multilayer complex films, Preferably more than 20%, more preferably no more than 15%, even more preferably from no more than 10%.
According to the present invention, the B layer thickness in the multilayer complex films is 5-30 μm, preferably 10-20 μm, A layers and C layer thickness Difference is no more than 20%, preferably more than 15%, more preferably no more than 10%.
According to the present invention, A layers of tensile strength is 1.5 in horizontal and vertical ratio in the multilayer complex films:1.0 arriving 7.0:1.0, preferably 2.0:1.0 to 5.0:1.0.
According to the present invention, C layers of tensile strength is 1.0 in horizontal and vertical ratio in the multilayer complex films:1.5 arriving 1.0:7.0, preferably 1.0:2.0 to 1.0:5.0.
According to the present invention, the cross directional stretch multiplying power of the A layers in the multilayer complex films is 7-12.5 times, longitudinal stretching multiplying power It it is 1-6 times, preferably laterally stretching ratio is 8-10 times, and longitudinal stretching multiplying power is 2-4 times.
According to the present invention, the cross directional stretch multiplying power of the C layers in the multilayer complex films is 1-6 times, and longitudinal stretching multiplying power is 7-12.5 times, preferably laterally stretching ratio is 2-4 times, and longitudinal stretching multiplying power is 8-10 times.
According to the present invention, horizontal and vertical survey in the tensile strength of the multilayer complex films, deflection and tear-resistant intensity Examination value ratio is 0.7:1.0 to 1.0:1.3.
The vertically and horizontally tensile strength of the multilayer complex films is more than 100MPa, preferably greater than 120MPa, more preferably greater than 140MPa。
According to the present invention, the acrylic polymer is preferably Noblen or propylene copolymer, typically entirely Same stereo-homopolymer, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have it is a small amount of The polypropylene blend of the atactic propene copolymer of comonomer and ethylene copolymer-modified isotactic polypropylene.Copolymerization Monomer is ethylene or higher alpha-olefin, such as ethylene, butylene, hexene or octene.
According to the present invention, the fusing point of the acrylic polymer is 148 to 170 DEG C, preferably 150-167 DEG C；More preferable 155 ℃-165℃；Molecular weight distribution (GPC tests) is 2-16, preferably 4-10；Melt index is 0.5-10g/10min, preferably 1- 8g/10min。
According to the present invention, the ethylene-based polymer is preferably high density polyethylene (HDPE), high-pressure process low-density polyethylene or low Platen press linear low density polyethylene.The density of high density polyethylene (HDPE) about 0.941g/cm3Or higher, preferably from about 0.948g/cm3 To about 0.968g/cm3, more preferably from about 0.952g/cm3To about 0.962g/cm3；About 130 DEG C to about 148 DEG C of fusing point；Melt index (being measured according to ASTM D1238) is 0.2-50g/10min, preferably 1-45g/10min, more preferable 2-40g/10min.Low-density The density of polyethylene is about 0.912g/cm3To about 0.94g/cm3, preferably 0.915g/cm3To 0.928g/cm3；Melt index (root Measured according to ASTM D1238) it is 0.2-50g/10min, preferably 1-45g/10min, more preferable 2-40g/10min.Linea low density Polyethylene is ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2-50g/10min The melt index (being measured according to ASTM D1238) of (such as 1-10g/10min) is and in 0.857g/cm3To 0.950g/cm3, it is excellent Select 0.905g/cm3To 0.940g/cm3, more preferable 0.910g/cm3To 0.928g/cm3Range density.Ethylene-based polymer It can also be terpolymer, such as ethylene/butene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/ Octene copolymer；Melt index of these copolymers with 0.2-50g/10min (such as 1-10g/10min) is (according to ASTM D1238 is measured) and in 0.857g/cm3To 0.950g/cm3, preferably 0.905g/cm3To 0.940g/cm3, more preferably 0.910g/cm3To 0.928g/cm3Range density.
According to the present invention, another resin can be also added in A layers, B layers or C layers, such as Petropols or hydrogenation stone Oleoresin, to change the performances, preferably C such as heat sealer, gas permeability, deflection and intensity5-C9Petropols or C5-C9Hydrogenation Petropols.Its addition is the 1-30% weight of each layer total weight, preferably 2-20% weight, and more preferable 3-15% weight is gone back More preferable 4-10% weight.
The present invention also provides the preparation methods of the multilayer complex films comprising following steps：
(1) A layers, B layers and C layers of preparation
It is squeezed out by single layer or multi-layer co-extruded, polyolefin sheets is prepared, then under 130-185 DEG C of temperature environment It carries out biaxial tension and processes A layer, B layers and C layers, wherein A layers of vertically and horizontally draw ratio is similar and different with C layers, and B layers are indulged It is identical as cross directional stretch multiplying power to stretching ratio；
(2) rolling method is used, with X layers for adhesive, to A layers, B layers and C layers progress gluing, wherein outermost the two of composite membrane Layer carries out single spreading, and intermediate each layer carries out one or two sides gluing, and after gluing, each layer is dried at 40-80 DEG C；
(3) A of gluing layers, B layers and C layers be laminated compound, obtain the composite membrane.
According to the present invention, the two-sided of A layers obtained by step (1) and/or C layers all passes through sided corona treatment, makes its initial surface Tension reaches 44 dynes per centimeters or more.The surface tension of gained composite membrane is more than 36 dynes per centimeters.It is further preferred that surface tension Reach 38 dynes per centimeters or more.
Film prepared by the present invention can be used for needing high-stiffness, tear-resistant bill, marketable securities, printed matter and packing timber Material.
The present invention also provides a kind of application of aforementioned any one of them multilayer complex films, be used for bill, marketable securities, Printed matter and packaging material.
The present invention also provides a kind of product, the face coat by aforementioned any one of them multilayer complex films and printing It is made, the product includes printed matter (such as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.
Beneficial effects of the present invention：
Acrylic polymer prepared by the present invention-ethylene-based polymer multilayer complex films has excellent comprehensive performance, Tensile strength, deflection and tear-resistant intensity are all very high, and its vertical and horizontal performance has good balance, and with good The good transparency, specific performance is referring to table 1.
The performance of 1 composite membrane of the present invention of table
It is described in detail
[A layers, B layers and C layers of compositions]
According to the present invention, the acrylic polymer in described A layers or B layer or C layers is preferably Noblen or propylene Copolymer or polypropene composition；Typically isotaxy homopolymer, or for different isotactic polypropylene, random vertical Structure polypropylene, syndiotactic polypropylene, the atactic propene copolymer for having a small amount of comonomer and ethylene copolymer-modified complete same The polyacrylic polypropylene blend of vertical structure.Comonomer is ethylene or higher alpha-olefin, such as ethylene, butylene, hexene or octene. The content of comonomer is preferably 0.2wt% to 2.0wt%, more preferably 0.35wt% to 0.85wt%.The present invention these Acrylic polymer can be the mixture containing one kind or two or more polymer, such as the Noblen that molecular weight is different, Or the composition of propylene and a small amount of alpha-olefin random copolymer.The acrylic polymer of the present invention, generally according to polyacrylic The vistanex of title manufacture, sale, typically density are 0.890~0.930g/cm3, MFR (ASTM D1238, load 2160g, 230 DEG C of temperature) it is 0.5~60g/10min, preferably 0.5~20g/10min, more preferable 0.5-15g/10min, it goes back The more preferably Noblen of 1~5g/10min.
According to the present invention, the fusing point of the acrylic polymer is 148 to 170 DEG C, preferably 150-167 DEG C, more preferable 155 ℃-165℃；Molecular weight distribution (GPC tests) is 2-16, preferably 4-10；Melt index is 0.5-10g/10min, preferably 1- 8g/10min.The industrial common Noblen of BOPP film has：The T38F of Lanzhou Petrochemical and Daqing petrochemical；Dalian petrochemical industry T36F；This kind of Noblen tests melt index (MI) according to ASTMD-1238 and can be about 0.2-20g/10min, preferably 0.5- 15g/10min, fusing point can be about between 155 DEG C -165 DEG C.
According to the present invention, the ethylene-based polymer in described A layers or B layer or C layers be preferably high density polyethylene (HDPE) (HDPE), Low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE is not or single with a small amount of copolymerization Body, comonomer is propylene or higher alpha-olefin, such as butylene, hexene or octene, and has about 0.941g/cm3Or more High (for example, about 0.948g/cm3To about 0.968g/cm3, preferably from about 0.952g/cm3To about 0.962g/cm3) density, such as About 130 DEG C to about 148 DEG C of fusing point and 0.2-50g/10min, preferably 1-45g/10min, more preferable 2-40g/10min's Melt index (measures) according to ASTM D1238.LDPE has in 0.912g/cm3To 0.94g/cm3(such as 0.915g/cm3It arrives 0.928g/cm3) range density and 0.2-50g/10min (preferably 1-45g/10min, more preferable 2-40g/10min) Melt index (measures) according to ASTM D1238.LLDPE point for ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/ Octene copolymer and the melt index (being measured according to ASTM D1238) with 0.2-50g/10min (such as 1-10g/10min) And in 0.857g/cm3To 0.950g/cm3, preferably 0.905g/cm3To 0.940g/cm3, more preferable 0.910g/cm3It arrives 0.928g/cm3Range density.In addition ethylene-based polymer can also be terpolymer, as ethylene/butene/hexene is total Polymers, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymers have 0.2-50g/10min The melt index (being measured according to ASTM D1238) of (such as 1-10g/10min) is and in 0.857g/cm3To 0.950g/cm3, it is excellent Select 0.905g/cm3To 0.940g/cm3, more preferable 0.910g/cm3To 0.928g/cm3Range density.
If A layers described, B layers and C layers of polymer acrylic polymer then wherein can also be mixed into the polymerization of part ethylene system Object, such as high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE not or has a small amount of comonomer, and comonomer is propylene or higher alpha-olefin, such as ethylene, butylene, hexene or pungent Alkene etc., and there is about 0.941g/cm3Or higher (for example, about 0.948g/cm3To about 0.968g/cm3, preferably from about 0.952g/cm3To about 0.962g/cm3) density, for example, about 130 DEG C to about 148 DEG C of fusing point and 0.2-50g/10min, It is preferred that the melt index (being measured according to ASTM D1238) of 1-45g/10min, more preferable 2-40g/10min.LDPE has 0.912g/cm3To 0.94g/cm3(such as 0.915g/cm3To 0.928g/cm3) range density and 0.2-50g/10min The melt index (being measured according to ASTM D1238) of (preferably 1-45g/10min, more preferable 2-40g/10min).LLDPE points are second Alkene/butylene copolymer, ethylene/hexene copolymer and ethylene/octene and with 0.2-50g/10min (such as 1-10g/ Melt index (being measured according to ASTM D1238) 10min) is and in 0.857g/cm3To 0.950g/cm3, preferably 0.905g/ cm3To 0.940g/cm3, more preferable 0.910g/cm3To 0.928g/cm3Range density.In addition ethylene-based polymer may be used also To be terpolymer, such as ethylene/butene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene Copolymer；Melt index of these copolymers with 0.2-50g/10min (such as 1-10g/10min) is (according to ASTM D1238 Measure) and in 0.857g/cm3To 0.950g/cm3, preferably 0.905g/cm3To 0.940g/cm3, more preferable 0.910g/cm3It arrives 0.928g/cm3Range density.
Deflection of the present invention refers to that Paper or cardboard supports resistant to bending strength character.Deflection is directly proportional to EI/W values, Middle W, E and I are respectively quality, elasticity modulus and the moment of inertia of Paper or cardboard.Wherein, the deflection or flexural rigidity of cardboard be Refer to and certain load is applied to the sample vertically clipped at away from fixture 5cm, observation is tried from sample camber 3.81mm width Sample is indicated to the moment of flexure needed for 15 ° with gcm.Paper sheet stiffness is a critically important index, directly affects the big of folding line deflection Small (another influence factor is d ie cutting press), to influence finished product molding.Deflection is small, and finished product is easy to conquassation, warpage；Deflection is big, Finished product is difficult to be molded.
In order to further increase the deflection, and heat sealer, gas permeability and intensity of multilayer complex films etc. of the present invention Another resin, such as Petropols, hydrogenated petroleum resin etc., preferably C can be added in A layers, B layers or C layers in performance5-C9 Petropols or C5-C9Hydrogenated petroleum resin.Its addition is the 1-30% weight of each layer total weight, preferred 2-20% weight, more It is preferred that 3-15% weight, even more preferably from 4-10% weight.
The addition of about 0.01~5.0 mass % can be added in A layers described, B layers and C layers of polymer with master batch form Agent.The additive is preferably 0.01~3.0 mass %, more preferable 0.05~1.0 mass %.
The additive has：It is antiblocking agent, slipping agent (i.e. lubricant or slipping agent), antistatic agent, nucleating agent, heat-resisting steady Determine usually be added to known to agent, weathering stabilizers, ultra-violet absorber, turbid dose anti-, pigment, dyestuff etc. various in polyolefin Additive.
As the antiblocking agent, antiblocking agent well known in the art can be used, such as silica, talcum, mica, zeolite, or The inorganic compound particles such as the metal oxide that metal alkoxide is sintered；Or polymethyl methacrylate, melamine first The organic compounds such as urea formaldehyde, melamine urea resin, polyester resin.Wherein, particularly preferred from resistance to blocking aspect Use silica, polymethyl methacrylate.
As the lubricant, amide based compound etc. such as stearmide, erucyl amide, oleamide can be used.
As the antistatic agent, ethylene oxide adduct, quaternary amine based compound, alkane such as betanin derivative can be used Base diethanol amine aliphatic ester, fatty acid glyceride, tristerin etc..
As the nucleating agent, such as D-sorbite system, organophosphate metal salt system, metal salt of organic carboxylic acid can be used System, rosin series nucleating agent etc..
As the heat-resisting stabilizing agent, such as 2,6- di-tert-butyl-4-methy phenols (BHT) etc. can be used.
Also delustring masterbatch can be added in A layers described, B layers or C layers of polymer to produce Extinctive thin film, or pearly-lustre is added Masterbatch produces pearly-lustre film.
Laminate stretch acrylic polymer-ethylene-based polymer film of the present invention can be as needed, to single or double Implement the surface treatments such as sided corona treatment, flame treatment.It, can be overleaf independent on layer to assign heat sealability in addition, according to purposes It is laminated containing high-pressure process low-density polyethylene, linear low density polyethylene (LLDPE), crystallinity or low-crystalline ethylene and carbon number 3~10 The random copolymer or propylene of alpha-olefin and ethylene or random copolymer, polybutene, the ethylene-of the alpha-olefin of 4 or more carbon number The film of the low melting point polymers such as vinyl acetate copolymer, or film of the lamination containing their compositions.In addition, in order to carry Processing can be fixed to adhesives such as oriented film surface imines, carbamates in the high cementability with other materials, Maleic anhydride modified polyolefin can be laminated.
[X layers of compositions]
According to the present invention, the material identical or difference of the binder in described any one X layers are selected from：Chlorination poly- third Alkene, polyurethane, acrylic resin, or mixtures thereof epoxy resin.
Polypropylene chlorination is made using solwution method, suspension method or solid phase method for the chlorinated polypropylene of the present invention.The matter of chlorine Amount content is 20%-70%, and fusing point is less than 150 DEG C.
According to the present invention, the polyurethane is that either no-solvent type one-component or multicomponent are poly- for solvent type, water-dispersion type Urethane adhesive.
According to the present invention, the acrylic resin is solvent type, water-dispersion type either no-solvent type one-component or multigroup Divide the adhesive containing acrylic acid or acrylates.
According to the present invention, the epoxy resin is solvent type, water-dispersion type either no-solvent type one-component or multicomponent Epoxy type adhesive.
The present invention polyurethane resin can be selected from generally as containing polyurethane well known to film adhesive dry lamination, Waterborne dry-type lamination, solventless liminating, the polyester-polyurethane of electronic beam solidified laminating adhesive manufacture, polyether-polyurethane or poly- Urethane carbamide resin etc..The polyurethane resin can be water-dispersion type or solvent type any, but be covered from polyurethane resin The degree of cross linking of layer is easy to adjust, and from the operating environment aspect of production scene, preferably water dispersant type polyaminoester resin.
As water dispersant type polyaminoester resin, preferably to the main chain of polyurethane resin or side chain introduce carboxylate (- COONa etc.), sulfonate (- SO3Na etc.) etc. hydrophilic groups self-emulsifying type polyurethane resin.In the case that solvent type, by isocyanide Acid esters system resin is used for crosslinking agent, forms the polyurethane with three-dimensional structure, but water-dispersion type becomes linear polyurethane or poly- ammonia The case where ester carbamide resin, is in the majority, therefore relative to polyurethane resin, can add the melamine series tree of 3~10 mass % or so The crosslinking agents such as fat, epoxy system resin, imines system resin, can also add the acid catalyst of 0.5~1 mass % or so, come further Promote curing reaction.The crosslinking agent can not only improve water resistance, the solvent resistance of easy-adhesion overlay film, can also improve bonding Property.
In addition, when using water dispersant type polyaminoester resin, the surfactants such as antifoaming agent or emulsifier are contained in ingredient When, it is possible to so that the surface of Biaxially stretched multilayer propylene polymer thin film is whitened, leads to bad order.In addition, the present invention In polyurethane resin, for example, in order to prevent adhesion the purpose of, as needed, inorganic particles or organic fine particles etc. can also be added.
On the one or both sides of acrylic polymer-ethylene-based polymer film, (lamination) polyurethane resin (X) is covered When, it can be by the way that the aqueous solution of polyurethane resin or dispersion liquid Kohler coater, direct gravure coater, intaglio offset be coated with The gravure coaters such as mechanical, electrical arc gravure coater, reverse rotating gravure and nozzle mode；Top feed reverse roll coating machine, bottom charging The reverse roll coatings machine such as reverse roll coating machine and nozzle material-feeding reverse roll coating machine, coating machine, the lip of 5 rollers apply machine, bar coater, inverse bar type Itself various well known coating machine such as coating machine, die head formula coating machine, according to making contained combination in polyurethane resin aqueous solution The amount of object is 0.1~20g/m2, preferably 0.3~2g/m2It is 10 seconds dry or more at a temperature of 50~140 DEG C after being coated And it obtains.
[preparation methods of multilayer complex films]
According to the present invention, using biaxial tension, i.e., in stretching-machine, at certain temperature and speed, vertical two It is stretched on a direction (longitudinally, laterally) and film is made.So-called longitudinal direction refers to the direction that processing is squeezed out along film, so-called It refer to laterally the direction that vertical thin-film squeezes out processing.Vertically and horizontally draw ratio refers to the ratio of longitudinal stretching multiplying power and cross directional stretch multiplying power Value.
The present invention provides the preparation method of the multilayer complex films comprising following steps：
(1) preparation of A layers, B layers and C tunics
It is prepared using the method for biaxial tension, for biaxial tension, substep sequentially biaxial tension method may be used, can also adopt With synchro-draw method.
The drawing process includes plain film method and periosteum method.For biaxial tension, the technical process of the plain film method includes Synchro-draw process, includes the following steps：
At the synchro-draw → traction of dispensing → extrusion → chilling → vertically and horizontally and optional surface treatment → winding → timeliness Reason → cutting → product.
The technical process of the plain film method further includes step drawing process, is included the following steps：
Dispensing → extrusion → chilling → longitudinal stretching → cross directional stretch → traction and it is optional surface treatment → winding → when Effect processing → cutting → product.
According to the present invention, the longitudinal stretching includes preheating, micro-stretching and sizing.
According to the present invention, the cross directional stretch includes preheating, big to stretch, and is shaped and cooling.
According to the present invention, the chilling refers to being cooled down using coolant liquid, and preferably coolant liquid is cooling water.The chilling Effect be in order to make crystallization refine, so as to improve transparency and deflection.
According to the present invention, the extrusion includes single layer extrusion or multi-layer co-extruded.Described squeeze out uses melting extrusion.
According to the present invention, the dispensing includes carrying out dispensing according to the requirement of formula, can pass through electronic measurement.
The technical process of the periosteum method includes synchro-draw process, is included the following steps：
Dispensing → extrusion (including single layer squeezes out or multilayered molten squeezes out) → chilling → mother's film → water removal → baker far infrared Heating → vertically and horizontally synchro-draw → collapser flattens → cut open side → heat treatment → cooling → winding → ageing treatment → cutting → Product.
The technical process of the periosteum method further includes step drawing process, is included the following steps：
Dispensing → extrusion (including single layer squeezes out or multilayered molten squeezes out) → chilling → mother's film → water removal → baker far infrared Heating → longitudinal stretching → cross directional stretch → collapser flattens → cut open side → heat treatment → cooling → winding → ageing treatment → point Cut → product.
According to the present invention, the chilling refers to being cooled down using coolant liquid, and preferably coolant liquid is cooling water.The chilling Effect be in order to make crystallization refine, so as to improve transparency and deflection.
When the plain film method is plain film substep biaxial tension, specifically comprise the following steps：
(a) dispensing is carried out by the requirement of formula, be added in the hopper above the extruder of single-layer or multi-layer co-extrusion, plastics are logical After crossing external heating and the screw rod rotational shear plasticizing of extruder barrel, the rack-style into single-layer or multi-layer coextru-lamination is flat Die head.Go out the sheet-like melt after die head to be attached on chilling roller by air knife, by sheet-like melt chilling at sheet, then as chilling The rotation of roller, sheet enter sink and carry out further two-sided cooling.The thickness of sheet can pass through the extrusion capacity and urgency of extruder The rotating speed of chilling roller controls.Wherein, extruder controlled at 150-260 DEG C, preferably 180-250 DEG C；Die head temperature is general It it is 190-240 DEG C, chilling roll temperature is 15-30 DEG C, preferably 20-25 DEG C.
(b) a certain number of pre- hot-rollings that sheet enters back into vertically and horizontally tensioning system carry out two-sided preheating, preheat roller temperature Degree general control is at 90-150 DEG C, preferably 100-120 DEG C.After reaching defined draft temperature (more than softening point, below fusing point), By draw roll carry out longitudinal stretching, draft temperature control at 90-150 DEG C, preferably 100-120 DEG C, drawing process can with a step, It can also stretch or stretch three times twice.Longitudinal stretching multiplying power is set according to the requirement of A layers, B layers and C tunics.It stretches Film afterwards is heat-treated by setting roller, the setting temperature be 100-140 DEG C, preferably 110-120 DEG C, with eliminate The internal stress of film reduces longitudinal shrinking percentage.
(c) film after longitudinal stretching enters cross directional stretch system, carries out preheating section preheating first, and pre- heat roller temperature is general Control is at 100-160 DEG C, preferably 110-140 DEG C, more preferable 115-130 DEG C.Reach defined draft temperature (it is more than softening point, Below fusing point) after, then by expand spoke track carry out cross directional stretch, general 130-180 DEG C of the control temperature of stretching-machine, preferably 140-160 DEG C, thermal finalization processing is then carried out, setting temperature is 60-120 DEG C, preferably 70-110 DEG C.Cross directional stretch multiplying power according to The requirement of A layers, B layers and C tunics is set.
(d) film gone out after cross directional stretch system is cooled down by chill roll, followed by trimming, is sided corona treatment with that, It is finally to be wound.
(e) the big wound membrane after equipment is left after the ageing treatment of several days of storage, can be cut, Rack is made A layers, B layers and C layer films.
When the plain film method is that plain film synchronous bidirectional stretches, plain film synchro-draw preparation method and plain film step drawing system Preparation Method is similar, difference be only during synchro-draw longitudinal stretching and cross directional stretch be it is synchronous carry out, that is, What longitudinal stretching was synchronously completed with cross directional stretch in a system, and longitudinal stretching and cross directional stretch are asynchronous in step drawing It carries out.Thus specific operating condition is similar with step drawing.Currently, in the world synchro-draw machine there are two types of form, one is Mechanically, one is linear electric machine formulas.
When the periosteum method is that synchronous bidirectional stretches, it is synchronous with plain film method double that periosteum method synchronous bidirectional stretches preparation method To stretching, preparation method is similar, and longitudinal stretching is also synchronous carry out with cross directional stretch.The difference is that the mould of periosteum method Head is that circular, entire film formation is completed in the form of steeping pipe.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, draft temperature It is 140 DEG C.Vertically and horizontally draw ratio is then carried out according to the requirement of the draw ratio of each tunic.
When the periosteum method is substep biaxial tension, periosteum method substep biaxial tension preparation method and plain film method substep are double To stretching, preparation method is similar, and longitudinal stretching is also synchronous carry out with cross directional stretch.The difference is that the mould of periosteum method Head is that circular, entire film formation is completed in the form of steeping pipe.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, draft temperature It is 140 DEG C.Vertically and horizontally draw ratio is then carried out according to the requirement of the draw ratio of each tunic.
(2) gluing
Using rolling method, using X as adhesive, to A layers, B layers and C layers progress gluings, wherein outermost two layers of composite membrane into Row single spreading, intermediate each layer carry out one or two sides gluing.
According to the present invention, the gluing carries out at normal temperatures.After gluing, each layer of composite membrane is dried at 40-80 DEG C It is dry.
(3) it is laminated
The A layers of gluing, B layers and C layers be laminated compound, obtains the composite membrane.
According to the present invention, the lamination is compound to be carried out by hot pressing, and the laminating temperature is 40-100 DEG C, preferably 60-80 ℃。
According to the present invention, the A layers obtained by step (1), B layers and/or C layers two-sided all passes through sided corona treatment, keeps it initial Surface tension reaches 44 dynes per centimeters or more.The surface tension of gained composite membrane is more than 36 dynes per centimeters.It is further preferred that surface Tension reaches 38 dynes per centimeters or more.
[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 packing timber Material.
The present invention also provides a kind of application of aforementioned any one of them multilayer complex films, be used for bill, marketable securities, Printed matter and packaging material.
The present invention also provides a kind of products, are made by the face coat and printing of any one of aforementioned multilayer complex films , the product includes printed matter (such as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.
Description of the drawings
Fig. 1 is the structural schematic diagram of composite membrane prepared by the embodiment of the present invention 1.
Specific implementation mode
Illustrate the present invention with reference to embodiments, but skilled in the art realises that, the embodiment is not to the present invention The limitation of protection domain, any improvement made on the basis of the present invention, variation are all within protection scope of the present invention.
Embodiment 1：AXBXC type structures, layer thickness profile：33μm/2μm/10μm/2μm/33μm
A layers and C layers are all the ethylene contents 0.35wt% with the polypropylene copolymer containing ethylene, and molecular weight distribution is 5.5, melt index 2.8g/10min, isotacticity 95.6%.
B layers use high density polyethylene (HDPE), density 0.955g/cm3, fusing point is 135 DEG C, melt index 3.8g/ 10min。
A layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 1 Times.
C layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinal stretching multiplying power is 9 Times.
B layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 Times.
A layers, B layers and C layers are passed through sided corona treatment respectively, and initial surface tension is 45 dynes, then roll coating model is used to apply Cloth chlorinated polypropylene, by being compounded to form composite membrane.Wherein A layer thickness is 33 μm, and B layers are 10 μm, and C layer thickness is 33 μm, X Thickness be 2 μm, overall film thickness be 80 μm.
The performance test results of the film of preparation are listed in table 2.
Embodiment 2：AXBXC type structures, layer thickness profile：38μm/2μm/30μm/2μm/38μm
A layers and C layers are all the ethylene contents 0.35wt% with the polypropylene copolymer containing ethylene, and molecular weight distribution is 5.5, melt index 2.8g/10min, isotacticity 95.6%.
B layers are high density polyethylene (HDPE), density 0.955g/cm3, fusing point is 135 DEG C, melt index 3.8g/10min.
A layers, B layers and C layers are all added Petropols respectively, and Petropols addition is 30% weight of each layer total weight.
A layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 Times.
C layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 Times.
B layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 Times.
A layers, B layers and C layers are passed through sided corona treatment respectively, and initial surface tension is 45 dynes, then roll coating model is used to apply Cloth chlorinated polypropylene, by being compounded to form composite membrane.Wherein A layer thickness is 38 μm, and B layers are 30 μm, and C layer thickness is 38 μm, X Thickness be 2 μm, overall film thickness be 110 μm.
The performance test results of the film of preparation are listed in table 2.
Embodiment 3：AXBXC type structures, layer thickness profile：23μm/2μm/10μm/2μm/23μm
A layers are low density polyethylene (LDPE), density 0.916g/cm3, melt index 2.8g/10min.C layers poly- for low-density Ethylene, density 0.916g/cm3, melt index 2.8g/10min.
B layers are the polypropylene copolymer containing ethylene, and ethylene contents 0.35wt%, molecular weight distribution 5.5, melting refers to Number is 2.8g/10min.
A layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 Times.
C layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 Times.
B layers are processed by plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 Times.
A layers, B layers and C layers are passed through sided corona treatment respectively, and initial surface tension is 45 dynes, then roll coating model is used to apply Cloth polyacrylic acid, by being compounded to form composite membrane.Wherein A layer thickness is 23 μm, and B layers are 10 μm, and C layer thickness is 23 μm, X's Thickness is 2 μm, and overall film thickness is 60 μm.
The performance test results of the film of preparation are listed in table 2 as follows.
Embodiment 4：AXBXC type structures, layer thickness profile：43μm/2μm/20μm/2μm/43μm
A layers are polypropylene homopolymer, and molecular weight distribution 5.1, melt index 2.8g/10min, isotacticity is 96.2%.C layers are the polypropylene copolymer containing ethylene, and ethylene contents 0.35wt%, molecular weight distribution 5.5, melting refers to Number is 2.8g/10min.
B layers are linear low density polyethylene, density 0.915g/cm3, melt index 2.8g/10min.
A layers, B layers and C layers are all added Petropols respectively, and Petropols addition is 10% weight of each layer total weight.
A layers and C are processed by periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
B layers are processed by periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and it is 7 longitudinally to draw high multiplying power Times.
A layers, B layers and C layers are passed through sided corona treatment respectively, and initial surface tension is 45 dynes, then roll coating model is used to apply Cloth chlorinated polypropylene, by being compounded to form composite membrane.Wherein A layer thickness is 43 μm, and B layers are 20 μm, and C layer thickness is 43 μm, X Thickness be 2 μm, overall film thickness be 110 μm.
The performance test results of the film of preparation are listed in table 2.
The results of property of the multilayer complex films of 2 embodiment 1-4 of table

Claims (18)

1. a kind of for bill, the multilayer complex films of marketable securities, Front cover of book and periodical, picture album or packaging material comprising AXBXC layers Structure, wherein X is adhesive layer；A layers in the layer structure, B layers and the C layers of polymer for including are one of following combinations：
(a) A layers include acrylic polymer, C layer comprising with A layers of identical or different acrylic polymer, B layers include ethylene system Polymer；
(b) A layers include ethylene-based polymer, C layer comprising with A layers of identical or different ethylene-based polymer, B layers include propylene Polymer；
Also, A layers described, B layers and C layers be biaxial tension and：B layers of the cross directional stretch multiplying power and longitudinal stretching multiplying power phase Together；Described A layers of longitudinal stretching multiplying power is more than cross directional stretch multiplying power, and C layers of the cross directional stretch multiplying power is more than longitudinal stretching Multiplying power；Also, described A layers of vertically and horizontally draw ratio is inversely proportional with described C layers of vertically and horizontally draw ratio, i.e., described A layers of the longitudinal direction Stretching ratio and the ratio of cross directional stretch multiplying power are equal to the ratio of C layers of the cross directional stretch multiplying power and longitudinal stretching multiplying power；
A layers of tensile strength is 1.5 in horizontal and vertical ratio in the multilayer complex films:1.0 to 7.0:1.0；
C layers of tensile strength is 1.0 in horizontal and vertical ratio in the multilayer complex films:1.5 to 1.0:7.0.
2. multilayer complex films according to claim 1, which is characterized in that described A layers of longitudinal stretching multiplying power with it is C layers described Cross directional stretch multiplying power it is identical, and A layers of the cross directional stretch multiplying power is identical as described C layers of longitudinal stretching multiplying power.
3. multilayer complex films according to claim 1, which is characterized in that B layers of the stretching ratio and the one of described A layers A stretching ratio is identical, i.e., described B layers of the stretching ratio is identical as A layers of the cross directional stretch multiplying power, or with described A layers Longitudinal stretching multiplying power is identical.
4. according to claim 1-3 any one of them multilayer complex films, which is characterized in that the thickness of the multilayer complex films is 50-150μm；
A layers or C layers of thickness is 5-65 μm in the multilayer complex films；
Each X layers of thickness is 0.5-10 μm in the multilayer complex films；
The summation of all X layer thickness is no more than the 30% of the composite film thickness in the multilayer complex films；
B layer thickness in the multilayer complex films is 5-30 μm；
A layers are no more than 20% with C layer thickness difference.
5. according to claim 1-3 any one of them multilayer complex films, which is characterized in that the A layers in the multilayer complex films Or B layers or C layers are single layer structure or multi-layer co-extruded structure.
6. multilayer complex films according to claim 5, which is characterized in that A layers described, B layers or C layers of multi-layer co-extruded knot Structure is 2-15 layers.
7. multilayer complex films according to any one of claims 1 to 3, which is characterized in that the third of described A layers or B layer or C layers Alkene based polymer is Noblen or propylene copolymer, and comonomer is ethylene or higher ɑ-alkene.
8. multilayer complex films according to claim 7, which is characterized in that the Noblen or propylene copolymer are Isotaxy homopolymer, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have it is few Measure the polypropylene blend of the atactic propene copolymer and ethylene copolymer-modified isotactic polypropylene of comonomer；Altogether Polycondensation monomer is ethylene, butylene, hexene or octene.
9. multilayer complex films according to claim 8, which is characterized in that described A layers or B layer or C layers of propylene polymerization The fusing point of object is 148-170 DEG C；Molecular weight distribution through GPC tests is 2-16；Melt index is 0.5-10g/10min.
10. according to claim 1-3 any one of them multilayer complex films, which is characterized in that A layers described, B layers or C layers of second Alkene based polymer is high density polyethylene (HDPE), high-pressure process low-density polyethylene or low-pressure process linear low density polyethylene.
11. multilayer complex films according to claim 10, which is characterized in that A layers described, B layers or C layers of ethylene system polymerization The fusing point of object is 130-150 DEG C；Melt index is 0.2-50g/10min.
12. multilayer complex films according to any one of claims 1 to 3, which is characterized in that A layers in the multilayer complex films Tensile strength horizontal and vertical ratio be 2.0:1.0 to 5.0:1.0；
C layers of tensile strength is 1.0 in horizontal and vertical ratio in the multilayer complex films:2.0 to 1.0:5.0.
13. according to claim 1-3 any one of them multilayer complex films, which is characterized in that the anti-tensile of the multilayer complex films Horizontal and vertical test value ratio is 0.7 in intensity, deflection and tear-resistant intensity:1.0 to 1.0:1.3.
14. according to claim 1-3 any one of them multilayer complex films, which is characterized in that the multilayer complex films are in length and breadth It is more than 100MPa to tensile strength.
15. multilayer complex films according to any one of claims 1 to 3, which is characterized in that add again in A layers, B layers or C layers Enter another resin, is selected from Petropols or hydrogenated petroleum resin；Its addition is the 1-30 weight % of each layer total weight.
16. a kind of method for the multilayer complex films preparing any one of claim 1 to 15 comprising following steps：
(1) A layers, B layers and C layers of preparation
It is squeezed out by single layer or multi-layer co-extruded, prepares polyolefin sheets, then carried out under 130-185 DEG C of temperature environment Biaxial tension processes A layers, B layers and C layers, wherein described A layers of longitudinal stretching multiplying power is more than cross directional stretch multiplying power, and the C The cross directional stretch multiplying power of layer is more than longitudinal stretching multiplying power, and B layers of longitudinal stretching multiplying power is identical as cross directional stretch multiplying power；Also, institute It states A layers of vertically and horizontally draw ratio to be inversely proportional with described C layers of vertically and horizontally draw ratio, i.e., described A layers of the longitudinal stretching multiplying power and cross It is equal to the ratio of C layers of the cross directional stretch multiplying power and longitudinal stretching multiplying power to the ratio of stretching ratio；
(2) use rolling method, with X layer for adhesive, to A layers, B layers and C layers carry out gluings, wherein outermost two layers of composite membrane into Row single spreading, intermediate each layer carry out one or two sides gluing, and after gluing, each layer is dried at 40-80 DEG C；
(3) A of gluing layers, B layers and C layers be laminated compound, obtain the composite membrane.
17. a kind of application of the multilayer complex films of any one of claim 1 to 15 is used for bill, marketable securities, books and periodicals envelope Face, picture album or packaging material.
18. a kind of product is made by the multilayer complex films face coat and printing of any one of claim 1 to 15, described Product includes Front cover of book and periodical, picture album, bill, marketable securities or packaging material.
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CN1968870A (en) * 2004-09-13 2007-05-23 利乐拉瓦尔集团及财务有限公司 A strip tape, a packaging container having such a strip tape, and a method of producing such a strip tape

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CN1062496A (en) * 1990-12-18 1992-07-08 唐化学原料公司 Polymeric reflective body with multiple layer types
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
CN1968870A (en) * 2004-09-13 2007-05-23 利乐拉瓦尔集团及财务有限公司 A strip tape, a packaging container having such a strip tape, and a method of producing such a strip tape

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Inventor after: Chen Dakui

Inventor after: Huang Xusheng

Inventor after: Zhan Yueqiang

Inventor after: Yun Xiaobing

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