CN105774168A - Multilayer propylene polymer and ethylene polymer composite membrane, preparation method and application of multilayer composite membrane, and products containing multilayer composite membrane - Google Patents

Abstract

The invention provides a multilayer composite membrane. The multilayer composite membrane comprises a layer structure formed by n AXBXC layer structures which are mutually composited through X(s), wherein n is greater than or equal to 2, all the A(s) are the same or different, all the B(s) are the same or different, all the C(s) are the same or different, and all the X(s) are the same or different; in the layer structure, each A layer independently comprises the propylene polymers which are the same or different, each C layer independently comprises the propylene polymers which are the same or different, each B layer independently comprises the ethylene polymers which are the same or different, the X(s) are binder layers, and the A layers and the C layers are uniaxially stretched or biaxially stretched separately and independently. The invention further provides a preparation method and application of the multilayer composite membrane, and products containing the multilayer composite membrane. The multilayer propylene polymer and ethylene polymer composite membrane, disclosed by the invention, has the properties of high stiffness, high transparency, low temperature resistance, high tear strength and the like.

Description

A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof

Technical field

The present invention relates to a kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, use Way and comprise the goods of this composite membrane, belongs to field of compound material.

Background technology

Biaxially oriented polypropylene (BOPP) film effectively utilize its excellent light weight, the transparency, mechanical strength, The characteristics such as nontoxic, moistureproof, gas permeability is low, rigidity, for the wide spectrum with packaging material as representative.Example Packaging and lamination as being widely used in the products such as food, medicine, daily light industry, cigarette are compound.BOPP is thin A kind of purposes of film is to fit in paper surface, such as books, packing carton etc., rises moistureproof and increases surface light The effect of pool degree.

BOPP film is generally the coextrusion structure of 3-5 layer, and step drawing production technology is mainly by following operation Composition: dispensing batch mixing, extruder are extruded, are extruded sheet, sheet chilling by T-shaped die head, led to sheet Cross heating roller preheating, sheet longitudinal stretching, thermal finalization, preheat again, cross directional stretch, thermal finalization, cooling, Sided corona treatment, rolling, cut and put in storage.Disclosed in CN101160209A (Oji Paper) A kind of Biaxially stretched multilayer polypropylene film, it adds inorganic compound powder in by acrylic polymer The two sides of bidirectional stretching polypropylene film substrate layer that obtains of propylene polymer composition, possess and contain Have in A layer and the back layer of acrylic polymer, the acrylic polymer in described substrate layer and surface/back layer Acrylic polymer can be identical or different.It is by adding inorganic compound powder in substrate layer, Excellent to uniform hidden power and whiteness, be the thin of 25-55 μm almost without the preferred thickness of concave-convex surface Film.Described film obtains by the following method: will form the acrylic polymer of substrate layer by itself public affairs The method co-extrusion modling known and obtain multi-layer sheet, use simultaneously bi-directionally pulling method or sequentially biaxial tension method It is stretched to face multiplying power (longitudinal × horizontal) 45～65 times Deng biaxially oriented film forming method and obtains.To use As a example by sequentially biaxial tension method, can be by drawing with the scope of 4.5～7.5 times at a temperature of longitudinally 70～140 DEG C After stretching, then under the temperature range of horizontal 120～190 DEG C under 7～12 times and face multiplying power (longitudinally × laterally) After being stretched to 45～65 times, obtain at the temperature range heat fixation of 110～180 DEG C.

BOPP film has many preferably performances, such as high tensile, high-stiffness, the high grade of transparency etc..But, The use cycle of BOPP film is short, generally some months to a year, some physical properties such as resistance to low temperature, Fall strength of briquette, tearing strength etc. are poor, are not suitable for the printed matter of Long-Time Service, packaging material etc..Separately Outward, the thickness of existing bidirectional stretching polypropylene film is generally less than 50 μm, and its deflection can not meet high-end need Ask.Therefore its some ranges of application are constrained.

The density polyethylene film with high of stretching has been used for plastics package field.British Patent No. 1287527 In describe more such films, they are at machine direction (MD) with laterally in (TD) both direction It is biaxially stretched the degree more than 6.5 times.U.S. Patent No. 4680207 relates to LLDPE Twin shaft imbalance oriented film, it stretches in the direction of the machine less than 6 times, is orientated in the horizontal and does not surpass Cross 3 times and less than stretching in the direction of the machine.

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 are thin Film ratio is great, and cost is high, and solvent resistance is poor.

Therefore, industrial quarters need a kind of high transparent with traditional B OPP film and high-stiffness but the most again There is the novel thin film of resistance to low temperature, high-tear strength.

Summary of the invention

The present invention is for overcoming the deficiencies in the prior art, it is provided that a kind of acrylic polymer-ethylene-based polymer multilayer Composite membrane, has the performances such as high-stiffness, high transparent, low temperature resistant and high-tear strength.

It is a further object to provide the preparation method of above-mentioned multilayer complex films.

It is a further object to provide the purposes of above-mentioned multilayer complex films.

It is also another object of the present invention to provide the goods including above-mentioned multilayer complex films.

The present invention is achieved through the following technical solutions:

A kind of multilayer complex films, it includes what n AXBXC Rotating fields was composited by X each other Rotating fields, n is more than or equal to 2, and each A is identical or different, and each B is identical or different, and each C is identical Or different, each X is identical or different, and A layer and C layer in described Rotating fields include identical independently of one another Or different acrylic polymers, B layer includes identical or different ethylene-based polymer independently of one another, and X is Adhesive layer is that described A layer and C layer are each independently simple tension or biaxial tension.

According to the present invention, in described multilayer complex films, n AXBXC Rotating fields is combined by X order, I.e. it is combined according to the order of AXBXCXAXBXC.

According to the present invention, in described multilayer complex films, n AXBXC Rotating fields is the most compound by X, I.e. it is combined according to the order of AXBXCXCXBXA.

According to the present invention, in described multilayer complex films, n AXBXC Rotating fields is unordered compound by X.

According to the present invention, in described multilayer complex films, the acrylic polymer of A layer is polymerized with the propylene of C layer Thing is identical.

According to the present invention, described Rotating fields also includes one layer of A layer, is compound in outermost C layer by X Outer layer, preferably its structure are (AXBXCX)_nA, n are more than or equal to 2；Or it is compound in outermost A by X The outer layer of layer, preferably its structure is A (XAXBXC)_n, n is more than or equal to 2.

According to the present invention, described Rotating fields also includes one layer of B layer, is compound in outermost C layer by X Outer layer, preferably its structure are (AXBXCX)_nB, n are more than or equal to 2；Or it is compound in outermost A by X The outer layer of layer, preferably its structure is B (XAXBXC)_n, n is more than or equal to 2.

According to the present invention, described Rotating fields also includes one layer of C layer, is compound in outermost C layer by X Outer layer, preferably its structure are (AXBXCX)_nC, n are more than or equal to 2；Or it is compound in outermost A by X The outer layer of layer, preferably its structure is C (XAXBXC)_n, n is more than or equal to 2.

According to the present invention, the A layer in described multilayer complex films is single layer structure or multi-layer co-extruded structure.

According to the present invention, the B layer in described multilayer complex films is single layer structure or multi-layer co-extruded structure.

According to the present invention, the C layer in described multilayer complex films is single layer structure or multi-layer co-extruded structure.

According to the present invention, the multi-layer co-extruded structure of described A layer or B layer or C layer is at least 2 layers, such as For 2-15 layer, preferably 3-11 layer, more preferably 5-9 layer, even more preferably from 6-8 layer.

In accordance with the present invention it is preferred that, described B layer be do not stretch or simple tension or biaxial tension.

According to the present invention, when described B layer is not stretch, described A layer or C layer are biaxial tension.

According to the present invention, when described B layer is not stretch, the cross directional stretch multiplying power of described A layer and longitudinal direction Stretching ratio is same or like.Cross directional stretch multiplying power and the longitudinal stretching multiplying power of described C layer are same or like. Or, the vertically and horizontally draw ratio of described A layer is inversely proportional to the vertically and horizontally draw ratio of C layer.

In accordance with the present invention it is preferred that, when described B layer be do not stretch and time n is even number, described A layer two Two pair-wise combination, described C layer combines in pairs.Wherein, the longitudinal stretching of an A layer (or C layer) Multiplying power is more than cross directional stretch multiplying power, and the longitudinal stretching multiplying power of another A layer (or C layer) is less than cross directional stretch Multiplying power；It is highly preferred that the vertically and horizontally draw ratio of one A layer (or C layer) and another A layer (or C layer) vertically and horizontally draw ratio be inversely proportional to, i.e. the longitudinal stretching of one A layer (or C layer) with laterally The ratio of stretching is equal to the cross directional stretch of another A layer (or C layer) and the ratio of longitudinal stretching；More preferably Ground, the longitudinal stretching multiplying power of one A layer (or C layer) is horizontal with another A layer (or C layer) Stretching ratio is same or like, and the cross directional stretch multiplying power of one A layer (or C layer) and another A The longitudinal stretching multiplying power of layer (or C layer) is same or like；It is more preferred still that one A layer (or C Layer) longitudinal stretching multiplying power identical with the cross directional stretch multiplying power of another A layer (or C layer), and described one The longitudinal stretching multiplying power phase of the cross directional stretch multiplying power of individual A layer (or C layer) and another A layer (or C layer) With.

According to the present invention, when described B layer be do not stretch and time n is odd number, described A layer group in pairs After conjunction, remaining A layer individually combines, described C layer after combining in pairs remaining C layer individually combine.Its In, in paired two-layer, the longitudinal stretching multiplying power of an A layer (or C layer) is more than cross directional stretch multiplying power, separately The longitudinal stretching multiplying power of one A layer (or C layer) is less than cross directional stretch multiplying power, the A layer of individually combination (or C layer) cross directional stretch multiplying power and longitudinal stretching multiplying power same or like；It is highly preferred that the most paired two-layer In the vertically and horizontally stretching of vertically and horizontally draw ratio and another A layer (or C layer) of an A layer (or C layer) Ratio is inversely proportional to, and i.e. the longitudinal stretching of one A layer (or C layer) and the ratio of cross directional stretch are equal to another The cross directional stretch of individual A layer (or C layer) and the ratio of longitudinal stretching, individually the A layer (or C layer) of combination Cross directional stretch multiplying power and longitudinal stretching multiplying power same or like；It is highly preferred that in the most paired two-layer one The cross directional stretch multiplying power phase of the longitudinal stretching multiplying power of individual A layer (or C layer) and another A layer (or C layer) Same or close, and the cross directional stretch multiplying power of one A layer (or C layer) and another A layer (or C layer) Longitudinal stretching multiplying power same or like, the individually cross directional stretch multiplying power of the A layer (or C layer) of combination and vertical Same or like to stretching ratio；It is more preferred still that an A layer (or C layer) in the most paired two-layer Longitudinal stretching multiplying power identical with the cross directional stretch multiplying power of another A layer (or C layer), and one A The cross directional stretch multiplying power of layer (or C layer) is identical with the longitudinal stretching multiplying power of another A layer (or C layer), Individually cross directional stretch multiplying power and the longitudinal stretching multiplying power of the A layer (or C layer) of combination are same or like.

According to the present invention, when n is even number, between B layer, include one of following combination two-by-two:

(1 ') two B layers are simple tension, and stretching ratio is identical, laterally drawing of a preferably B layer Stretch multiplying power identical with the longitudinal stretching multiplying power of another B layer；

(2 ') B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension Identical with biaxial tension stretching ratio (cross directional stretch multiplying power or longitudinal stretching multiplying power)；Or

(3 ') two B layers are biaxial tension, and the draw ratio of the two is identical.

When n is odd number, between B layer, include one of following combination two-by-two:

(1 ') two B layers are simple tension, and stretching ratio is identical；

(2 ') B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension Identical with biaxial tension stretching ratio (cross directional stretch multiplying power or longitudinal stretching multiplying power)；Or

(3 ') two B layers are biaxial tension, and the draw ratio of the two is identical；

The draw ratio of remaining B layer or stretching ratio then with draw ratio or the stretching ratio of the above-mentioned layer of B two-by-two Identical or different.

According to the present invention, under above-mentioned B layer restrictive condition, it is preferable that the draw ratio of A layer or stretching ratio Different from B layer and/or the draw ratio of C layer or stretching ratio.Preferably, the draw ratio of each A layer or stretching Multiplying power is different.Preferably, draw ratio or the stretching ratio of each B layer are different.Preferably, each C layer Draw ratio or stretching ratio are different.Preferably, described A layer, B layer and C layer include one of following combination:

(1) described A layer is simple tension, and described B layer is simple tension, and described C layer is biaxial tension；

(2) described A layer is simple tension, and described B layer is biaxial tension, and described C layer is biaxial tension；

(3) described A layer is simple tension, and described B layer is biaxial tension, and described C layer is simple tension；

(4) described A layer is biaxial tension, and described B layer is simple tension, and described C layer is simple tension；

(5) described A layer is biaxial tension, and described B layer is biaxial tension, and described C layer is simple tension；

(6) described A layer is biaxial tension, and described B layer is simple tension, and described C layer is biaxial tension；

(7) A layer, B layer and C layer are biaxial tension；Or

(8) A layer, B layer and C layer are simple tension.

According to the present invention, for scheme (1).Including following scheme:

To laterally stretching of described A layer, to laterally stretching of described B layer, and to described C layer Horizontal and vertical all stretch；Or

To laterally stretching of described A layer, the longitudinal direction of described B layer is stretched, and to described C layer Horizontal and vertical all stretch；Or

The longitudinal direction of described A layer is stretched, to laterally stretching of described B layer, and to described C layer Horizontal and vertical all stretch；Or

The longitudinal direction of described A layer is stretched, the longitudinal direction of described B layer is stretched, and to described C layer Horizontal and vertical all stretch.

It is highly preferred that the cross directional stretch multiplying power of described A layer/C layer is identical with the longitudinal stretching multiplying power of described B layer Or it is close；Or, the longitudinal stretching multiplying power of described A layer/C layer is identical with the cross directional stretch multiplying power of described B layer Or it is close.

According to the present invention, for scheme (2).Including following scheme:

To laterally stretching of described A layer, described the horizontal and vertical of B layer is stretched, and to institute State the horizontal and vertical of C layer all to stretch；Or

The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B layer is stretched, and to institute State the horizontal and vertical of C layer all to stretch.

It is highly preferred that the cross directional stretch multiplying power of described A layer/C layer is identical with the longitudinal stretching multiplying power of described B layer Or it is close；Or, the longitudinal stretching multiplying power of described A layer/C layer is identical with the cross directional stretch multiplying power of described B layer Or it is close.

According to the present invention, for scheme (3).Including following scheme:

To laterally stretching of described A layer, described the horizontal and vertical of B layer is all stretched, and right Laterally stretching of described C layer；Or

To laterally stretching of described A layer, described the horizontal and vertical of B layer is all stretched, and right The longitudinal direction of described C layer stretches；Or

The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B layer is all stretched, and right Laterally stretching of described C layer；Or

The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B layer is all stretched, and right The longitudinal direction of described C layer stretches.

It is highly preferred that the cross directional stretch multiplying power of described A layer/C layer is identical with the longitudinal stretching multiplying power of described B layer Or it is close；Or, the longitudinal stretching multiplying power of described A layer/C layer is identical with the cross directional stretch multiplying power of described B layer Or it is close.

According to the present invention, for scheme (4).Including following scheme:

Described the horizontal and vertical of A layer is all stretched, to laterally stretching of described B layer and right Laterally stretching of described C layer；Or

Described the horizontal and vertical of A layer is all stretched, to laterally stretching of described B layer and right The longitudinal direction of described C layer stretches；Or

Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B layer is stretched, and right Laterally stretching of described C layer；Or

Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B layer is stretched, and right The longitudinal direction of described C layer stretches.

It is highly preferred that the cross directional stretch multiplying power of described A layer/C layer is identical with the longitudinal stretching multiplying power of described B layer Or it is close；Or, the longitudinal stretching multiplying power of described A layer/C layer is identical with the cross directional stretch multiplying power of described B layer Or it is close.

According to the present invention, for scheme (5).Including following scheme:

Described the horizontal and vertical of A layer is all stretched, described the horizontal and vertical of B layer is stretched, And laterally stretching described C layer；Or

Described the horizontal and vertical of A layer is all stretched, described the horizontal and vertical of B layer is stretched, And the longitudinal direction of described C layer is stretched.

It is highly preferred that the cross directional stretch multiplying power of described A layer/C layer is identical with the longitudinal stretching multiplying power of described B layer Or it is close；Or, the longitudinal stretching multiplying power of described A layer/C layer is identical with the cross directional stretch multiplying power of described B layer Or it is close.

According to the present invention, for scheme (6).Including following scheme:

Described the horizontal and vertical of A layer is all stretched, to laterally stretching of described B layer and right Described the horizontal and vertical of C layer stretches；Or

Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B layer is stretched, and right Described the horizontal and vertical of C layer stretches.

It is highly preferred that the cross directional stretch multiplying power of described A layer/C layer is identical with the longitudinal stretching multiplying power of described B layer Or it is close；Or, the longitudinal stretching multiplying power of described A layer/C layer is identical with the cross directional stretch multiplying power of described B layer Or it is close.

According to the present invention, for scheme (7).Including following scheme: the vertically and horizontally stretching of described A layer/C layer Ratio is different from the vertically and horizontally draw ratio of B layer；Preferably, the longitudinal stretching multiplying power of described A layer/C layer is more than horizontal stroke To stretching ratio, and the cross directional stretch multiplying power of B layer is more than longitudinal stretching multiplying power；It is highly preferred that described A layer The vertically and horizontally draw ratio of/C layer is inversely proportional to the vertically and horizontally draw ratio of B layer, i.e. the longitudinal stretching of A layer/C layer with The ratio of cross directional stretch is equal to the cross directional stretch of B layer and the ratio of longitudinal stretching.It is highly preferred that described A layer The longitudinal stretching multiplying power of/C layer is same or like with the cross directional stretch multiplying power of described B layer, and described A layer/C layer Cross directional stretch multiplying power same or like with the longitudinal stretching multiplying power of described B layer；It is more preferred still that described A The longitudinal stretching multiplying power of layer/C layer is identical with the cross directional stretch multiplying power of described B layer, and the horizontal stroke of described A layer/C layer Identical with the longitudinal stretching multiplying power of described B layer to stretching ratio.

According to the present invention, for scheme (8).The stretching ratio of described A layer/C layer and the stretching of described B layer Multiplying power is different；Preferably, the stretching ratio of described A layer/C layer is more than the stretching ratio of described B layer, or The stretching ratio of described A layer/C layer is less than the stretching ratio of described B layer.Preferably, to described A layer/C Laterally stretching of layer, and the longitudinal direction of described B layer is stretched；Or described A layer/C layer is indulged To stretching, and laterally stretching described B layer.It is highly preferred that described A layer/C layer is horizontal Stretching ratio is identical or close with the longitudinal stretching multiplying power of described B layer；Or, the longitudinal direction of described A layer/C layer Stretching ratio is identical or close with the cross directional stretch multiplying power of described B layer.

According to the present invention, the thickness of above-mentioned multilayer complex films is 50-120 μm, preferably 60-100 μm, more preferably 70-80μm。

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 uses solwution method, suspension method or solid phase method by polypropylene chlorination And prepare.The mass content of chlorine is 20%-70%, and fusing point is less than 150 DEG C.

According to the present invention, described polyurethane is solvent-borne type, water-dispersion type or no-solvent type one-component or many Part polyurethane adhesive.

According to the present invention, described acrylic resin be solvent-borne type, water-dispersion type or no-solvent type one-component or Person's multicomponent contains the adhesive of acrylic acid or acrylates.

According to the present invention, described epoxy resin be 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, preferably 60-120 μm, more preferably 70-100 μm, even more preferably from 80-90 μm.

According to the present invention, in described multilayer complex films, the thickness of each A layer or B layer or C layer is 5-65 μm, Preferably 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, 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 less than this composite film thickness 30%, preferably more than 20%, more preferably no more than 15%, even more preferably from less than 10%.

According to the present invention, in described multilayer complex films, the tensile strength of A layer at horizontal and vertical ratio is 1.5:1.0 to 7.0:1.0, preferably 2.0:1.0 to 5.0:1.0.

According to the present invention, in described multilayer complex films, the tensile strength of B layer at horizontal and vertical ratio is 1.0:1.5 to 1.0:7.0, preferably 1.0:2.0 to 1.0:5.0.

According to the present invention, in described multilayer complex films, the tensile strength of C layer at horizontal and vertical ratio is 1.5:1.0 to 7.0:1.0, preferably 2.0:1.0 to 5.0:1.0.

According to the present invention, for biaxial tension, the cross directional stretch multiplying power of the A layer in described multilayer complex films is 7-12.5 times, longitudinal stretching multiplying power is 1-6 times, and preferably laterally stretching ratio is 8-10 times, longitudinal stretching times Rate is 2-4 times.

According to the present invention, for biaxial tension, the cross directional stretch multiplying power of the B layer in described multilayer complex films is 1-6 times, longitudinal stretching multiplying power is 7-12.5 times, and preferably laterally stretching ratio is 2-4 times, longitudinal stretching multiplying power For 8-10 times.

According to the present invention, for biaxial tension, the cross directional stretch multiplying power of the C layer in described multilayer complex films is 7-12.5 times, longitudinal stretching multiplying power is 1-6 times, and preferably laterally stretching ratio is 8-10 times, longitudinal stretching times Rate is 2-4 times.

According to the present invention, for simple tension, the drawing laterally or longitudinally of the A layer in described multilayer complex films Stretching multiplying power and be 1-12.5 times, preferably laterally stretching ratio is 7-12.5 times or longitudinal stretching multiplying power is 1-6 times；B The vertical or horizontal stretching ratio of layer is 1-12.5 times, and preferably longitudinally stretching ratio is 7-12.5 times or horizontal Stretching ratio is 1-6 times；The stretching ratio laterally or longitudinally of C layer is 1-12.5 times, preferably laterally stretching times Rate is 7-12.5 times or longitudinal stretching multiplying power is 1-6 times；.

According to the present invention, horizontal and vertical in the tensile strength of described multilayer complex films, deflection and tear-resistant intensity To test value ratio be 0.7:1.0 to 1.0:1.3.

The vertically and horizontally hot strength of described multilayer complex films is more than 100MPa, preferably greater than 120MPa, more excellent Choosing is more than 140MPa.

According to the present invention, the acrylic polymer of described A layer or C layer is preferably Noblen or propylene Copolymer, typically isotaxy homopolymers, or be by different isotactic polypropylenes, atactic Polypropylene, syndiotactic polypropylene, the atactic propene copolymer having a small amount of comonomer and ethylene copolymer The polypropylene blend of modified isotactic polypropylene.Comonomer is ethene or higher alpha-olefin, as ethene, Butylene, hexene or octene etc..

According to the present invention, the fusing point of the acrylic polymer of described A layer or C layer is 148 to 170 DEG C, excellent Select 150-167 DEG C；More preferably 155 DEG C-165 DEG C；Molecular weight distribution (GPC test) is 2-16, is preferably 4-10；Melt index is 0.5-10g/10min, preferably 1-8g/10min.

According to the present invention, it is low close that the ethylene-based polymer of described B layer is preferably high density polyethylene (HDPE), high-pressure process Degree polyethylene or low-pressure process LLDPE.The density of high density polyethylene (HDPE) about 0.941g/cm³Or Higher, preferably from about 0.948g/cm³To about 0.968g/cm³, more preferably from about 0.952g/cm³To about 0.962 g/cm³；Fusing point about 130 DEG C to about 148 DEG C；Melt index (measuring according to ASTM D1238) is 0.2-50g/10min, preferably 1-45g/10min, more preferably 2-40g/10min.The density of low density polyethylene (LDPE) It is about 0.912g/cm³To about 0.94g/cm³, preferably 0.915g/cm³To 0.928g/cm³；Melt index (root Measure according to ASTM D1238) it is 0.2-50g/10min, preferably 1-45g/10min, more preferably 2-40g/10min. LLDPE is ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has There is the melt index (measuring according to ASTM D1238) of 0.2-50g/10min (such as 1-10g/10min) And at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910 g/cm³To 0.928g/cm³The density of scope.Ethylene-based polymer can also is that terpolymer, such as ethene / butylene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymerization Thing has the melt index of 0.2-50g/10min (such as 1-10g/10min) and (surveys according to ASTM D1238 Amount) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.

According to the present invention, A layer or B layer or C layer also can add another resin, such as oil tree Fat or hydrogenated petroleum resin, preferably C₅-C₉Petropols or C₅-C₉Hydrogenated petroleum resin.Its addition is The 1-30% weight of each layer gross weight, preferably 2-20% weight, more preferably 3-15% weight, even more preferably from 4-10% Weight.

The present invention also provides for the preparation method of above-mentioned multilayer complex films, and it comprises the following steps:

(1) A layer and the preparation of C layer

Extruded by individual layer or multi-layer co-extruded, prepare polyolefin sheets, then the temperature of 130-185 DEG C Carry out simple tension under environment or biaxial tension processes A layer and C layer；

(2) preparation of B layer

Extruded by individual layer or multi-layer co-extruded, prepare polyethylene sheets, may select and do not stretch or simple tension Or biaxial tension processes B layer；

(3) use rolling method, with X as adhesive, each A layer, B layer and each layer of C carried out gluing, Wherein the outermost two-layer of composite membrane carries out single spreading, and middle each layer carries out one or two sides gluing, after gluing, Each layer is dried at 40-80 DEG C；

(4) the A layer of gluing, B layer and C layer are carried out lamination compound, obtain described composite membrane.

According to the present invention, step (1) and the A layer of (2) gained and/or B layer and/or C layer two-sided all Through sided corona treatment so that it is initial surface tension reaches more than 44 dynes per centimeter.The surface of gained composite membrane is opened Power is more than 36 dynes per centimeter.It is further preferred that surface tension reaches more than 38 dynes per centimeter.

Film prepared by the present invention can be used for needing high-stiffness, tear-resistant bill, marketable securities, printed matter and Packaging material.

The present invention also provides for the application of the multilayer complex films described in a kind of aforementioned any one, and it is used for bill, has Valency security, printed matter and packaging material.

The present invention also provides for a kind of goods, and it is by the face coat of the multilayer complex films described in aforementioned any one Preparing with printing, described goods include printed matter (such as Front cover of book and periodical or picture album), bill, marketable securities and bag Package material.

Beneficial effects of the present invention:

Polypropylene multi-layer composite membrane prepared by the present invention, has a combination property of excellence, its tensile strength, very Degree and tear-resistant intensity are the highest, and its vertical and horizontal performance has good balance, and have good The good transparency, concrete performance sees table 1.

The performance of table 1 composite membrane of the present invention

Describe in detail

[A layer, B layer and the composition of C layer]

According to the present invention, described A layer and C layer mainly include acrylic polymer.Described acrylic polymer It is preferably Noblen or propylene copolymer or polypropene composition；Typically isotaxy homopolymers, Or be with different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have a small amount of being total to The atactic propene copolymer of poly-monomer and ethylene copolymer-modified isotactic polypropylene polypropene blended Thing.Comonomer is ethene or higher alpha-olefin, such as ethene, butylene, hexene or octene etc..Comonomer Content is preferably 0.2wt% to 2.0wt%, more preferably 0.35wt% to 0.85wt%.These of the present invention Acrylic polymer can be that the mixture containing one kind or two or more polymer, such as molecular weight are different Noblen, 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 title manufacture, the vistanex of sale, it is common that density be 0.890～ 0.930g/cm³, MFR (ASTM D1238, load 2160g, temperature 230 DEG C) be 0.5～60g/10min, It is preferably 0.5～20g/10min, more preferably 0.5-15g/10min, still more preferably 1～the third of 5g/10min Polyamino alkenyl thing.

According to the present invention, the fusing point of described acrylic polymer is 148 to 170 DEG C, preferably 150-167 DEG C； More preferably 155 DEG C-165 DEG C；Molecular weight distribution (GPC test) is 2-16, preferably 4-10；Melted finger Number is 0.5-10g/10min, preferably 1-8g/10min.The Noblen that industrial BOPP film is conventional has: Lanzhou Petrochemical and the T38F of Daqing petrochemical；The T36F of Dalian petrochemical industry；The basis of this kind of Noblen ASTMD-1238 test melt index (MI) can be about 0.2-20g/10min, preferably 0.5-15g/10min, Fusing point can be about between 155 DEG C-165 DEG C.

The polymer of described A layer and C layer also can be mixed into part ethylene-based polymer, such as high-density polyethylene Alkene (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, as ethene, Butylene, hexene or octene etc., and there is about 0.941g/cm³Or higher (e.g., from about 0.948g/cm³ To about 0.968g/cm³, preferably from about 0.952g/cm³To about 0.962g/cm³) density, e.g., from about 130 DEG C To fusing point and the 0.2-50g/10min, preferably 1-45g/10min, more preferably 2-40g/10min of about 148 DEG C Melt index (according to ASTM D1238 measure).LDPE has at 0.912g/cm³To 0.94g/cm³ (such as 0.915g/cm³To 0.928g/cm³) the density of scope and 0.2-50g/10min (preferably 1-45g/10min, more preferably 2-40g/10min) melt index (according to ASTM D1238 measure). LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has The melt index of 0.2-50g/10min (such as 1-10g/10min) (measuring according to ASTM D1238) and At 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³ To 0.928g/cm³The density of scope.In addition ethylene-based polymer can also is that terpolymer, as ethene/ Butylene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymerization Thing has the melt index of 0.2-50g/10min (such as 1-10g/10min) and (surveys according to ASTM D1238 Amount) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.

According to the present invention, described B layer mainly includes ethylene-based polymer, and described ethylene-based polymer is preferably High density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (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, as Butylene, hexene or octene etc., and there is about 0.941g/cm³Or higher (e.g., from about 0.948g/cm³ To about 0.968g/cm³, preferably from about 0.952g/cm³To about 0.962g/cm³) density, e.g., from about 130 DEG C To fusing point and the 0.2-50g/10min, preferably 1-45g/10min, more preferably 2-40g/10min of about 148 DEG C Melt index (according to ASTM D1238 measure).LDPE has at 0.912g/cm³To 0.94g/cm³ (such as 0.915g/cm³To 0.928g/cm³) the density of scope and 0.2-50g/10min (preferably 1-45g/10min, more preferably 2-40g/10min) melt index (according to ASTM D1238 measure). LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has The melt index of 0.2-50g/10min (such as 1-10g/10min) (measuring according to ASTM D1238) and At 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³ To 0.928g/cm³The density of scope.In addition ethylene-based polymer can also is that terpolymer, as ethene/ Butylene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymerization Thing has the melt index of 0.2-50g/10min (such as 1-10g/10min) and (surveys according to ASTM D1238 Amount) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.

Deflection of the present invention refers to that Paper or cardboard supports resistant to bending strength character.Deflection just becomes with EI/W value Ratio, wherein W, E and I are respectively the quality of Paper or cardboard, elastic modelling quantity and the moment of inertia.Wherein, cardboard Deflection or claim flexural rigidity, refer to, at fixture 5cm, the sample that vertically clips is being applied certain load, Observe from sample camber 3.81mm width, the moment of flexure that sample to 15 ° is required, represent with g cm. Paper sheet stiffness is a critically important index, and (another influence factor is mould to directly affect the size of folding line deflection Hob power), thus affect finished product shaping.Deflection is little, and finished product is prone to conquassation, warpage；Deflection is big, and finished product is difficult In shaping.In order to improve the deflection of the multilayer complex films of the present invention further and such as heat sealer, ventilative Property and the performance such as intensity, another resin can be added in A layer or B layer, such as Petropols, hydrogenation Petropols etc., preferably C₅-C₉Petropols or C₅-C₉Hydrogenated petroleum resin.Its addition is each layer gross weight The 1-30% weight of amount, preferably 2-20% weight, more preferably 3-15% weight, even more preferably from 4-10% weight.

The polymer of described A layer, B layer and C layer can add about 0.01～5.0 mass % with master batch form Additive.Described additive is preferably 0.01～3.0 mass %, more preferably 0.05～1.0 mass %.

Described additive has: antiblocking agent, slipping agent (i.e. lubricant or slipping agent), antistatic additive, nucleation Agent, heat-resisting stabilizing agent, weathering stabilizers, ultra-violet absorber, anti-turbid dose, pigment, dyestuff etc. known logical Often can add the various additives in polyolefin to.

As described antiblocking agent, antiblocking agent well known in the art can be used, as silica, talcum, mica, Zeolite, or by inorganic compound particles such as the metal alkoxide metal oxides that obtains of sintering；Or polymethyl The organic compounds such as acid methyl esters, melamine resin, melamine urea resin, polyester resin.Its In, particularly preferably use silica, polymethyl methacrylate from resistance to blocking aspect.

As described lubricant, the acid amides system chemical combination such as such as stearmide, erucyl amide, oleamide can be used Thing etc..

As described antistatic additive, the ethylene oxide adduct such as betanin derivative, quaternary amine system can be used Compound, alkyldiethanolamine fatty acid ester, fatty acid glyceride, tristerin etc..

As described nucleator, such as D-sorbite system, organophosphate metal salt system, organic carboxylic can be used Acid metal salt system, rosin series nucleator etc..

As described heat-resisting stabilizing agent, such as 2 can be used, 6-di-tert-butyl-4-methy phenol (BHT) etc..

The polymer of described A layer, B layer and C layer also can add delustring masterbatch to produce Extinctive thin film, or Person adds pearly-lustre masterbatch to produce pearly-lustre film.

Laminate stretch acrylic polymer-ethylene-based polymer the film of the present invention can as required, to one side or The surfaces such as two-sided enforcement sided corona treatment, flame treatment process.It addition, according to purposes, for giving heat sealability, Can overleaf on layer individually lamination containing high-pressure process low-density polyethylene, linear low density polyethylene (LLDPE), crystallization Property or the random copolymer of alpha-olefin of low-crystalline ethene and carbon number 3～10 or propylene and ethene or carbon number The low melting point polymers such as the random copolymer of the alpha-olefin of more than 4, polybutene, ethene-vinyl acetate copolymer Film, or lamination is containing the film of combinations thereof thing.It addition, it is viscous in order to improve with other material Connecing property, can be fixed process to adhesives such as oriented film surface imines, carbamates, it is also possible to It is laminated maleic anhydride modified polyolefin.

[composition of X layer]

According to the present invention, the material of the binding agent in any one X layer described is identical or different, is selected from: Chlorinated polypropylene, polyurethane, acrylic resin, epoxy resin or its mixture.

The chlorinated polypropylene of the present invention uses solwution method, suspension method or solid phase method polypropylene chlorination to be prepared. The mass content of chlorine is 20%-70%, and fusing point is less than 150 DEG C.

According to the present invention, described polyurethane is solvent-borne type, water-dispersion type or no-solvent type one-component or many Part polyurethane adhesive.

According to the present invention, described acrylic resin be solvent-borne type, water-dispersion type or no-solvent type one-component or Person's multicomponent contains the adhesive of acrylic acid or acrylates.

According to the present invention, described epoxy resin be solvent-borne type, water-dispersion type or no-solvent type one-component or Multicomponent epoxy type adhesive.

The polyurethane resin of the present invention is selected from generally as the dry type containing polyurethane known to film adhesive The poly-ammonia of polyester that lamination, waterborne dry-type lamination, solventless liminating, electronic beam solidified laminating adhesive manufacture Ester, polyether-polyurethane or polyurethane polyureas carbamide resin etc..This polyurethane resin can be water-dispersion type or solvent-borne type Any one, but easily dimmable from the degree of cross linking of polyurethane resin cover layer, and from the operation ring of production scene Border aspect is set out, preferably water dispersant type polyaminoester resin.

As water dispersant type polyaminoester resin, it is preferably main chain or side chain to polyurethane resin and introduces carboxylic acid Salt (-COONa etc.), sulfonate (-SO₃Na etc.) etc. the self-emulsifying type polyurethane resin of hydrophilic group.At solvent-borne type In the case of, isocyanates system resin is used for crosslinking agent, forms the polyurethane with three-dimensional structure, but water The situation that decentralized becomes linear polyurethane or polyurethane polyureas carbamide resin is in the majority, therefore relative to polyurethane resin, The crosslinkings such as the melamine series resin about 3～10 mass %, epoxy system resin, imines system resin can be added Agent, it is possible to add the acid catalyst about 0.5～1 mass %, promote curing reaction further.This crosslinking Agent is possible not only to improve the resistance to water of easy-adhesion overlay film, solvent resistance, it is also possible to improve cementability.

It addition, when using water dispersant type polyaminoester resin, containing the surface such as defoamer or emulsifying agent in composition During activating agent, it is possible to make the surface of Biaxially stretched multilayer propylene polymer thin film turn white, cause outward appearance not Good.It addition, in the polyurethane resin of the present invention, such as, in order to prevent the purposes such as adhesion, as required, Inorganic particles or organic fine particles etc. can also be added.

On the one or both sides of propylene polymer thin film, when covering (lamination) polyurethane resin (X), can lead to Cross the aqueous solution of polyurethane resin or dispersion liquid Kohler coater, direct gravure coater, intaglio offset The gravure coater such as coating machine, electric arc gravure coater, reverse rotating gravure and nozzle mode；Its top feed is against roller The reverse roll coating machines such as coating machine, bottom feed reverse roll coating machine and nozzle material-feeding reverse roll coating machine, the painting of 5 rollers Cloth machine, lip are coated with machine, bar coater, itself known painting various such as inverse rod coater, die head formula coating machine etc. Cloth machine, is 0.1～20g/m according to making the amount of contained composition in the polyurethane resin aqueous solution², preferably 0.3～ 2g/m²After being coated, it is dried more than 10 seconds at a temperature of 50～140 DEG C and obtains.

[preparation method of multilayer complex films]

According to the present invention, use simple tension or biaxial tension, i.e. in stretching-machine, in certain temperature and Under speed, a direction (vertical or horizontal) or enterprising in vertical both direction (longitudinally, laterally) Row stretches and makes film.The so-called direction longitudinally referred to along film extrusion processing, what is called laterally refers to hang down The direction of straight film extrusion 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 described multilayer complex films, and it comprises the following steps:

(1) A layer and the preparation of C tunic

Prepared by the method using simple tension or biaxial tension, for biaxial tension, can use substep sequentially Biaxial tension method, also can use synchro-draw method.

Described drawing process includes plain film method and periosteum method.For biaxial tension, the technique mistake of described plain film method Journey includes synchro-draw process, comprises the steps:

Synchro-draw → the traction of dispensing → extrusion → chilling → vertically and horizontally and optional surface process → rolling → time Effect processes → cuts → product.

The technical process of described plain film method also includes step drawing process, comprises the steps:

Dispensing → extrusion → chilling → longitudinal stretching → cross directional stretch → traction and optional surface process → rolling → Ageing Treatment → cut → product.

According to the present invention, described longitudinal stretching includes preheating, micro-stretching and sizing.

According to the present invention, described cross directional stretch includes preheating, stretches greatly, shapes and cool down.

According to the present invention, described chilling refers to use coolant to cool down, and preferably coolant is cooling water. The effect of described chilling is to make crystallization refine, thus improves transparency and deflection.

According to the present invention, described extrusion includes individual layer extrusion or multi-layer co-extruded.Described extrusion uses melted squeezing Go out.

According to the present invention, described dispensing includes that the requirement according to formula carries out dispensing, can pass through electronic measurement.

The technical process of described periosteum method includes synchro-draw process, comprises the steps:

Dispensing → extrusion (including individual layer extrusion or multilayered molten extrusion) → chilling → mother's film → except water → baker Synchro-draw → the collapser of Far-infrared Heating → vertically and horizontally flatten → cut open limit → heat treatment → cooling → rolling → time Effect processes → cuts → product.

The technical process of described periosteum method also includes step drawing process, comprises the steps:

Dispensing → extrusion (including individual layer extrusion or multilayered molten extrusion) → chilling → mother's film → except water → baker Far-infrared Heating → longitudinal stretching → cross directional stretch → collapser flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.

According to the present invention, described chilling refers to use coolant to cool down, and preferably coolant is cooling water. The effect of described chilling is to make crystallization refine, thus improves transparency and deflection.

When described plain film method is plain film substep biaxial tension, specifically include following steps:

A () carries out dispensing by the requirement of formula, add in the hopper above the extruder of single or multiple lift co-extrusion, After plastics pass through external heat and the screw rod rotational shear plasticizing of extruder barrel, enter single or multiple lift co-extrusion Compound rack-style flat die.Go out the sheet melt after die head to be attached on chilling roller by air knife, by sheet Melt supercooled becomes sheet, and then as the rotation of chilling roller, sheet enters tank and carries out further two-sided cold But.The thickness of sheet can be controlled by the rotating speed of the extrusion capacity of extruder and chilling roller.Wherein, extruder Control temperature be 150-260 DEG C, preferably 180-250 DEG C；Die head temperature is generally 190-240 DEG C, chilling Roll temperature is 15-30 DEG C, preferably 20-25 DEG C.

B a number of pre-hot-rolling that () sheet enters back in vertically and horizontally tensioning system carries out two-sided preheating, in advance Heat roller temperature general control at 90-150 DEG C, preferably 100-120 DEG C.Reach the draft temperature (softening point of regulation Above, below fusing point) after, carrying out longitudinal stretching by draw roll, draft temperature controls at 90-150 DEG C, Preferably 100-120 DEG C, drawing process can a step, it is also possible to twice stretching or three stretchings.Longitudinal stretching Multiplying power is set according to the requirement of A layer and C tunic.Film after stretching is carried out at heat by setting roller Reason, described setting temperature is 100-140 DEG C, preferably 110-120 DEG C, to eliminate the internal stress of film, subtracts Few longitudinal shrinkage factor.

C the film after () longitudinal stretching enters cross directional stretch system, first carry out preheating section preheating, pre-hot-rolling Temperature general control at 100-160 DEG C, preferably 110-140 DEG C, more preferably 115-130 DEG C.Reach drawing of regulation After stretching temperature (more than softening point, below fusing point), the track then passing through expansion spoke carries out cross directional stretch, draws Stretch general 130-180 DEG C of the control temperature of machine, preferably 140-160 DEG C, then carry out thermal finalization process, sizing Temperature is 60-120 DEG C, preferably 70-110 DEG C.Cross directional stretch multiplying power is carried out according to the requirement of A layer and C tunic Set.

Film d () goes out cross directional stretch system after is cooled down by chill roll, followed by trimming, is electricity with that Dizzy process, is finally by rolling.

(e) leave equipment after big wound membrane after depositing the Ageing Treatment of several days, just can cut, make The A layer of Rack and C layer film.

When described plain film method is the stretching of plain film synchronous bidirectional, plain film synchro-draw preparation method and plain film substep Stretching preparation method is similar to, difference be only during synchro-draw longitudinal stretching and cross directional stretch be with Step is carried out, and namely longitudinal stretching and cross directional stretch complete a system inter-sync, and step drawing Middle longitudinal stretching and cross directional stretch is asynchronous carries out.Thus concrete operating condition is similar with step drawing.Mesh Before, synchro-draw machine has two kinds of forms in the world, and one is mechanical type, and one is linear electric machine formula.

When described periosteum method is synchronous bidirectional stretching, periosteum method synchronous bidirectional stretching preparation method and plain film method Synchronous bidirectional stretching preparation method is similar to, and its longitudinal stretching and cross directional stretch also synchronize to carry out.Difference Place is, the die head of periosteum method is circular, and it is all that the form steeping pipe completes that whole film is formed. Main production parameter: extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, cools down water Temperature is 11-18 DEG C, oven drying temperature: 330-450 DEG C, and draft temperature is 140 DEG C.Vertically and horizontally draw ratio is then The requirement of the draw ratio according to each tunic is carried out.

When described periosteum method is substep biaxial tension, periosteum method substep biaxial tension preparation method and plain film method Biaxial tension preparation method step by step is similar to, and its longitudinal stretching and cross directional stretch also synchronize to carry out.Difference Place is, the die head of periosteum method is circular, and it is all that the form steeping pipe completes that whole film is formed. Main production parameter: extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, cools down water Temperature is 11-18 DEG C, oven drying temperature: 330-450 DEG C, and draft temperature is 140 DEG C.Vertically and horizontally draw ratio is then The requirement of the draw ratio according to each tunic is carried out.

For simple tension, the technical process of described plain film method comprises the steps:

Dispensing → extrusion → chilling → vertical or horizontal stretching → traction and optional surface process → rolling → time Effect processes → cuts → product.

The technical process of described periosteum method comprises the steps:

Dispensing → extrusion (including individual layer extrusion or multilayered molten extrusion) → chilling → mother's film → except water → baker Far-infrared Heating → vertical or horizontal stretching → collapser flatten → cut open limit → heat treatment → cooling → rolling → time Effect processes → cuts → product.

Concrete step is similar with above-mentioned biaxial tension method.

(2) preparation of B tunic

Employing does not stretches or prepared by the method for simple tension or biaxial tension, if simple tension or biaxial tension, Identical with step (1).

(3) use rolling method, with X as adhesive, each A layer, B layer and C layer carried out gluing, Wherein the outermost two-layer of composite membrane carries out single spreading, and middle each layer carries out one or two sides gluing.

According to the present invention, described gluing is carried out at normal temperatures.After gluing, each layer of composite membrane is at 40-80 DEG C Dry.

(4) lamination

The A layer of gluing, B layer and C layer are carried out lamination compound, obtain described composite membrane.

According to the present invention, described lamination is compound to be carried out by hot pressing, and described laminating temperature is 40-100 DEG C, excellent Select 60-80 DEG C.

Two-sided according to the present invention, step (1) and the A layer of step (2) gained and/or B layer and/or C layer All through sided corona treatment so that it is initial surface tension reaches more than 44 dynes per centimeter.The surface of gained composite membrane Tension force is more than 36 dynes per centimeter.It is further preferred that surface tension reaches more than 38 dynes per centimeter.

[purposes of multilayer complex films]

Film prepared by the present invention can be used for needing high-stiffness, tear-resistant bill, marketable securities, printed matter and Packaging material.

The present invention also provides for the application of the multilayer complex films described in a kind of aforementioned any one, and it is used for bill, has Valency security, printed matter and packaging material.

The present invention also provides for a kind of goods, and it is by the face coat of the multilayer complex films of aforementioned any one and print Brush prepares, and described goods include printed matter (such as Front cover of book and periodical or picture album), bill, marketable securities and packing timber Material.

Accompanying drawing explanation

Fig. 1 is the structural representation of the composite membrane of embodiment 1 preparation, and it is AXBXCXAXBXC structure.

Fig. 2 is the structural representation of the composite membrane of embodiment 1 preparation, and it is AXBXCXCXBXA structure.

Detailed description of the invention

Below in conjunction with embodiment, the present invention being described, but skilled in the art realises that, described embodiment is not right The restriction of scope, any make on the basis of the present invention improvement, change all the present invention's Within protection domain.

Embodiment 1:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 10 μm/10, μm/1, μm/20, μm/1, μm/10, μm/1, μm/10, μm/1, μm/20, μm/1 μm

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm³, fusing point is 135 DEG C, molten Melting index is 3.8g/10min.

A layer, B layer and C layer the most all add Petropols, and Petropols addition is each layer gross weight 10% weight.

Two A layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.

Two B layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 9 times, and thickness is 20 μm.

Two C layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 85 μm.Two The mechanical property planting film prepared by Rotating fields is suitable, the wherein performance of the film of AXBXCXAXBXC structure Test data are listed in table 2.

Embodiment 2:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 8 μm/8, μm/1, μm/16, μm/1, μm/8, μm/1, μm/8, μm/1, μm/16, μm/1 μm

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm³, fusing point is 135 DEG C, molten Melting index is 3.8g/10min.

A layer, B layer and C layer the most all add Petropols, and Petropols addition is each layer gross weight 15% weight.

Two A layers are all by plain film method simple tension processes, and wherein longitudinal stretching multiplying power is 12.5 times, Thickness is 8 μm.

Two B layers are all by plain film method simple tension processes, and wherein cross directional stretch multiplying power is 12.5 times, Thickness is 16 μm.

Two C layers are all by plain film method simple tension processes, and wherein longitudinal stretching multiplying power is 12.5 times, Thickness is 8 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 40 dynes per centimeter, then Using roll coating model coating polyurethane, then be compounded to form composite membrane through hot pressing, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 69 μm.Two The mechanical property planting film prepared by Rotating fields is suitable, the wherein performance of the film of AXBXCXAXBXC structure Test data are listed in table 2.

Embodiment 3:AXBXCXAXBXC structure or AXBXCXCXBXA structure, layer thickness profile: 7.5μm/1μm/15μm/1μm/7.5μm/1μm/7.5μm/1μm/15μm/1μm/7.5μm

A layer and C layer are Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, etc. Normality is 96.2%.

B layer is low density polyethylene (LDPE), and density is 0.916g/cm³, melt index is 2.8g/10min.

A layer, B layer and C layer the most all add hydrogenated petroleum resin, and hydrogenated petroleum resin addition is each layer 20% weight of gross weight.

Two A layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 7.5 μm.

Two B layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 8 times, and thickness is 15 μm.

Two C layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 7.5 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating polyurethane, then through being compounded to form composite membrane, wherein the thickness of X is 1 μm, knot Structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 65 μm.Two kinds of layer knots The mechanical property of the film that body plan is standby is suitable, the wherein performance test number of the film of AXBXCXAXBXC structure According to being listed in table 2.

Embodiment 4:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 10 μm/10, μm/1, μm/20, μm/1, μm/10, μm/1, μm/10, μm/1, μm/20, μm/1 μm

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer is low density polyethylene (LDPE), and density is 0.916g/cm³, melt index is 2.8g/10min.

Two A layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.

Two B layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 8 times, and thickness is 20 μm.

Two C layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 85 μm.Two The mechanical property planting film prepared by Rotating fields is suitable, the wherein performance of the film of AXBXCXAXBXC structure Test data are listed in table 3.

Embodiment 5:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 8 μm/8, μm/1, μm/16, μm/1, μm/8, μm/1, μm/8, μm/1, μm/16, μm/1 μm

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer is low density polyethylene (LDPE), and density is 0.916g/cm³, melt index is 2.8g/10min.

Two A layers are all by plain film method simple tension processes, and wherein longitudinal stretching multiplying power is 10 times, thick Degree is 8 μm.

Two B layers are all by plain film method simple tension processes, and wherein cross directional stretch multiplying power is 10 times, thick Degree is 16 μm.

Two C layers are all by plain film method simple tension processes, and wherein longitudinal stretching multiplying power is 10 times, thick Degree is 8 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 40 dynes per centimeter, then Using roll coating model coating polyurethane, then be compounded to form composite membrane through hot pressing, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 69 μm.Two The mechanical property planting film prepared by Rotating fields is suitable, the wherein performance of the film of AXBXCXAXBXC structure Test data are listed in table 3.

Embodiment 6:AXBXCXAXBXC structure or AXBXCXCXBXA structure, layer thickness profile: 7.5μm/1μm/15μm/1μm/7.5μm/1μm/7.5μm/1μm/15μm/1μm/7.5μm

A layer and C layer are Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, etc. Normality is 96.2%.

B layer is linear low density polyethylene (LLDPE), and density is 0.915g/cm³, melt index is 2.8g/10min.

Two A layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 7.5 μm.

Two B layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 9 times, and thickness is 15 μm.

Two C layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 7.5 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating polyurethane, then through being compounded to form composite membrane, wherein the thickness of X is 1 μm, knot Structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 65 μm.Two kinds of layer knots The mechanical property of the film that body plan is standby is suitable, the wherein performance test number of the film of AXBXCXAXBXC structure According to being listed in table 3.

Embodiment 7:

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer is linear low density polyethylene (LLDPE), and density is 0.915g/cm³, melt index is 2.8g/10min.

A layer, B layer and C layer the most all add Petropols, and Petropols addition is each layer gross weight 10% weight.

Four A layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 7 μm.

Two B layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 9 times, and thickness is 10 μm.

Two B layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.

Four C layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 7 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating chlorinated polypropylene, then be compounded to form composite membrane through 4 AXBXC Rotating fields, Wherein, the thickness of X layer is 1 μm, structure be AXBXCXAXBXCXAXBXCXAXBXC (sequentially Structure) or AXBXCXCXBXAXAXBXCXCXBXA (alternating structure) or AXBXCXCXBXAXCXBXAXCXBXA (disordered structure), overall film thickness is 107 μm.Two kinds The mechanical property of film prepared by Rotating fields is suitable, and wherein the performance of the film of AXBXCXAXBXC structure is surveyed Examination data are listed in table 4.

Embodiment 8:

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm³, fusing point is 135 DEG C, molten Melting index is 3.8g/10min.

Four A layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 8 μm.

Two B layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 8 times, and thickness is 11 μm.

Two B layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 11 μm.

Four C layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 8 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, wherein, the thickness of X layer is 1 μm, structure be AXBXCXAXBXCXAXBXCXAXBXC (sequential organization) or AXBXCXCXBXAXAXBXCXCXBXA (alternating structure) or AXBXCXCXBXAXCXBXAXCXBXA (disordered structure), overall film thickness is 119 μm.Two kinds The mechanical property of film prepared by Rotating fields is suitable, and wherein the performance of the film of AXBXCXAXBXC structure is surveyed Examination data are listed in table 4.

Embodiment 9:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 10 μm/10, μm/1, μm/20, μm/1, μm/10, μm/1, μm/10, μm/1, μm/20, μm/1 μm

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm³, fusing point is 135 DEG C, molten Melting index is 3.8g/10min.

A layer, B layer and C layer the most all add Petropols, and Petropols addition is each layer gross weight 10% weight.

In A layer, B layer and C layer one layer is processed, the most laterally by plain film method substep stretch processes Stretching ratio is 9 times, and longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.

Another layer in A layer, B layer and C layer passes through plain film method simple tension processes, its cross directional stretch Multiplying power is 5 times, and thickness is 20 μm.

Another layer in A layer, B layer and C layer passes through plain film method simple tension processes, its longitudinal stretching Multiplying power is 5 times, and thickness is 10 μm.

But the processing method of above-mentioned two A layer is processing method identical, two B layers is identical and two The processing method of individual C layer is identical.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 85 μm.Respectively The mechanical property planting the film that combination obtains is suitable, and wherein the A layer of AXBXCXAXBXC structure is two-way Stretching, B layer be cross directional stretch, C layer be that the performance test data of the film of longitudinal stretching is listed in table 4.

Embodiment 10:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 8 μm/8, μm/1, μm/16, μm/1, μm/8, μm/1, μm/8, μm/1, μm/16, μm/1 μm

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer all uses low density polyethylene (LDPE) to process, and density is 0.916g/cm³, melt index is 2.8 g/10min。

A layer, B layer and C layer the most all add Petropols, and Petropols addition is each layer gross weight 15% weight.

In A layer, B layer and C layer one layer is processed, wherein longitudinally by plain film method substep stretch processes Stretching ratio is 12.5 times, and cross directional stretch multiplying power is 1.1 times, and thickness is 8 μm.

Another layer in A layer, B layer and C layer is processed by plain film method substep stretch processes, wherein horizontal Being 12.5 times to stretching ratio, longitudinal stretching multiplying power is 1.1 times, and thickness is 16 μm.

Another layer in A layer, B layer and C layer passes through plain film method simple tension processes, its longitudinal stretching Multiplying power is 12.5 times, and thickness is 8 μm.

But the processing method of above-mentioned two A layer is processing method identical, two B layers is identical and two The processing method of individual C layer is identical.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 40 dynes per centimeter, then Using roll coating model coating polyurethane, then be compounded to form composite membrane through hot pressing, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 69 μm.Respectively The mechanical property planting the film that combination obtains is suitable, and wherein the A layer of AXBXCXAXBXC structure is two-way Stretching, B layer be biaxial tension, C layer be that the performance test data of the film of longitudinal stretching is listed in table 4.

Embodiment 11:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 10 μm/10, μm/1, μm/20, μm/1, μm/10, μm/1, μm/10, μm/1, μm/20, μm/1 μm

A layer and C layer all use the propylene copolymer containing ethene to process, and ethylene contents is 0.35wt%, Molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm³, fusing point is 135 DEG C, molten Melting index is 3.8g/10min.

A layer, B layer and C layer the most all add Petropols, and Petropols addition is each layer gross weight 10% weight.

Two A layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, Longitudinal stretching multiplying power is 5 times, and thickness is 10 μm.

Two B layers are all processed into, by conventional method, the film that thickness is 20 μm.

Two C layers are all processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 9 times, and thickness is 10 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating chlorinated polypropylene, then through being compounded to form composite membrane, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 85 μm.Two The mechanical property planting film prepared by Rotating fields is suitable, the wherein performance of the film of AXBXCXAXBXC structure Test data are listed in table 5.

Embodiment 12:AXBXCXAXBXC structure or AXBXCXCXBXA structure,

Layer thickness profile: 8 μm/8, μm/1, μm/16, μm/1, μm/8, μm/1, μm/8, μm/1, μm/16, μm/1 μm

.A layer is polypropylene homopolymer, and molecular distribution is 5.1, and melt index is 2.8g/10min, isotacticity It is 96.2%.C layer is the polypropylene copolymer containing ethene, and ethylene contents is 0.35wt%, molecular distribution Being 5.5, melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer all uses high density polyethylene (HDPE) to process, and density is 0.955g/cm³, fusing point is 135 DEG C, molten Melting index is 3.8g/10min.

A layer, B layer and C layer the most all add Petropols, and Petropols addition is each layer gross weight 15% weight.

Two A layers are all by plain film method simple tension processes, and wherein longitudinal stretching multiplying power is 12.5 times, Thickness is 8 μm.

Two B layers are processed into, by conventional method, the film that thickness is 16 μm.

Two C layers are all by plain film method simple tension processes, and wherein cross directional stretch multiplying power is 12.5 times, Thickness is 8 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 40 dynes per centimeter, then Using roll coating model coating polyurethane, then be compounded to form composite membrane through hot pressing, wherein, the thickness of X layer is 1 μm, structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 69 μm.Two The mechanical property planting film prepared by Rotating fields is suitable, the wherein performance of the film of AXBXCXAXBXC structure Test data are listed in table 5.

Embodiment 13:AXBXCXAXBXC structure or AXBXCXCXBXA structure, layer thickness profile: 7.5μm/1μm/15μm/1μm/7.5μm/1μm/7.5μm/1μm/15μm/1μm/7.5μm

A layer is Noblen, 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 distribution is 5.5, melt index is 2.8g/10min, and isotacticity is 95.6%.

B layer is low density polyethylene (LDPE), and density is 0.916g/cm³, melt index is 2.8g/10min.

A layer, B layer and C layer the most all add hydrogenated petroleum resin, and hydrogenated petroleum resin addition is each layer 20% weight of gross weight.

Two A layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, Longitudinal stretching multiplying power is 5 times, and thickness is 7.5 μm.

Two B layers are processed into, by conventional method, the film that thickness is 15 μm.

Two C layers are all processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, Longitudinal stretching multiplying power is 8 times, and thickness is 7.5 μm.

A layer, B layer and C layer are respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, then Use roll coating model coating polyurethane, then through being compounded to form composite membrane, wherein the thickness of X is 1 μm, knot Structure is AXBXCXAXBXC or AXBXCXCXBXA, and overall film thickness is 65 μm.Two kinds of layer knots The mechanical property of the film that body plan is standby is suitable, the wherein performance test number of the film of AXBXCXAXBXC structure According to being listed in table 5.

The results of property of table 2 multilayer complex films

The results of property of table 3 multilayer complex films

The results of property of table 4 multilayer complex films

The results of property of table 5 multilayer complex films

Claims (10)

1. a multilayer complex films, it includes that n AXBXC Rotating fields is composited by X each other Rotating fields, n be more than or equal to 2, each A is identical or different, and each B is identical or different, each C phase Same or different, each X is identical or different, and A layer and C layer in described Rotating fields include phase independently of one another Same or different acrylic polymer, B layer includes identical or different ethylene-based polymer, X independently of one another For adhesive layer, that described A layer and C layer are each independently simple tension or biaxial tension；Described B Layer is each independently that do not stretch or simple tension or biaxial tension；

When described B layer is not stretch, described A layer is biaxial tension and the cross directional stretch of described A layer Multiplying power and longitudinal stretching multiplying power are same or like, or described C layer is biaxial tension and the horizontal stroke of described C layer Same or like to stretching ratio and longitudinal stretching multiplying power；

When described B layer be simple tension or biaxial tension time, the draw ratio of described A layer or stretching ratio Different from B layer and/or the draw ratio of C layer or stretching ratio.

Optional, draw ratio or the stretching ratio of each A layer are identical or different；The draw ratio of each B layer or Stretching ratio is identical or different；Draw ratio or the stretching ratio of each C layer are identical or different.

Multilayer complex films the most according to claim 1, it is characterised in that when described B layer be do not stretch and When n is even number, described A layer combines in pairs, and described C layer combines in pairs；Wherein, an A The longitudinal stretching multiplying power of layer or C layer is more than cross directional stretch multiplying power, the longitudinal stretching of another A layer or C layer times Rate is less than cross directional stretch multiplying power.Preferably, one A layer or the vertically and horizontally draw ratio of C layer and another The vertically and horizontally draw ratio of A layer or C layer is inversely proportional to, and i.e. the longitudinal stretching of one A layer or C layer is with horizontal The ratio of stretching is equal to the cross directional stretch of another A layer or C layer and the ratio of longitudinal stretching.It is furthermore preferred that The longitudinal stretching multiplying power of one A layer or C layer is identical with the cross directional stretch multiplying power of another A layer or C layer Or close, and the longitudinal direction of the cross directional stretch multiplying power of one A layer or C layer and another A layer or C layer is drawn Stretch multiplying power same or like.

Or, when described B layer be do not stretch and time n is odd number, described A layer is surplus after combining in pairs Remaining A layer individually combines, described C layer after combining in pairs remaining C layer individually combine；Wherein, become To two-layer in the longitudinal stretching multiplying power of an A layer or C layer more than cross directional stretch multiplying power, another A layer or The longitudinal stretching multiplying power of C layer is less than cross directional stretch multiplying power, the A layer of individually combination or the cross directional stretch of C layer times Rate and longitudinal stretching multiplying power are same or like.Preferably, an A layer or C layer in the most paired two-layer Vertically and horizontally draw ratio is inversely proportional to the vertically and horizontally draw ratio of another A layer or C layer, i.e. one A layer or The longitudinal stretching of C layer draws with longitudinal equal to the cross directional stretch of another A layer or C layer with the ratio of cross directional stretch The ratio stretched, the A layer of individually combination or the cross directional stretch multiplying power of C layer and longitudinal stretching multiplying power are same or like. It is furthermore preferred that in the most paired two-layer the longitudinal stretching multiplying power of an A layer or C layer and another A layer or The cross directional stretch multiplying power of C layer is same or like, and the cross directional stretch multiplying power of one A layer or C layer is with another The longitudinal stretching multiplying power of one A layer or C layer is same or like, the A layer of individually combination or laterally drawing of C layer Stretch multiplying power and longitudinal stretching multiplying power is same or like.Even more preferably from, an A layer in the most paired two-layer Or the longitudinal stretching multiplying power of C layer is identical with the cross directional stretch multiplying power of another A layer or C layer, and one The cross directional stretch multiplying power of A layer or C layer is identical with the longitudinal stretching multiplying power of another A layer or C layer, independent group Close A layer or the cross directional stretch multiplying power of C layer and longitudinal stretching multiplying power same or like.

Multilayer complex films the most according to claim 1 and 2, it is characterised in that

When n is even number, between B layer, include one of following combination two-by-two:

(1 ') two B layers are simple tension, and stretching ratio is identical, laterally drawing of a preferably B layer Stretch multiplying power identical with the longitudinal stretching multiplying power of another B layer；

(2 ') B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension Identical with biaxial tension stretching ratio (cross directional stretch multiplying power or longitudinal stretching multiplying power)；Or

(3 ') two B layers are biaxial tension, and the draw ratio of the two is identical；

When n is odd number, between B layer, include one of following combination two-by-two:

(1 ') two B layers are simple tension, and stretching ratio is identical；

(2 ') B layer is simple tension, a B layer biaxial tension, and the stretching ratio of simple tension Identical with biaxial tension stretching ratio；Or

(3 ') two B layers are biaxial tension, and the draw ratio of the two is identical；

The draw ratio of remaining B layer or stretching ratio then with draw ratio or the stretching ratio of the above-mentioned layer of B two-by-two Identical or different.

4. according to the multilayer complex films of any one of claim 1-3, it is characterised in that described A layer, B layer One of following combination is included with C layer:

(1) described A layer is simple tension, and described B layer is simple tension, and described C layer is biaxial tension；

(2) described A layer is simple tension, and described B layer is biaxial tension, and described C layer is biaxial tension；

(3) described A layer is simple tension, and described B layer is biaxial tension, and described C layer is simple tension；

(4) described A layer is biaxial tension, and described B layer is simple tension, and described C layer is simple tension；

(5) described A layer is biaxial tension, and described B layer is biaxial tension, and described C layer is simple tension；

(6) described A layer is biaxial tension, and described B layer is simple tension, and described C layer is biaxial tension；

(7) A layer, B layer and C layer are biaxial tension；Or

(8) A layer, B layer and C layer are simple tension.

Preferably, for scheme (1), including following scheme:

To laterally stretching of described A layer, to laterally stretching of described B layer, and to described C layer Horizontal and vertical all stretch；Or

To laterally stretching of described A layer, the longitudinal direction of described B layer is stretched, and to described C layer Horizontal and vertical all stretch；Or

The longitudinal direction of described A layer is stretched, to laterally stretching of described B layer, and to described C layer Horizontal and vertical all stretch；Or

The longitudinal direction of described A layer is stretched, the longitudinal direction of described B layer is stretched, and to described C layer Horizontal and vertical all stretch；

For scheme (2), including following scheme:

To laterally stretching of described A layer, described the horizontal and vertical of B layer is stretched, and to institute State the horizontal and vertical of C layer all to stretch；Or

The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B layer is stretched, and to institute State the horizontal and vertical of C layer all to stretch；

For scheme (3), including following scheme:

To laterally stretching of described A layer, described the horizontal and vertical of B layer is all stretched, and right Laterally stretching of described C layer；Or

To laterally stretching of described A layer, described the horizontal and vertical of B layer is all stretched, and right The longitudinal direction of described C layer stretches；Or

The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B layer is all stretched, and right Laterally stretching of described C layer；Or

The longitudinal direction of described A layer is stretched, described the horizontal and vertical of B layer is all stretched, and right The longitudinal direction of described C layer stretches；

For scheme (4), including following scheme:

Described the horizontal and vertical of A layer is all stretched, to laterally stretching of described B layer and right Laterally stretching of described C layer；Or

Described the horizontal and vertical of A layer is all stretched, to laterally stretching of described B layer and right The longitudinal direction of described C layer stretches；Or

Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B layer is stretched, and right Laterally stretching of described C layer；Or

Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B layer is stretched, and right The longitudinal direction of described C layer stretches；

For scheme (5), including following scheme:

Described the horizontal and vertical of A layer is all stretched, described the horizontal and vertical of B layer is stretched, And laterally stretching described C layer；Or

Described the horizontal and vertical of A layer is all stretched, described the horizontal and vertical of B layer is stretched, And the longitudinal direction of described C layer is stretched；

For scheme (6), including following scheme:

Described the horizontal and vertical of A layer is all stretched, to laterally stretching of described B layer and right Described the horizontal and vertical of C layer stretches；Or

Described the horizontal and vertical of A layer is all stretched, the longitudinal direction of described B layer is stretched, and right Described the horizontal and vertical of C layer stretches；

For scheme (7), the vertically and horizontally draw ratio of described A layer/C layer is different from the vertically and horizontally draw ratio of B layer；

For scheme (8), the stretching ratio of described A layer/C layer is different from the stretching ratio of described B layer.

It is furthermore preferred that for scheme (1)-(6), the cross directional stretch multiplying power of described A layer/C layer and described B The longitudinal stretching multiplying power of layer is identical or close；Or, the longitudinal stretching multiplying power of described A layer/C layer and described B The cross directional stretch multiplying power of layer is identical or close；

For scheme (7), the longitudinal stretching multiplying power of described A layer/C layer is more than cross directional stretch multiplying power, and B layer Cross directional stretch multiplying power more than longitudinal stretching multiplying power；

For scheme (8), the stretching ratio of described A layer/C layer is more than the stretching ratio of described B layer, or The stretching ratio of described A layer/C layer is less than the stretching ratio of described B layer.

Even more preferably from, for scheme (7), the vertically and horizontally draw ratio of described A layer/C layer is with B layer in length and breadth Be inversely proportional to draw ratio, i.e. the longitudinal stretching of A layer/C layer and the ratio of cross directional stretch laterally drawing equal to B layer Stretch the ratio with longitudinal stretching；

For scheme (8), the described vertically and horizontally draw ratio of A layer/C layer becomes anti-with the vertically and horizontally draw ratio of B layer Ratio, i.e. the longitudinal stretching of A layer/C layer and the ratio of cross directional stretch are equal to cross directional stretch and the longitudinal stretching of B layer Ratio.

Even more preferably from, for scheme (7), the longitudinal stretching multiplying power of described A layer/C layer and described B layer Cross directional stretch multiplying power is same or like, and the cross directional stretch multiplying power of described A layer/C layer and the longitudinal direction of described B layer Stretching ratio is same or like；

For scheme (8), the longitudinal stretching multiplying power of described A layer/C layer and the cross directional stretch multiplying power of described B layer Same or like, and the cross directional stretch multiplying power of described A layer/C layer is identical with the longitudinal stretching multiplying power of described B layer Or it is close.

5. according to the multilayer complex films described in any one of claim 1-4, it is characterised in that described multilayer is multiple Close n AXBXC Rotating fields in film to be combined by X order, i.e. according to AXBXCXAXBXC's Order is compound；Or, in described multilayer complex films, n AXBXC Rotating fields is the most compound by X, I.e. it is combined according to the order of AXBXCXCXBXA；Or, n AXBXC in described multilayer complex films Rotating fields is unordered compound by X.

Preferably, described Rotating fields also includes one layer of A layer, is compound in the outer layer of outermost C layer by X, Its structure is (AXBXCX)_nA, n are more than or equal to 2；Or the outer layer of outermost A layer it is compound in by X, Its structure is A (XAXBXC)_n, n is more than or equal to 2；Or, described Rotating fields also includes one layer of B layer, Be compound in the outer layer of outermost C layer by X, its structure is (AXBXCX)_nB, n are more than or equal to 2；Or Be compound in the outer layer of outermost A layer by X, its structure is B (XAXBXC)_n, n is more than or equal to 2； Or, described Rotating fields also includes one layer of C layer, is compound in the outer layer of outermost C layer by X, its knot Structure is (AXBXCX)_nC, n are more than or equal to 2；Or the outer layer of outermost A layer it is compound in by X, its Structure is C (XAXBXC)_n, n is more than or equal to 2.

6. according to the multilayer complex films described in any one of claim 1-5, it is characterised in that described A layer or The acrylic polymer of C layer is Noblen or propylene copolymer, comonomer be ethene or higher α- Alkene.

Preferably, described Noblen or propylene copolymer are isotaxy homopolymers, or for different Isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, have the nothing of a small amount of comonomer Rule propylene copolymer and the polypropylene blend of ethylene copolymer-modified isotactic polypropylene；Copolymerization list Body is ethene, butylene, hexene or octene.

Preferably, the ethylene-based polymer of described B layer is high density polyethylene (HDPE), high-pressure process low-density polyethylene Or low-pressure process LLDPE.

Preferably, the fusing point of the acrylic polymer of described A layer or C layer is 148 to 170 DEG C, preferably 150-167 DEG C, more preferably 155 DEG C-165 DEG C；The molecular weight distribution of GPC test is 2-16, preferably 4-10； Melt index is 0.5-10g/10min, preferably 1-8g/10min.

Preferably, in A layer, B layer or C layer, another resin is added, selected from Petropols or hydrogen Fossil oleoresin, it is therefore preferable to C₅-C₉Petropols or C₅-C₉Hydrogenated petroleum resin；Its addition is each layer 1-30 weight % of gross weight, preferably 2-20 weight %, more preferably 3-15% weight, even more preferably from 4-10 Weight %.

Preferably, the thickness of described multilayer complex films is 50-150 μm, preferably 60-120 μm, more preferably 70-100 μm, even more preferably from 80-90 μm.

Multilayer complex films the most according to any one of claim 1 to 6, it is characterised in that described many A layer in layer composite membrane, the tensile strength of B layer or C layer is that 1.5:1.0 arrives at horizontal and vertical ratio 7.0:1.0, preferably 2.0:1.0 to 5.0:1.0.

Preferably, horizontal and vertical in the tensile strength of described multilayer complex films, deflection and tear-resistant intensity Test value ratio is 0.7:1.0 to 1.0:1.3.

Preferably, the cross directional stretch multiplying power of the A layer in described multilayer complex films is 7-12.5 times, longitudinal stretching Multiplying power is 1-6 times,

Preferably, the cross directional stretch multiplying power of the A layer in described multilayer complex films is 8-10 times, longitudinal stretching times Rate is 2-4 times.

Preferably, the cross directional stretch multiplying power of the B layer in described multilayer complex films is 1-6 times, longitudinal stretching times Rate is 7-12.5 times.

Preferably, the cross directional stretch multiplying power of the B layer in described multilayer complex films is 2-4 times, longitudinal stretching times Rate is 8-10 times.

Preferably, the cross directional stretch multiplying power of the C layer in described multilayer complex films is 7-12.5 times, longitudinal stretching Multiplying power is 1-6 times.

Preferably, the cross directional stretch multiplying power of the C layer in described multilayer complex films is 8-10 times, longitudinal stretching times Rate is 2-4 times.

Preferably, for simple tension, the stretching laterally or longitudinally of the A layer in described multilayer complex films times Rate is 1-12.5 times；The vertical or horizontal stretching ratio of B layer is 1-12.5 times；C layer laterally or longitudinally Stretching ratio is 1-12.5 times.

Preferably, for simple tension, the cross directional stretch multiplying power of the A layer in described multilayer complex films is 7-12.5 Times or longitudinal stretching multiplying power be 1-6 times；The longitudinal stretching multiplying power of B layer is 7-12.5 times or cross directional stretch multiplying power is 1-6 times；The cross directional stretch multiplying power of C layer is 7-12.5 times or longitudinal stretching multiplying power is 1-6 times.

Preferably, the vertically and horizontally hot strength of described multilayer complex films is more than 100MPa.

8. the method for the multilayer complex films preparing any one of claim 1 to 7, it is characterised in that institute The method of stating comprises the following steps:

(1) A layer and the preparation of C layer

Extruded by individual layer or multi-layer co-extruded, prepare polyolefin sheets, then the temperature of 130-185 DEG C Carry out simple tension under environment or biaxial tension processes A layer and C layer；

(2) preparation of B layer

Extruded by individual layer or multi-layer co-extruded, prepare polyethylene sheets, may select and do not stretch or simple tension Or biaxial tension processes B layer；

(3) use rolling method, with X as adhesive, each A layer, B layer and each layer of C carried out gluing, Wherein the outermost two-layer of composite membrane carries out single spreading, and middle each layer carries out one or two sides gluing, after gluing, Each layer is dried at 40-80 DEG C；

(4) the A layer of gluing, B layer and C layer are carried out lamination compound, obtain described composite membrane.

9. an application for the multilayer complex films of any one of claim 1 to 7, it is used for bill, has valency to demonstrate,prove Certificate, Front cover of book and periodical, picture album or packaging material.

10. goods, it is by the face coat of the multilayer complex films of any one of claim 1 to 7 and print Brush prepares, and described goods include Front cover of book and periodical, picture album, bill, marketable securities or packaging material.