CN105774168B - A kind of acrylic polymer ethylene-based polymer multilayer complex films, its preparation method, purposes and its product - Google Patents

Abstract

The present invention provides a kind of multilayer complex films, it includes the Rotating fields that n AXBXC Rotating fields are combined by X each other, n is more than or equal to 2, each A is identical or different, each B is identical or different, each C is identical or different, each X is identical or different, A layers and C layers in the Rotating fields include identical or different acrylic polymer independently of one another, B layers include identical or different ethylene-based polymer independently of one another, X is adhesive layer, and the A layers and C layers are simple tension or biaxial tension independently of one another.The present invention also provides the preparation method, its purposes and the product comprising the multilayer complex films of above-mentioned multilayer complex films.The acrylic polymer ethylene-based polymer multilayer complex films of the present invention have the performance such as high-stiffness, high transparency, low temperature resistant, high-tear strength.

Description

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

Technical field

The present invention relates to a kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and bag Product containing the composite membrane, belongs to field of compound material.

Background technology

Biaxially oriented polypropylene (BOPP) film effectively utilizes its excellent light, transparent, mechanical strength, nontoxic, anti- Tide, gas permeability be low, the characteristic such as rigid, for the wide spectrum using packaging material as representative.For example, be widely used for food, medicine, The packaging of the products such as daily light industry, cigarette and lamination are compound.A kind of purposes of BOPP film is to fit in paper surface, such as book This, packing carton etc., plays moistureproof and increase surface gloss.

BOPP film is generally the coextrusion structure of 3-5 layers, and step drawing production technology is mainly made up of following process：Match somebody with somebody Material batch mixing, extruder are extruded, sheet, sheet chilling are extruded by T-shaped mould head, sheet is preheated by heating roller, sheet longitudinal direction Stretching, thermal finalization, preheat again, cross directional stretch, thermal finalization, cooling, sided corona treatment, winding, cutting and storage.CN101160209A A kind of Biaxially stretched multilayer polypropylene film is disclosed in (Oji Paper), it is added in by acrylic polymer The two sides for the bidirectional stretching polypropylene film substrate layer that the propylene polymer composition that inorganic compound powder forms obtains, tool Standby A layers and back layer containing acrylic polymer, the acrylic polymer in the substrate layer and the propylene in surface/back layer Based polymer can be with identical or different.It obtains uniform hidden power and white by adding inorganic compound powder in substrate layer The film that colourity is excellent, preferred thickness almost without concave-convex surface is 25-55 μm.The film obtains by the following method Arrive：The acrylic polymer for forming substrate layer is obtained into multi-layer sheet by itself known method co-extrusion modling, adopted Face multiplying power (longitudinal direction × horizontal is stretched to simultaneously bi-directionally pulling method or sequentially the biaxially oriented film forming method such as biaxial tension method To) 45~65 times and obtain.By using exemplified by sequentially biaxial tension method, can by a temperature of 70~140 DEG C of longitudinal direction with 4.5 After~7.5 times of scope stretching, then under laterally 120~190 DEG C of temperature range under 7~12 times and face multiplying power (longitudinal direction × laterally) be stretched to 45~65 times after, obtained in 110~180 DEG C of temperature range heat fixation.

BOPP film has many preferable performances, such as high tensile, high-stiffness, high grade of transparency etc..However, BOPP film Service life it is short, generally some months to 1 year, some physical properties such as resistance to low temperature, fall strength of briquette, tearing strength etc. It is poor, be not suitable for printed matter, packaging material of long-term use etc..In addition, the thickness of existing bidirectional stretching polypropylene film Generally less than 50 μm, its deflection can not meet the needs of high-end.Therefore its some applications are constrained.

The density polyethylene film with high of stretching has been used for plastics package field.Introduced in British Patent No. 1287527 Some such films, they are biaxially stretched more than 6.5 times in machine direction (MD) and laterally in (TD) both direction Degree.The twin shaft imbalance oriented film that U.S. Patent No. 4680207 is related to LLDPE, it is in processing side It is pulled up being no more than 6 times, orientation is no more than 3 times and less than stretching in the direction of the machine in the horizontal.

At present, industrial quarters is in some applications high to physical property requirements, typically using biaxial stretching polyester (BOPET) Film or biaxial tension nylon (BOPA) film.But BOPET film and BOPA films ratio are great, cost is high, and solvent resistance is poor.

Therefore, industrial quarters needs a kind of high transparency and high-stiffness with traditional BOPP film but simultaneously again with resistance to low The novel thin film of warm nature energy, high-tear strength.

The content of the invention

The present invention is overcome the deficiencies in the prior art, there is provided a kind of acrylic polymer-ethylene-based polymer MULTILAYER COMPOSITE Film, there is the performances such as high-stiffness, high transparency, 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 product for including above-mentioned multilayer complex films.

The present invention is achieved through the following technical solutions：

A kind of multilayer complex films, it includes the Rotating fields that n AXBXC Rotating fields are combined by X each other, and n is big In equal to 2, each A is identical or different, and each B is identical or different, and each C is identical or different, and each X is identical or different, described A layers and C layers in Rotating fields include identical or different acrylic polymer independently of one another, and B layers include phase independently of one another Same or different ethylene-based polymers, X are adhesive layer, and the A layers and C layers are each independently simple tension or two-way drawing Stretch.

According to the present invention, n AXBXC Rotating fields are compound by X orders in the multilayer complex films, i.e., according to AXBXCXAXBXC order is compound.

According to the present invention, in the multilayer complex films n AXBXC Rotating fields be replaced by X it is compound, i.e., according to AXBXCXCXBXA order is compound.

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

According to the present invention, the acrylic polymer of A layers is identical with the acrylic polymer of C layers in the multilayer complex films.

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

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

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

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

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

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

According to the present invention, the multi-layer co-extruded structure of the A layers or B layers or C layers is at least 2 layers, for example, 2-15 layers, excellent 3-11 layers, more preferably 5-9 layers are selected, even more preferably from 6-8 layers.

In accordance with the present invention it is preferred that the B layers are not stretching or simple tension or biaxial tensiones.

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

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

In accordance with the present invention it is preferred that when the B layers be do not stretch and n be even number when, the A layers combine in pairs, The C layers combine in pairs.Wherein, the longitudinal stretching multiplying power of an A layer (or C layers) is more than cross directional stretch multiplying power, another A The longitudinal stretching multiplying power of layer (or C layers) is less than cross directional stretch multiplying power；It is highly preferred that the vertically and horizontally drawing of one A layers (or C layers) Stretch than being inversely proportional with the vertically and horizontally draw ratio of another A layer (or C layers), i.e., longitudinal stretching and the horizontal stroke of one A layers (or C layers) It is equal to the cross directional stretch of another A layer (or C layers) and the ratio of longitudinal stretching to the ratio of stretching；It is highly preferred that one A The longitudinal stretching multiplying power and the cross directional stretch multiplying power of another A layer (or C layers) of layer (or C layers) are same or like, and one A The cross directional stretch multiplying power and the longitudinal stretching multiplying power of another A layer (or C layers) of layer (or C layers) are same or like；It is more preferred still that The longitudinal stretching multiplying power of one A layers (or C layers) is identical with the cross directional stretch multiplying power of another A layer (or C layers), and described one The cross directional stretch multiplying power of individual A layers (or C layers) is identical with the longitudinal stretching multiplying power of another A layer (or C layers).

According to the present invention, when the B layers be do not stretch and n be odd number when, the A layers are remaining after combining in pairs A layers individually combine, the C layers after combining in pairs remaining C layers individually combine.Wherein, an A layer in two layers in pairs The longitudinal stretching multiplying power of (or C layers) is more than cross directional stretch multiplying power, and the longitudinal stretching multiplying power of another A layer (or C layers) is less than laterally Stretching ratio, the cross directional stretch multiplying power and longitudinal stretching multiplying power of the A layers individually combined (or C layers) are same or like；It is highly preferred that The vertically and horizontally draw ratio of the vertically and horizontally draw ratio of an A layer (or C layers) and another A layer (or C layers) in wherein paired two layers It is inversely proportional, i.e., the longitudinal stretching of one A layers (or C layers) and the ratio of cross directional stretch are equal to the horizontal stroke of another A layer (or C layers) To stretching and the ratio of longitudinal stretching, the cross directional stretch multiplying power of the A layers individually combined (or C layers) it is identical with longitudinal stretching multiplying power or It is close；It is highly preferred that the longitudinal stretching multiplying power of an A layer (or C layers) and another A layer (or C layers) in wherein paired two layers Cross directional stretch multiplying power it is same or like, and the cross directional stretch multiplying power of one A layers (or C layers) and another A layer (or C layers) Longitudinal stretching multiplying power it is same or like, the cross directional stretch multiplying power of the A layers (or C layers) individually combined is identical with longitudinal stretching multiplying power It is or close；It is more preferred still that the longitudinal stretching multiplying power of an A layer (or C layers) and another A layer in wherein paired two layers (or C Layer) cross directional stretch multiplying power it is identical, and the cross directional stretch multiplying power of one A layers (or C layers) and another A layer (or C layers) Longitudinal stretching multiplying power is identical, and the cross directional stretch multiplying power and longitudinal stretching multiplying power of the A layers (or C layers) individually combined are same or like.

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

(1 ') two B layers are simple tension, and stretching ratio is identical, the cross directional stretch multiplying power of preferably one B layer with it is another The longitudinal stretching multiplying power of one B layer is identical；

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

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

When n is odd number, include one of following combination between B layers 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 and biaxial tension A stretching ratio (cross directional stretch multiplying power or longitudinal stretching multiplying power) it is identical；Or

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

And the draw ratio or stretching ratio of remaining B layer it is then identical with the draw ratio or stretching ratio of the above-mentioned layers of B two-by-two or It is different.

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

(1) the A layers are simple tension, and the B layers are simple tension, and the C layers are biaxial tension；

(2) the A layers are simple tension, and the B layers are biaxial tension, and the C layers are biaxial tension；

(3) the A layers are simple tension, and the B layers are biaxial tension, and the C layers are simple tension；

(4) the A layers are biaxial tension, and the B layers are simple tension, and the C layers are simple tension；

(5) the A layers are biaxial tension, and the B layers are biaxial tension, and the C layers are simple tension；

(6) the A layers are biaxial tension, and the B layers are simple tension, and the C layers are biaxial tension；

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

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

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

The transverse direction of the A layers is stretched, the transverse direction of the B layers is stretched, and to the transverse direction of the C layers and vertical To being stretched；Or

The transverse direction of the A layers is stretched, the longitudinal direction of the B layers is stretched, and to the transverse direction of the C layers and vertical To being stretched；Or

The longitudinal direction of the A layers is stretched, the transverse direction of the B layers is stretched, and to the transverse direction of the C layers and vertical To being stretched；Or

The longitudinal direction of the A layers is stretched, the longitudinal direction of the B layers is stretched, and to the transverse direction of the C layers and vertical To being stretched.

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

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

The transverse direction of the A layers is stretched, the horizontal and vertical of B layers is stretched, and to the horizontal stroke of the C layers Stretched to longitudinal direction；Or

The longitudinal direction of the A layers is stretched, the horizontal and vertical of B layers is stretched, and to the horizontal stroke of the C layers Stretched to longitudinal direction.

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

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

The transverse direction of the A layers is stretched, the horizontal and vertical of the B layers is stretched, and to the C layers Laterally stretched；Or

The transverse direction of the A layers is stretched, the horizontal and vertical of the B layers is stretched, and to the C layers Longitudinal direction is stretched；Or

The longitudinal direction of the A layers is stretched, the horizontal and vertical of the B layers is stretched, and to the C layers Laterally stretched；Or

The longitudinal direction of the A layers is stretched, the horizontal and vertical of the B layers is stretched, and to the C layers Longitudinal direction is stretched.

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

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

The horizontal and vertical of the A layers is stretched, the transverse direction of the B layers is stretched, and to the C layers Laterally stretched；Or

The horizontal and vertical of the A layers is stretched, the transverse direction of the B layers is stretched, and to the C layers Longitudinal direction is stretched；Or

The horizontal and vertical of the A layers is stretched, the longitudinal direction of the B layers is stretched, and to the C layers Laterally stretched；Or

The horizontal and vertical of the A layers is stretched, the longitudinal direction of the B layers is stretched, and to the C layers Longitudinal direction is stretched.

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

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

The horizontal and vertical of the A layers is stretched, the horizontal and vertical of B layers is stretched, and to institute The transverse direction for stating C layers is stretched；Or

The horizontal and vertical of the A layers is stretched, the horizontal and vertical of B layers is stretched, and to institute The longitudinal direction for stating C layers is stretched.

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

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

The horizontal and vertical of the A layers is stretched, the transverse direction of the B layers is stretched, and to the C layers It is horizontal and vertical to be stretched；Or

The horizontal and vertical of the A layers is stretched, the longitudinal direction of the B layers is stretched, and to the C layers It is horizontal and vertical to be stretched.

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

According to the present invention, for scheme (7).Including following scheme：The vertically and horizontally draw ratio of the A layers/C layers and B layers Vertically and horizontally draw ratio is different；Preferably, the longitudinal stretching multiplying power of the A layers/C layers is more than cross directional stretch multiplying power, and the transverse direction of B layers Stretching ratio is more than longitudinal stretching multiplying power；It is highly preferred that the vertically and horizontally stretching of the vertically and horizontally draw ratio of the A layers/C layers and B layers Than being inversely proportional, i.e. the longitudinal stretching of A layers/C layers and the ratio of cross directional stretch are equal to the cross directional stretch of B layers and the ratio of longitudinal stretching Value.It is highly preferred that the longitudinal stretching multiplying power and the cross directional stretch multiplying power of the B layers of the A layers/C layers are same or like, and it is described The cross directional stretch multiplying power of A layers/C layers and the longitudinal stretching multiplying power of the B layers are same or like；It is more preferred still that the A layers/C layers Longitudinal stretching multiplying power it is identical with the cross directional stretch multiplying power of the B layers, and the cross directional stretch multiplying power of A layers/C layers and the B The longitudinal stretching multiplying power of layer is identical.

According to the present invention, for scheme (8).The stretching ratio of the A layers/C layers is different from the stretching ratio of the B layers； Preferably, the stretching ratio of the A layers/C layers is more than the stretching ratio of the B layers, or the stretching ratio of A layers/C layers is small In the stretching ratio of the B layers.Preferably, the transverse direction of the A layers/C layers is stretched, and the longitudinal direction of the B layers is carried out Stretching；Or the longitudinal direction of the A layers/C layers is stretched, and the transverse direction of the B layers is stretched.It is highly preferred that the A The cross directional stretch multiplying power of layer/C layers is identical or close with the longitudinal stretching multiplying power of the B layers；Or the longitudinal direction of the A layers/C layers Stretching ratio is identical or close with the cross directional stretch multiplying power of the B layers.

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

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

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

According to the present invention, the polyurethane is solvent-borne type, either no-solvent type one-component or multicomponent gather water-dispersion type Urethane adhesive.

According to the present invention, the acrylic resin is solvent-borne type, water-dispersion type either no-solvent type one-component or multigroup Divide the adhesive containing acrylic acid or acrylates.

According to the present invention, the epoxy resin is solvent-borne type, water-dispersion type either no-solvent type one-component or multicomponent Epoxy type adhesive.

According to the present invention, the thickness of the multilayer complex films is 50-150 μm, preferably 60-120 μm, more preferably 70-100 μ M, even more preferably from 80-90 μm.

According to the present invention, each A layer or the thickness of B layers or C layers are 5-65 μm in the multilayer complex films, preferably 10- 55 μm, more preferably 20-40 μm.

According to the present invention, in the multilayer complex films thickness of each X layer be 0.5-10 μm, preferably 1-6 μm, more preferably 2-5μm。

According to the present invention, the summation of all X thickness degree is no more than the 30% of the composite film thickness in the multilayer complex films, Preferably more than 20%, more preferably no more than 15%, even more preferably from no more than 10%.

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

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

According to the present invention, the tensile strength of C layers is 1.5 in horizontal and vertical ratio in the multilayer complex films:1.0 arrive 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 layers in the 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, and longitudinal stretching multiplying power is 2-4 times.

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

According to the present invention, for biaxial tension, the cross directional stretch multiplying power of the C layers in the 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, and longitudinal stretching multiplying power is 2-4 times.

According to the present invention, for simple tension, the stretching ratio laterally or longitudinally of the A layers in the multilayer complex films is 1-12.5 times, preferably laterally stretching ratio is 7-12.5 times or longitudinal stretching multiplying power is 1-6 times；The vertical or horizontal drawing of B layers Multiplying power is stretched for 1-12.5 times, and preferably longitudinally stretching ratio is 7-12.5 times or cross directional stretch multiplying power is 1-6 times；The transverse direction of C layers or The stretching ratio of longitudinal direction is 1-12.5 times, and preferably laterally stretching ratio is 7-12.5 times or longitudinal stretching multiplying power is 1-6 times；.

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

The vertically and horizontally tensile strength of the multilayer complex films is more than 100MPa, preferably greater than 120MPa, more preferably greater than 140MPa。

According to the present invention, the acrylic polymer of the A layers or C layers is preferably Noblen or propylene copolymer, Typically isotaxy homopolymer, or be with different isotactic polypropylenes, atactic polypropylene, syndiotaxy poly- third The polypropylene of alkene, the atactic propene copolymer for having a small amount of comonomer and ethylene copolymer-modified isotactic polypropylene is total to Mixed thing.Comonomer is ethene or higher alpha-olefin, such as ethene, butylene, hexene or octene.

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

According to the present invention, the ethylene-based polymer of the B layers is preferably high density polyethylene (HDPE), high-pressure process low-density polyethylene Or low-pressure process LLDPE.The density of high density polyethylene (HDPE) about 0.941g/cm³Or it is higher, preferably from about 0.948g/cm³To about 0.968g/cm³, more preferably from about 0.952g/cm³To about 0.962g/cm³；About 130 DEG C to about 148 of fusing point ℃；Melt index (being measured 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) is about 0.912g/cm³To about 0.94g/cm³, preferably 0.915g/cm³To 0.928g/ cm³；Melt index (being measured according to ASTM D1238) 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 had There is 0.2-50g/10min (such as 1-10g/10min) melt index (being measured according to ASTM D1238) and in 0.857g/ cm³To 0.950g/cm³, preferably 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³Scope Density.Ethylene-based polymer can also be terpolymer, such as ethylene/butene/hexene copolymer, ethylene/butylene/octene copolymer Thing or ethylene/hexene/octene copolymer；These copolymers have 0.2-50g/10min (such as 1-10g/10min) melting Index (being measured according to ASTM D1238) is and in 0.857g/cm³To 0.950g/cm³, preferably 0.905g/cm³To 0.940g/ cm³, more preferably 0.910g/cm³To 0.928g/cm³Scope density.

According to the present invention, another resin can be also added in A layers or B layers or C layers, such as Petropols or hydrogenation stone Oleoresin, preferably C₅-C₉Petropols or C₅-C₉Hydrogenated petroleum resin.Its addition is heavy for the 1-30% of each layer gross weight Amount, preferably 2-20% weight, more preferably 3-15% weight, even more preferably from 4-10% weight.

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

(1) preparation of A layers and C layers

By individual layer extrusion or multi-layer co-extruded, polyolefin sheets are prepared, then under 130-185 DEG C of temperature environment Carry out simple tension or biaxial tension processes A layers and C layers；

(2) preparation of B layers

By individual layer extrusion or multi-layer co-extruded, polyethylene sheets are prepared, may be selected not stretch or simple tension or two-way Stretch process goes out B layers；

(3) rolling method is used, using X as adhesive, gluing, wherein composite membrane are carried out most to each A layers, B layers and each layers of C Outer two layers of progress single spreading, middle each layer carry out one or two sides gluing, and after gluing, each layer is dried at 40-80 DEG C；

(4) the A layers, B layers and C layers of gluing be laminated compound, obtain the composite membrane.

According to the present invention, the two-sided of A layers and/or B layers and/or C layers obtained by step (1) and (2) all passes through sided corona treatment, Its initial surface tension is set to reach more than 44 dynes per centimeters.The surface tension of gained composite membrane is more than 36 dynes per centimeters.More It is preferred that surface tension reaches more than 38 dynes per centimeters.

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

The present invention also provides a kind of application of multilayer complex films described in foregoing any one, its be used for bill, marketable securities, Printed matter and packaging material.

The present invention also provides a kind of product, its face coat and printing by the multilayer complex films described in foregoing any one It is made, the product includes printed matter (such as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.

Beneficial effects of the present invention：

Polypropylene multi-layer composite membrane prepared by the present invention, has an excellent combination property, its tensile strength, deflection and resistance to tears Resistance to spalling is all very high, and its vertical and horizontal performance has good balance, and has the good transparency, specific property Can be referring to table 1.

The performance of 1 composite membrane of the present invention of table

Describe in detail

[composition of A layers, B layers and C layers]

According to the present invention, the A layers and C layers mainly include acrylic polymer.The acrylic polymer is preferably third Polyamino alkenyl thing or propylene copolymer or polypropene composition；Typically isotaxy homopolymer, or for it is different it is complete together Vertical structure polypropylene, atactic polypropylene, syndiotactic polypropylene, the atactic propene copolymer and second for having a small amount of comonomer The polypropylene blend for the isotactic polypropylene that alkene copolymer is modified.Comonomer is ethene or higher alpha-olefin, as ethene, Butylene, hexene or octene etc..The content of comonomer is preferably 0.2wt% to 2.0wt%, and more preferably 0.35wt% is arrived 0.85wt%.These acrylic polymers of the present invention can be the mixture containing one kind or two or more polymer, such as divide Son measures different Noblens, or the composition of propylene and a small amount of alpha-olefin random copolymer.The propylene polymerization of the present invention Thing, generally according to the vistanex of the manufacture of polyacrylic title, sale, typically density is 0.890~0.930g/cm³、 MFR (ASTM D1238, load 2160g, 230 DEG C of temperature) is 0.5~60g/10min, is preferably 0.5~20g/10min, is more excellent Select 0.5-15g/10min, still more preferably 1~5g/10min Noblen.

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

Part ethylene-based polymer, such as high density polyethylene (HDPE) can be also mixed into the polymer of the A layers and C layers (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE is not or with a small amount of Comonomer, comonomer are propylene or higher alpha-olefin, such as ethene, butylene, hexene or octene, and with about 0.941g/cm³Or higher (e.g., from about 0.948g/cm³To about 0.968g/cm³, preferably from about 0.952g/cm³To about 0.962g/cm³) density, e.g., from about 130 DEG C to about 148 DEG C of fusing point and 0.2-50g/10min, preferably 1-45g/ 10min, more preferably 2-40g/10min melt index (being measured according to ASTM D1238).LDPE has in 0.912g/cm³Arrive 0.94g/cm³(such as 0.915g/cm³To 0.928g/cm³) scope density and 0.2-50g/10min (preferably 1-45g/ 10min, more preferably 2-40g/10min) melt index (according to ASTM D1238 measure).LLDPE points are copolymerized for ethylene/butylene Thing, ethylene/hexene copolymer and ethylene/octene and the melting with 0.2-50g/10min (such as 1-10g/10min) Index (being measured according to ASTM D1238) is and in 0.857g/cm³To 0.950g/cm³, preferably 0.905g/cm³To 0.940g/ cm³, more preferably 0.910g/cm³To 0.928g/cm³Scope density.In addition ethylene-based polymer can also be ternary polymerization Thing, such as ethylene/butene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These are common Polymers have 0.2-50g/10min (such as 1-10g/10min) melt index (according to ASTM D1238 measure) and 0.857g/cm³To 0.950g/cm³, preferably 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³ Scope density.

According to the present invention, the B layers mainly include ethylene-based polymer, and the ethylene-based polymer is preferably high density and gathered Ethene (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE not or has A small amount of comonomer, comonomer are propylene or higher alpha-olefin, such as butylene, hexene or octene, and have about 0.941g/ cm³Or higher (e.g., from about 0.948g/cm³To about 0.968g/cm³, preferably from about 0.952g/cm³To about 0.962g/cm³) Density, e.g., from about 130 DEG C to about 148 DEG C of fusing point and 0.2-50g/10min, more preferably preferably 1-45g/10min, 2- 40g/10min melt index (being measured according to ASTM D1238).LDPE has in 0.912g/cm³To 0.94g/cm³(such as 0.915g/cm³To 0.928g/cm³) scope density and 0.2-50g/10min (preferably 1-45g/10min, more preferably 2- Melt index (being measured according to ASTM D1238) 40g/10min).LLDPE point is ethylene/butylene copolymers, ethylene/hexene is common Polymers and ethylene/octene simultaneously have 0.2-50g/10min (such as 1-10g/10min) melt index (according to ASTM D1238 is measured) and in 0.857g/cm³To 0.950g/cm³, preferably 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³Scope density.In addition ethylene-based polymer can also be terpolymer, as ethene/ Butylene/hexene copolymer, ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer；These copolymers have 0.2-50g/10min (such as 1-10g/10min) melt index (being measured according to ASTM D1238) is and in 0.857g/cm³ To 0.950g/cm³, preferably 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³Scope it is close Degree.

Deflection of the present invention refers to that Paper or cardboard supports resistant to bending strength character.Deflection is directly proportional to EI/W values, its Middle W, E and I are respectively quality, modulus of elasticity and the moment of inertia of Paper or cardboard.Wherein, the deflection or flexural rigidity of cardboard, it is Refer to and certain load is applied to the sample vertically clipped at away from fixture 5cm, observe from sample camber 3.81mm width, examination Moment of flexure needed for sample to 15 °, is represented with gcm.Paper sheet stiffness is a critically important index, directly affects the big of folding line deflection Small (another influence factor is d ie cutting press), so as to influence finished product shaping.Deflection is small, and finished product is easy to conquassation, warpage；Deflection is big, Finished product is difficult to be molded.In order to further improve the deflection of the multilayer complex films of the present invention, and such as heat sealer, gas permeability and strong The performances such as degree, can add another resin, such as Petropols, hydrogenated petroleum resin etc., preferably C in A layers or B layers₅-C₉ Petropols or C₅-C₉Hydrogenated petroleum resin.Its addition is the 1-30% weight of each layer gross weight, preferred 2-20% weight, more It is preferred that 3-15% weight, even more preferably from 4-10% weight.

About 0.01~5.0 mass % addition can be added in the polymer of the A layers, B layers and C layers with master batch form Agent.The additive is preferably 0.01~3.0 mass %, more preferably 0.05~1.0 mass %.

The additive has：It is antiblocking agent, slipping agent (i.e. lubricant or slipping agent), antistatic additive, nucleator, heat-resisting steady Determine can be generally added to known to agent, weathering stabilizers, ultra-violet absorber, anti-turbid dose, pigment, dyestuff etc. various in polyolefin Additive.

As the antiblocking agent, antiblocking agent well known in the art can be used, such as silica, talcum, mica, zeolite, or The inorganic compound particles such as the metal oxide that metal alkoxide is sintered to obtain；Or polymethyl methacrylate, melamine first The organic compounds such as urea formaldehyde, melamine urea resin, polyester resin.Wherein, it is particularly preferred from resistance to blocking aspect Use silica, polymethyl methacrylate.

As the lubricant, acid amides based compound etc. such as stearmide, erucyl amide, oleamide can be used.

As the antistatic additive, ethylene oxide adduct, quaternary amine based compound, the alkane such as betanin derivative can be used Base diethanol amine fatty acid ester, fatty acid glyceride, tristerin etc..

As the nucleator, such as D-sorbite system, organophosphate metal salt system, metal salt of organic carboxylic acid can be used System, rosin series nucleator etc..

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

Also delustring masterbatch can be added in the polymer of the A layers, B layers and C layers to produce Extinctive thin film, or adds pearly-lustre Masterbatch produces pearly-lustre film.

Laminate stretch acrylic polymer-ethylene-based polymer film of the present invention can be as needed, to single or double Implement the surface treatment such as sided corona treatment, flame treatment.In addition, according to purposes, can be overleaf independent on layer to assign heat sealability It is laminated containing high-pressure process low-density polyethylene, linear low density polyethylene (LLDPE), crystallinity or low-crystalline ethene and carbon number 3~10 The random copolymer of the random copolymer or propylene and ethene of alpha-olefin or the alpha-olefin of carbon number more than 4, polybutene, ethene- The film of the low melting point polymers such as vinyl acetate copolymer, or film of the lamination containing their compositions.In addition, in order to carry The high cementability with other materials, processing can be fixed with adhesives such as imines, carbamates to oriented film surface, Maleic anhydride modified polyolefin can be laminated.

[composition of X layers]

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

Polypropylene chlorination is made using solwution method, suspension method or solid phase method for the chlorinated polypropylene of the present invention.The matter of chlorine Amount content is 20%-70%, and fusing point is less than 150 DEG C.

According to the present invention, the polyurethane is solvent-borne type, either no-solvent type one-component or multicomponent gather water-dispersion type Urethane adhesive.

According to the present invention, the acrylic resin is solvent-borne type, water-dispersion type either no-solvent type one-component or multigroup Divide the adhesive containing acrylic acid or acrylates.

According to the present invention, the epoxy resin is solvent-borne type, water-dispersion type either no-solvent type one-component or multicomponent Epoxy type adhesive.

The polyurethane resin of the present invention may be selected from generally as the dry lamination containing polyurethane known to film adhesive, Waterborne dry-type lamination, solventless liminating, the polyester-polyurethane of electronic beam solidified laminating adhesive manufacture, polyether-polyurethane or poly- Urethane carbamide resin etc..The polyurethane resin can be water-dispersion type or solvent type any, but be covered from polyurethane resin The degree of cross linking of layer is easily adjusted, and from the operating environment aspect of production scene, preferably water dispersant type polyaminoester resin.

As water dispersant type polyaminoester resin, preferably the main chain to polyurethane resin or side chain introduce carboxylate (- COONa etc.), sulfonate (- SO₃Na etc.) etc. hydrophilic group self-emulsifying type polyurethane resin.In the case of solvent type, by isocyanide Acid esters system resin is used for crosslinking agent, forms the polyurethane with three-dimensional structure, but water-dispersion type turns into linear polyurethane or poly- ammonia The situation of ester carbamide resin is in the majority, therefore relative to polyurethane resin, can add 3~10 mass % or so melamine series tree The crosslinking agents such as fat, epoxy system resin, imines system resin, 0.5~1 mass % or so acid catalyst can be also added, come further Promote curing reaction.The crosslinking agent can not only improve water resistance, the solvent resistance of easy-adhesion overlay film, can also improve bonding Property.

In addition, when using water dispersant type polyaminoester resin, contain the surfactants such as defoamer or emulsifying agent in composition When, it is possible to the surface of Biaxially stretched multilayer propylene polymer thin film is turned white, cause bad order.In addition, the present invention In polyurethane resin, for example, the purpose of in order to prevent adhesion, as needed, inorganic particles or organic fine particles etc. can also be added.

, can be by that will gather when covering (lamination) polyurethane resin (X) on the one or both sides of propylene polymer thin film The aqueous solution or dispersion liquid Kohler coater, direct gravure coater, intaglio offset coating machine, the electric arc intaglio plate of urethane resin apply The gravure coaters such as cloth machine, reverse rotating gravure and nozzle mode；Its top feed reverse roll coating machine, bottom feed reverse roll coating machine and spray The reverse roll coating machines such as mouth charging reverse roll coating machine, coating machine, the lip of 5 rollers apply machine, bar coater, inverse rod coater, die head formula Itself various known coating machine such as coating machine, according to make the amount of contained composition in the polyurethane resin aqueous solution for 0.1~ 20g/m², preferably 0.3~2g/m²After being coated, dry more than 10 seconds and obtain at a temperature of 50~140 DEG C.

[preparation methods of multilayer complex films]

According to the present invention, using simple tension or biaxial tension, i.e., in stretching-machine, at certain temperature and speed, (vertical or horizontal) or stretched in vertical both direction (longitudinally, laterally) in one direction and film is made.It is so-called Longitudinal direction refers to that, along the direction of film extrusion processing, so-called transverse direction refers to the direction of vertical thin-film extrusion processing.Vertically and horizontally stretch Than the ratio for referring to longitudinal stretching multiplying power and cross directional stretch multiplying power.

The present invention provides the preparation method of the multilayer complex films, and it comprises the following steps：

(1) preparation of A layers and C tunics

Prepared using the method for simple tension or biaxial tension, for biaxial tension, substep sequentially two-way drawing can be used Method is stretched, can also use synchro-draw method.

The drawing process includes plain film method and periosteum method.For biaxial tension, the technical process of the plain film method includes Synchro-draw process, comprises the following steps：

At the synchro-draw → traction of dispensing → extrusion → chilling → vertically and horizontally and optional surface treatment → winding → timeliness Reason → cutting → product.

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

Dispensing → extrusion → chilling → longitudinal stretching → cross directional stretch → traction and it is optional surface treatment → winding → when Effect processing → cutting → product.

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

According to the present invention, the cross directional stretch includes preheating, big stretching, sizing and cooling.

According to the present invention, the chilling refers to be cooled down using coolant, and preferably coolant is cooling water.The chilling Effect be in order that crystallization refinement, so as to improve transparency and deflection.

According to the present invention, the extrusion includes individual layer extrusion or multi-layer co-extruded.The extrusion uses melting extrusion.

According to the present invention, the dispensing includes carrying out dispensing according to the requirement of formula, can pass through electronic measurement.

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

Dispensing → extrusion (including individual layer extrusion or multilayered molten extrusion) → chilling → female film → water removal → baker far infrared Heating → vertically and horizontally synchro-draw → collapser flattens → cut open side → heat treatment → cooling → winding → Ageing Treatment → cutting → Product.

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

Dispensing → extrusion (including individual layer extrusion or multilayered molten extrusion) → chilling → female film → water removal → baker far infrared Heating → longitudinal stretching → cross directional stretch → collapser flattens → cut open side → heat treatment → cooling → winding → Ageing Treatment → point Cut → product.

According to the present invention, the chilling refers to be cooled down using coolant, and preferably coolant is cooling water.The chilling Effect be in order that crystallization refinement, so as to improve transparency and deflection.

When the plain film method is plain film substep biaxial tension, specifically comprise the following steps：

(a) dispensing is carried out by the requirement of formula, added in the hopper above the extruder of single or multiple lift co-extrusion, plastics lead to After crossing external heat and the screw rod rotational shear plasticizing of extruder barrel, the rack-style into single or multiple lift coextru-lamination is flat Die head.Go out the sheet-like melt after die head to be attached on chilling roller by air knife, by sheet-like melt chilling into sheet, then as chilling The rotation of roller, sheet enter tank and carry out further two-sided cooling.The thickness of sheet can pass through the extrusion capacity and urgency of extruder The rotating speed of chilling roller controls.Wherein, the temperature that controls of extruder is 150-260 DEG C, preferably 180-250 DEG C；Die head temperature is general For 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 is entered back into vertically and horizontally tensioning system carries out two-sided preheating, preheats roller temperature General control is spent at 90-150 DEG C, preferably 100-120 DEG C.After reaching defined draft temperature (more than softening point, below fusing point), By draw roll carry out longitudinal stretching, draft temperature control at 90-150 DEG C, preferably 100-120 DEG C, drawing process can with a step, It can also twice stretch or stretch three times.Longitudinal stretching multiplying power is set according to the requirement of A layers and C tunics.After stretching Film is heat-treated by setting roller, the setting temperature be 100-140 DEG C, preferably 110-120 DEG C, to eliminate film Internal stress, reduce longitudinal shrinkage factor.

(c) film after longitudinal stretching enters cross directional stretch system, carries out preheating section preheating first, and pre- heat roller temperature is general Control is at 100-160 DEG C, preferably 110-140 DEG C, more preferably 115-130 DEG C.Reach defined draft temperature (it is more than softening point, Below fusing point) after, then by expand spoke track carry out cross directional stretch, general 130-180 DEG C of the control temperature of stretching-machine, preferably 140-160 DEG C, thermal finalization processing is then carried out, setting temperature is 60-120 DEG C, preferably 70-110 DEG C.Cross directional stretch multiplying power according to The requirement of A layers and C tunics is set.

(d) film gone out after cross directional stretch system is cooled down by chill roll, followed by trimming, is sided corona treatment with that, It is finally to be wound.

(e) the big wound membrane after equipment is left after the Ageing Treatment of several days of storage, can be cut, Rack is made A layers and C layer films.

When the plain film method is that plain film synchronous bidirectional stretches, plain film synchro-draw preparation method and plain film step drawing system Preparation Method is similar, and difference is only during synchro-draw that longitudinal stretching and cross directional stretch are synchronously carried out, that is, What longitudinal stretching synchronously completed with cross directional stretch in a system, and longitudinal stretching and cross directional stretch are asynchronous in step drawing Carry out.Thus specific operating condition is similar with step drawing.At present, synchro-draw machine has two kinds of forms, Yi Zhongshi in the world Mechanically, one kind is linear electric machine formula.

When the periosteum method is that synchronous bidirectional stretches, periosteum method synchronous bidirectional stretching preparation method is synchronous with plain film method double Similar to stretching preparation method, its longitudinal stretching and cross directional stretch are also synchronously to carry out.Difference is, the mould of periosteum method Head is that circular, whole film formation is completed in the form of steeping pipe.Main production parameter：Extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, and cooling water temperature is 11-18 DEG C, oven drying temperature：330-450 DEG C, draft temperature For 140 DEG C.Vertically and horizontally draw ratio is then carried out according to the requirement of the draw ratio of each tunic.

When the periosteum method is substep biaxial tension, periosteum method substep biaxial tension preparation method and plain film method substep are double Similar to stretching preparation method, its longitudinal stretching and cross directional stretch are also synchronously to carry out.Difference is, the mould of periosteum method Head is that circular, whole film formation is completed in the form of steeping pipe.Main production parameter：Extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, and cooling water temperature is 11-18 DEG C, oven drying temperature：330-450 DEG C, draft temperature For 140 DEG C.Vertically and horizontally draw ratio is then carried out according to the requirement of the draw ratio of each tunic.

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

At dispensing → extrusion → chilling → vertical or horizontal stretching → traction and optional surface treatment → winding → timeliness Reason → cutting → product.

The technical process of the periosteum method comprises the following steps：

Dispensing → extrusion (including individual layer extrusion or multilayered molten extrusion) → chilling → female film → water removal → baker far infrared Heating → vertical or horizontal stretching → collapser flattens → cut open side → heat treatment → cooling → winding → Ageing Treatment → cutting → Product.

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

(2) preparation of B tunics

Using do not stretch or the method for simple tension or biaxial tension prepare, if simple tension or biaxial tension, with step Suddenly (1) it is identical.

(3) rolling method is used, using X as adhesive, the outermost of gluing, wherein composite membrane is carried out to each A layers, B layers and C layers Two layers of progress single spreading, middle each layer carry out one or two sides gluing.

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

(4) it is laminated

The A layers, B layers and C layers of gluing be laminated compound, obtain the composite membrane.

According to the present invention, the lamination is compound to be carried out by hot pressing, and the laminating temperature is 40-100 DEG C, preferably 60-80 ℃。

According to the present invention, A layers and/or B layers and/or the two-sided of C layers obtained by step (1) and step (2) all pass through corona Processing, makes its initial surface tension reach more than 44 dynes per centimeters.The surface tension of gained composite membrane 36 dynes per centimeters with On.It is further preferred that surface tension reaches more than 38 dynes per centimeters.

[purposes of multilayer complex films]

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

The present invention also provides a kind of application of multilayer complex films described in foregoing any one, its be used for bill, marketable securities, Printed matter and packaging material.

The present invention also provides a kind of product, and it is made by the face coat and printing of any one of foregoing multilayer complex films , the product includes printed matter (such as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.

Brief description of the drawings

Fig. 1 is the structural representation of composite membrane prepared by embodiment 1, and it is AXBXCXAXBXC structures.

Fig. 2 is the structural representation of composite membrane prepared by embodiment 1, and it is AXBXCXCXBXA structures.

Embodiment

The explanation present invention with reference to embodiments, but skilled in the art realises that, the embodiment is not to the present invention The limitation of protection domain, any improvement made on the basis of the present invention, change are all within protection scope of the present invention.

Embodiment 1：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are all process using high density polyethylene (HDPE), density 0.955g/cm³, fusing point is 135 DEG C, and melt index is 3.8g/10min。

A layers, B layers and C layers all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.

Two A layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 10 μm.

Two B layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 9 times, and thickness is 20 μm.

Two C layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 10 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with chlorinated polypropylene, then by being compounded to form composite membrane, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 85 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 2.

Embodiment 2：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are all process using high density polyethylene (HDPE), density 0.955g/cm³, fusing point is 135 DEG C, and melt index is 3.8g/10min。

A layers, B layers and C layers all add Petropols respectively, and Petropols addition is 15% weight of each layer gross weight.

Two A layers are processed by plain film method simple tension technique, and wherein longitudinal stretching multiplying power is 12.5 times, and thickness is 8 μ m。

Two B layers are processed by plain film method simple tension technique, and wherein cross directional stretch multiplying power is 12.5 times, thickness 16 μm。

Two C layers are processed by plain film method simple tension technique, and wherein longitudinal stretching multiplying power is 12.5 times, and thickness is 8 μ m。

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 40 dynes per centimeters, then using roller coat side Formula is coated with polyurethane, then is compounded to form composite membrane by hot pressing, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 69 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 2.

Embodiment 3：AXBXCXAXBXC structures or AXBXCXCXBXA structures, layer thickness profile：7.5μm/1μm/15μm/1μ m/7.5μm/1μm/7.5μm/1μm/15μm/1μm/7.5μm

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

B layers are low density polyethylene (LDPE)s, density 0.916g/cm³, melt index 2.8g/10min.

A layers, B layers and C layers all add hydrogenated petroleum resin respectively, and hydrogenated petroleum resin addition is each layer gross weight 20% weight.

Two A layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 7.5 μm.

Two B layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 8 times, and thickness is 15 μm.

Two C layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 7.5 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with polyurethane, then by being compounded to form composite membrane, wherein X thickness is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 65 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 2.

Embodiment 4：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are low density polyethylene (LDPE)s, density 0.916g/cm³, melt index 2.8g/10min.

Two A layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 10 μm.

Two B layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 8 times, and thickness is 20 μm.

Two C layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 10 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with chlorinated polypropylene, then by being compounded to form composite membrane, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 85 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 3.

Embodiment 5：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are low density polyethylene (LDPE)s, density 0.916g/cm³, melt index 2.8g/10min.

Two A layers are processed by plain film method simple tension technique, and wherein longitudinal stretching multiplying power is 10 times, and thickness is 8 μm.

Two B layers are processed by plain film method simple tension technique, and wherein cross directional stretch multiplying power is 10 times, and thickness is 16 μ m。

Two C layers are processed by plain film method simple tension technique, and wherein longitudinal stretching multiplying power is 10 times, and thickness is 8 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 40 dynes per centimeters, then using roller coat side Formula is coated with polyurethane, then is compounded to form composite membrane by hot pressing, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 69 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 3.

Embodiment 6：AXBXCXAXBXC structures or AXBXCXCXBXA structures, layer thickness profile：7.5μm/1μm/15μm/1μ m/7.5μm/1μm/7.5μm/1μm/15μm/1μm/7.5μm

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

B layers are linear low density polyethylene (LLDPE)s, density 0.915g/cm³, melt index 2.8g/10min.

Two A layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 7.5 μm.

Two B layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 9 times, and thickness is 15 μm.

Two C layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 7.5 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with polyurethane, then by being compounded to form composite membrane, wherein X thickness is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 65 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 3.

Embodiment 7：

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are linear low density polyethylene (LLDPE)s, density 0.915g/cm³, melt index 2.8g/10min.

A layers, B layers and C layers all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.

Four A layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 7 μm.

Two B layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 9 times, and thickness is 10 μm.

Two B layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 10 μm.

Four C layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 7 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with chlorinated polypropylene, then is compounded to form composite membrane by 4 AXBXC Rotating fields, wherein, the thickness of X layers is 1 μm, structure For AXBXCXAXBXCXAXBXCXAXBXC (sequential organization) or AXBXCXCXBXAXAXBXCXCXBXA (alternating structure) or AXBXCXCXBXAXCXBXAXCXBXA (disordered structure), overall film thickness are 107 μm.The power of film prepared by two kinds of Rotating fields Performance is suitable, and the performance test data of the wherein film of AXBXCXAXBXC structures is listed in table 4.

Embodiment 8：

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are all process using high density polyethylene (HDPE), density 0.955g/cm³, fusing point is 135 DEG C, and melt index is 3.8g/10min。

Four A layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 8 μm.

Two B layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 8 times, and thickness is 11 μm.

Two B layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 11 μm.

Four C layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 8 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with chlorinated polypropylene, then by being compounded to form composite membrane, wherein, the thickness of X layers is 1 μm, and structure is AXBXCXAXBXCXAXBXCXAXBXC (sequential organization) or AXBXCXCXBXAXAXBXCXCXBXA (alternating structure) or AXBXCXCXBXAXCXBXAXCXBXA (disordered structure), overall film thickness are 119 μm.The power of film prepared by two kinds of Rotating fields Performance is suitable, and the performance test data of the wherein film of AXBXCXAXBXC structures is listed in table 4.

Embodiment 9：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are all process using high density polyethylene (HDPE), density 0.955g/cm³, fusing point is 135 DEG C, and melt index is 3.8g/10min。

A layers, B layers and C layers all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.

One layer in A layers, B layers and C layers is 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.

Another layer in A layers, B layers and C layers is processed by plain film method simple tension technique, and its cross directional stretch multiplying power is 5 times, Thickness is 20 μm.

Another layer in A layers, B layers and C layers is processed by plain film method simple tension technique, and its longitudinal stretching multiplying power is 5 times, Thickness is 10 μm.

But the processing method of above-mentioned two A layers is that identical, the processing method of two B layers are identical and two C layers Processing method is identical.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with chlorinated polypropylene, then by being compounded to form composite membrane, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 85 μm.The mechanical property for the film that various combinations obtain is suitable, wherein AXBXCXAXBXC The performance test data for the film that the A layers of structure are biaxial tension, B layers are cross directional stretch, C layers are longitudinal stretching is listed in table 4.

Embodiment 10：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are all process using low density polyethylene (LDPE), density 0.916g/cm³, melt index 2.8g/10min.

A layers, B layers and C layers all add Petropols respectively, and Petropols addition is 15% weight of each layer gross weight.

One layer in A layers, B layers and C layers is processed by plain film method substep stretch processes, and wherein longitudinal stretching multiplying power is 12.5 times, cross directional stretch multiplying power is 1.1 times, and thickness is 8 μm.

Another layer in A layers, B layers and C layers is processed by plain film method substep stretch processes, wherein cross directional stretch multiplying power For 12.5 times, longitudinal stretching multiplying power is 1.1 times, and thickness is 16 μm.

Another layer in A layers, B layers and C layers is processed by plain film method simple tension technique, and its longitudinal stretching multiplying power is 12.5 Times, thickness is 8 μm.

But the processing method of above-mentioned two A layers is that identical, the processing method of two B layers are identical and two C layers Processing method is identical.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 40 dynes per centimeters, then using roller coat side Formula is coated with polyurethane, then is compounded to form composite membrane by hot pressing, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 69 μm.The mechanical property for the film that various combinations obtain is suitable, wherein AXBXCXAXBXC The performance test data for the film that the A layers of structure are biaxial tension, B layers are biaxial tension, C layers are longitudinal stretching is listed in table 4.

Embodiment 11：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

A layers and C layers all use the propylene copolymer containing ethene to be process, ethylene contents 0.35wt%, molecular weight It is distributed as 5.5, melt index 2.8g/10min, isotacticity 95.6%.

B layers are all process using high density polyethylene (HDPE), density 0.955g/cm³, fusing point is 135 DEG C, and melt index is 3.8g/10min。

A layers, B layers and C layers all add Petropols respectively, and Petropols addition is 10% weight of each layer gross weight.

Two A layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 10 μm.

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

Two C layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 9 times, and thickness is 10 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with chlorinated polypropylene, then by being compounded to form composite membrane, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 85 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 5.

Embodiment 12：AXBXCXAXBXC structures or AXBXCXCXBXA structures,

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

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

B layers are all process using high density polyethylene (HDPE), density 0.955g/cm³, fusing point is 135 DEG C, and melt index is 3.8g/10min。

A layers, B layers and C layers all add Petropols respectively, and Petropols addition is 15% weight of each layer gross weight.

Two A layers are processed by plain film method simple tension technique, and wherein longitudinal stretching multiplying power is 12.5 times, and thickness is 8 μ m。

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

Two C layers are processed by plain film method simple tension technique, and wherein cross directional stretch multiplying power is 12.5 times, and thickness is 8 μ m。

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 40 dynes per centimeters, then using roller coat side Formula is coated with polyurethane, then is compounded to form composite membrane by hot pressing, wherein, the thickness of X layers is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 69 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 5.

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

A layers are Noblen, molecular weight distribution 5.1, melt index 2.8g/10min, isotacticity 96.2%.C Layer is the polypropylene copolymer containing ethene, ethylene contents 0.35wt%, molecular distribution 5.5, melt index 2.8g/ 10min, isotacticity 95.6%.

B layers are low density polyethylene (LDPE)s, density 0.916g/cm³, melt index 2.8g/10min.

A layers, B layers and C layers all add hydrogenated petroleum resin respectively, and hydrogenated petroleum resin addition is each layer gross weight 20% weight.

Two A layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal direction is drawn Multiplying power is stretched for 5 times, and thickness is 7.5 μm.

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

Two C layers are processed by periosteum method substep stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal direction is drawn Multiplying power is stretched for 8 times, and thickness is 7.5 μm.

A layers, B layers and C layers pass through sided corona treatment respectively, and initial surface tension is 45 dynes per centimeters, then using roller coat side Formula is coated with polyurethane, then by being compounded to form composite membrane, wherein X thickness is 1 μm, structure be AXBXCXAXBXC or AXBXCXCXBXA, overall film thickness are 65 μm.The mechanical property of film prepared by two kinds of Rotating fields is suitable, wherein The performance test data of the film of AXBXCXAXBXC structures is listed in table 5.

The results of property of the multilayer complex films of table 2

The results of property of the multilayer complex films of table 3

The results of property of the multilayer complex films of table 4

The results of property of the multilayer complex films of table 5

Claims (24)

1. a kind of multilayer complex films, it includes the Rotating fields that n AXBXC Rotating fields are combined by X each other, and n is more than Equal to 2, each A is identical or different, and each B is identical or different, and each C is identical or different, and each X is identical or different, the layer A layers and C layers in structure include identical or different acrylic polymer independently of one another, and B layers include identical independently of one another Or different ethylene-based polymers, X are adhesive layer, the A layers and C layers are each independently simple tension or biaxial tension 's；The B layers are each independently what is do not stretched；

The A layers are that the cross directional stretch multiplying power of biaxial tension and the A layers is identical with longitudinal stretching multiplying power, or the C layers Be biaxial tension and the C layers cross directional stretch multiplying power it is identical with longitudinal stretching multiplying power.

2. a kind of multilayer complex films, it is characterised in that it includes the layer that n AXBXC Rotating fields are combined by X each other Structure, n are 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, and each X is identical or not Together, the A layers in the Rotating fields and C layers include identical or different acrylic polymer independently of one another, and B layers are independently of one another Including identical or different ethylene-based polymer, X is adhesive layer, the A layers and C layers be each independently simple tension or Biaxial tension；The B layers are each independently what is do not stretched；

When the B layers be do not stretch and n be even number when, the A layers combine in pairs, and the C layers combine in pairs；Its In, the longitudinal stretching multiplying power of an A layer or C layers is more than cross directional stretch multiplying power, and the longitudinal stretching multiplying power of another A layer or C layers is small In cross directional stretch multiplying power；

Or when the B layers be do not stretch and n be odd number when, the A layers remaining independent group of A layers after combining in pairs Close, the C layers after combining in pairs remaining C layers individually combine；Wherein, the longitudinal direction of an A layer or C layers in two layers in pairs Stretching ratio is more than cross directional stretch multiplying power, and the longitudinal stretching multiplying power of another A layer or C layers is less than cross directional stretch multiplying power, independent group The A layers of conjunction or the cross directional stretch multiplying power of C layers are identical with longitudinal stretching multiplying power.

3. multilayer complex films according to claim 2, it is characterised in that when the B layers be do not stretch and n be even number When, the vertically and horizontally draw ratio of the vertically and horizontally draw ratio and another A layer or C layers of one A layers or C layers is inversely proportional, i.e., described The ratio of the longitudinal stretching and cross directional stretch of one A layer or C layers is equal to the cross directional stretch and longitudinal stretching of another A layer or C layers Ratio.

4. multilayer complex films according to claim 3, it is characterised in that when the B layers be do not stretch and n be even number When, the longitudinal stretching multiplying power of one A layers or C layers is identical with the cross directional stretch multiplying power of another A layer or C layers, and described one The cross directional stretch multiplying power of individual A layers or C layers is identical with the longitudinal stretching multiplying power of another A layer or C layers.

5. multilayer complex films according to claim 2, it is characterised in that when the B layers be do not stretch and n be odd number When, wherein in paired two layers the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of an A layer or C layers and another A layer or C layers into Inverse ratio, i.e., the longitudinal stretching of one A layers or C layers and the ratio of cross directional stretch are equal to the cross directional stretch of another A layer or C layers With the ratio of longitudinal stretching, the A layers or the cross directional stretch multiplying power of C layers individually combined is identical with longitudinal stretching multiplying power.

6. multilayer complex films according to claim 5, it is characterised in that when the B layers be do not stretch and n be odd number When, wherein the longitudinal stretching multiplying power of an A layer or C layers and the cross directional stretch multiplying power phase of another A layer or C layers in paired two layers Together, the cross directional stretch multiplying power of one A layers or C layers is identical with the longitudinal stretching multiplying power of another A layer or C layers, independent group The A layers of conjunction or the cross directional stretch multiplying power of C layers are identical with longitudinal stretching multiplying power.

7. a kind of multilayer complex films, it includes the Rotating fields that n AXBXC Rotating fields are combined by X each other, and n is more than Equal to 2, each A is identical or different, and each B is identical or different, and each C is identical or different, and each X is identical or different, the layer A layers and C layers in structure include identical or different acrylic polymer independently of one another, and B layers include identical independently of one another Or different ethylene-based polymers, X are adhesive layer, the A layers and C layers are each independently simple tension or biaxial tension 's；The B layers are each independently simple tension or biaxial tension；

The draw ratio or stretching ratio of the A layers are different from the draw ratio or stretching ratio of B layers and/or C layers；

When n is even number, include one of following combination between B layers 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 and the horizontal stroke of biaxial tension It is identical to stretching ratio 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, include one of following combination between B layers two-by-two：

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

(2 ') B layer is the one of simple tension, a B layer biaxial tension, and the stretching ratio of simple tension and biaxial tension Individual stretching ratio is identical；Or

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

And the draw ratio or stretching ratio of remaining B layer are then identical or different with the draw ratio or stretching ratio of the above-mentioned layers of B two-by-two.

8. multilayer complex films according to claim 7, it is characterised in that n is that two B layers are list in (1 ') of odd number To stretching, and the cross directional stretch multiplying power of a B layer is identical with the longitudinal stretching multiplying power of another B layer.

9. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that n in the multilayer complex films AXBXC Rotating fields be it is compound by X orders, i.e., it is compound according to AXBXCXAXBXC order；Or the multilayer complex films Middle n AXBXC Rotating fields be replaced by X it is compound, i.e., it is compound according to AXBXCXCXBXA order；Or the multilayer is answered It is unordered compound by X to close n AXBXC Rotating fields in film.

10. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that the Rotating fields also include one layer of A Layer, the outer layer of outermost C layers is compound in by X, its structure is (AXBXCX)_nA, n are more than or equal to 2；Or it is compound in most by X The outer layer of the A layers of outer layer, its structure are A (XAXBXC)_n, n is more than or equal to 2；Or the Rotating fields also include one layer of B layer, lead to The outer layer that X is compound in outermost C layers is crossed, its structure is (AXBXCX)_nB, n are more than or equal to 2；Or outermost layer is compound in by X A layers outer layer, its structure is B (XAXBXC)_n, n is more than or equal to 2；Or the Rotating fields also include one layer of C layer, pass through X The outer layer of outermost C layers is compound in, its structure is (AXBXCX)_nC, n are more than or equal to 2；Or outermost A is compound in by X The outer layer of layer, its structure is C (XAXBXC)_n, n is more than or equal to 2.

11. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that the propylene of the A layers or C layers Polymer is Noblen or propylene copolymer, and comonomer is ethene or higher alpha-olefin.

12. multilayer complex films according to claim 11, it is characterised in that the acrylic polymer is that isotaxy is equal Polymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have a small amount of comonomer Atactic propene copolymer and ethylene copolymer-modified isotactic polypropylene polypropylene blend；Comonomer is second Alkene, butylene, hexene or octene.

13. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that the ethylene-based polymer of the B layers It is high density polyethylene (HDPE), high-pressure process low-density polyethylene or low-pressure process LLDPE.

14. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that the propylene of the A layers or C layers The fusing point of polymer is 148 to 170 DEG C；The molecular weight distribution of GPC tests is 2-16；Melt index is 0.5-10g/10min.

15. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that add again in A layers, B layers or C layers Enter another resin, selected from Petropols or hydrogenated petroleum resin；Its addition is the 1-30 weight % of each layer gross weight.

16. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that the thickness of the multilayer complex films For 50-150 μm.

17. multilayer complex films according to claim 16, it is characterised in that the thickness of the multilayer complex films is 80-90 μ m。

18. multilayer complex films according to any one of claim 1 to 8, it is characterised in that A in the multilayer complex films The tensile strength of layer is 1.5 in horizontal and vertical ratio:1.0 to 7.0:1.0；

The tensile strength of B layers is 1.0 in horizontal and vertical ratio:1.5 to 1.0:7.0；

The tensile strength of C layers is 1.5 in horizontal and vertical ratio:1.0 to 7.0:1.0.

19. multilayer complex films according to claim 18, it is characterised in that the anti-tensile of A layers is strong in the multilayer complex films Degree is 2.0 in horizontal and vertical ratio:1.0 to 5.0:1.0；

The tensile strength of B layers is 1.0 in horizontal and vertical ratio:2.0 to 1.0:5.0；

The tensile strength of C layers is 2.0 in horizontal and vertical ratio:1.0 to 5.0:1.0.

20. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that the anti-tensile of the multilayer complex films Horizontal and vertical test value ratio is 0.7 in intensity, deflection and tear-resistant intensity:1.0 to 1.0:1.3.

21. according to the multilayer complex films described in claim any one of 1-8, it is characterised in that the multilayer complex films are in length and breadth It is more than 100MPa to tensile strength.

A kind of 22. method for the multilayer complex films for preparing any one of claim 1 to 21, it is characterised in that methods described includes Following steps：

(1) preparation of A layers and C layers

By individual layer extrusion or multi-layer co-extruded, polyolefin sheets are prepared, are then carried out under 130-185 DEG C of temperature environment Simple tension or biaxial tension process A layers and C layers；

(2) preparation of B layers

By individual layer extrusion or multi-layer co-extruded, polyethylene sheets are prepared, may be selected not stretch or simple tension or biaxial tension Process B layers；

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

(4) the A layers, B layers and C layers of gluing be laminated compound, obtain the composite membrane.

23. a kind of application of the multilayer complex films of any one of claim 1 to 21, it is used for bill, marketable securities, books and periodicals envelope Face, picture album or packaging material.

24. a kind of product, it is made by the face coat and printing of the multilayer complex films of any one of claim 1 to 21, institute Stating product includes Front cover of book and periodical, picture album, bill, marketable securities or packaging material.