CN104149440B

CN104149440B - A kind of acrylic polymer-ethylene-based polymer multilayer complex films containing composite tie layer, its preparation method, purposes and goods thereof

Info

Publication number: CN104149440B
Application number: CN201310177465.XA
Authority: CN
Inventors: 陈大魁; 黄旭生; 詹越强; 谷汉进; 云小兵
Original assignee: ZHEJIANG ZHONGCHENG PACKING MATERIAL CO Ltd
Current assignee: ZHEJIANG ZHONGCHENG PACKING MATERIAL CO Ltd
Priority date: 2013-05-13
Filing date: 2013-05-13
Publication date: 2016-07-06
Anticipated expiration: 2033-05-13
Also published as: CN104149440A

Abstract

The present invention provides a kind of multilayer complex films, and it includes AYB Rotating fields, and wherein, the A layer in described Rotating fields includes acrylic polymer, and B layer includes ethylene-based polymer, and Y is composite tie layer, selected from the fusing point olefin polymer lower than 130 DEG C.The present invention also provides for the preparation method of above-mentioned multilayer complex films, its purposes and the goods comprising this multilayer complex films.The acrylic polymer of the present invention-ethylene-based polymer multilayer complex films has the performances such as high-stiffness, high transparent, low temperature resistant, high-tear strength.

Description

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

Technical field

The present invention relates to a kind of acrylic polymer multilayer complex films, its preparation method and application thereof, the invention still further relates to the goods comprising described composite membrane, belong to field of compound material.

Background technology

Biaxially oriented polypropylene (BOPP) thin film effectively utilizes the characteristics such as its excellent light weight, the transparency, mechanical strength, nontoxic, moistureproof, breathability is low, rigidity, for the wide spectrum being representative with packaging material.For example, be widely used for the packaging of the products such as food, medicine, daily light industry, medicated cigarette and lamination compound.A kind of purposes of BOPP thin film is to fit in paper surface, such as books, packing carton etc., plays effect that is moistureproof and that increase surface gloss.

BOPP thin film is generally the coextrusion structure of 3-5 layer, and step drawing production technology is mainly made up of following operation: dispensing batch mixing, extruder extrusion, extruded by T-shaped die head sheet, sheet chilling, to sheet by heating roller preheating, sheet longitudinal stretching, thermal finalization, preheat again, cross directional stretch, thermal finalization, cooling, sided corona treatment, rolling, cut and put in storage.CN101160209A(Oji Paper) disclosed in a kind of Biaxially stretched multilayer polypropylene film, the two sides of the bidirectional stretching polypropylene film substrate layer that its propylene polymer composition adding inorganic compound powder in by acrylic polymer obtains, possessing the surface layer containing acrylic polymer and back layer, the acrylic polymer in described substrate layer can be identical or different with the acrylic polymer in surface/back layer.It by adding inorganic compound powder in substrate layer, obtain uniform hidden power and whiteness excellent, almost without the thin film that thickness is 25-55 μm of concave-convex surface.Described thin film obtains by the following method: by itself known method co-extrusion modling, the acrylic polymer forming substrate layer is obtained multi-layer sheet, adopts the simultaneously bi-directionally biaxially oriented film forming method such as pulling method or sequentially biaxial tension method to be stretched to face multiplying power (longitudinal × horizontal) 45～65 times and obtain.To adopt sequentially biaxial tension method, can pass through at the temperature of longitudinally 70～140 ° of C with after the scope stretching of 4.5～7.5 times, then, under the temperature range of laterally 120～190 ° of C under 7～12 times and after face multiplying power (longitudinally × laterally) is stretched to 45～65 times, obtain at the temperature range heat fixation of 110～180 ° of C.

BOPP thin film has many desirable performances, such as high tensile, high-stiffness, the high grade of transparency etc..But, the life cycle of BOPP thin film is short, is generally some months to a year, and some physical properties such as resistance to low temperature, fall strength of briquette, tearing strength etc. is poor, is not suitable for the leaflet of life-time service, packaging material etc..It addition, the thickness of existing bidirectional stretching polypropylene film is generally less than 50 μm, its deflection can not meet high-end demand.Therefore its some ranges of application are constrained.

The density polyethylene film with high stretched has been used for plastics package field.Describing more such thin film in British Patent No. 1287527, they are biaxially stretched the degree more than 6.5 times on machine direction (MD) and horizontal (TD) both direction.U.S. Patent No. 4680207 relates to the twin shaft imbalance oriented film of linear low density polyethylene, and it stretches less than 6 times in the direction of the machine, and orientation is less than 3 times and less than stretching in the direction of the machine in the horizontal.

At present, industrial quarters, in the application that some are high to physical property requirements, generally uses biaxial stretching polyester (BOPET) thin film or biaxial tension nylon (BOPA) thin film.But BOPET film and BOPA thin film ratio are great, cost is high, and solvent resistance is poor.

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

Summary of the invention

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

The preparation method that it is a further object to provide above-mentioned multilayer complex films.

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

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

The present invention is achieved through the following technical solutions:

A kind of multilayer complex films, it is characterised in that it includes AYB Rotating fields, and in described Rotating fields, A layer includes acrylic polymer, and B layer includes ethylene-based polymer, and Y is composite tie layer, selected from the fusing point olefin polymer lower than 130 DEG C.

According to the present invention, the fusing point of described A layer or B layer is higher than the fusing point of Y layer, and its fusing point difference is more than 30 DEG C, it is preferable that more than 40 DEG C, more preferably greater than 50 DEG C.

According to the invention it is preferred to the fusing point of the olefin polymer of Y layer is lower than 120 DEG C, more preferably less than 110 DEG C, it is still more preferably less than 100 DEG C, it is most preferred that lower than 90 DEG C.The fusing point of the olefin polymer of preferred Y layer is 75-120 DEG C, more preferably 60-115 DEG C；Even more preferably from 50-105 DEG C.

According to the present invention, the olefin polymer lower than 130 DEG C of the fusing point in described Y layer is selected from propylene copolymer, ethylene copolymer or its mixture.

According to the present invention, the propylene copolymer in described Y layer is propylene and α-C_2-10The copolymer of alkene.I.e. α-C_2-10Alkene is as comonomer, it is preferred to ethylene, butylene, hexene or octene co-monomer.The fusing point of preferred described propylene copolymer is at 75-120 DEG C.

According to the present invention, the ethylene copolymer in described Y layer is ethylene and α-C_2-10The copolymer of alkene, wherein said ethylene copolymer is selected from linear low density polyethylene (LLDPE) (LLDPE), very low density polyethylene (VLDPE), polyethylene plastomers or elastomer.Preferably, the ethylene copolymer in Y layer is ultra-low density polyethylene.Described α-C_2-10Alkene is selected from propylene, butylene, hexene or octene co-monomer.The fusing point of preferred described ethylene copolymer is at 50-105 DEG C.

According to the present invention, the ethylene copolymer in described Y layer is selected from the copolymer of ethylene and polar monomer, and described polar monomer is selected from vinylacetate, acrylate, acrylic acid, methacrylate, methacrylic acid.The fusing point of preferred described ethylene copolymer is at 60-115 DEG C.

According to the present invention, the olefin polymer lower than 130 DEG C of the fusing point in described Y layer is selected from metallocene class polypropylene, and its fusing point is lower than 120 DEG C, it is preferable that lower than 110 DEG C, more preferably less than 100 DEG C.

According to the present invention, the olefin polymer lower than 130 DEG C of the fusing point in described Y layer is selected from metallocene quasi-polyethylene, for instance for the copolymer of ethylene with butylene, hexene or octene.Preferably, described metallocene quasi-polyethylene is the metallocene quasi-polyethylene having an obvious melting peak on DSC curve, its fusing point is lower than 110 DEG C, it is preferably shorter than 100 DEG C, or described metallocene quasi-polyethylene is the metallocene quasi-polyethylene of the rarest two obvious melting peaks on DSC curve, wherein the fusing point at first peak is between 75 DEG C 105 DEG C；The fusing point at second peak is between 105 DEG C 125 DEG C.

According to the present invention, described A layer is biaxial tension, and described B layer is biaxial tension.

According to the present invention, described A layer is that biaxial tension and cross directional stretch multiplying power and longitudinal stretching multiplying power are same or like, and described B layer is that biaxial tension and cross directional stretch multiplying power and longitudinal stretching multiplying power are same or like.

According to the present invention, the longitudinal stretching multiplying power of described A layer is more than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described B layer is more than longitudinal stretching multiplying power, or the cross directional stretch multiplying power of described A layer is more than longitudinal stretching multiplying power, and the longitudinal stretching multiplying power of described B layer is more than cross directional stretch multiplying power；It is highly preferred that the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of described A layer and described B layer is inversely proportional to, namely the longitudinal stretching of described A layer is equal to the cross directional stretch of described B layer and the ratio of longitudinal stretching with the ratio of cross directional stretch.It is highly preferred that the longitudinal stretching multiplying power of described A layer is same or like with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is same or like with the longitudinal stretching multiplying power of described B layer；It is more preferred still that the longitudinal stretching multiplying power of described A layer is identical with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is identical with the longitudinal stretching multiplying power of described B layer.

According to the present invention, the vertically and horizontally stretching ratio of described A layer is identical, and the vertically and horizontally stretching ratio of described B layer is identical, it is further preferred that described A layer and the vertically and horizontally draw ratio of B layer be 1 and stretching ratio identical.

According to the present invention, described A layer, B layer preferably include one of following combination:

(1) the multiplying power biaxial tensiones such as plain film method synchronization it are；Or

(2) the multiplying power biaxial tensiones such as plain film method substep it are.

According to the present invention, also comprising an A ' layer combined by Y layer in described multilayer complex films, be positioned at B layer outer layer or A layer outer layer, described A ' layer includes the acrylic polymer identical or different with A layer, and described A ' layer is biaxial tension.Preferably, the cross directional stretch multiplying power of described A ' layer is same or like with longitudinal stretching multiplying power, it is more preferred to, the stretching ratio of described A ' layer is same or like with the stretching ratio of A layer.

According to the present invention, it is more preferred still that the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of described A ' layer and described A layer is inversely proportional to, or the vertically and horizontally draw ratio of A ' layer is same or like with the vertically and horizontally draw ratio of described A layer.

According to the present invention, also comprising a B ' layer combined by Y layer in described multilayer complex films, be positioned at B layer outer layer or A layer outer layer, described B ' layer includes the ethylene-based polymer identical or different with B layer, and described B ' layer is biaxial tension.Preferably, the cross directional stretch multiplying power of described B ' layer is same or like with longitudinal stretching multiplying power.It is highly preferred that the stretching ratio of described B ' layer is same or like with the stretching ratio of B layer.

According to the present invention, it is more preferred still that the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of described B ' layer and described B layer is inversely proportional to, or the vertically and horizontally draw ratio of B ' layer is same or like with the vertically and horizontally draw ratio of described B layer.

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

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

According to the present invention, described A layer, A ' layer, the multi-layer co-extruded structure of B layer or B ' layer is at least 2 layers, for instance for 2-15 layer, it is preferable that 3-11 layer, more preferably 5-9 layer, even more preferably from 6-8 layer.

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

According to the present invention, in above-mentioned multilayer complex films, the thickness of each A layer, A ' layer, B layer or B ' layer is 5-65 μm, it is preferable that 10-55 μm, more preferably 20-40 μm.

According to the present invention, in above-mentioned multilayer complex films, each Y layer is identical or different, and described Y layer is monolayer or double-decker.

According to the present invention, described Y layer thickness is Y_aAnd Y_bThickness sum, or be Y_a’And Y_bThickness sum, or be Y_b’And Y_aThickness sum, or be Y_a’And Y_aThickness sum, or be Y_bAnd Y_b’Thickness sum, wherein each Y_aAnd Y_bIdentical or different.

Described Y is that double-deck structure of composite membrane preferably includes one of following combination:

(1) described AYB Rotating fields is AY_aY_bB, wherein the thickness of Y layer is Y_aAnd Y_bThickness sum.

(2) described AYBYA ' Rotating fields is AY_aY_bBY_bY_a’A ', wherein the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_a’And Y_bThickness sum.

(3) described A ' YAYB Rotating fields is A ' Y_a’Y_aAY_aY_bB, wherein the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_a’And Y_aThickness sum.

(4) described AYBYB ' Rotating fields is AY_aY_bBY_bY_b’B ', wherein the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_bAnd Y_b’Thickness sum.

(5) described B ' YAYB Rotating fields is B ' Y_b’Y_aAY_aY_bB, wherein the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_b’And Y_aThickness sum.

According to the present invention, in above-mentioned multilayer complex films, the thickness of each Y layer is 0.5-24 μm, it is preferable that 1-20 μm, more preferably 2-15 μm, even more preferably from 5-10 μm, it is most preferred that 6-8 μm.Wherein, Y_a、Y_b、Y_a’And Y_b’Thickness respectively 0.1-24 μm, 0.5-20 μm, more preferably 1-15 μm, even more preferably from 2-10 μm, it is most preferred that 5-8 μm, and the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_a’And Y_bThickness sum, or be Y_a’And Y_aThickness sum, or be Y_bAnd Y_b’Thickness sum, or be Y_b’And Y_aThickness sum, i.e. Y=Y_a+Y_b, Y=Y_a’+Y_b, Y=Y_a’+Y_a, Y=Y_b’+Y_b, Y=Y_b’+Y_a。

According to the present invention, in above-mentioned multilayer complex films, the summation of all Y layer thicknesses is less than the 20% of this composite film thickness, it is preferable that less than 15%, more preferably no more than 10%.

According to the present invention, in above-mentioned multilayer complex films, the tensile strength of A layer, A ' layer, Y layer, B layer or B ' layer is 1.5:1.0 to 7.0:1.0 at horizontal and vertical ratio, it is preferable that 2.0:1.0-5.0:1.0.

Or, in above-mentioned multilayer complex films, the tensile strength of A layer, A ' layer, Y layer, B layer or B ' layer is 1.0:1.5 to 1.0:7.0 at horizontal and vertical ratio, it is preferable that 1.0:2.0-1.0:5.0.

According to the present invention, the cross directional stretch multiplying power of A layer in above-mentioned multilayer complex films, A ' layer, B layer or B ' layer is 7-12.5 times, and longitudinal stretching multiplying power is 1-6 times, it is preferable that cross directional stretch multiplying power is 8-10 times, and longitudinal stretching multiplying power is 2-4 times.Or, the cross directional stretch multiplying power of A layer in above-mentioned multilayer complex films, A ' layer, B layer or B ' layer is 1-6 times, and longitudinal stretching multiplying power is 7-12.5 times, it is preferable that cross directional stretch multiplying power is 2-4 times, and longitudinal stretching multiplying power is 8-10 times.

According to the present invention, stretching ratio or the draw ratio of the Y layer in above-mentioned multilayer complex films are identical with A layer.Or, the stretching ratio of Y layer or draw ratio are identical with B layer.Preferably, Y_aStretching ratio or the draw ratio of layer are identical with A layer, Y_bStretching ratio or the draw ratio of layer are identical with B layer, Y_a’Stretching ratio or the draw ratio of layer are identical with A ' layer.

According to the present invention, the Y layer in above-mentioned multilayer complex films (includes Y_a, Y_b, Y_a’, Y_b’) cross directional stretch multiplying power be 7-12.5 times, longitudinal stretching multiplying power is 1-6 times, it is preferable that cross directional stretch multiplying power is 8-10 times, and longitudinal stretching multiplying power is 2-4 times.Or Y layer (includes Y_a, Y_b, Y_a’, Y_b’) cross directional stretch multiplying power be 1-6 times, longitudinal stretching multiplying power is 7-12.5 times, it is preferable that cross directional stretch multiplying power is 2-4 times, and longitudinal stretching multiplying power is 8-10 times.

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

The vertically and horizontally hot strength of described multilayer complex films is more than 100MPa, it is preferable that more than 120MPa, more preferably greater than 140MPa.According to the present invention, described acrylic polymer is preferably Noblen or propylene copolymer, it is typically isotaxy homopolymer, or is with different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, has the atactic polypropylene copolymer of a small amount of comonomer and the polypropylene blend of ethylene copolymer-modified isotactic polypropylene.Comonomer is ethylene or higher-alkene, such as ethylene, butylene, hexene or octene etc..

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

According to the present invention, described ethylene-based polymer is preferably high density polyethylene (HDPE), high-pressure process low-density polyethylene or low-pressure process linear low density polyethylene.The density of high density polyethylene (HDPE) is about 0.941g/cm³Or it is higher, it is preferable that about 0.948g/cm³To about 0.968g/cm³, more preferably from about 0.952g/cm³To about 0.962g/cm³；About 130 ° of C to about 148 ° C of fusing point；Melt index (is measured) as 0.2-50g/10min according to ASTMD1238, it is preferable that 1-45g/10min, more preferably 2-40g/10min.The density of Low Density Polyethylene is about 0.912g/cm³To about 0.94g/cm³, it is preferable that 0.915g/cm³To 0.928g/cm³；Melt index (is measured) as 0.2-50g/10min according to ASTMD1238, it is preferable that 1-45g/10min, more preferably 2-40g/10min.Linear low density polyethylene is ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.Ethylene-based polymer can also is that terpolymer, such as ethylene/butene/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 (measuring according to ASTMD1238) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.According to the present invention, A layer, A ' layer, B layer or B ' layer also can add another resin, such as Petropols or hydrogenated petroleum resin, to change the performances such as such as heat sealer, breathability, deflection and intensity, it is preferred to C₅-C₉Petropols or C₅-C₉Hydrogenated petroleum resin.Its addition is the 1-30% weight of gross weight, it is preferable that 2-20% weight, more preferably 3-15% weight, even more preferably from 4-10% weight.

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

(1) extruded by monolayer or multi-layer co-extruded, prepare polyolefin sheets, under uniform temperature environment, then carry out biaxial tension process:

(i) AY_aLayer and Y_bB layer, wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y；Y_a、Y_bCan be identical or different；

If possibly together with A ' layer, then optionally processing:

(ii) A ' Y_a’Layer, Y_aAY_aLayer and Y_bB layer, wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_a< Y, Y_a’< Y, Y_a+Y_a’=Y, wherein Y_a、Y_b、Y_a’Can be identical or different, Y can be identical or different；

(iii) AY_aLayer, Y_bBY_bLayer and Y_a’A ' layer；Wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_b< Y, Y_a’< Y, Y_b+Y_a’=Y, wherein Y_a、Y_b、Y_a’Can be identical or different, Y can be identical or different；

If possibly together with B ' layer, then optionally processing:

(iv) B ' Y_b’Layer, Y_aAY_aLayer and Y_bB layer, wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_a< Y, Y_b’< Y, Y_a+Y_b’=Y, wherein Y_a、Y_b、Y_b’Can be identical or different, Y can be identical or different；

(v) AY_aLayer, Y_bBY_bLayer and Y_b’B ' layer；Wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_b< Y, Y_b’< Y, Y_b+Y_a’=Y, wherein Y_a、Y_b、Y_b’Can be identical or different, Y can be identical or different.

(2) by each layer after stretching in step (1) (such as AY_aLayer and Y_bB layer, or A ' Y_a’Layer, Y_aAY_aLayer and Y_bB layer, or AY_aLayer, Y_bBY_bLayer and Y_a’A ' layer, or B ' Y_b’Layer, Y_aAY_aLayer and Y_bB layer, or AY_aLayer, Y_bBY_bLayer and Y_b’B ' layer) carry out lamination compound, formed:

(i) AYB composite membrane (AY_aY_bB layer), wherein, Y_aLayer and Y_bLayer is compounded to form Y layer, Y_a, and Y_bLayer is identical or different；Or

(ii) A ' YAYB(A ' Y_a’Y_aAY_aY_bB), wherein, Y_aLayer and Y_bLayer is compounded to form Y layer, Y_aLayer and Y_a’Layer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_a’Layer is identical or different；Or

(iii) AYBYA ' (AY_aY_bBY_bY_a’A ' layer) composite membrane, wherein, Y_aLayer and Y_bLayer is compounded to form Y layer or Y_a’Layer and Y_bLayer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_a’Layer is identical or different.

(iv) B ' YAYB(B ' Y_b’Y_aAY_aY_bB), wherein, Y_aLayer and Y_bLayer is compounded to form Y layer, Y_aLayer and Y_b’Layer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_b’Layer is identical or different；Or

(v) AYBYB ' (AY_aY_bBY_bY_b’B ' layer) composite membrane, wherein, Y_aLayer and Y_bLayer is compounded to form Y layer or Y_b’Layer and Y_bLayer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_b’Layer is identical or different.

According to the present invention, stretching preferably under the temperature environment of 130-185 ° of C in described step (1), it is preferred that each layer described has identical stretching ratio, for instance A and Y_aLayer has identical stretching ratio or draw ratio, Y_bThere is identical stretching ratio or draw ratio or A ' and Y with B layer_a’There is identical stretching ratio or draw ratio.

According to the present invention, the AY of step (1) gained_aLayer, Y_bB layer, A ' Y_a’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer, Y_a’A ' layer, B ' Y_b’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer and Y_b’The two-sided of B ' layer both passes through sided corona treatment so that it is initial surface tension reaches more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.It is further preferred that surface tension reaches more than 38 dynes per centimeter.

The present invention also provides for a kind of method (wherein A layer, B layer, Y layer, A ' layer and B ' layer have identical stretching ratio or draw ratio) preparing above-mentioned multilayer complex films, and it comprises the following steps:

(1) extruded by monolayer or multi-layer co-extruded, prepare the polyolefin sheets that structure is AYB layer, if possibly together with A ' layer, then optional structure of preparing is AYBYA ' or the polyolefin sheets of A ' YAYB, if possibly together with B ' layer, then optional structure of preparing is AYBYB ' or the polyolefin sheets of B ' YAYB；

(2) then at a certain temperature by the sheet material in plain film method biaxial tension procedure of processing (1), described composite membrane is obtained.

Stretching preferably under the temperature environment of 130-185 ° of C in described step (2), it is preferable that carry out same multiplying power and stretch (synchronize or substep can).

According to the present invention, the two-sided of composite membrane of step (2) gained both passes through sided corona treatment so that it is initial surface tension reaches more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.It is further preferred that surface tension reaches more than 38 dynes per centimeter.

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

The present invention also provides for the application of the multilayer complex films described in a kind of aforementioned any one, and it is for bill, marketable securities, leaflet and packaging material.

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

Beneficial effects of the present invention:

Acrylic polymer prepared by the present invention-ethylene-based polymer multilayer complex films, having the combination property of excellence, its tensile strength, deflection and tear-resistant intensity are all significantly high, and its vertical and horizontal performance has good balance, and having the good transparency, concrete performance is referring to table 1.

The performance of table 1 composite membrane of the present invention

Describe in detail

[composition of A layer, B layer, A ' layer and B ' layer]

According to the present invention, described A layer and A ' layer mainly include acrylic polymer.Described acrylic polymer is preferably Noblen or propylene copolymer or polypropene composition；It is typically isotaxy homopolymer, or is with different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, has the atactic polypropylene copolymer of a small amount of comonomer and/or the polypropylene blend of ethylene copolymer-modified isotactic polypropylene.The comonomer of polypropylene copolymer is ethylene or higher-alkene, such as ethylene, butylene, hexene or octene etc..The content of comonomer is preferably 0.2wt% to 2.0wt%, more preferably 0.35wt% to 0.85wt%.These acrylic polymers of the present invention can be the mixture containing one kind or two or more polymer, for instance the Noblen that molecular weight is different, or the compositions of propylene and a small amount of alpha-olefin random copolymer.The polypropylene-based polymer of the present invention, is generally the vistanex according to polyacrylic title manufacture, sale, it is common that density is 0.890～0.930g/cm³, MFR(ASTMD1238, load 2160g, temperature 230 DEG C) be 0.5～60g/10 minute, be preferably 0.5～20g/10 minute, more preferably 0.5-15g/10min, be still more preferably the Noblen of 1～5g/10 minute.

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

According to the present invention, described B layer and B ' layer mainly include ethylene-based polymer, and described ethylene-based polymer is preferably high density polyethylene (HDPE) (HDPE), Low Density Polyethylene (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE not or has a small amount of comonomer, and comonomer is propylene or higher alpha-olefin, such as butylene, hexene or octene etc., and has about 0.941g/cm³Or higher (such as about 0.948g/cm³To about 0.968g/cm³, it is preferable that about 0.952g/cm³To about 0.962g/cm³) density, the fusing point of such as about 130 ° of C to about 148 ° of C and 0.2-50g/10min, it is preferable that 1-45g/10min, the more preferably melt index (measuring according to ASTMD1238) of 2-40g/10min.LDPE has at 0.912g/cm³To 0.94g/cm³(such as 0.915g/cm³To 0.928g/cm³) the density of scope and the preferred 1-45g/10min of 0.2-50g/10min(, more preferably 2-40g/10min) melt index (measuring according to ASTMD1238).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.In addition ethylene-based polymer can also is that terpolymer, such as ethylene/butene/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 (measuring according to ASTMD1238) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.

The polymer of described A layer and A ' layer also can be mixed into part ethylene-based polymer, for instance high density polyethylene (HDPE) (HDPE), Low Density Polyethylene (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, HDPE not or has a small amount of comonomer, and comonomer is propylene or higher alpha-olefin, such as ethylene, butylene, hexene or octene etc., and has about 0.941g/cm³Or higher (such as about 0.948g/cm³To about 0.968g/cm³, it is preferable that about 0.952g/cm³To about 0.962g/cm³) density, the fusing point of such as about 130 ° of C to about 148 ° of C and 0.2-50g/10min, it is preferable that 1-45g/10min, the more preferably melt index (measuring according to ASTMD1238) of 2-40g/10min.LDPE has at 0.912g/cm³To 0.94g/cm³(such as 0.915g/cm³To 0.928g/cm³) the density of scope and the preferred 1-45g/10min of 0.2-50g/10min(, more preferably 2-40g/10min) melt index (measuring according to ASTMD1238).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2-50g/10min(such as 1-10g/10min) melt index (measuring according to ASTMD1238) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.In addition ethylene-based polymer can also is that terpolymer, such as ethylene/butene/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 (measuring according to ASTMD1238) and at 0.857g/cm³To 0.950g/cm³, preferred 0.905g/cm³To 0.940g/cm³, more preferably 0.910g/cm³To 0.928g/cm³The density of scope.

Deflection of the present invention refers to that Paper or cardboard supports resistant to bending strength character.Deflection is directly proportional to EI/W value, wherein the quality of W, E and I respectively Paper or cardboard, elastic modelling quantity and the moment of inertia.Wherein, the deflection of cardboard or claim flexural rigidity, refer to applying certain load from the fixture 5cm place sample to vertically clipping, observing from sample camber 3.81mm width, sample, to moment of flexure 15 ° required, represents with g cm.Paper sheet stiffness is a critically important index, directly affects the size (another influence factor is d ie cutting press) of folding line deflection, thus affecting finished product molding.Deflection is little, and finished product is prone to conquassation, warpage；Deflection is big, and finished product is difficult to molding.

In order to improve the deflection of the multilayer complex films of the present invention further, and the such as performance such as heat sealer, breathability and intensity, it is possible in A layer, A ' layer, B layer or B ' layer, add another resin, such as Petropols, hydrogenated petroleum resin etc., it is preferable that C₅-C₉Petropols or C₅-C₉Hydrogenated petroleum resin.Its addition is the 1-30% weight of each layer gross weight, it is preferable that 2-20% weight, more preferably 3-15% weight, even more preferably from 4-10% weight.

In the polymer of described A layer, B layer, A ' layer and B ' layer, all right master batch form adds the additive of about 0.01～5.0 mass %.Described additive is preferably 0.01～3.0 mass %, more preferably 0.05～1.0 mass %.

Described additive has: antiblocking agent, slipping agent (i.e. lubricant), antistatic additive, nucleator, heat-resisting stabilizing agent, weathering stabilizers, UV absorbent, anti-turbid dose, pigment, dyestuff, the known various additives that generally can add in polyolefin such as slipping agent.

As described antiblocking agent, antiblocking agent well known in the art can be used, such as Silicon stone, Talcum, Muscovitum, zeolite, or the inorganic compound particles such as the metal-oxide that metal alkoxide sintering is obtained；Or the organic compound such as polymethyl methacrylate, melamine resin, melamine urea resin, polyester resin.Wherein, Silicon stone, polymethyl methacrylate are particularly preferably used from resistance to blocking aspect.

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

As described antistatic additive, can use such as the ethylene oxide adduct of betanin derivative, quaternary amine based compound, alkyldiethanolamine fatty acid ester, fatty acid glyceride, tristerin etc..

As described nucleator, such as Sorbitol system, organophosphate metal salt system, metal salt of organic carboxylic acid system, rosin series nucleator etc. can be used.

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

Described A layer, B layer, A ' layer or B ' one polymer also can add delustring masterbatch to produce Extinctive thin film, or addition pearly-lustre masterbatch produces pearly-lustre thin film.

Single or double as required, can be implemented the surface treatment such as sided corona treatment, flame treatment by the laminate stretch acrylic polymer-ethylene-based polymer thin film of the present invention.Additionally, according to purposes, for giving heat sealability, can overleaf on layer independent lamination contain the thin film of the low melting point polymers such as random copolymer or the random copolymer of alpha-olefin of propylene and ethylene or carbon number more than 4, polybutene, the ethene-vinyl acetate copolymer of high-pressure process low-density polyethylene, linear low density polyethylene (LLDPE), crystallinity or low-crystalline ethylene and the alpha-olefin of carbon number 3～10, or lamination contains their thin film of compositions.It addition, in order to improve the cementability with other material, the binding agents such as oriented film surface imines, carbamate can be fixed process, it is also possible to the maleic anhydride modified polyolefin of lamination.

[preparation method of multilayer complex films]

According to the present invention, adopt simple tension or biaxial tension, namely in stretching-machine, at certain temperature and speed, a direction (vertical or horizontal) or carry out stretching in vertical both direction (longitudinally, laterally) and make thin film.The so-called direction longitudinally referred to along thin film extrusion processing, the so-called direction laterally referring to vertical thin-film extrusion processing.Vertically and horizontally draw ratio refers to the ratio of longitudinal stretching multiplying power and cross directional stretch multiplying power.

So-called plain film method, it is the melt of olefin polymer is first passed through long and narrow head make sheet material or thick film, then, in stretching-machine, at certain temperature and speed, above in vertical both direction (longitudinally, laterally) or carry out in a single direction stretching and make thin film.

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

(1) AY_aLayer, Y_bB layer, A ' Y_a’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer, Y_a’A ' layer, B ' Y_b’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer and Y_b’The preparation of B ' tunic

Prepared by the method adopting biaxial tension, it is possible to adopt substep sequentially biaxial tension method, also can adopt synchro-draw method.

Described drawing process can be plain film method.The technical process of described plain film method includes synchro-draw process, comprises the steps:

Synchro-draw → the traction of dispensing → extrusion → chilling → vertically and horizontally and optional surface treatment → rolling → Ageing Treatment → cut → product.

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

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

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

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

According to the present invention, described chilling refers to that use coolant cools down, it is preferable that coolant is cooling water.The effect of described chilling is to make crystallization refine, thus improving transparency and deflection.

According to the present invention, described in be extruded as multi-layer co-extruded.Described extrusion employing melt extrudes.

According to the present invention, described dispensing includes the requirement according to formula and carries out dispensing, it is possible to pass through electronic measurement.

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

A () carries out dispensing by the requirement of formula, add in the hopper above multi-layer co-extruded extruder, and plastics enter the rack-style flat die of multi-layer co-extruded compound after passing through external heat and the screw rod rotational shear plasticizing of extruder barrel.Going out the lamellar melt after die head and be attached on chilling roller by air knife, lamellar melt supercooled is become sheet, then as the rotation of chilling roller, sheet enters tank and carries out further two-sided cooling.The thickness of sheet can be controlled by the rotating speed of the extrusion capacity of extruder and chilling roller.Wherein, the control temperature of extruder is 150-260 DEG C, it is preferable that 180-250 DEG C；Die head temperature is generally 190-240 DEG C, and chilling roll temperature is 15-30 DEG C, it is preferable that 20-25 DEG C.

B a number of pre-hot-rolling that () sheet enters back in vertically and horizontally tensioning system carries out two-sided preheating, and pre-heat roller temperature general control is at 90-150 DEG C, it is preferable that 100-120 DEG C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, carrying out longitudinal stretching by draw roll, draft temperature controls at 90-150 DEG C, it is preferable that 100-120 DEG C, and drawing process can a step, it is also possible to twice stretching or stretch for three times.Longitudinal stretching multiplying power is according to AY_aLayer, Y_bB layer, A ' Y_a’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer, Y_a’A ' layer, B ' Y_b’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer and Y_b’The requirement of B ' tunic is set.Thin film after stretching carries out heat treatment by setting roller, and described setting temperature is 100-140 DEG C, it is preferred to 110-120 DEG C, to eliminate the internal stress of thin film, reduces longitudinal shrinkage factor.

C the thin film after () longitudinal stretching enters cross directional stretch system, first carry out preheating section preheating, and pre-heat roller temperature general control is at 100-160 DEG C, it is preferable that 110-140 DEG C, more preferably 115-130 DEG C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, then pass through the track expanding spoke and carry out cross directional stretch, general 130-180 DEG C of the control temperature of stretching-machine, it is preferable that 140-160 DEG C, then carries out thermal finalization process, setting temperature is 60-120 DEG C, it is preferable that 70-110 DEG C.Cross directional stretch multiplying power is according to AY_aLayer, Y_bB layer, A ' Y_a’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer, Y_a’A ' layer, B ' Y_b’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer and Y_b’The requirement of B ' tunic is set.

(d) go out cross directional stretch system after thin film cooled down by chill roll, followed by trimming, be sided corona treatment with that, be finally by rolling.

E () leaves the big wound membrane after equipment after the Ageing Treatment depositing several days, just can cut, make the AY of Rack_aLayer, Y_bB layer, A ' Y_a’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer, Y_a’A ' layer, B ' Y_b’Layer, Y_aAY_aLayer, Y_bB layer, AY_aLayer, Y_bBY_bLayer and Y_b’B ' layer film.

When described plain film method is the stretching of plain film synchronous bidirectional, plain film synchro-draw preparation method is similar with plain film step drawing preparation method, difference is only in that in synchro-draw process, and longitudinal stretching and cross directional stretch are synchronously performed, namely longitudinal stretching and cross directional stretch complete a system inter-sync, and longitudinal stretching and cross directional stretch is asynchronous carries out in step drawing.Thus concrete operating condition is similar with step drawing.At present, synchro-draw machine has two kinds of forms in the world, and one is mechanical type, and one is linear electric machine formula.

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

Dispensing → extrusion → chilling → vertical or horizontal stretching → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.

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

(2) lamination

By AY_aLayer, Y_bB layer is (if desired, by A ' Y_a’Layer, Y_aAY_aLayer, Y_bB layer, or, AY_aLayer, Y_bBY_bLayer, Y_a’A ' layer, or B ' Y_b’Layer, Y_aAY_aLayer, Y_bB layer, or AY_aLayer, Y_bBY_bLayer and Y_b’B ' layer) carry out lamination compound, obtain described composite membrane.

According to the present invention, described lamination compound is undertaken by hot pressing, and described laminating temperature is 40-100 ° of C, it is preferable that 60-80 ° of C.

The plain film method simple tension method or the bidirectional extending method that use in the method are identical with the plain film method simple tension related in above-mentioned first method or biaxial tension.

[purposes of multilayer complex films]

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

Accompanying drawing explanation

Fig. 1 is the structural representation of the composite membrane of the embodiment of the present invention 1 preparation.

Detailed description of the invention

Below in conjunction with embodiment, the present invention being described, but skilled in the art realises that, described embodiment is not limiting the scope of the invention, any make on basis of the present invention improvement, change all within protection scope of the present invention.

Embodiment 1:AYB type structure, layer thickness profile: 39 μm/2 μm/39 μm

A layer uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.B layer is high density polyethylene (HDPE), and density is 0.955g/cm3, and fusing point is 140 ° of C, and melt index is 2.8g/10min.

Y layer is polyacrylic copolymer, and containing ethylene and butene comonomer, its fusing point (DSC mensuration) is 103 DEG C.

Preparation AY_aLayer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 times, and A layer thickness is 39 μm, Y_aLayer thickness is 1 μm.

Preparation Y_bB layer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 times, and B layer thickness is 39 μm, Y_bLayer thickness is 1 μm.

AY_aLayer and Y_bB layer is respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, is then compounded to form composite membrane by hot pressing, and structure is AY_aY_bB, namely the thickness of AYB, Y is 2 μm, and overall film thickness is 80 μm.

Test data are listed in table 2.

Embodiment 2:AYB type structure, layer thickness profile: 59 μm/2 μm/59 μm

A layer uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.B layer is high density polyethylene (HDPE), and density is 0.955g/cm3, and fusing point is 135 ° of C, and melt index is 3.8g/10min.

Y is ultra-low density polyethylene, and containing octene co-monomer, fusing point is 90.2 DEG C.

By multi-layer co-extruded preparation AYB layer, by above-mentioned coextruded layer by the processing of plain film method stretch processes, wherein cross directional stretch multiplying power is 12.5 times, and longitudinal stretching multiplying power is 12.5 times.

A layer thickness is 59 μm, and B layer thickness is 59 μm, and the thickness of Y is 2 μm, and overall film thickness is 120 μm.

Described composite bed is through sided corona treatment, and initial surface tension is 45 dyne.

Test data are listed in table 2.

Embodiment 3:AYBYA ' product structure, layer thickness profile: 33 μm/2 μm/10 μm/2 μm/33 μm.

A layer is the propylene copolymer containing ethylene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.B layer is high density polyethylene (HDPE), and density is 0.955g/cm3, and fusing point is 140 ° of C, and melt index is 2.8g/10min.A ' layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.

Y is the copolymer of ethylene and vinylacetate, and fusing point is at 86 DEG C.

By multi-layer co-extruded preparation AYBYA ' layer, by above-mentioned coextruded layer by the processing of plain film method stretch processes, wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 9 times.

A layer thickness is 33 μm, and B layer thickness is 10 μm, and A ' layer thickness is 33 μm, and the thickness of Y is 2 μm, and overall film thickness is 80 μm.

Test data are listed in table 2.

Embodiment 4:B ' YAYB type structure, layer thickness profile: 38 μm/2 μm/30 μm/2 μm/38 μm

The A layer polypropylene copolymer containing ethylene, ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.B layer and B ' layer are all high density polyethylene (HDPE)s, and density is 0.955g/cm3, and fusing point is 140 ° of C, and melt index is 2.8g/10min.

Y is polyacrylic copolymer, and containing ethylene and butene comonomer, its fusing point (DSC mensuration) is 103 DEG C.

Preparation B ' Y_b’Layer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 6 times, and B ' layer thickness is 38 μm, Y_b’Layer thickness is 1 μm.

Preparation Y_aAY_aLayer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 times, and A layer thickness is 30 μm, Y_aLayer thickness is 1 μm.

Preparation Y_bB layer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 6 times, and B layer thickness is 38 μm, Y_bLayer thickness is 1 μm.

B’Y_b’Layer, Y_aAY_aLayer and Y_bB layer is respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, is then compounded to form composite membrane by hot pressing, and the thickness that structure is B ' YAYB, Y is 2 μm, and overall film thickness is 110 μm.

Test data are listed in table 2.

Embodiment 5:AYBYA ' product structure, layer thickness profile: 14 μm/2 μm/28 μm/2 μm/14 μm.

A layer and A ' layer are all Noblens, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is Low Density Polyethylene, and density is 0.920g/cm³, melt index is 2.8g/10min.

Y layer is ultra-low density polyethylene, and containing octene co-monomer, fusing point is 90.2 DEG C.

Preparation AY_aLayer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 5 times, and A layer thickness is 14 μm, Y_aLayer thickness is 1 μm.

Preparation Y_bBY_bLayer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 times, and B layer thickness is 28 μm, Y_bLayer, Y_bLayer thickness is 1 μm.

Preparation Y_a’A ' layer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 6 times, and A ' layer thickness is 14 μm, Y_a’Layer thickness is 1 μm.

AY_aLayer, Y_bBY_bLayer and Y_a’A ' layer is respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, is then compounded to form composite membrane by hot pressing, and the thickness that structure is AYBYA ', Y is 2 μm, and overall film thickness is 60 μm.

Test data are listed in table 2.

Embodiment 6:B ' YAYB type structure, layer thickness profile: 27 μm/2 μm/54 μm/2 μm/27 μm

A layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is Low Density Polyethylene, and density is 0.920g/cm³, melt index is 2.8g/10min.B ' layer is high density polyethylene (HDPE), and density is 0.955g/cm3, and fusing point is 140 ° of C, and melt index is 2.8g/10min..

By multi-layer co-extruded preparation B ' YAYB layer, by above-mentioned coextruded layer by the processing of plain film method stretch processes, wherein cross directional stretch multiplying power is 11 times, and longitudinal stretching multiplying power is 11 times.

A layer thickness is 54 μm, and B layer thickness is 27 μm, and B ' layer thickness is 27 μm, and the thickness of Y is 2 μm, and overall film thickness is 112 μm.

Test data are listed in table 2.

Embodiment 7:AYB type structure, layer thickness profile: 35 μm/5 μm/35 μm

A layer uses the propylene copolymer containing ethylene to process, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.B layer uses linear low density polyethylene, and for ethylene/butylene copolymers, melt index is 2.0g/10min, and density is 0.920g/cm³。

A layer thickness is 35 μm, and B layer thickness is 35 μm, and the thickness of Y is 5 μm, and overall film thickness is 75 μm.

Test data are listed in table 2.

Embodiment 8:AYB type structure, layer thickness profile: 55 μm/8 μm/55 μm

Preparation AY_aLayer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 7 times, and longitudinal stretching multiplying power is 7 times, and A layer thickness is 55 μm, Y_aLayer thickness is 3 μm.

Preparation Y_bB layer: prepare sheet material by multi-layer co-extruded, again through the substep stretch processes processing of plain film method, wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 6 times, and B layer thickness is 55 μm, Y_bLayer thickness is 5 μm.

AY_aLayer and Y_bB layer is respectively through sided corona treatment, and initial surface tension is 45 dynes per centimeter, is then compounded to form composite membrane by hot pressing, and structure is AY_aY_bB, namely the thickness of AYB, Y is 8 μm, and overall film thickness is 118 μm.

Test data are listed in table 2.

Embodiment 9:AYBYA ' product structure, layer thickness profile: 15 μm/2 μm/26 μm/2 μm/15 μm..

A layer and A ' layer are Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer uses linear low density polyethylene, and for ethylene/butylene copolymers, melt index is 2.0g/10min, and density is 0.920g/cm³。

By multi-layer co-extruded preparation AYBYA ' layer, by above-mentioned coextruded layer by the processing of plain film method stretch processes, wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.

A layer thickness is 15 μm, and B layer thickness is 26 μm, and A ' layer thickness is 15 μm, and the thickness of Y is 2 μm, and overall film thickness is 60 μm.

Test data are listed in table 2.

Embodiment 10:B ' YAYB type structure, layer thickness profile: 26 μm/3 μm/52 μm/3 μm/26 μm

A layer is Noblen, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer or B ' layer are all linear low density polyethylene, and for ethylene/butylene copolymers, melt index is 2.0g/10min, and density is 0.920g/cm³。

By multi-layer co-extruded preparation B ' YAYB layer, by above-mentioned coextruded layer by the processing of plain film method stretch processes, wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 times.

A layer thickness is 52 μm, and B layer thickness is 26 μm, and B ' layer thickness is 26 μm, and the thickness of Y is 3 μm, and overall film thickness is 110 μm.

Test data are listed in table 2.

The results of property of table 2 multilayer complex films

Table 2(continues) results of property of multilayer complex films

Claims

1. a multilayer complex films, it is characterised in that it includes AYB Rotating fields, in described Rotating fields, A layer includes acrylic polymer, and B layer includes ethylene-based polymer, and Y is composite tie layer, selected from the fusing point olefin polymer lower than 130 DEG C；Described A layer is biaxial tension, described B layer is biaxial tension, the longitudinal stretching multiplying power of described A layer is more than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described B layer is more than longitudinal stretching multiplying power, or the cross directional stretch multiplying power of described A layer is more than longitudinal stretching multiplying power, and the longitudinal stretching multiplying power of described B layer is more than cross directional stretch multiplying power.

2. multilayer complex films according to claim 1, it is characterized in that: the vertically and horizontally draw ratio of the vertically and horizontally draw ratio of described A layer and described B layer is inversely proportional to, namely the longitudinal stretching of described A layer is equal to the cross directional stretch of described B layer and the ratio of longitudinal stretching with the ratio of cross directional stretch.

3. multilayer complex films according to claim 2, it is characterised in that: the longitudinal stretching multiplying power of described A layer is same or like with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is same or like with the longitudinal stretching multiplying power of described B layer.

4. the composite membrane according to any one of claim 1-3, it is characterised in that the fusing point of described A layer or B layer is higher than the fusing point of Y layer.

5. multilayer complex films according to claim 4, it is characterised in that the fusing point difference of described A layer or B layer is more than 30 DEG C.

6. multilayer complex films according to claim 4, it is characterised in that the fusing point difference of described A layer or B layer is more than 40 DEG C.

7. multilayer complex films according to claim 4, it is characterised in that the fusing point difference of described A layer or B layer is more than 50 DEG C.

8. the multilayer complex films according to any one of claim 1-3, it is characterised in that the fusing point of the olefin polymer of described Y layer is lower than 120 DEG C.

9. multilayer complex films according to claim 8, it is characterised in that the fusing point of the olefin polymer of described Y layer is lower than 110 DEG C.

10. multilayer complex films according to claim 8, it is characterised in that the fusing point of the olefin polymer of described Y layer is lower than 100 DEG C.

11. multilayer complex films according to claim 8, it is characterised in that the fusing point of the olefin polymer of described Y layer is lower than 90 DEG C.

12. multilayer complex films according to claim 8, it is characterised in that the fusing point of the olefin polymer of described Y layer is 75-120 DEG C.

13. multilayer complex films according to claim 8, it is characterised in that the fusing point of the olefin polymer of described Y layer is 60-115 DEG C.

14. multilayer complex films according to claim 8, it is characterised in that the fusing point of the olefin polymer of described Y layer is 50-105 DEG C.

15. according to the multilayer complex films described in any one of claim 1-3, it is characterised in that the olefin polymer lower than 130 DEG C of the fusing point in described Y layer is selected from propylene copolymer, ethylene copolymer or its mixture.

16. the composite membrane according to any one of claim 1-3, it is characterized in that, described multilayer complex films is also comprised an A ' layer combined by Y layer, be positioned at B layer outer layer or A layer outer layer, described A ' layer includes the acrylic polymer identical or different with A layer, and described A ' layer is biaxial tension.

17. composite membrane according to claim 16, it is characterised in that the cross directional stretch multiplying power of described A ' layer is same or like with longitudinal stretching multiplying power.

18. composite membrane according to claim 16, it is characterised in that the stretching ratio of described A ' layer is same or like with the stretching ratio of A layer.

19. the composite membrane according to any one of claim 1-3, it is characterized in that, described multilayer complex films is also comprised a B ' layer combined by Y layer, be positioned at B layer outer layer or A layer outer layer, described B ' layer includes the ethylene-based polymer identical or different with B layer, and described B ' layer is biaxial tension.

20. composite membrane according to claim 19, it is characterised in that the cross directional stretch multiplying power of described B ' layer is same or like with longitudinal stretching multiplying power.

21. composite membrane according to claim 19, it is characterised in that the stretching ratio of described B ' layer is same or like with the stretching ratio of B layer.

22. the composite membrane according to any one of claim 1-3, it is characterised in that described Y layer is double-decker, one of the combination as follows of described double-decker:

(1) described AYB Rotating fields is AY_aY_bB, wherein the thickness of Y layer is Y_aAnd Y_bThickness sum；

(2) described AYBYA ' Rotating fields is AY_aY_bBY_bY_a’A ', wherein the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_a’And Y_bThickness sum；

(3) described A ' YAYB Rotating fields is A ' Y_a’Y_aAY_aY_bB, wherein the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_a’And Y_aThickness sum；

(4) described AYBYB ' Rotating fields is AY_aY_bBY_bY_b’B ', wherein the thickness of Y layer is Y_aAnd Y_bThickness sum, or be Y_bAnd Y_b’Thickness sum；

23. the preparation method of the multilayer complex films of any one of claim 1-22, it is characterised in that comprise the following steps:

(i)AY_aLayer and Y_bB layer, wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y；Y_a、Y_bCan be identical or different；

If possibly together with A ' layer, then optionally processing:

(ii)A’Y_a’Layer, Y_aAY_aLayer and Y_bB layer, wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_a< Y, Y_a’< Y, Y_a+Y_a’=Y, wherein Y_a、Y_b、Y_a’Can be identical or different, Y can be identical or different；

(iii)AY_aLayer, Y_bBY_bLayer and Y_a’A ' layer；Wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_b< Y, Y_a’< Y, Y_b+Y_a’=Y, wherein Y_a、Y_b、Y_a’Can be identical or different, Y can be identical or different；

If possibly together with B ' layer, then optionally processing:

(iv)B’Y_b’Layer, Y_aAY_aLayer and Y_bB layer, wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_a< Y, Y_b’< Y, Y_a+Y_b’=Y, wherein Y_a、Y_b、Y_b’Can be identical or different, Y can be identical or different；

(v)AY_aLayer, Y_bBY_bLayer and Y_b’B ' layer；Wherein Y_a< Y, Y_b< Y, Y_a+Y_b=Y, Y_b< Y, Y_b’< Y, Y_b+Y_a’=Y, wherein Y_a、Y_b、Y_b’Can be identical or different, Y can be identical or different,

(2) by each layer after stretching in step (1), i.e. AY_aLayer and Y_bB layer, or A ' Y_a’Layer, Y_aAY_aLayer and Y_bB layer, or AY_aLayer, Y_bBY_bLayer and Y_a’A ' layer, or B ' Y_b’Layer, Y_aAY_aLayer and Y_bB layer, or AY_aLayer, Y_bBY_bLayer and Y_b’B ' layer, carries out lamination compound, is formed:

(i) AYB composite membrane, i.e. AY_aY_bB layer, wherein, Y_aLayer and Y_bLayer is compounded to form Y layer, Y_a, and Y_bLayer is identical or different；Or

(ii) A ' YAYB composite membrane, i.e. A ' Y_a’Y_aAY_aY_bB, wherein, Y_aLayer and Y_bLayer is compounded to form Y layer, Y_aLayer and Y_a’Layer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_a’Layer is identical or different；Or

(iii) AYBYA ' composite membrane, i.e. AY_aY_bBY_bY_a’A ' layer, wherein, Y_aLayer and Y_bLayer is compounded to form Y layer or Y_a’Layer and Y_bLayer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_a’Layer is identical or different,

(iv) B ' YAYB composite membrane, i.e. B ' Y_b’Y_aAY_aY_bB, wherein, Y_aLayer and Y_bLayer is compounded to form Y layer, Y_aLayer and Y_b’Layer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_b’Layer is identical or different；Or

(v) AYBYB ' composite membrane, i.e. AY_aY_bBY_bY_b’B ' layer, wherein, Y_aLayer and Y_bLayer is compounded to form Y layer or Y_b’Layer and Y_bLayer is compounded to form Y layer, and each Y layer is identical or different, each Y_a、Y_bAnd Y_b’Layer is identical or different.

24. the application of the multilayer complex films of any one of claim 1-22, it is for bill, marketable securities, leaflet and packaging material.

25. goods, it is prepared by the multilayer complex films face coat described in any one of claim 1-22 and printing, and described goods include leaflet, bill, marketable securities and packaging material.

26. goods as claimed in claim 25, it is characterised in that described leaflet is Front cover of book and periodical or picture album.