CN104149439B - A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof containing composite tie layer - Google Patents

Abstract

The invention provides a kind of multilayer complex films, it comprises n AYB Rotating fields each other by Rotating fields that Y is composited, n is more than or equal to 2, each A is identical or different, each B is identical or different, and each Y is identical or different, and the A layer in described Rotating fields and B layer comprise identical or different acrylic polymer independently of one another, Y is composite tie layer, is selected from fusing point lower than the olefin polymer of 130 DEG C.The present invention also provides the preparation method of above-mentioned multilayer complex films, its purposes and comprises the goods of described multilayer complex films.Acrylic polymer multilayer complex films of the present invention has the performances such as high-stiffness, high transparent, low temperature resistant, high-tear strength.

Description

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

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

The characteristics such as Biaxially oriented polypropylene (BOPP) film effectively utilizes its excellent light weight, the transparency, mechanical strength, nontoxic, moistureproof, gas permeability is low, rigidity, for taking packaging material as the wide spectrum of representative.Such as be widely used in packaging and the lamination compound of the products such as food, medicine, daily light industry, cigarette.A kind of purposes of BOPP film fits in paper surface, and as books, packing carton etc., play a part moistureproof and increase surface gloss.

BOPP film is generally the coextrusion structure of 3-5 layer, and step drawing production technology forms primarily of following operation: batching batch mixing, extruder are extruded, extruded sheet by T-shaped die head, sheet chilling, to sheet by warm-up mill preheating, sheet longitudinal stretching, thermal finalization, again preheating, cross directional stretch, thermal finalization, cooling, sided corona treatment, rolling, cut and put in storage.CN101160209A(Oji Paper) in disclose a kind of Biaxially stretched multilayer polypropylene film, the two sides of the bidirectional stretching polypropylene film substrate layer that its propylene polymer composition adding inorganic compound powder in by acrylic polymer obtains, possess the superficial layer containing acrylic polymer and back layer, the acrylic polymer in the acrylic polymer in described substrate layer and surface/back layer can be identical or different.It by adding inorganic compound powder in substrate layer, obtain even hidden power and whiteness excellent, the thickness that almost do not have concave-convex surface is the film of 25-55 μm.Described film obtains by the following method: the acrylic polymer forming substrate layer is obtained multi-layer sheet by itself known method co-extrusion modling, adopts the biaxially oriented film such as biaxial tension method or biaxial tension method in turn forming method be simultaneously stretched to face multiplying power (longitudinal × horizontal) 45 ~ 65 times and obtain.To adopt biaxial tension method in turn, after stretching with the scope of 4.5 ~ 7.5 times at the temperature of longitudinal 70 ~ 140 ° of C, then under the temperature range of horizontal 120 ~ 190 ° of C under 7 ~ 12 times and after face multiplying power (longitudinally × laterally) is stretched to 45 ~ 65 times, 110 ~ 180 ° of C temperature range heat fixation and obtain.

BOPP film has many desirable performances, as high tensile, and high-stiffness, the high grade of transparency etc.But the life cycle of BOPP film is short, be generally some months by 1 year, some physical properties are as poor in resistance to low temperature, fall strength of briquette, tearing strength etc., are not suitable for the printed matter of Long-Time Service, packaging material etc.In addition, the thickness of existing bidirectional stretching polypropylene film is generally less than 50 μm, and its deflection can not meet high-end demand.Therefore its some ranges of application are constrained.

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

Therefore, industrial quarters need a kind of there is traditional B OPP film high transparent and high-stiffness but there is the film of resistance to low temperature, high-tear strength simultaneously.

Summary of the invention

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

Another object of the present invention is to provide the preparation method of above-mentioned multilayer complex films.

Another object of the present invention is to provide the purposes of above-mentioned multilayer complex films.

Another object of the present invention is to provide the goods comprising above-mentioned multilayer complex films.

The present invention is achieved through the following technical solutions:

A kind of multilayer complex films, it comprises n AYB Rotating fields each other by Rotating fields that Y is composited, n is more than or equal to 2, each A is identical or different, each B is identical or different, and each Y is identical or different, and the A layer in described Rotating fields and B layer comprise identical or different acrylic polymer independently of one another, Y is composite tie layer, is selected from fusing point lower than the olefin polymer of 130 DEG C.

According to the present invention, described A layer be simple tension or biaxial tension, described B layer be simple tension or biaxial tension.

According to the present invention, in described multilayer complex films, n AYB Rotating fields is by Y order compound, namely according to the order compound of AYBYAYB.

According to the present invention, in described multilayer complex films, n AYB Rotating fields replaces compound by Y, namely according to the order compound of AYBYBYA.

According to the present invention, in described multilayer complex films, n AYB Rotating fields is by the unordered compound of Y.

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

According to the present invention, described Rotating fields also comprises one deck A layer, is compound in the skin of outermost B layer by Y, and preferably its structure is (AYBY) _na, n are more than or equal to 2; Or the skin of outermost A layer is compound in by Y, preferably its structure is A (YAYB) _n, n is more than or equal to 2.

According to the present invention, described Rotating fields also comprises one deck B layer, is compound in the skin of outermost B layer by Y, and preferably its structure is (AYBY) _nb, n are more than or equal to 2; Or the skin of outermost A layer is compound in by Y, preferably its structure is B (YAYB) _n, n is more than or equal to 2.

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 greater than 30 DEG C, is preferably greater than 40 DEG C, more preferably greater than 50 DEG C.

According to the present invention, the fusing point of the olefin polymer of preferred Y layer lower than 120 DEG C, more preferably less than 110 DEG C, also more preferably less than 100 DEG C, most preferably 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, also more preferably 50-105 DEG C.

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

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, as comonomer, is preferably ethene, 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 ethene 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 ethene and polar monomer, and 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 fusing point in described Y layer is selected from metallocene class polypropylene lower than the olefin polymer of 130 DEG C, its fusing point lower than 120 DEG C, preferably lower than 110 DEG C, more preferably less than 100 DEG C.

According to the present invention, the fusing point in described Y layer is selected from metallocene quasi-polyethylene lower than the olefin polymer of 130 DEG C, such as, be the copolymer of ethene and butylene, hexene or octene.Preferably, described metallocene quasi-polyethylene is metallocene quasi-polyethylene DSC curve having an obvious melting peak, its fusing point is lower than 110 DEG C, preferably lower 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, the A layer in described multilayer complex films is single layer structure or multi-layer co-extruded structure.

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

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

According to the present invention, preferably, the draw ratio of the draw ratio of A layer or stretching ratio and B layer or stretching ratio different.Preferably, the draw ratio of each A layer or stretching ratio different.Preferably, the draw ratio of each B layer or stretching ratio different.Preferably, described A layer and B layer comprise one of following combination:

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

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

(3) A layer and B layer are biaxial tension; Or

(4) A layer and B layer are simple tension;

According to the present invention, for scheme (1).The transverse direction of described A layer is stretched, and described the horizontal and vertical of B layer is all stretched; Or the longitudinal direction of described A layer is stretched, and described the horizontal and vertical of B layer is all stretched.More preferably, the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (2).Described the horizontal and vertical of A layer is stretched, and the transverse direction of described B layer is stretched; Or described the horizontal and vertical of A layer is stretched, and the longitudinal direction of described B layer is stretched.More preferably, the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (3).Different to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer; Preferably, the longitudinal stretching multiplying power of described A layer is greater than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described B layer is greater than longitudinal stretching multiplying power, or the cross directional stretch multiplying power of described A layer is greater than longitudinal stretching multiplying power, and the longitudinal stretching multiplying power of described B layer is greater than cross directional stretch multiplying power; More preferably, being inversely proportional to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer, namely the described longitudinal stretching of A layer and the ratio of cross directional stretch equal the described cross directional stretch of B layer and the ratio of longitudinal stretching.More preferably, the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described B layer; Also more preferably, 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, for scheme (4).The stretching ratio of described A layer is different from the stretching ratio of described B layer; Preferably, the stretching ratio of described A layer is greater than the stretching ratio of described B layer, or the stretching ratio of described A layer is less than the stretching ratio of described B layer.

According to the present invention, for scheme (4).Preferably, the transverse direction of described A layer is stretched, and the longitudinal direction of described B layer is stretched; Or the longitudinal direction of described A layer is stretched, and the transverse direction of described B layer is stretched.More preferably, the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer.

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 is synchronous are; Or

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

According to the present invention, the thickness of above-mentioned multilayer complex films is 50-120 μm, preferred 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 or B layer is 5-65 μm, preferred 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 individual layer or double-decker.

According to the present invention, described Y layer thickness is Y _aand Y _bthickness sum, or be Y _band Y _bthickness sum, or be Y _aand Y _athickness sum, wherein each Y _aand Y _bidentical or different.

According to the present invention, described double-deck technical scheme is preferably as follows one of combination:

(1) AYBYAYB Rotating fields, is preferably AY _ay _bbY _by _aaY _ay _bb, wherein the thickness of each Y layer is Y _aand Y _bthickness sum.

(2) AYBYBYA Rotating fields, is preferably AY _ay _bbY _by _bbY _by _aa, wherein the thickness of Y layer is Y _aand Y _bthickness sum, or be Y _band Y _bthickness sum.

(3) AYBYAYBYA Rotating fields, is preferably AY _ay _bbY _by _aaY _ay _bbY _by _aa, wherein the thickness of Y layer is Y _aand Y _bthickness sum.

(4) AYAYBYAYB Rotating fields, is preferably AY _ay _aaY _ay _bbY _by _aaY _ay _bb, wherein the thickness of Y layer is Y _aand Y _bthickness sum, or be Y _aand Y _athickness sum.

(5) AYBYAYBYB Rotating fields, is preferably AY _ay _bbY _by _aaY _ay _bbY _by _bb, wherein the thickness of Y layer is Y _aand Y _bthickness sum, or be Y _band Y _bthickness sum.

(6) BYAYBYAYB Rotating fields, is preferably BY _by _aaY _ay _bbY _by _aaY _ay _bb, wherein the thickness of Y layer is Y _aand Y _bthickness sum.

(7) AYBYAYBYAYB Rotating fields, is preferably AY _ay _bbY _by _aaY _ay _bbY _by _aaY _ay _bb, wherein the thickness of each Y layer is Y _aand Y _bthickness sum.

(8) AYBYBYAYAYB Rotating fields, is preferably AY _ay _bbY _by _bbY _by _aaY _ay _bb, wherein the thickness of Y layer is Y _aand Y _bthickness sum, or be Y _band Y _bthickness sum, or be Y _aand Y _athickness sum.

(9) AYBYAYBYBYA Rotating fields, is preferably AY _ay _bbY _by _aaY _ay _bbY _by _bbY _by _aa, wherein the thickness of each Y layer is Y _aand Y _bthickness sum, or be Y _band Y _bthickness sum.

According to the present invention, in above-mentioned multilayer complex films, the thickness of each Y layer is 0.5-24 μm, preferred 1-20 μm, more preferably 2-15 μm, also more preferably 5-10 μm, most preferably 6-8 μm.

Wherein, Y _a, Y _bthickness be respectively 0.1-24 μm, 0.5-20 μm, more preferably 1-15 μm, also more preferably 2-10 μm, most preferably 5-8 μm, and the thickness Y of Y layer _aand Y _bthickness sum, or be Y _aand Y _athickness sum, or be Y _band Y _bthickness sum, i.e. Y=Y _a+ Y _b, Y=Y _a+ Y _a, Y=Y _b+ Y _b.

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

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

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

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

According to the present invention, for biaxial tension, 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 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.

According to the present invention, for biaxial tension, the Y layer in above-mentioned multilayer complex films (comprises Y _a, Y _b) cross directional stretch multiplying power be 7-12.5 doubly, longitudinal stretching multiplying power be 1-6 doubly, preferred cross directional stretch multiplying power be 8-10 doubly, longitudinal stretching multiplying power be 2-4 doubly.Or Y layer (comprises Y _a, Y _b) cross directional stretch multiplying power be 1-6 doubly, longitudinal stretching multiplying power be 7-12.5 doubly, preferred cross directional stretch multiplying power be 2-4 doubly, longitudinal stretching multiplying power be 8-10 doubly.

According to the present invention, for simple tension, the stretching ratio of the A layer in above-mentioned multilayer complex films or the transverse direction of B layer or longitudinal direction be 1-12.5 doubly, preferred cross directional stretch multiplying power be 7-12.5 doubly or longitudinal stretching multiplying power be 1-6 doubly.

According to the present invention, for simple tension, the stretching ratio of the Y layer in above-mentioned multilayer complex films is identical with A layer, or the stretching ratio of Y layer is identical with B layer.Preferably, Y _athe stretching ratio of layer is identical with A layer, Y _bthe stretching ratio of layer is identical with B layer.

According to the present invention, for simple tension, the Y layer in above-mentioned multilayer complex films (comprises Y _a, Y _b) stretching ratio be 1-12.5 doubly, preferred cross directional stretch multiplying power be 7-12.5 doubly or longitudinal stretching multiplying power be 1-6 doubly.

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

The vertical transverse tensile strength of described multilayer complex films is greater than 100MPa, is preferably greater than 120MPa, more preferably greater than 140MPa.According to the present invention, described A layer or B layer acrylic polymer are preferably Noblen or propylene copolymer, typically be isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the polypropylene blend of the atactic polypropylene copolymer of a small amount of comonomer and ethylene copolymer-modified isotactic polypropylene.Comonomer is ethene or higher ɑ-alkene, as ethene, butylene, hexene or octene etc.

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

According to the present invention, in A layer or B layer, also can add another resin again, as Petropols or hydrogenated petroleum resin, to change the performances such as such as heat sealer, gas permeability, deflection and intensity, be preferably C ₅-C ₉petropols or C ₅-C ₉hydrogenated petroleum resin.Its addition is the 1-30% weight of each layer gross weight, preferred 2--20% weight, more preferably 3-15% weight, also more preferably 4-10% weight.

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

(1) by multi-layer co-extruded, prepare polyolefin sheets, then under uniform temperature environment, carry out simple tension or biaxial tension processes: AY _alayer, Y _aaY _alayer, Y _bbY _blayer, Y _bb layer, wherein Y _a<Y, Y _b<Y, Y _a+ Y _b=Y, Y _a+ Y _a=Y, Y _b+ Y _b=Y; Y _a, Y _bcan be identical or different;

(2) by each layer after stretching in step (1) (as AY _alayer, Y _aaY _alayer, Y _bbY _blayer, Y _bb layer) carry out lamination compound, obtain described composite membrane, wherein, Y _alayer and Y _blayer is compounded to form Y layer, Y _alayer and Y _alayer is compounded to form Y layer, Y _blayer and Y _blayer is compounded to form Y layer, Y _aand Y _blayer is identical or different;

According to the present invention, the stretching in described step (1) is preferably under the temperature environment of 130-185 ° of C, and preferred each layer described has identical stretching ratio, such as A and Y _alayer has identical stretching ratio or draw ratio, Y _bwith B layer, there is identical stretching ratio or draw ratio.

According to the present invention, each layer of step (1) gained two-sided all through sided corona treatment, makes its initial surface tension reach more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, surface tension reaches more than 38 dynes per centimeter.

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

(1) by multi-layer co-extruded, prepare n AYB Rotating fields each other by polyolefin sheets that Y is composited, n is more than or equal to 2, each A is identical or different, and each B is identical or different, and each Y is identical or different, if also comprise one deck A layer, then prepare another A layer is compound in said polyolefins sheet material outermost B layer or A layer outer field polyolefin sheets by Y, preferably its structure is (AYBY) _na, n are more than or equal to 2; Or A (YAYB) _n, n is more than or equal to 2; If also comprise one deck B layer, then prepare another B layer is compound in said polyolefins sheet material outermost B layer or A layer outer field polyolefin sheets by Y, preferably its structure is (AYBY) _nb, n are more than or equal to 2; Or B (YAYB) _n, n is more than or equal to 2.

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

Stretching in described step (2), preferably under the temperature environment of 130-185 ° of C, is preferably carried out same multiplying power and is stretched (synchronous or substep can).

The present invention also provides a kind of periosteum legal system that uses to be (AYBY) for structure _maYBYBYA (YBYA) _mthe method (wherein m is more than or equal to 0, and wherein A layer, B layer and Y layer have identical stretching ratio or draw ratio) of multilayer complex films, it comprises the following steps:

(1) by multi-layer co-extruded, prepare concentric periosteum, under uniform temperature environment, then carry out simple tension or biaxial tension process structure for (AYBY) _maYBY _1/2concentric periosteum;

(2) periosteum after stretching in step (1) is carried out lamination compound at the above 10-30 of the peak melting point that Y layer is raw materials used DEG C, obtain structure for (AYBY) _maYBYBYA (YBYA) _mmultilayer complex films, wherein two Y _1/2be compounded to form Y.

Stretching in described step (1) is preferably under the temperature environment of 130-185 ° of C, and preferred described periosteum carries out synchronously stretching with multiplying power.

According to the present invention, the multilayer complex films of above-mentioned preparation method's gained is two-sided all through sided corona treatment, makes its initial surface tension reach more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, surface tension reaches more than 38 dynes per centimeter.

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

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

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

Beneficial effect of the present invention:

Acrylic polymer multilayer complex films prepared by the present invention, have excellent combination property, its tensile strength, deflection and tear-resistant intensity are all very high, and its vertical and horizontal performance has good balance, and have the good transparency, concrete performance is see table 1.

The performance of table 1 composite membrane of the present invention

Describe in detail

[composition of A layer and B layer]

According to the present invention, the polymer of described A layer and B layer mainly comprises acrylic polymer.Described acrylic polymer is preferably Noblen or propylene copolymer or polypropene composition; Typically be isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the polypropylene blend of the atactic polypropylene copolymer of a small amount of comonomer and/or ethylene copolymer-modified isotactic polypropylene.The comonomer of polypropylene copolymer is ethene or higher ɑ-alkene, as ethene, butylene, hexene or octene etc.The content of comonomer is preferably 0.2wt% to 2.0wt%, is more preferably 0.35wt% to 0.85wt%.These acrylic polymers of the present invention can be the mixtures containing one kind or two or more polymer, the Noblen that such as molecular weight is different, or the composition of propylene and a small amount of alpha-olefin random copolymer.Polypropylene-based polymer of the present invention, is generally the vistanex according to polyacrylic title manufacture, sale, and normally density is 0.890 ~ 0.930g/cm ³, MFR(ASTMD1238, load 2160g, temperature 230 DEG C) be 0.5 ~ 60g/10 minute, be preferably 0.5 ~ 20g/10 minute, more preferably 0.5-15g/10min, be also 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, preferred 150-167 DEG C; More preferably 155 ° of C-165 ° of C; Molecular weight distribution (GPC test) is 2-16, is preferably 4-10; Melt index is 0.5-10g/10min, preferred 1-8g/10min.The polypropylene homopolymer that industrial BOPP film is conventional has: the T38F of Lanzhou Petrochemical and Daqing petrochemical; The T36F of Dalian petrochemical industry; This kind of polypropylene homopolymer according to ASTMD-1238 test melt index (MI) can be about 0.2-20g/10min, preferred 0.5-15g/10min, fusing point can be between about 155 ° of C-165 ° of C.

Also ethylene-based polymer can be mixed into, such as part high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE) in the polymer of described A layer and B layer.Wherein, HDPE not or have a small amount of comonomer, and does not have about 0.941g/cm ³or higher (such as about 0.948g/cm ³-0.968g/cm ³, preferred 0.952g/cm ³to about 0.962g/cm ³) density, such as about 130 ° of C to the fusing point of about 148 ° of C and 1 to 50g/10min, the preferably melt index (measuring according to ASTMD1238) of 1 to 45g/10min.LDPE is homopolymer polymer, and has at 0.912g/cm ³to 0.94g/cm ³(such as 0.915g/cm ³to 0.928g/cm ³) the density of scope and 0.2 to 50g/10min(such as 1 to 10g/10min) melt index (measuring according to ASTMD1238); LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has 0.2 to 50g/10min(such as 1 to 10g/10min) melt index (measuring according to ASTMD1238) and 0.857 to 0.950g/cm ³, preferably 0.905 to 0.940g/cm ³, more preferably 0.910 to 0.928g/cm ³the density of scope.In addition ethylene-based polymer can also be terpolymer, as ethylene/butene/hexene, and ethylene/butylene/octene or ethylene/hexene/octene; These copolymers have 0.2 to 50g/10min(such as 1 to 10g/10min) melt index (measuring according to ASTMD1238) and 0.857 to 0.950g/cm ³, preferably 0.905 to 0.940g/cm ³, more preferably 0.910 to 0.928g/cm ³the density of scope.

Deflection of the present invention refers to that Paper or cardboard supports resistant to bending strength character.Deflection is directly proportional to EI/W value, and wherein W, E and I are respectively the quality of Paper or cardboard, elastic modelling quantity and the moment of inertia.Wherein, the deflection of cardboard or claim flexural rigidity, referring to applying certain load apart from fixture 5cm place to the sample vertically clipped, observing from sample camber 3.81mm width, and the moment of flexure needed for sample to 15 °, represents with gcm.Paper sheet stiffness is a very important index, directly affect the size (another influence factor is d ie cutting press) of folding line deflection, thus it is shaping to affect finished product.Deflection is little, and finished product is easy to conquassation, warpage; Deflection is large, and finished product is difficult to shaping.

In order to improve the deflection of multilayer complex films of the present invention further, and the performance such as such as heat sealer, gas permeability and intensity, can add another resin in A layer and B layer, as Petropols, hydrogenated petroleum resin etc., preferably as C ₅-C ₉petropols or C ₅-C ₉hydrogenated petroleum resin.Its addition is the 1-30% weight of each layer gross weight, preferred 2-20% weight, more preferably 3-15% weight, also more preferably 4-10% weight.

Master batch form the additive of about 0.01%-5% can also be added in the polymer of described A layer and B layer.Described additive is preferably 0.01 ~ 3.0 quality %, more preferably 0.05 ~ 1.0 quality %.

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

As described antiblocking agent, antiblocking agent well known in the art can be used, as silica, talcum, mica, zeolite, or metal alkoxide be sintered the inorganic compound particles such as the metal oxide that obtains; Or the organic compound such as polymethyl methacrylate, melamine resin, melamine urea resin, mylar.Wherein, silica, polymethyl methacrylate is particularly preferably used from resistance to blocking aspect.

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

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

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

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

Also can add delustring masterbatch in the polymer of described A layer and B layer to produce Extinctive thin film, or add pearly-lustre masterbatch to produce pearly-lustre film.

Biaxially stretched multilayer polypropylene film of the present invention as required, can implement the surface treatment such as sided corona treatment, flame treatment to single or double.In addition, according to purposes, for giving heat sealability, can overleaf on layer independent lamination contain the film of high-pressure process low-density polyethylene, linear low density polyethylene (LLDPE), crystallinity or the random copolymer of alpha-olefin of low-crystalline ethene and carbon number 3 ~ 10 or the low melting point polymer such as random copolymer, polybutene, ethene-vinyl acetate copolymer of the alpha-olefin of propylene and ethene or carbon number more than 4, or lamination contains the film of their composition.In addition, in order to improve the cementability with other material, process can be fixed to adhesives such as oriented film surface imines, carbamates, also can the maleic anhydride modified polyolefin of lamination.

[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 film.What is called longitudinally refers to the direction of extruding processing along film, and what is called laterally refers to that vertical thin-film extrudes the direction of processing.The ratio of longitudinal stretching multiplying power and cross directional stretch multiplying power is referred in length and breadth to draw ratio.

So-called plain film method, that first the melt of olefin polymer is made sheet material or thick film by long and narrow head, then, in stretching-machine, at certain temperature and speed, go up in vertical both direction (longitudinal direction, transverse direction) or carry out in a single direction stretching and make film.

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

(1) AY _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _bthe preparation of tunic

Adopt the method preparation of simple tension or biaxial tension, for biaxial tension, substep biaxial tension method in turn can be adopted, also can adopt synchro-draw method.

Described drawing process can be plain film method.

For biaxial tension, the technical process of described plain film method comprises synchro-draw process, comprises the steps:

Prepare burden → extrude → chilling → is in length and breadth to synchro-draw → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.

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

Prepare burden → extrude → chilling → longitudinal stretching → cross directional stretch → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.

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

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

According to the present invention, described chilling refers to and uses cooling fluid to cool, and preferred cooling fluid is cooling water.The effect of described chilling is to make crystallization refinement, thus improves transparency and deflection.

According to the present invention, described in extrude as multi-layer co-extruded.Describedly extrude employing and melt extrude.

According to the present invention, described batching comprises prepares burden according to the requirement of formula, can pass through electronic measurement.

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

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

B () sheet enters and carries out two-sided preheating to the preheat roll of the some in tensioning system in length and breadth, preheat roll temperature general control at 90-150 DEG C, preferred 100-120 DEG C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, carry out longitudinal stretching by draw roll, draft temperature controls at 90-150 DEG C, preferred 100-120 DEG C, and drawing process can a step, also can twice stretching or stretch for three times.Longitudinal stretching multiplying power is according to AY _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _bthe requirement of tunic sets.Film after stretching is heat-treated by setting roller, and described setting temperature is 100-140 DEG C, is preferably 110-120 DEG C, to eliminate the internal stress of film, reduces longitudinal shrinkage factor.

C the film after () longitudinal stretching enters cross directional stretch system, first carry out preheating section preheating, preheat roll temperature general control at 100-160 DEG C, preferred 110-140 DEG C, more preferably 115-130 DEG C.After reaching the draft temperature (more than softening point, below fusing point) of regulation, the track then by expanding spoke carries out cross directional stretch, the general 130-180 DEG C of control temperature of stretching-machine, preferred 140-160 DEG C, then carries out thermal finalization process, setting temperature is 60-120 DEG C, preferred 70-110 DEG C.Cross directional stretch multiplying power is according to AY _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _bthe requirement of tunic sets.

Film d () goes out cross directional stretch system after is cooled by chill roll, is then trimming, is sided corona treatment with that, is finally carry out rolling.

E () leaves the large volume film after equipment after the Ageing Treatment depositing several days, just can cut, make the AY of Rack _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer film.

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

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

Prepare burden → extrude → chilling → vertical or horizontal stretching → traction and optional surface treatment → rolling → Ageing Treatment → cut → product.

Concrete step and above-mentioned biaxial tension method are similar.

(2) lamination

By above-mentioned AY _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer carries out lamination compound, obtains described composite membrane.

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

According to the present invention, the AY of step (1) gained _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer two-sided all through sided corona treatment, make its initial surface tension reach more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, surface tension reaches more than 38 dynes per centimeter.

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

(1) by multi-layer co-extruded, prepare n AYB Rotating fields each other by polyolefin sheets that Y is composited, n is more than or equal to 2, each A is identical or different, and each B is identical or different, and each Y is identical or different, if also comprise one deck A layer, then prepare another A layer is compound in said polyolefins sheet material outermost B layer or A layer outer field polyolefin sheets by Y, preferably its structure is (AYBY) _na, n are more than or equal to 2; Or A (YAYB) _n, n is more than or equal to 2; If also comprise one deck B layer, then prepare another B layer is compound in said polyolefins sheet material outermost B layer or A layer outer field polyolefin sheets by Y, preferably its structure is (AYBY) _nb, n are more than or equal to 2; Or B (YAYB) _n, n is more than or equal to 2.

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

Stretching in described step (2), preferably under the temperature environment of 130-185 ° of C, is preferably carried out same multiplying power and is stretched (synchronous or substep can).

The plain film method simple tension related in the plain film method simple tension used in the method or bidirectional extending method and above-mentioned first method or biaxial tension similar.

The present invention also provides a kind of periosteum legal system that uses to be (AYBY) for structure _maYBYBYA (YBYA) _mthe method (wherein m be more than or equal to 0, A layer, B layer and Y layer there is identical stretching ratio or draw ratio) of multilayer complex films, comprise the following steps:

(1) by multi-layer co-extruded, prepare concentric periosteum, under uniform temperature environment, then carry out simple tension or biaxial tension process structure for (AYBY) _maYBY _1/2concentric periosteum;

(2) periosteum after stretching in step (1) is carried out lamination compound at the above 10-30 of the peak melting point that Y layer is raw materials used DEG C, obtain structure for (AYBY) _maYBYBYA (YBYA) _mmultilayer complex films, wherein two Y _1/2be compounded to form Y.

Stretching in described step (1) is preferably under the temperature environment of 130-185 ° of C, and preferred described periosteum carries out synchronously stretching with multiplying power.

According to the present invention, described periosteum method comprises bidirectional extending method and simple tension method.

For bidirectional extending method, comprising synchro-draw and step drawing.

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

Prepare burden → extrude → chilling → female film → dewater → baker Far-infrared Heating → in length and breadth flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product to synchro-draw → collapser.

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

Prepare burden → extrude → chilling → female film → dewater → baker Far-infrared Heating → longitudinal stretching → cross directional stretch → collapser flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.

According to the present invention, described chilling refers to and uses cooling fluid to cool, and preferred cooling fluid is cooling water.The effect of described chilling is to make crystallization refinement, thus improves transparency and deflection.

According to the present invention, described in extrude as multi-layer co-extruded.Describedly extrude employing and melt extrude.

According to the present invention, described batching comprises prepares burden according to the requirement of formula, can pass through electronic measurement.

Preferably, the concrete preparation method of described periosteum method is as follows:

(1) substep biaxial tension preparation method:

Periosteum method substep biaxial tension preparation method and plain film method step by step biaxial tension preparation method are similar, and its longitudinal stretching and cross directional stretch also substep carry out.Difference is, the die head of periosteum method is circular, and whole film-shaped Chengdu is that the form of steeping pipe completes, and is flattened by bubble pipe afterwards and forms multilayer film.Main production parameter: extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, and chilled water temperature is 11-18 DEG C, oven drying temperature: 330-450 DEG C, and draft temperature is 140 DEG C.Then carry out according to the requirement of the draw ratio of multilayer film to draw ratio in length and breadth.

(2) synchronous bidirectional stretching preparation method:

Periosteum method synchronous bidirectional stretching preparation method and plain film method synchronous bidirectional stretching preparation method similar, its longitudinal stretching and cross directional stretch also synchronously carry out.Difference is, the die head of periosteum method is circular, and whole film-shaped Chengdu is that the form of steeping pipe completes, and is flattened by bubble pipe afterwards and forms multilayer film.Main production parameter: extruder temperature is 180-240 DEG C, die head temperature is 190-230 DEG C, and chilled water temperature is 11-18 DEG C, oven drying temperature: 330-450 DEG C, and draft temperature is 140 DEG C.Then carry out according to the requirement of the draw ratio of multilayer film to draw ratio in length and breadth.

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

(multilayered molten is extruded) → chilling → female film → dewater → baker Far-infrared Heating → vertical or horizontal stretching → collapser of preparing burden → extrude flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.

Concrete step and above-mentioned biaxial tension method are similar.

According to the present invention, the layer of above-mentioned gained two-sided all through sided corona treatment, makes its initial surface tension reach more than 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, surface tension reaches more than 38 dynes per centimeter.

[purposes of multilayer complex films]

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

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

The present invention also provides a kind of goods, and its face coat by the multilayer complex films of aforementioned any one and printing obtain, and described goods comprise printed matter (as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.

Accompanying drawing explanation

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

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

Detailed description of the invention

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

Embodiment 1:AYBYAYB structure or AYBYBYA structure,

Layer thickness profile: 19 μm/2 μm/19 μm/2 μm/19 μm/2 μm/19 μm.

A layer and B layer all use the propylene copolymer containing ethene 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 96.2%.

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

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

Preparation AY _alayer, Y _aaY _alayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 5 times, and A layer thickness is 19 μm, Y _alayer thickness is 1 μm.

Preparation Y _bb layer, Y _bbY _blayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 9 times, and B layer thickness is 19 μm, Y _blayer thickness is 1 μm.

AY _alayer, Y _bbY _blayer, Y _aaY _alayer, 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 AYBYAYB structure (Y _alayer and Y _bbe compounded to form Y), or by two AY _alayer, Y _bbY _blayer 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 AYBYBYA(Y _alayer and Y _bbe compounded to form Y, Y _blayer and Y _bbe compounded to form Y)), the thickness of Y is 2 μm, and overall film thickness is 82 μm.

The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYB or AYBYBYA structure lists in table 2.

Embodiment 2:AYBYAYB structure or AYBYBYA structure,

Layer thickness profile: 28 μm/2 μm/28 μm/2 μm/28 μm/2 μm/28 μm.

A layer and B layer all use the propylene copolymer containing ethene 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%.

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

By multi-layer co-extruded preparation AYBYAYB layer or AYBYBYA, 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 1.1 times.

A layer thickness is 28 μm, and B layer thickness is 28 μm, and the thickness of Y is 2 μm, and overall film thickness is 118 μm.

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

The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYB structure lists in table 2.

Embodiment 3:AYBYAYBYA structure,

Layer thickness profile: 9 μm/1 μm/14 μm/1 μm/9 μm/1 μm/14 μm/1 μm/9 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 the propylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 96.4%.

A layer and B layer all add Petropols respectively, and Petropols addition is 30% weight of each layer gross weight.

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

Preparation AY _alayer, Y _aaY _alayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 6 times, and longitudinal stretching multiplying power is 3 times, and A layer thickness is 9 μm, Y _alayer thickness is 1 μm.

Preparation Y _bb layer, Y _bbY _blayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 3 times, and longitudinal stretching multiplying power is 6 times, and B layer thickness is 14 μm, Y _blayer thickness is 1 μm.

AY _alayer, Y _bbY _blayer, Y _aaY _alayer, 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 AYBYAYB structure (Y _alayer and Y _bbe compounded to form Y), or by two AY _alayer, Y _bbY _blayer 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 the thickness of AYBYBYA, Y is 2 μm, and overall film thickness is 59 μm.

The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYB structure lists in table 2.

Embodiment 4:AYBYAYB structure or AYBYBYA structure,

Layer thickness profile: 17 μm/2 μm/17 μm/2 μm/17 μm/2 μm/17 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 the propylene copolymer containing ethene, and ethylene contents is 0.25wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.Isotacticity is 96.0%.

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

Preparation AY _alayer, Y _aaY _alayer: prepare sheet material by multi-layer co-extruded, then by plain film method simple tension processes, wherein longitudinal stretching multiplying power is 11 times, and A layer thickness is 17 μm, Y _alayer thickness is 1 μm.

Preparation Y _bb layer, Y _bbY _blayer: prepare sheet material by multi-layer co-extruded, then by plain film method simple tension processes, wherein cross directional stretch multiplying power is 11 times, and B layer thickness is 17 μm, Y _blayer thickness is 1 μm.

AY _alayer, Y _bbY _blayer, Y _aaY _alayer, 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 AYBYAYB structure (Y _alayer and Y _bbe compounded to form Y), or by two AY _alayer, Y _bbY _blayer 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 AYBYBYA(Y _alayer and Y _bbe compounded to form Y, Y _blayer and Y _bbe compounded to form Y)), the thickness of Y is 2 μm, and overall film thickness is 74 μm.

The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYB structure lists in table 2.

Embodiment 5:AYBYBYA structure

Layer thickness profile: 28 μm/2 μm/28 μm/2 μm/28 μm/2 μm/28 μm.

A layer is Noblen, and molecular weight distribution is 5.5, and melt index is 2.9g/10min, and isotacticity is 96.2%.B layer is the propylene copolymer containing ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.3, and melt index is 2.9g/10min, and isotacticity is 95.9%.

A layer and B layer all add Petropols respectively, and Petropols addition is 1% weight of each layer gross weight.

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

By multi-layer co-extruded, prepare concentric periosteum, then carrying out biaxial tension, to process structure be AYBY _1/2concentric periosteum, wherein cross directional stretch multiplying power is 7 times, and longitudinal stretching multiplying power is 4 times; Again by above-mentioned periosteum lamination compound, obtain the composite membrane that structure is AYBYBYA, wherein two Y _1/2be compounded to form Y.

The composite membrane of AYBYBYA is carried out sided corona treatment, and initial surface tension is 45 dynes per centimeter, and A layer thickness is 28 μm, and B layer thickness is 28 μm, and Y layer thickness is 2 μm, and overall film thickness is 118 μm.

Test data lists in table 2.

Embodiment 6:BYAYBYAYB product structure,

Layer thickness profile: 9 μm/1 μm/14 μm/1 μm/9 μm/1 μm/14 μm/1 μm/9 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 the propylene copolymer containing ethene, 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 ' is the propylene copolymer containing ethene, and ethylene contents is 0.30wt%, and molecular weight distribution is 5.2, and melt index is 3.1g/10min, and isotacticity is 96.2%.

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

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

Preparation Y _aaY _alayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times, and A layer thickness is 14 μm, Y _alayer thickness is 0.5 μm.

Preparation Y _bb layer, Y _bbY _blayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times, and B layer thickness is 9 μm, Y _blayer thickness is 0.5 μm.

By Y _bb layer, Y _aaY _alayer, Y _bbY _blayer, Y _aaY _alayer, 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 BYAYBYAYB structure (Y _aand Y _bbe compounded to form Y), the thickness of Y is 1 μm, and overall film thickness is 59 μm.

The performance test data of film lists in table 2.

Embodiment 7:AYBYAYBYAYBYAYB structure (sequential organization) or AYBYBYAYAYBYBYA structure (alternating structure) or AYBYBYAYBYAYBYA structure (disordered structure)

The thickness of A with B is identical is 10 μm, and the thickness of Y is 1 μm.

A layer and B layer all use the propylene copolymer containing ethene 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%.

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

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

By multi-layer co-extruded preparation AYBYAYBYAYBYAYB structure (sequential organization) or AYBYBYAYAYBYBYA structure (alternating structure) or AYBYBYAYBYAYBYA structure (disordered structure), 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 9 times.

A layer thickness is 10 μm, and B layer thickness is 10 μm, and the thickness of Y is 1 μm, and overall film thickness is 87 μm.

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

The mechanical property of film prepared by three kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYBYAYBYAYB structure lists in table 2.

Embodiment 8:AYBYAYBYAYBYAYB structure (sequential organization) or AYBYBYAYAYBYBYA structure (alternating structure) or AYBYBYAYBYAYBYA structure (disordered structure)

The thickness of A with B is identical is 12 μm, and the thickness of Y is 1 μm.

A layer and B layer all use the propylene copolymer containing ethene 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%.

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

Preparation AY _alayer, Y _aaY _alayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 12.5 times, and longitudinal stretching multiplying power is 1.1 times, and A layer thickness is 12 μm, Y _alayer thickness is 0.5 μm.

Preparation Y _bb layer, Y _bbY _blayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 1.1 times, and longitudinal stretching multiplying power is 12.5 times, and B layer thickness is 12 μm, Y _blayer thickness is 0.5 μm.

By multiple AY _alayer, Y _bb layer, Y _bbY _blayer and Y _aaY _alayer is respectively through sided corona treatment, initial surface tension is 45 dynes per centimeter, then be compounded to form composite membrane by hot pressing, structure is AYBYAYBYAYBYAYB structure (sequential organization) or AYBYBYAYAYBYBYA structure (alternating structure) or AYBYBYAYBYAYBYA structure (disordered structure), the thickness of Y is 1 μm, and overall film thickness is 103 μm.

The mechanical property of film prepared by three kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYBYAYBYAYB structure lists in table 2.

Embodiment 9:AYBYAYB structure or AYBYBYA structure

Layer thickness profile: 19 μm/2 μm/15 μm/2 μm/19 μm/2 μm/15 μm.

A layer and B layer all use the propylene copolymer containing ethene 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 96.2%.

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

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

Preparation AY _alayer, Y _aaY _alayer: prepare sheet material by multi-layer co-extruded, then by plain film method simple tension processes, wherein cross directional stretch multiplying power is 9 times, and A layer thickness is 19 μm, Y _alayer thickness is 1 μm.

Preparation Y _bb layer, Y _bbY _blayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 9 times, and B layer thickness is 15 μm, Y _blayer thickness is 1 μm.

AY _alayer, Y _bbY _blayer, Y _aaY _alayer, 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 AYBYAYB structure (Y _alayer and Y _bbe compounded to form Y), or by two AY _alayer, Y _bbY _blayer 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 the thickness of AYBYBYA, Y is 2 μm, and overall film thickness is 74 μm.

The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYB structure lists in table 2.

Embodiment 10:AYBYAYB structure or AYBYBYA structure,

Layer thickness profile: 28 μm/2 μm/25 μm/2 μm/28 μm/2 μm/25 μm.

A layer and B layer all use the propylene copolymer containing ethene 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%.

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

Preparation AY _alayer, Y _aaY _alayer: prepare sheet material by multi-layer co-extruded, then by plain film method simple tension processes, wherein cross directional stretch multiplying power is 12.5 times, and A layer thickness is 28 μm, Y _alayer thickness is 1 μm.

Preparation Y _bb layer, Y _bbY _blayer: prepare sheet material by multi-layer co-extruded, then by the processing of plain film method substep stretch processes, wherein cross directional stretch multiplying power is 1.1 times, and longitudinal stretching multiplying power is 12.5 times, and B layer thickness is 25 μm, Y _blayer thickness is 1 μm.

AY _alayer, Y _bbY _blayer, Y _aaY _alayer, 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 AYBYAYB structure (Y _alayer and Y _bbe compounded to form Y), or by two AY _alayer, Y _bbY _blayer 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 the thickness of AYBYBYA, Y is 2 μm, and overall film thickness is 112 μm.

The mechanical property of film prepared by two kinds of Rotating fields is suitable, and wherein the performance test data of the film of AYBYAYB structure lists in table 2.

The results of property of table 2 multilayer complex films

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

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

Claims (39)

1. a multilayer complex films, it is characterized in that, it comprises n AYB Rotating fields each other by Rotating fields that Y is composited, n is more than or equal to 2, and each A is identical or different, and each B is identical or different, each Y is identical or different, A layer in described Rotating fields and B layer comprise identical or different acrylic polymer independently of one another, and Y is composite tie layer, are selected from fusing point lower than the olefin polymer of 130 DEG C; Described A layer be simple tension or biaxial tension, described B layer be simple tension or biaxial tension, and the draw ratio of the draw ratio of A layer or stretching ratio and B layer or stretching ratio different.

2. multilayer complex films according to claim 1, is characterized in that, the draw ratio of each A layer or stretching ratio difference.

3. multilayer complex films according to claim 1, is characterized in that, the draw ratio of each B layer or stretching ratio difference.

4. the multilayer complex films according to any one of claim 1-3, is characterized in that, described A layer and B layer comprise one of following combination:

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

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

(3) A layer and B layer are biaxial tension; Or

(4) A layer and B layer are simple tension;

For scheme (1), the transverse direction of described A layer is stretched, and described the horizontal and vertical of B layer is all stretched; Or the longitudinal direction of described A layer is stretched, and the horizontal and vertical of described B layer is all stretched;

For scheme (2), described the horizontal and vertical of A layer is stretched, and the transverse direction of described B layer is stretched; Or described the horizontal and vertical of A layer is stretched, and the longitudinal direction of described B layer is stretched;

For scheme (3), different to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer;

For scheme (4), the transverse direction of described A layer is stretched, and the longitudinal direction of described B layer is stretched; Or stretch to the longitudinal direction of described A layer, and stretch to the transverse direction of described B layer, the stretching ratio of described A layer is different from the stretching ratio of described B layer.

5. multilayer complex films according to claim 4, is characterized in that, for scheme (1), (2), (4), the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer;

For scheme (3), the longitudinal stretching multiplying power of described A layer is identical or close with the cross directional stretch multiplying power of described B layer, and the cross directional stretch multiplying power of described A layer is identical or close with the longitudinal stretching multiplying power of described B layer.

6. multilayer complex films according to claim 4, it is characterized in that, for scheme (3), the longitudinal stretching multiplying power of described A layer is greater than cross directional stretch multiplying power, and the cross directional stretch multiplying power of described B layer is greater than longitudinal stretching multiplying power, or the cross directional stretch multiplying power of described A layer is greater than longitudinal stretching multiplying power, and the longitudinal stretching multiplying power of described B layer is greater than cross directional stretch multiplying power;

For scheme (4), the stretching ratio of described A layer is greater than the stretching ratio of described B layer, or the stretching ratio of described A layer is less than the stretching ratio of described B layer.

7. multilayer complex films according to claim 4, it is characterized in that, for scheme (3), being inversely proportional to draw ratio in length and breadth in length and breadth to draw ratio and described B layer of described A layer, namely the described longitudinal stretching of A layer and the ratio of cross directional stretch equal the described cross directional stretch of B layer and the ratio of longitudinal stretching.

8. the multilayer complex films according to any one of claim 1-3, is characterized in that, the fusing point of described A layer or B layer is higher than the fusing point of Y layer.

9. multilayer complex films according to claim 8, is characterized in that, the fusing point difference of described A layer or B layer is greater than 30 DEG C.

10. multilayer complex films according to claim 9, is characterized in that, the fusing point difference of described A layer or B layer is greater than 40 DEG C.

11. multilayer complex films according to claim 9, is characterized in that, the fusing point difference of described A layer or B layer is greater than 50 DEG C.

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

13. multilayer complex films according to claim 12, is characterized in that, the fusing point of the olefin polymer of described Y layer is lower than 110 DEG C.

14. multilayer complex films according to claim 12, is characterized in that, the fusing point of the olefin polymer of described Y layer is lower than 100 DEG C.

15. multilayer complex films according to claim 12, is characterized in that, the fusing point of the olefin polymer of described Y layer is lower than 90 DEG C.

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

17. multilayer complex films according to claim 12, is characterized in that, the fusing point of the olefin polymer of described Y layer is 60-115 DEG C.

18. multilayer complex films according to claim 12, is characterized in that, the fusing point of the olefin polymer of described Y layer is 50-105 DEG C.

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

20. multilayer complex films according to claim 19, is characterized in that, 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, and the fusing point of described propylene copolymer is at 75-120 DEG C.

21. multilayer complex films according to claim 20, is characterized in that, described α-C ₂- ₁₀alkene is ethene, butylene, hexene or octene.

22. multilayer complex films according to any one of claim 1-3, it is characterized in that, in described multilayer complex films, n AYB Rotating fields is by Y order compound, namely according to the order compound of AYBYAYB; Or n AYB Rotating fields replaces compound by Y in described multilayer complex films, namely according to the order compound of AYBYBYA; Moreover n AYB Rotating fields is by the unordered compound of Y in described multilayer complex films.

23. multilayer complex films according to any one of claim 1 to 3, is characterized in that, described Rotating fields also comprises one deck A layer, are compound in the skin of outermost B layer by Y, or are compound in the skin of outermost A layer by Y; Or described Rotating fields also comprises one deck B layer, be compound in the skin of outermost B layer by Y, or be compound in the skin of outermost A layer by Y.

24. multilayer complex films according to claim 23, is characterized in that, described Rotating fields is (AYBY) _na, n are more than or equal to 2; Or be A (YAYB) _n, n is more than or equal to 2; Or described Rotating fields is (AYBY) _nb, n are more than or equal to 2; Or be B (YAYB) _n, n is more than or equal to 2.

25. multilayer complex films according to any one of claim 1 to 3, is characterized in that, the acrylic polymer of described A layer or B layer is Noblen or propylene copolymer, and comonomer is ethene or higher alpha-olefin.

26. multilayer complex films according to claim 25, it is characterized in that, the acrylic polymer of described A layer or B layer is isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the polypropylene blend of the atactic propene copolymer of a small amount of comonomer and ethylene copolymer-modified isotactic polypropylene, comonomer is ethene, butylene, hexene or octene.

27. multilayer complex films according to claim 25, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer is 148 to 170 DEG C; The molecular weight distribution of GPC test is 2-16; Melt index is 0.5-10g/10min.

28. multilayer complex films according to claim 27, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer is the molecular weight distribution that 150-167 DEG C, GPC test is 4-10, and melt index is 1-8g/10min.

29. multilayer complex films according to claim 27, is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer is 155 DEG C-165 DEG C.

30. multilayer complex films according to any one of claim 1 to 3, is characterized in that, in A layer or B layer, add another resin again.

31. multilayer complex films according to claim 30, is characterized in that, another resin described is Petropols or hydrogenated petroleum resin.

32. multilayer complex films according to claim 30, is characterized in that, another resin described is C ₅-C ₉petropols or C ₅-C ₉hydrogenated petroleum resin.

33. multilayer complex films according to claim 30, is characterized in that, the addition of another resin described is the 1-30% weight of each layer gross weight.

34. multilayer complex films according to claim 30, is characterized in that, the addition of another resin described is the 2-20% weight of each layer gross weight.

35. multilayer complex films according to claim 30, is characterized in that, the addition of another resin described is the 3-15% weight of each layer gross weight.

The preparation method of the multilayer complex films any one of 36. 1 kinds of claims 1 to 35, it comprises the following steps:

(1) by multi-layer co-extruded, prepare polyolefin sheets, then under uniform temperature environment, carry out simple tension or biaxial tension processes: AY _alayer, Y _aaY _alayer, Y _bbY _blayer, Y _bb layer, wherein Y _a<Y, Y _b<Y, Y _a+ Y _b=Y, Y _a+ Y _a=Y, Y _b+ Y _b=Y; Y _a, Y _bcan be identical or different;

(2) by each layer after stretching in step (1), i.e. AY _alayer, Y _aaY _alayer, Y _bbY _blayer, Y _bb layer, carries out lamination compound, obtains described composite membrane, wherein, and Y _alayer and Y _blayer is compounded to form Y layer, Y _alayer and Y _alayer is compounded to form Y layer, Y _blayer and Y _blayer is compounded to form Y layer, Y _aand Y _blayer is identical or different.

The application of the multilayer complex films any one of 37. 1 kinds of claims 1 to 35, it is for bill, marketable securities, printed matter and packaging material.

38. 1 kinds of goods, its face coat by the multilayer complex films any one of claims 1 to 35 and printing obtain, and described goods comprise printed matter, bill, marketable securities and packaging material.

39. goods as claimed in claim 38, it is characterized in that, described printed matter is Front cover of book and periodical or picture album.