CN104149462A

CN104149462A - Propylene polymer multilayer composite membrane containing composite bonding layers as well as preparation method, application and products thereof

Info

Publication number: CN104149462A
Application number: CN201310179154.7A
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: 2014-11-19

Abstract

The invention provides a multilayer composite membrane. The multilayer composite membrane comprises a layer structure formed by compositing n AYBYC layer structures with each other via Y, wherein n is more than or equal to 2; A is the same or different; B is the same or different; C is the same or different; Y is the same or different; the A layers, B layers and C layers in the layer structure respectively independently comprise the same or different propylene polymers; Y is a composite bonding layer and is selected from an olefin polymer with melting point lower than 130 DEG C. The invention also provides a preparation method and application of the multilayer composite membrane as well as products comprising the multilayer composite membrane. The propylene polymer multilayer composite membrane has the performances of high stiffness, high transparency, low-temperature resistance, high tear strength and the like.

Description

A kind of acrylic polymer multilayer complex films, its preparation method, purposes and goods thereof that contain 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 that comprise described composite membrane, belong to field of compound material.

Background technology

Biaxially oriented polypropylene (BOPP) film effectively utilizes the characteristics such as its good light weight, the transparency, mechanical strength, nontoxic, moistureproof, gas permeability is low, rigidity, for take the wide spectrum that packaging material are representative.Compound such as the packing and the lamination that are widely used in the products such as food, medicine, daily light industry, cigarette.A kind of purposes of BOPP film is to fit in paper surface, and as books, packing carton etc., play moistureproof and increase surface gloss.

BOPP film is generally the coextrusion structure of 3-5 layer, and step drawing production technology is mainly comprised of following operation: batching batch mixing, extruder extrude, by T-shaped die head extrude sheet, sheet chilling, to sheet by warm-up mill preheating, sheet longitudinal stretching, thermal finalization, preheating again, cross directional stretch, thermal finalization, cooling, sided corona treatment, rolling, cut and put in storage.A kind of Biaxially stretched multilayer polypropylene film is disclosed CN101160209A(Oji Paper), it is adding the two sides of the bidirectional stretching polypropylene film substrate layer that propylene polymer composition that inorganic compound powder forms obtains in acrylic polymer, possess the superficial layer and the back layer that contain acrylic polymer, acrylic polymer and the acrylic polymer in table/back layer in described substrate layer can be identical or different.It by adding inorganic compound powder in substrate layer, and obtaining even hidden power and whiteness thickness good, that almost there is no concave-convex surface is the film of 25-55 μ m.Described film obtains by the following method: the acrylic polymer that forms substrate layer is obtained to multi-layer sheet by itself known method co-extrusion modling, adopt simultaneously the biaxially oriented film forming method such as biaxial tension method or biaxial tension method be in turn stretched to 45～65 times of face multiplying powers (longitudinally * laterally) and obtain.Take and adopt biaxial tension method in turn as example, can pass through at the temperature of longitudinal 70～140 ° of C with after the scope stretching of 4.5～7.5 times, then under the temperature range of horizontal 120～190 ° of C under 7～12 times and face multiplying power (longitudinally * laterally) be stretched to after 45～65 times, at the temperature range heat fixation of 110～180 ° of C, obtain.

BOPP film has many desirable performances, as high tensile, and high-stiffness, the high grade of transparency etc.Yet the life cycle of BOPP film is short, is generally some months to year, some physical properties are as poor in resistance to low temperature, fall strength of briquette, tearing strength etc., are not suitable for the long-term printed matter using, packaging material etc.In addition, the thickness of existing bidirectional stretching polypropylene film is generally less than 50 μ m, and its deflection can not meet high-end demand.Therefore its some ranges of application have been restricted.

At present, industrial quarters requires physical property at some in high application, 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 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, 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.

A further object of the present invention is to provide the goods that comprise above-mentioned multilayer complex films.

The present invention is achieved through the following technical solutions:

A kind of multilayer complex films, it is characterized in that, it comprises the layer structure that n AYBYC layer structure is composited by Y each other, and n is more than or equal to 2, each A is identical or different, each B is identical or different, and each C is identical or different, and each Y is identical or different, wherein, A layer, B layer and C layer in described layer structure 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 ℃.

According to the present invention, in described multilayer complex films, n AYBYC layer structure is compound by Y order, compound according to the order of AYBYCYAYBYC.

According to the present invention, in described multilayer complex films, n AYBYC layer structure replaces compound, compound according to the order of AYBYCYCYBYA by Y.

According to the present invention, in described multilayer complex films, n AYBYC layer structure is unordered compound by 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 and/or C layer.

According to the present invention, described layer structure also comprises one deck A layer, is compound in the skin of outermost C layer by Y, and preferably its structure is (AYBYCY) _na, n is more than or equal to 2; Or by Y, be compound in the skin of outermost A layer, preferably its structure is A (YAYBYC) _n, n is more than or equal to 2.

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

According to the present invention, described layer structure also comprises one deck C layer, is compound in the skin of outermost C layer by Y, and preferably its structure is (AYBYCY) _nc, n is more than or equal to 2; Or by Y, be compound in the skin of outermost A layer, preferably its structure is C (YAYBYC) _n, n is more than or equal to 2.

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

According to the present invention, preferably the fusing point of the olefin polymer of Y layer is lower than 120 ℃, more preferably less than 110 ℃, also more preferably less than 100 ℃, most preferably lower than 90 ℃.Preferably the fusing point of the olefin polymer of Y layer is 75-120 ℃, more preferably 60-115 ℃, also more preferably 50-105 ℃.

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 ℃.

According to the present invention, the propylene copolymer in described Y layer is propylene and α-C _2-10the copolymer of alkene.Be α-C _2-10alkene, as comonomer, is preferably ethene, butylene, hexene or octene copolymer monomer.The fusing point of preferred described propylene copolymer is at 75-120 ℃.

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 copolymer monomer.The fusing point of preferred described ethylene copolymer is at 50-105 ℃.

According to the present invention, the ethylene copolymer of 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 ℃.

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 ℃, and its fusing point is lower than 120 ℃, preferably lower than 110 ℃, more preferably less than 100 ℃.

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 ℃, for example, be the copolymer of ethene and butylene, hexene or octene.Preferably, described metallocene quasi-polyethylene is the metallocene quasi-polyethylene that has an obvious melting peak on DSC curve, its fusing point is lower than 110 ℃, preferably lower than 100 ℃, or the described metallocene quasi-polyethylene metallocene quasi-polyethylene that is the rarest two obvious melting peaks on DSC curve, wherein the fusing point at first peak is between 75 ℃-105 ℃; The fusing point at second peak is between 105 ℃-125 ℃.

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

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

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

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

According to the present invention, described A layer, B layer or C layer are simple tension or biaxial tension independently of one another.

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

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

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

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

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

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

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

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

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

According to the present invention, for scheme (1).To laterally stretching of described A layer, to laterally stretching of described B layer, and the horizontal and vertical of described C layer all stretched; Or to laterally stretching of described A layer, to longitudinally stretching of described B layer, and the horizontal and vertical of described C layer all stretched; Or to longitudinally stretching of described A layer, to laterally stretching of described B layer, and the horizontal and vertical of described C layer all stretched; Or to longitudinally stretching of described A layer, to longitudinally stretching of described B layer, and the horizontal and vertical of described C layer all stretched; More preferably, the cross directional stretch multiplying power of described A layer/C layer is identical or approaching with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer/C layer is identical or approaching with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (2).To laterally stretching of described A layer, the horizontal and vertical of described B layer stretched, and the horizontal and vertical of described C layer all stretched; Or to longitudinally stretching of described A layer, the horizontal and vertical of described B layer stretched, and the horizontal and vertical of described C layer all stretched; More preferably, the cross directional stretch multiplying power of described A layer/C layer is identical or approaching with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer/C layer is identical or approaching with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (3).To laterally stretching of described A layer, the horizontal and vertical of described B layer all stretched, and laterally stretching to described C layer; Or to laterally stretching of described A layer, the horizontal and vertical of described B layer all stretched, and longitudinally stretching to described C layer; Or to longitudinally stretching of described A layer, the horizontal and vertical of described B layer all stretched, and laterally stretching to described C layer; Or to longitudinally stretching of described A layer, the horizontal and vertical of described B layer all stretched, and longitudinally stretching to described C layer; More preferably, the cross directional stretch multiplying power of described A layer/C layer is identical or approaching with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer/C layer is identical or approaching with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (4).The horizontal and vertical of described A layer all stretched, to laterally stretching of described B layer, and laterally stretching to described C layer; Or the horizontal and vertical of described A layer all stretched, to laterally stretching of described B layer, and longitudinally stretching to described C layer; Or the horizontal and vertical of described A layer all stretched, to longitudinally stretching of described B layer, and laterally stretching to described C layer; Or the horizontal and vertical of described A layer all stretched, to longitudinally stretching of described B layer, and longitudinally stretching to described C layer; More preferably, the cross directional stretch multiplying power of described A layer/C layer is identical or approaching with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer/C layer is identical or approaching with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (5).The horizontal and vertical of described A layer all stretched, the horizontal and vertical of described B layer stretched, and laterally stretching to described C layer; Or the horizontal and vertical of described A layer all stretched, the horizontal and vertical of described B layer stretched, and longitudinally stretching to described C layer; More preferably, the cross directional stretch multiplying power of described A layer/C layer is identical or approaching with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer/C layer is identical or approaching with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (6).The horizontal and vertical of described A layer all stretched, to laterally stretching of described B layer, and the horizontal and vertical of described C layer stretched; Or the horizontal and vertical of described A layer all stretched, to longitudinally stretching of described B layer, and the horizontal and vertical of described C layer stretched; More preferably, the cross directional stretch multiplying power of described A layer/C layer is identical or approaching with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer/C layer is identical or approaching with the cross directional stretch multiplying power of described B layer.

According to the present invention, for scheme (7).Different to draw ratio in length and breadth to draw ratio and B layer in length and breadth of described A layer/C layer; Preferably, the longitudinal stretching multiplying power of described A layer/C layer is greater than cross directional stretch multiplying power, and the cross directional stretch multiplying power of B layer is greater than longitudinal stretching multiplying power; More preferably, described A layer/C layer in length and breadth to being inversely proportional to draw ratio in length and breadth of draw ratio and B layer, the longitudinal stretching of A layer/C layer and the ratio of cross directional stretch equal the cross directional stretch of B layer and the ratio of longitudinal stretching.More preferably, the longitudinal stretching multiplying power of described A layer/C 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/C 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/C 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/C layer is identical with the longitudinal stretching multiplying power of described B layer.

According to the present invention, for scheme (8).The stretching ratio of described A layer/C layer is different from the stretching ratio of described B layer; Preferably, the stretching ratio of described A layer/C layer is greater than the stretching ratio of described B layer, or the stretching ratio of described A layer/C layer is less than the stretching ratio of described B layer.

According to the present invention, for scheme (8).Preferably, to laterally stretching of described A layer/C layer, and longitudinally stretching to described B layer; Or to longitudinally stretching of described A layer/C layer, and laterally stretching to described B layer.More preferably, the cross directional stretch multiplying power of described A layer/C layer is identical or approaching with the longitudinal stretching multiplying power of described B layer; Or the longitudinal stretching multiplying power of described A layer/C layer is identical or approaching with the cross directional stretch multiplying power of described B layer

According to the present invention, the thickness of described multilayer complex films is 50-150 μ m, preferred 60-120 μ m, more preferably 70-100 μ m, also more preferably 80-90 μ m.

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

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, Y _band Y _cthickness sum, Y _aand Y _cthickness sum, Y _cand Y _cthickness sum, Y _aand Y _athickness sum.

According to the present invention, described Y layer is that individual layer or double-decker are selected from one of following combination:

(1) AYBYCYAYBYC layer structure, preferably Y is that double-deck structure of composite membrane is AY _ay _bbY _by _ccY _cy _aaY _ay _bbY _by _cc, wherein the thickness of Y layer is respectively Y _aand Y _bthickness sum, Y _band Y _cthickness sum, Y _aand Y _cthickness sum.

(2) AYBYCYCYBYA layer structure, preferably Y is that double-deck structure of composite membrane is AY _ay _bbY _by _ccY _cy _ccY _cy _bbY _by _aa, wherein the thickness of Y layer is respectively Y _aand Y _bthickness sum, Y _band Y _cthickness sum, Y _cand Y _cthickness sum.

(3) AYBYCYAYBYCYCYBYA layer structure, preferably Y is that double-deck structure of composite membrane is AY _ay _bbY _by _ccY _cy _aaY _ay _bbY _by _ccY _cy _ccY _cy _bbY _by _aa, wherein the thickness of Y layer is respectively Y _aand Y _bthickness sum, Y _band Y _cthickness sum, Y _cand Y _athickness sum, Y _cand Y _cthickness sum.

(4) AYBYCYCYBYAYAYBYC layer structure, preferably Y is that double-deck structure of composite membrane is AY _ay _bbY _by _ccY _cy _ccY _cy _bbY _by _aaY _ay _aaY _ay _bbY _by _cc, wherein the thickness of Y layer is respectively Y _aand Y _bthickness sum, Y _band Y _cthickness sum, Y _cand Y _cthickness sum, Y _aand Y _athickness sum.

(5) AYBYCYCYBYAYAYBYCYAYBYC layer structure, preferably Y is that double-deck structure of composite membrane is:

AY _ay _bbY _by _ccY _cy _ccY _cy _bbY _by _aaY _ay _aaY _ay _bbY _by _ccY _cy _aaY _ay _bbY _by _cc, wherein the thickness of Y layer is respectively Y _aand Y _bthickness sum, Y _band Y _cthickness sum, Y _cand Y _cthickness sum, Y _aand Y _athickness sum, or Y _band Y _bthickness sum, or Y _aand Y _cthickness sum.

According to the present invention, in above-mentioned multilayer complex films, the thickness of each Y layer is 0.5-24 μ m, preferred 1-20 μ m, more preferably 2-15 μ m, also more preferably 5-10 μ m, most preferably 6-8 μ m.Wherein, Y _a, Y _band Y _cthickness be respectively 0.1-24 μ m, 0.5-20 μ m, more preferably 1-15 μ m, more preferably 2-10 μ m also, the thickness of most preferably 5-8 μ m, and Y layer is Y _aand Y _bthickness sum, or Y _band Y _cthickness sum, or Y _aand Y _cthickness sum, or Y _aand Y _athickness sum, or Y _band Y _bthickness sum, or Y _cand Y _cthickness sum, i.e. Y=Y _a+ Y _b, Y=Y _b+ Y _c, Y=Y _a+ Y _c, Y=Y _a+ Y _a, Y=Y _b+ Y _b, Y=Y _c+ Y _c.

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 membrane thickness, is preferably no more 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 horizontal and vertical ratio be 1.5:1.0 to 7.0:1.0, preferred 2.0:1.0-5.0:1.0.

Or, in above-mentioned multilayer complex films the tensile strength of B layer horizontal and vertical ratio be 1.0:1.5 to 1.0:7.0, preferred 1.0:2.0-1.0:5.0.

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

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

According to the present invention, for simple tension, the laterally or longitudinally stretching ratio of the A layer in described multilayer complex films be 1-12.5 doubly, preferably cross directional stretch multiplying power be 7-12.5 doubly or longitudinal stretching multiplying power be 1-6 doubly; The vertical or horizontal stretching ratio of B layer be 1-12.5 doubly, preferably longitudinal stretching multiplying power be 7-12.5 doubly or cross directional stretch multiplying power be 1-6 doubly; Laterally or the longitudinally stretching ratio of C layer be 1-12.5 doubly, preferably cross directional stretch multiplying power be 7-12.5 doubly or longitudinal stretching multiplying power be 1-6 doubly; .

According to the present invention, in above-mentioned multilayer complex films tensile strength, deflection and tear-resistant intensity, horizontal and vertical test value ratio is that 0.7:1.0 is 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 or C layer acrylic polymer be Noblen or propylene copolymer preferably, typically be isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the atactic polypropylene copolymer of a small amount of comonomer and the polypropylene blend of 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 described A layer or B layer or C layer acrylic polymer is 148 to 170 ° of C, preferably 150-167 ℃; 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, preferably 1-8g/10min.

According to the present invention, in A layer or B layer or C layer, also can add again another resin, as Petropols or hydrogenated petroleum resin, to change performances 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 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 of preparing above-mentioned multilayer complex films, and it comprises the following steps:

(1) AY _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer, CY _clayer, Y _ccY _cthe preparation of layer:

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, BY _blayer, CY _clayer, Y _ccY _clayer;

(2) by each layer (AY obtaining in step (1) _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer, CY _clayer, Y _ccY _clayer) carry out lamination compound, obtain described composite membrane:

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

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

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

(1) by multi-layer co-extruded, preparing structure is n the polyolefin sheets that AYBYC layer structure is composited by Y each other, n is more than or equal to 2, each A is identical or different, and each B is identical or different, and each C is identical or different, each Y is identical or different, if also comprise one deck A layer, prepare another A layer and by Y, be compound in the outer field polyolefin sheets of the outermost C layer of said polyolefins sheet material or A layer, preferably its structure is (AYBYCY) _na, n is more than or equal to 2; Or A (YAYBYC) _n, n is more than or equal to 2; If also comprise one deck B layer, prepare another B layer and by Y, be compound in the outer field polyolefin sheets of the outermost C layer of said polyolefins sheet material or A layer, preferably its structure is (AYBYCY) _nb, n is more than or equal to 2; Or B (YAYBYC) _n, n is more than or equal to 2.If also comprise one deck C layer, prepare another C layer and by Y, be compound in the outer field polyolefin sheets of the outermost C layer of said polyolefins sheet material or A layer, preferably its structure is (AYBYCY) _nc, n is more than or equal to 2; Or C (YAYBYC) _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), obtain described composite membrane.

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

It is (AYBYCY) for structure that the present invention also provides a kind of use periosteum legal system _maYBYCYCYBYA (YCYBYA) _mthe method (wherein m is more than or equal to 0, and each A layer, B layer, C layer, 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, then under uniform temperature environment, carry out simple tension or biaxial tension and process structure for (AYBYCY) _maYBYCY _1/2concentric periosteum;

(2) periosteum after stretching in step (1) is carried out to lamination above 10-30 ℃ of the raw materials used peak melting point of Y layer compound, obtain structure for (AYBYCY) _maYBYCYCYBYA (YCYBYA) _mmultilayer complex films, two Y wherein _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 with multiplying power, stretching.

According to the present invention, the two-sided sided corona treatment of all passing through of the multilayer complex films of above-mentioned preparation method's gained is according to the present invention, and the two-sided sided corona treatment of all passing through of the composite membrane of step (2) gained makes more than its initial surface tension force reaches 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, more than surface tension reaches 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 makes by multilayer complex films face coat and the printing described in aforementioned any one, 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 referring to table 1.

The performance of table 1 composite membrane of the present invention

Describe in detail

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

According to the present invention, described A layer, B layer and C layer mainly comprise acrylic polymer.Described acrylic polymer is Noblen or propylene copolymer or polypropene composition preferably; Typically be isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have 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 ethene or higher ɑ-alkene, as ethene, butylene, hexene or octene etc.The content of comonomer is preferably 0.2wt% to 2.0wt%, and more preferably 0.35wt% is to 0.85wt%.These acrylic polymers of the present invention can be the mixtures that contains one kind or two or more polymer, the composition of for example different Noblen of molecular weight, or propylene and a small amount of alpha-olefin random copolymer.Polypropylene-based polymer of the present invention, is generally according to the vistanex of polyacrylic title manufacture, sale, and normally density is 0.890～0.930g/cm ³, MFR(ASTM D1238, load 2160g, 230 ℃ of temperature) be 0.5～60g/10 minute, be preferably 0.5～20g/10 minute, more preferably 0.5-15g/10min, the also Noblen of 1～5g/10 minute more preferably.

According to the present invention, the fusing point of described acrylic polymer is 148 to 170 ° of C, preferably 150-167 ℃; 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, preferably 1-8g/10min.The conventional Noblen of industrial BOPP film has: the T38F of Lanzhou Petrochemical and Daqing petrochemical; The T36F of Dalian petrochemical industry; This class Noblen 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 approximately 155 ° of C-165 ° of C.

In the polymer of described A layer, B layer and C layer, also can sneak into part ethylene-based polymer, for example high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE).Wherein, not or have a small amount of comonomer, comonomer is not propylene or higher alpha-olefin to HDPE, as ethene, butylene, hexene or octene etc., and has about 0.941g/cm ³or higher (about 0.948g/cm for example ³to about 0.968g/cm ³, preferred about 0.952g/cm ³to about 0.962g/cm ³) density, for example approximately 130 ° of C are to fusing point and the 0.2-50g/10min of approximately 148 ° of C, preferably 1-45g/10min, the more preferably melt index of 2-40g/10min (measuring according to ASTM D1238).LDPE has at 0.912g/cm ³to 0.94g/cm ³(0.915g/cm for example ³to 0.928g/cm ³) density and the preferred 1-45g/10min of 0.2-50g/10min(, the more preferably 2-40g/10min of scope) melt index (measuring according to ASTM D1238).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has for example 1-10g/10min of 0.2-50g/10min() melt index (measuring according to ASTM D1238) and at 0.857g/cm ³to 0.950g/cm ³, preferred 0.905g/cm ³to 0.940g/cm ³, more preferably 0.910g/cm ³to 0.928g/cm ³the density of scope.In addition ethylene-based polymer can also be terpolymer, as ethylene/butene/hexene copolymer, and ethylene/butylene/octene copolymer or ethylene/hexene/octene copolymer; These copolymers have for example 1-10g/10min of 0.2-50g/10min() melt index (measuring according to ASTM D1238) and at 0.857g/cm ³to 0.950g/cm ³, preferred 0.905g/cm ³to 0.940g/cm ³, more preferably 0.910g/cm ³to 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 quality, elastic modelling quantity and the moment of inertia of Paper or cardboard.Wherein, the deflection of cardboard or title flexural rigidity, refer to, apart from fixture 5cm place, the sample vertically clipping applied to certain load, observes from the crooked 3.81mm width of sample center line, and sample to 15 ° required moment of flexure, represents with gcm.Paper sheet stiffness is a very important index, directly affects the size (another influence factor is cross cutting pressure) of folding line deflection, thereby affects finished product moulding.Deflection is little, and finished product is easy to conquassation, warpage; Deflection is large, and finished product is difficult to moulding.

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

The additive that can also master batch form in the polymer of described A layer, B layer and C layer adds approximately 0.01～5.0 quality %.Described additive is preferably 0.01～3.0 quality %, more preferably 0.05～1.0 quality %.

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

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

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

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

As described nucleator, can use such as D-sorbite system, organophosphorus ester slaine system, metal salt of organic carboxylic acid system, rosin series nucleator etc.

As described heat-resisting stabilizing agent, for example can use 2,6-di-tert-butyl-4-methy phenol (BHT) etc.

In described A layer, B layer and C strata compound, also can add delustring masterbatch to produce Extinctive thin film, or add pearly-lustre masterbatch to produce pearly-lustre film.

Propylene polymer thin film of the present invention can as required, be implemented the surface treatments such as sided corona treatment, flame treatment to single or double.In addition, according to purposes, for giving heat sealability, can be overleaf the film of the low melting point polymer such as the upper independent lamination of the layer random copolymer of alpha-olefin that contains high-pressure process low density polyethylene (LDPE), linear low density polyethylene (LLDPE), crystallinity or low-crystalline ethene and carbon number 3～10 or the random copolymer of propylene and ethene or more than 4 alpha-olefin of carbon number, polybutene, ethene-vinyl acetate copolymer, or the film of the lamination composition that contains them.In addition, in order to improve the cementability with other material, can with adhesives such as imines, carbamates, be fixed processing to oriented film surface, 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, in stretching-machine, at certain temperature and speed, in a direction (vertical or horizontal) or on vertical both direction (longitudinally, laterally), stretch and make film.The so-called direction of extruding processing along film that longitudinally refers to, so-calledly laterally refers to that vertical thin-film extrudes the direction of processing.To draw ratio, refer in length and breadth the ratio of longitudinal stretching multiplying power and cross directional stretch multiplying power.

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

(1) AY _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer, Y _ccY _clayer, CY _cthe preparation of tunic

Adopt the method preparation of simple tension or biaxial tension, for biaxial tension, can adopt substep biaxial tension method in turn, 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 → 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, stretch greatly, and sizing and cooling.

According to the present invention, described chilling refers to that to use cooling fluid to carry out cooling, and preferably cooling fluid is cooling water.The effect of described chilling is in order to make crystallization refinement, thereby improves transparency and deflection.

According to the present invention, described in extrude as multi-layer co-extruded.Described extrude to adopt melt extrude.

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

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

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

(b) sheet enters in length and breadth to the preheat roll of the some in tensioning system again and carries out two-sided preheating, and preheat roll temperature general control is at 90-150 ℃, preferably 100-120 ℃.Reach after the draft temperature (more than softening point, fusing point following) of regulation, by draw roll, carry out longitudinal stretching, draft temperature is controlled at 90-150 ℃, preferred 100-120 ℃, 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 _blayer, Y _ccY _clayer, CY _cthe requirement of tunic is set.Film after stretching is heat-treated by setting roller, and described setting temperature is 100-140 ℃, is preferably 110-120 ℃, to eliminate the internal stress of film, reduces shrinkage factor longitudinally.

(c) film after longitudinal stretching enters cross directional stretch system, first carries out preheating section preheating, and preheat roll temperature general control is at 100-160 ℃, preferably 110-140 ℃, more preferably 115-130 ℃.Reach after the draft temperature (more than softening point, fusing point is following) of regulation, then by expanding the track of spoke, carry out cross directional stretch, the general 130-180 ℃ of control temperature of stretching-machine, preferably 140-160 ℃, then carries out thermal finalization processing, setting temperature is 60-120 ℃, preferably 70-110 ℃.Cross directional stretch multiplying power is according to AY _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer, Y _ccY _clayer, CY _cthe requirement of tunic is set.

(d) film going out after cross directional stretch system is cooling by chill roll, is then trimming, is sided corona treatment with that, is finally to carry out rolling.

(e) leave large volume film after equipment after depositing the Ageing Treatment of several days, just can cut, make the AY of Rack _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer, Y _ccY _clayer, CY _clayer 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 are similar, difference is only in synchro-draw process that longitudinal stretching and cross directional stretch synchronously carry out, namely longitudinal stretching and cross directional stretch complete a system inter-sync, and longitudinal stretching is asynchronous with cross directional stretch in step drawing, carry out.Thereby concrete operating condition and step drawing similar.At present, synchro-draw machine has two kinds of forms in the world, and a kind of is mechanical type, and a kind of 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 a plurality of AY _alayer, Y _aaY _alayer, Y _bbY _blayer, Y _ccY _clayer, CY _clayer, Y _bit is compound that B layer carries out lamination, obtains described composite membrane.

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

According to the present invention, the AY of step (1) gained _alayer, Y _aaY _alayer, Y _ccY _clayer, CY _clayer, Y _bbY _blayer, Y _bthe two-sided sided corona treatment of all passing through of B layer, makes more than its initial surface tension force reaches 44 dynes per centimeter.The surface tension of gained composite membrane is more than 36 dynes per centimeter.More preferably, more than surface tension reaches 38 dynes per centimeter.

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

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 → to synchro-draw → collapser, flatten → cut open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product in length and breadth.

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.

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 substep 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 will steep afterwards pipe and flatten and form multilayer film.Main production parameter: extruder temperature is 180-240 ℃, die head temperature is 190-230 ℃, chilled water temperature is 11-18 ℃, oven drying temperature: 330-450 ℃, draft temperature is 140 ℃.To draw ratio, according to the requirement of the draw ratio of multilayer film, carry out 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 are similar, and 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 will steep afterwards pipe and flatten and form multilayer film.Main production parameter: extruder temperature is 180-240 ℃, die head temperature is 190-230 ℃, chilled water temperature is 11-18 ℃, oven drying temperature: 330-450 ℃, draft temperature is 140 ℃.To draw ratio, according to the requirement of the draw ratio of multilayer film, carry out 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.

[purposes of multilayer complex films]

The present invention also provides a kind of goods, and its face coat by the multilayer complex films of aforementioned any one and printing make, 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 the composite membrane of embodiment 1 preparation, and it is AYBYCYAYBYC structure.

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

The specific embodiment

Below in conjunction with embodiment, the present invention is described, but those skilled in the art's understanding, described embodiment is not limiting the scope of the invention, any improvement of making on basis of the present invention, variation are all within protection scope of the present invention.

Embodiment 1:AYBYCYAYBYC structure or AYBYCYCYBYA structure,

Layer thickness profile: 10 μ m/1 μ m/20 μ m/1 μ m/10 μ m/1 μ m/10 μ m/1 μ m/20 μ m/1 μ m/10 μ m

A layer, B layer and C layer are all used the propylene copolymer that contains 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, B layer and C layer all add respectively Petropols, 10% weight that Petropols addition is each layer of gross weight.

Y layer is polyacrylic copolymer, contains ethene and butylene comonomer, and its fusing point (DSC mensuration) is 103 ℃.

Preparation AY _alayer and Y _aaY _alayer or two AY _alayer: by the multi-layer co-extruded sheet material of preparing, then process by 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 10 μ m, Y _alayer thickness is 0.5 μ m.

Prepare two Y _bbY _blayer: by the multi-layer co-extruded sheet material of preparing, then process by 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 20 μ m, Y _blayer thickness is 0.5 μ m.

Preparation Y _ccY _clayer and Y _cc layer or two Y _ccY _clayer: by the multi-layer co-extruded sheet material of preparing, then process by plain film method substep stretch processes, wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 5 times, and C layer thickness is 10 μ m, Y _clayer thickness is 0.5 μ m.

By AY _alayer, Y _bbY _blayer, Y _ccY _clayer, Y _aaY _alayer, Y _bbY _blayer, Y _cc layer passes through respectively sided corona treatment, and initial surface tension force is 45 dynes per centimeter, then by hot pressing, is compounded to form composite membrane, and structure is AYBYCYAYBYC structure (Y _aand Y _bbe compounded to form Y, Y _band Y _cbe compounded to form Y, Y _aand Y _cbe compounded to form Y), or by two AY _alayer, two Y _bbY _blayer and two Y _ccY _clayer passes through respectively sided corona treatment, and initial surface tension force is 45 dynes per centimeter, then by hot pressing, is compounded to form composite membrane, and structure is AYBYCYCYBYA(Y _aand Y _bbe compounded to form Y, Y _band Y _cbe compounded to form Y, Y _cand Y _cbe compounded to form Y), the thickness of Y is 1 μ m, overall film thickness is 85 μ m.

The mechanical property of film prepared by two kinds of layer structures is suitable, and wherein the performance test data of the film of AYBYCYAYBYC structure is listed in table 2.

Embodiment 2:AYBYCYAYBYC structure or AYBYCYCYBYA structure,

Layer thickness profile: 8 μ m/1 μ m/16 μ m/1 μ m/8 μ m/1 μ m/8 μ m/1 μ m/16 μ m/1 μ m/8 μ m

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

Y is ultra-low density polyethylene, contains octene copolymer monomer, and fusing point is 90.2 ℃.

By multi-layer co-extruded preparation AYBYCYAYBYC layer or AYBYCYCYBYA, above-mentioned coextruded layer is processed by plain film method stretch processes, wherein cross directional stretch multiplying power is 8 times, longitudinal stretching multiplying power is 5 times.

A layer thickness is 8 μ m, and B layer thickness is 16 μ m, and C layer thickness is 8 μ m, and the thickness of Y is 1 μ m, and overall film thickness is 69 μ m.

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

Embodiment 3:AYBYCYCYBYA structure,

Layer thickness profile: 7.5 μ m/1 μ m/15 μ m/1 μ m/7.5 μ m/1 μ m/7.5 μ m/1 μ m/15 μ m/1 μ m/7.5 μ m

A layer and C layer are 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 that contains ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.

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

Y layer is ultra-low density polyethylene, contains octene copolymer monomer, and fusing point is 90.2 ℃.

By multi-layer co-extruded, prepare concentric periosteum, then carrying out biaxial tension, to process structure be AYBYCY _1/2concentric periosteum, wherein cross directional stretch multiplying power is 8 times, longitudinal stretching multiplying power is 5 times; Again that above-mentioned periosteum lamination is compound, obtain the composite membrane that structure is AYBYCYCYBYA, wherein two Y _1/2be compounded to form Y.

A layer thickness is 7.5 μ m, and B layer thickness is 15 μ m, and C layer thickness is 7.5 μ m, and Y layer thickness is 1 μ m, and overall film thickness is 65 μ m.

The composite membrane of above-mentioned AYBYCYCYBYA is carried out to sided corona treatment, and initial surface tension force is 45 dyne.

Test data is listed in table 2.

Embodiment 4:AYBYCYAYBYC structure or AYBYCYCYBYA structure,

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

The preparation method of AYBYCYAYBYC structure or AYBYCYCYBYA structure is similar to embodiment 1, only:

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

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

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

A layer thickness is 10 μ m, and B layer thickness is 20 μ m, and C layer thickness is 10 μ m, and Y layer thickness is 1 μ m, and overall film thickness is 85 μ m.

The mechanical property of film prepared by two kinds of layer structures is suitable, and wherein the performance test data of the film of AYBYCYAYBYC structure is listed in table 3.

Embodiment 5:AYBYCYAYBYC structure or AYBYCYCYBYA structure,

Two A layers are all by simple tension processes, and wherein longitudinal stretching multiplying power is 10 times.

Two B layers are all by simple tension processes, and wherein cross directional stretch multiplying power is 10 times.

Two C layers are all by simple tension processes, and wherein longitudinal stretching multiplying power is 10 times.

A layer thickness is 8 μ m, and B layer thickness is 16 μ m, and C layer thickness is 8 μ m, and Y layer thickness is 1 μ m, and overall film thickness is 69 μ m.

Embodiment 6:AYBYCYAYBYC structure or AYBYCYCYBYA structure,

Layer thickness profile: 7.5 μ m/1 μ m/15 μ m/1 μ m/7.5 μ m/1 μ m/7.5 μ m/1 μ m/15 μ m/1 μ m/7.5 μ m.

Two A layers are all processed by stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 5 times.

Two equal pass two-way drawing process processing of B layer, wherein cross directional stretch multiplying power is 5 times, longitudinal stretching multiplying power is 9 times.

Two C layers are all processed by stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 5 times.

Embodiment 7:AYBYCYAYBYCYAYBYCYAYBYC structure (sequential organization) or AYBYCYCYBYAYAYBYCYCYBYA structure (alternating structure) or AYBYCYCYBYAYCYBYAYCYBYA structure (disordered structure)

A layer thickness is 7 μ m, and B layer thickness is 10 μ m, and C layer thickness is 7 μ m, and the thickness of Y is 1 μ m.

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

The preparation method of described layer structure is all similar to embodiment 1, only:

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

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

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

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

A layer thickness is 7 μ m, and B layer thickness is 10 μ m, and C layer thickness is 7 μ m, and Y layer thickness is 1 μ m, and overall film thickness is 107 μ m.

The mechanical property of film prepared by three kinds of layer structures is suitable, and wherein the performance test data of the film of AYBYCYAYBYCYAYBYCYAYBYC structure is listed in table 4.

Embodiment 8:AYBYCYAYBYCYAYBYCYAYBYC structure (sequential organization) or AYBYCYCYBYAYAYBYCYCYBYA structure (alternating structure) or AYBYCYCYBYAYCYBYAYCYBYA structure (disordered structure)

A layer thickness is 8 μ m, and B layer thickness is 11 μ m, and C layer thickness is 8 μ m, and the thickness of Y is 1 μ m.

By the described layer of multi-layer co-extruded preparation structure, above-mentioned coextruded layer is processed by plain film method stretch processes, wherein cross directional stretch multiplying power is 5 times, longitudinal stretching multiplying power is 8 times.

A layer thickness is 8 μ m, and B layer thickness is 11 μ m, and C layer thickness is 8 μ m, and the thickness of Y is 1 μ m, and overall film thickness is 119 μ m.

The mechanical property of film prepared by several layers of structure is suitable, and wherein the performance test data of the film of AYBYCYAYBYCYAYBYCYAYBYC structure is listed in table 4.

Embodiment 9:AYBYCYAYBYC structure or AYBYCYCYBYA structure,

Layer thickness profile: 10 μ m/1 μ m/20 μ m/1 μ m/10 μ m/1 μ m/10 μ m/1 μ m/20 μ m/1 μ m/10 μ m.

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

Two B layers are all by plain film method simple tension processes, and its cross directional stretch multiplying power is 5 times.

Two C layers are all by plain film method simple tension processes, and its longitudinal stretching multiplying power is 5 times.

The mechanical property of film prepared by two kinds of layer structures is suitable, and wherein the performance test data of the film of AYBYCYAYBYC structure is listed in table 4.

Embodiment 10:AYBYCYAYBYC structure or AYBYCYCYBYA structure,

Two A layers are processed by plain film method substep stretch processes, and wherein longitudinal stretching multiplying power is 12.5 times, and cross directional stretch multiplying power is 1.1 times, and thickness is 8 μ m.

Two B layers are processed by plain film method substep stretch processes, and wherein cross directional stretch multiplying power is 12.5 times, and longitudinal stretching multiplying power is 1.1 times, and thickness is 16 μ m.

Two C layers are by plain film method simple tension processes, and its longitudinal stretching multiplying power is 12.5 times, and thickness is 8 μ m.

The results of property of table 2 multilayer complex films

The results of property of table 3 multilayer complex films

The results of property of table 4 multilayer complex films

Claims

1. a multilayer complex films, it is characterized in that, it comprises the layer structure that n AYBYC layer structure is composited by Y each other, and n is more than or equal to 2, each A is identical or different, each B is identical or different, and each C is identical or different, and each Y is identical or different, wherein, A layer, B layer and C layer in described layer structure 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 ℃.

Preferably, described A layer, B layer and C layer are simple tension or biaxial tension independently of one another; Preferably, the draw ratio of A layer or stretching ratio are different from draw ratio or the stretching ratio of B layer and/or C layer; Preferably, the draw ratio of each A layer or stretching ratio are different; Preferably, the draw ratio of each B layer or stretching ratio are different; Preferably, the draw ratio of each C layer or stretching ratio are different.

2. according to the composite membrane of claim 1, it is characterized in that, the fusing point of described A layer or B layer is higher than the fusing point of Y layer, and its fusing point is poor is greater than 30 ℃, is preferably greater than 40 ℃, more preferably greater than 50 ℃;

Preferably the fusing point of the olefin polymer of Y layer is lower than 120 ℃, more preferably less than 110 ℃, also more preferably less than 100 ℃, most preferably lower than 90 ℃; Preferably the fusing point of the olefin polymer of Y layer is 75-120 ℃, more preferably 60-115 ℃, also more preferably 50-105 ℃;

Fusing point in preferred described Y layer is selected from propylene copolymer, ethylene copolymer or its mixture lower than the olefin polymer of 130 ℃;

Propylene copolymer in preferred 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 copolymer monomer, and the fusing point of preferred described propylene copolymer is at 75-120 ℃.

3. according to the multilayer complex films described in claim 1 to 2 any one, it is characterized in that, in described multilayer complex films, n AYBYC layer structure is compound by Y order, compound according to the order of AYBYCYAYBYC; Or n AYBYC layer structure replaces compound, compound according to the order of AYBYCYCYBYA in described multilayer complex films by Y; Moreover n AYBYC layer structure is unordered compound by Y in described multilayer complex films.

4. according to the multilayer complex films described in any one in claims 1 to 3, it is characterized in that, described layer structure also comprises one deck A layer, is compound in the skin of outermost C layer by Y, and preferably its structure is (AYBYCY) _na, n is more than or equal to 2; Or by Y, be compound in the skin of outermost A layer, preferably its structure is A (YAYBYC) _n, n is more than or equal to 2; Or described layer structure also comprises one deck B layer, is compound in the skin of outermost C layer by Y, preferably its structure is (AYBYCY) _nb, n is more than or equal to 2; Or by Y, be compound in the skin of outermost A layer, preferably its structure is B (YAYBYC) _n, n is more than or equal to 2; Or described layer structure also comprises one deck C layer, is compound in the skin of outermost C layer by Y, preferably its structure is (AYBYCY) _nc, n is more than or equal to 2; Or by Y, be compound in the skin of outermost A layer, preferably its structure is C (YAYBYC) _n, n is more than or equal to 2.

5. according to the multilayer complex films described in any one in claim 1 to 4, it is characterized in that,

The acrylic polymer of described A layer or B layer or C layer is Noblen or propylene copolymer preferably, typically be isotaxy homopolymers, or for different isotactic polypropylenes, atactic polypropylene, syndiotactic polypropylene, have the atactic propene copolymer of a small amount of comonomer and the polypropylene blend of ethylene copolymer-modified isotactic polypropylene, comonomer is ethene or higher alpha-olefin, as ethene, butylene, hexene or octene etc.;

Preferably, the fusing point of the acrylic polymer of described A layer or B layer or C layer is 148 to 170 ° of C, preferably 150-167 ° of 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, preferably 1-8g/10min;

Preferably, in A layer or B layer or C layer, also can add again another resin, as Petropols or hydrogenated petroleum resin, be preferably C ₅-C ₉petropols or C ₅-C ₉hydrogenated petroleum resin; Its addition is the 1-30% weight of each layer of gross weight, preferred 2-20% weight, more preferably 3-15% weight, also more preferably 4-10% weight.

6. a preparation method for the multilayer complex films of any one in claim 1 to 5, it comprises the following steps:

(2) by each layer (AY obtaining in step (1) _alayer, Y _aaY _alayer, Y _bbY _blayer, BY _blayer, CY _clayer, Y _ccY _clayer) carry out lamination compound, obtain described composite membrane.

7. the preparation method of the multilayer complex films of any one (wherein each A layer, B layer, C layer, Y layer have identical stretching ratio or draw ratio) in a claim 1 to 5, it comprises the following steps:

(1) by multi-layer co-extruded, preparing structure is n the polyolefin sheets that AYBYC layer structure is composited by Y each other, n is more than or equal to 2, each A is identical or different, and each B is identical or different, and each C is identical or different, each Y is identical or different, if also comprise one deck A layer, prepare another A layer and by Y, be compound in the outer field polyolefin sheets of the outermost C layer of said polyolefins sheet material or A layer, preferably its structure is (AYBYCY) _na, n is more than or equal to 2; Or A (YAYBYC) _n, n is more than or equal to 2; If also comprise one deck B layer, prepare another B layer and by Y, be compound in the outer field polyolefin sheets of the outermost C layer of said polyolefins sheet material or A layer, preferably its structure is (AYBYCY) _nb, n is more than or equal to 2; Or B (YAYBYC) _n, n is more than or equal to 2.If also comprise one deck C layer, prepare another C layer and by Y, be compound in the outer field polyolefin sheets of the outermost C layer of said polyolefins sheet material or A layer, preferably its structure is (AYBYCY) _nc, n is more than or equal to 2; Or C (YAYBYC) _n, n is more than or equal to 2;

In a claim 1 to 5 preparation method of the multilayer complex films of any one (wherein the structure of composite membrane is (AYBYCY) _maYBYCYCYBYA (YCYBYA) _m, m is more than or equal to 0, and each A layer, B layer, C layer, Y layer have identical stretching ratio or draw ratio), it comprises the following steps:

9. an application for the multilayer complex films of any one in claim 1 to 5, it is for bill, marketable securities, printed matter and packaging material.

10. goods, its face coat by the multilayer complex films of any one in claim 1 to 5 and printing make, and described goods comprise printed matter (as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.