CN104149460A - Propylene polymer- ethene polymer multi-layer composite membrane, preparation method therefor, applications thereof and product thereof - Google Patents
Propylene polymer- ethene polymer multi-layer composite membrane, preparation method therefor, applications thereof and product thereof Download PDFInfo
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Abstract
The invention provides a multi-layer composite membrane. The multi-layer composite membrane comprises an AXBXCXD-layer structure. Two layers of the A layer, the B layer, the C layer and the D layer in the layer structure contain the same propylene polymer or different propylene polymers and the other two layers contain the same ethene polymer or different ethene polymers. The X layers are binder layers. The A layer, the B layer, the C layer and the D layer are subjected to two-way stretch. The invention also provides a preparation method for the multi-layer composite membrane, applications and a product containing the multi-layer composite membrane. The multi-layer composite membrane has performances of high stiffness, high transparency, low temperature resistance, high tearing intensity and the like.
Description
Technical field
The present invention relates to a kind of acrylic polymer-ethylene-based 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 the wide spectrum taking packaging material as representative.The packaging and the lamination that are for example widely used in the products such as food, medicine, daily light industry, cigarette are compound.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 made up of following operation: batching batch mixing, extruder extrude, by T-shaped die head extrude sheet, sheet chilling, 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.CN101160209A(Oji Paper) in a kind of Biaxially stretched multilayer polypropylene film is disclosed, it adds the two sides of the bidirectional stretching polypropylene film substrate layer that propylene polymer composition that inorganic compound powder forms obtains in by acrylic polymer, possess the superficial layer and the back layer that contain acrylic polymer, the acrylic polymer in acrylic polymer and table/back layer in described substrate layer can be identical or different.It is by adding inorganic compound powder in substrate layer, obtain even hidden power and whiteness good, the preferred thickness 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.To adopt biaxial tension method in turn as example, can be by after at the temperature of longitudinal 70～140 ° of C, the scope with 4.5～7.5 times stretches, 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, obtain at the temperature range heat fixation of 110～180 ° of C.
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, 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 long-term printed matter, the packaging material etc. that use.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, has therefore restricted its some ranges of application.
The density polyethylene film with high stretching has been used to plastics package field.In No. 1287527th, BP, introduced some such films, they machine direction (MD) and laterally on (TD) both direction by the biaxial stretch-formed degree to being greater than 6.5 times.United States Patent (USP) relates to the uneven oriented film of twin shaft of LLDPE for No. 4680207, and it stretches and be no more than 6 times on machine direction, is orientated in the horizontal and is no more than 3 times and be less than the stretching on machine direction.
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-ethylene-based 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.
A further 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, described composite membrane comprises AXBXCXD layer structure, wherein, two-layerly in A layer, B layer, C layer and D layer in described layer structure contain identical or different acrylic polymer, two-layerly in addition contain identical or different ethylene-based polymer, X is adhesive layer, described A layer, B layer, C layer and D layer be biaxial tension and comprise one of following combination:
(1) described in, contain two-layer being inversely proportional to draw ratio in length and breadth of acrylic polymer, described in contain ethylene-based polymer two-layer being inversely proportional to draw ratio in length and breadth;
(2) described in, contain two-layer being inversely proportional to draw ratio in length and breadth of acrylic polymer, described in contain ethylene-based polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical;
(3) described in, contain acrylic polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical, described in contain ethylene-based polymer two-layer being inversely proportional to draw ratio in length and breadth;
(4) described in, contain acrylic polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical, described in contain ethylene-based polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical.
According to the present invention, describedly two-layer be inversely proportional to and represent that wherein the longitudinal stretching multiplying power of one deck and the ratio of cross directional stretch multiplying power equal the ratio of cross directional stretch multiplying power and the longitudinal stretching multiplying power of another layer to draw ratio in length and breadth, two-layer is that 1 expression cross directional stretch multiplying power equals longitudinal stretching multiplying power to draw ratio in length and breadth.
According to the present invention, for scheme (1).Preferably, the longitudinal stretching multiplying power of described two-layer middle one deck being inversely proportional to draw ratio is in length and breadth identical or close with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical or close with the longitudinal stretching multiplying power of another layer; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck being inversely proportional to draw ratio is in length and breadth identical with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical with the longitudinal stretching multiplying power of another layer.In addition, preferably, the longitudinal stretching multiplying power of described two-layer middle one deck that contains acrylic polymer with described in contain ethylene-based polymer the cross directional stretch multiplying power of two-layer middle one deck identical or close, and its cross directional stretch multiplying power with described in contain ethylene-based polymer the longitudinal stretching multiplying power of two-layer middle one deck identical or close; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck that contains acrylic polymer with described in contain ethylene-based polymer the cross directional stretch multiplying power of two-layer middle one deck identical, and its cross directional stretch multiplying power with described in contain ethylene-based polymer the longitudinal stretching multiplying power of two-layer middle one deck identical.
According to the present invention, for scheme (2).Preferably, the longitudinal stretching multiplying power of described two-layer middle one deck being inversely proportional to draw ratio is in length and breadth identical or close with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical or close with the longitudinal stretching multiplying power of another layer; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck being inversely proportional to draw ratio is in length and breadth identical with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical with the longitudinal stretching multiplying power of another layer.In addition, preferably, the described two-layer stretching ratio that contains ethylene-based polymer with described in contain acrylic polymer the cross directional stretch multiplying power of two-layer middle one deck identical or close, or, described in contain ethylene-based polymer two-layer stretching ratio with described in contain acrylic polymer the longitudinal stretching multiplying power of two-layer middle one deck identical or close; Also more preferably, the described two-layer stretching ratio that contains ethylene-based polymer with described in contain acrylic polymer the cross directional stretch multiplying power of two-layer middle one deck identical, or, described in contain ethylene-based polymer two-layer stretching ratio with described in contain acrylic polymer the longitudinal stretching multiplying power of two-layer middle one deck identical.
According to the present invention, for scheme (3).Preferably, the longitudinal stretching multiplying power of described two-layer middle one deck being inversely proportional to draw ratio is in length and breadth identical or close with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical or close with the longitudinal stretching multiplying power of another layer; Also more preferably, the longitudinal stretching multiplying power of described two-layer middle one deck being inversely proportional to draw ratio is in length and breadth identical with the cross directional stretch multiplying power of another layer, and its cross directional stretch multiplying power is identical with the longitudinal stretching multiplying power of another layer.In addition, preferably, the described two-layer stretching ratio that contains acrylic polymer with described in contain ethylene-based polymer the cross directional stretch multiplying power of two-layer middle one deck identical or close, or, described in contain acrylic polymer two-layer stretching ratio with described in contain ethylene-based polymer the longitudinal stretching multiplying power of two-layer middle one deck identical or close; Also more preferably, the described two-layer stretching ratio that contains acrylic polymer with described in contain ethylene-based polymer the cross directional stretch multiplying power of two-layer middle one deck identical, or, described in contain acrylic polymer two-layer stretching ratio with described in contain ethylene-based polymer the longitudinal stretching multiplying power of two-layer middle one deck identical.
According to the present invention, for scheme (4).Preferably, the two-layer stretching ratio that contains acrylic polymer described in described in contain ethylene-based polymer two-layer stretching ratio identical or close; More preferably, the two-layer stretching ratio that contains acrylic polymer described in described in contain ethylene-based polymer two-layer stretching ratio identical.
According to the present invention, A layer, B layer, C layer or the D 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, B layer, C layer or D layer is at least 2 layers, for example, be 2-15 layer, preferably 3-11 layer, more preferably 5-9 layer, also more preferably 6-8 layer.
According to the present invention, the material of the binding agent in described any one X layer is identical or different, is selected from: chlorinated polypropylene, polyurethane, acrylic resin, epoxy resin or its mixture.
According to the present invention, described chlorinated polypropylene adopts solwution method, suspension method or solid phase method that polypropylene chlorination is made.The mass content of chlorine is 20%-70%, and fusing point is less than 150 ° of C.
According to the present invention, described polyurethane is solvent-borne type, water-dispersion type or no-solvent type one-component or Multi-component Polyurethane adhesive.
According to the present invention, described acrylic resin is the adhesive that solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent contain acrylic acid or acrylates.
According to the present invention, described epoxy resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent epoxy type adhesive.
According to the present invention, the thickness of described multilayer complex films is 50-150 μ m, preferably 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 A layer, B layer, C layer or D layer is 5-65 μ m, preferably 10-55 μ m, more preferably 20-40 μ m.
According to the present invention, in described multilayer complex films, the thickness of each X layer is 0.5-10 μ m, is preferably 1-6 μ m, more preferably 2-5 μ m.
According to the present invention, in described multilayer complex films, the summation of all X layer thicknesses is no more than 30% of this composite membrane thickness, is preferably no more than 20%, more preferably no more than 15%, also more preferably no more than 10%.
According to the present invention, described two-layer thickness arbitrarily differs and is no more than 20%, is preferably no more than 15%, more preferably no more than 10%.
According to the present invention, the tensile strength that contains the one deck in same polymer two-layer in described multilayer complex films 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; The tensile strength of another layer horizontal and vertical ratio be 1.0:1.5 to 1.0:7.0, preferably 1.0:2.0 is to 1.0:5.0.
According to the present invention, the cross directional stretch multiplying power that contains the one deck in same polymer two-layer in described multilayer complex films be 7-12.5 doubly, longitudinal stretching multiplying power be 1-6 doubly, preferably cross directional stretch multiplying power be 8-10 doubly, longitudinal stretching multiplying power be 2-4 doubly; The cross directional stretch multiplying power of another layer 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, in the tensile strength of described multilayer complex films, 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 acrylic polymer 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.
According to the present invention, the fusing point of described acrylic polymer 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.
According to the present invention, described ethylene-based polymer is high density polyethylene (HDPE), high-pressure process low density polyethylene (LDPE) or low-pressure process LLDPE preferably.The about 0.941g/cm of density of high density polyethylene (HDPE)
3or higher, preferred about 0.948g/cm
3to about 0.968g/cm
3, more preferably from about 0.952g/cm
3to about 0.962g/cm
3; Approximately 130 ° of C of fusing point are to approximately 148 ° of C; Melt index (measuring according to ASTM D1238) is 0.2-50g/10min, preferably 1-45g/10min, more preferably 2-40g/10min.The density of low density polyethylene (LDPE) is about 0.912g/cm
3to about 0.94g/cm
3, preferably 0.915g/cm
3to 0.928g/cm
3; Melt index (measuring according to ASTM D1238) is 0.2-50g/10min, preferably 1-45g/10min, more preferably 2-40g/10min.LLDPE is ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has such as 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.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 such as 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.
According to the present invention, in A layer, B layer, C layer or D 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 each layer of gross weight, preferably 2-20% weight, more preferably 3-15% weight, also more preferably 4-10% weight.
The present invention also provides the preparation method of described multilayer complex films, and it comprises the following steps:
(1) preparation of A layer, B layer, C layer and D layer
Extrude or multi-layer co-extruded by individual layer, prepare polyolefin sheets, then under the temperature environment of 130-185 ° of C, carry out biaxial tension and process A layer, B layer, C layer and D layer, the cross directional stretch multiplying power of each layer and longitudinal stretching multiplying power are set according to the restriction in above-mentioned multilayer complex films;
(2) use rolling method, taking X layer as adhesive, A layer, B layer, C layer and D layer are carried out to gluing, the wherein two-layer single spreading that carries out of the outermost of composite membrane, middle each layer is carried out one or two sides gluing, after gluing, dries for each layer under 40-80 ° of C;
(3) the A layer of gluing, B layer, C layer and D layer are carried out to lamination compound, obtain described composite membrane.
According to the present invention, the two-sided sided corona treatment of all passing through of the A layer of step (1) gained and/or B layer and/or C layer and/or D 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.
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 and printing by the multilayer complex films described in aforementioned any one makes, 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-ethylene-based 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, C layer and D layer]
According to the present invention, the acrylic polymer in described A layer or B layer or C layer or D layer 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 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.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 Noblen that for example molecular weight is different, or the composition of propylene and a small amount of alpha-olefin random copolymer.Acrylic 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 C of temperature) be 0.5～60g/10min, be preferably 0.5～20g/10min, more preferably 0.5-15g/10min, the also Noblen of 1～5g/10min more preferably.
According to the present invention, the fusing point of described acrylic polymer 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.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 is tested melt index (MI) according to ASTMD-1238 and be can be about 0.2-20g/10min, preferably 0.5-15g/10min, and fusing point can be between approximately 155 ° of C-165 ° of C.
According to the present invention, the ethylene-based polymer in described A layer or B layer or C layer or D layer is high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) or linear low density polyethylene (LLDPE) (LLDPE) preferably.Wherein, not or have a small amount of comonomer, comonomer is not propylene or higher alpha-olefin to HDPE, as butylene, hexene or octene etc., and has about 0.941g/cm
3or higher (for example about 0.948g/cm
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(for example 0.915g/cm
3to 0.928g/cm
3) density and the preferred 1-45g/10min of 0.2-50g/10min(of scope, more preferably 2-40g/10min) melt index (measuring according to ASTM D1238).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has such as 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 such as 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.
For example, if the polymer acrylic polymer of described A layer, B layer, C layer or D layer wherein also can be sneaked into part ethylene-based polymer, 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 (for example about 0.948g/cm
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(for example 0.915g/cm
3to 0.928g/cm
3) density and the preferred 1-45g/10min of 0.2-50g/10min(of scope, more preferably 2-40g/10min) melt index (measuring according to ASTM D1238).LLDPE is divided into ethylene/butylene copolymers, ethylene/hexene copolymer and ethylene/octene and has such as 1-10g/10min of 0.2-50g/10min() melt index (measuring according to ASTMD1238) 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 such as 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 bending 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, C layer or D 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, preferably 2-20% weight, more preferably 3-15% weight, also more preferably 4-10% weight.
Can also master batch form in the polymer of described A layer, B layer, C layer or D layer add the additive of 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 or slipping agent), antistatic additive, nucleator, heat-resisting stabilizing agent, weather-proof stabilizing agent, ultra-violet absorber, anti-turbid dose, pigment, dyestuff.
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 the metal oxide that metal alkoxide sintering is obtained; Or the organic compound such as polymethyl methacrylate, melamine resin, melamine urea resin, mylar.Wherein, particularly preferably use silica, polymethyl methacrylate from resistance to blocking aspect.
As described lubricant, can use the acid amides based compounds such as such as stearmide, erucyl amide, oleamide etc.
As described antistatic additive, can use as the ethylene oxide adduct of 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 the polymer of described A layer, B layer, C layer or D layer, also can add delustring masterbatch to produce Extinctive thin film, or add pearly-lustre masterbatch to produce pearly-lustre film.
Lamination stretching acrylic polymer-ethylene-based polymer 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 and the cementability of other material, can be fixed processing with the adhesive such as imines, carbamate to oriented film surface, also can the maleic anhydride modified polyolefin of lamination.
[composition of X layer]
According to the present invention, the material of the binding agent in described any one X layer is identical or different, is selected from: chlorinated polypropylene, polyurethane, acrylic resin, epoxy resin or its mixture.
Chlorinated polypropylene of the present invention adopts solwution method, suspension method or solid phase method that polypropylene chlorination is made.The mass content of chlorine is 20%-70%, and fusing point is less than 150 ° of C.
According to the present invention, described polyurethane is solvent-borne type, water-dispersion type or no-solvent type one-component or Multi-component Polyurethane adhesive.
According to the present invention, described acrylic resin is the adhesive that solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent contain acrylic acid or acrylates.
According to the present invention, described epoxy resin is solvent-borne type, water-dispersion type or no-solvent type one-component or multicomponent epoxy type adhesive.
Polyurethane resin of the present invention can be selected from polyester-polyurethane, polyether-polyurethane or the polyurethane polyureas carbamide resin etc. generally manufactured as the known dry lamination that contains polyurethane of film adhesive, waterborne dry-type lamination, solventless liminating, electronic beam solidified laminating adhesive.This polyurethane resin can be water-dispersion type or solvent type any, but easily regulate from the tectal degree of cross linking of polyurethane resin, and from the operating environment aspect of production scene, be preferably water dispersant type polyaminoester resin.
As water dispersant type polyaminoester resin, be preferably to main chain or the side chain of polyurethane resin and introduced carboxylate (COONa etc.), sulfonate (SO
3na etc.) etc. the self-emulsifying type polyurethane resin of hydrophilic group.In solvent type situation, isocyanate-based resin is used for to crosslinking agent, formation has the polyurethane of three-dimensional structure, but it is in the majority that water-dispersion type becomes the situation of linear polyurethane or polyurethane polyureas carbamide resin, therefore with respect to polyurethane resin, melamine series resin, the epoxy that can add 3～10 quality % left and right are that resin, imines are the crosslinking agents such as resin, also can add the acid catalyst of 0.5～1 quality % left and right, further promote curing reaction.This crosslinking agent not only can improve resistance to water, the solvent resistance of easy-adhesion overlay film, can also improve cementability.
In addition, in the time using water dispersant type polyaminoester resin, while containing the surfactant such as defoamer or emulsifying agent in composition, likely make the surface of Biaxially stretched multilayer propylene polymer thin film turn white, cause bad order.In addition, in polyurethane resin of the present invention, for example, in order to prevent the objects such as adhesion, as required, can also add inorganic particles or organic fine particles etc.
On the one or both sides of acrylic polymer-ethylene-based polymer film, cover (lamination) polyurethane resin when (X), can by by the aqueous solution of polyurethane resin or Kohler coater dispersion liquid for, directly intaglio plate coating machine, intaglio offset coating machine, electric arc intaglio plate coating machine, the intaglio plate coating machines such as intaglio plate and nozzle mode reverse; Its top feed against roll-coater, bottom feed against roll-coater and nozzle material-feeding against contrary roll-coater such as roll-coater, the coating machine of 5 rollers, lip are coated with various itself known coating machine such as machine, excellent painting machine, contrary rod coater, die head formula coating machine, are 0.1～20g/m according to the amount that makes contained composition in the polyurethane resin aqueous solution
2, preferred 0.3～2g/m
2after being coated with, dry more than 10 seconds and obtain at the temperature of 50～140 ° of C.
[preparation method of multilayer complex films]
According to the present invention, adopt biaxial tension, in stretching-machine, at certain temperature and speed, 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.Refer in length and breadth the ratio of longitudinal stretching multiplying power and cross directional stretch multiplying power to draw ratio.
The preparation method who the invention provides described multilayer complex films, it comprises the following steps:
(1) preparation of A layer, B layer, C layer and D tunic
Adopt the method preparation of biaxial tension, for biaxial tension, can adopt substep biaxial tension method in turn, also can adopt synchro-draw method.
Described drawing process comprises plain film method and periosteum 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 and comprise that individual layer is extruded or multi-layer co-extruded.Described extrude 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.
The technical process of described periosteum method comprises synchro-draw process, comprises the steps:
Prepare burden → extrude (comprising that individual layer is extruded or multilayered molten is extruded) → chilling → female film → dewater → baker Far-infrared Heating → flatten → cut open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product to synchro-draw → collapser in length and breadth.
The technical process of described periosteum method also comprises step drawing process, comprises the steps:
(comprising that individual layer is extruded or multilayered molten the is extruded) → chilling → female film → dewater → baker Far-infrared Heating → longitudinal stretching → cross directional stretch → collapser of preparing burden → extrude flattens → cuts open limit → heat treatment → cooling → rolling → Ageing Treatment → cut → product.
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.
In the time that described plain film method is the biaxial tension of plain film substep, specifically comprise the steps:
(a) prepare burden by the requirement of formula, add in the hopper of extruder top of single or multiple lift co-extrusion, after the external heat and screw rod rotational shear plasticizing of plastics by extruder barrel, enter the rack-style flat die of single or multiple lift coextru-lamination.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 rotating speed of the extrusion capacity of extruder and chilling roller.Wherein, the control temperature of extruder is 150-260 ° of C, preferably 180-250 ° of C; Die head temperature is generally 190-240 ° of C, and chilling roll temperature is 15-30 ° of C, preferably 20-25 ° of C.
(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 ° of C, preferably 100-120 ° of C.Reach after the draft temperature (more than softening point, fusing point following) of regulation, carry out longitudinal stretching by draw roll, draft temperature is controlled at 90-150 ° of C, preferably 100-120 ° of C, and drawing process can a step, also can twice stretching or stretch for three times.Longitudinal stretching multiplying power is set according to the requirement of A layer, B layer, C layer and D tunic.Film after stretching is heat-treated by setting roller, and described setting temperature is 100-140 ° of C, is preferably 110-120 ° of C, to eliminate the internal stress of film, reduces longitudinal shrinkage factor.
(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 ° of C, preferably 110-140 ° of C, more preferably 115-130 ° of C.Reach after the draft temperature (more than softening point, fusing point is following) of regulation, then carry out cross directional stretch by the track that expands spoke, the general 130-180 of the control temperature ° C of stretching-machine, preferably 140-160 ° of C, then carries out thermal finalization processing, setting temperature is 60-120 ° of C, preferably 70-110 ° of C.Cross directional stretch multiplying power is set according to the requirement of A layer, B layer, C layer and D tunic.
(d) going out film after cross directional stretch system 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 A layer, B layer, C layer and the D layer film of Rack.
In the time that 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, carry out and longitudinal stretching is asynchronous with cross directional stretch in step drawing.Thereby 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.
In the time that described periosteum method is synchronous bidirectional stretching, 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.Main production parameter: extruder temperature is 180-240 ° of C, die head temperature is 190-230 ° of C, cooling water temperature is 11-18 ° of C, oven drying temperature: 330-450 ° C, draft temperature is 140 ° of C.Carry out according to the requirement of the draw ratio of each tunic to draw ratio in length and breadth.
In the time that described periosteum method is substep biaxial tension, 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 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.Main production parameter: extruder temperature is 180-240 ° of C, die head temperature is 190-230 ° of C, cooling water temperature is 11-18 ° of C, oven drying temperature: 330-450 ° C, draft temperature is 140 ° of C.Carry out according to the requirement of the draw ratio of each tunic to draw ratio in length and breadth.
(2) gluing
Use rolling method, taking X as adhesive, A layer, B layer, C layer and D layer are carried out to gluing, the wherein two-layer single spreading that carries out of the outermost of composite membrane, middle each layer is carried out one or two sides gluing.
According to the present invention, described gluing carries out at normal temperatures.After gluing, under 40-80 ° of C, dry for each layer of composite membrane.
(3) lamination
The A layer of gluing, B layer, C layer and D layer are carried out to lamination compound, obtain 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 two-sided sided corona treatment of all passing through of A layer, B layer, C layer and/or the D layer of step (1) 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.
[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 make, and described goods comprise printed matter (as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.
Brief description of the drawings
Fig. 1 is the structural representation of the composite membrane prepared of the embodiment of the present invention 1.
Detailed description of the invention
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:AXBXCXD type structure, layer thickness profile: 33 μ m/2 μ m/10 μ m/2 μ m/33 μ m/2 μ m/10 μ m
A layer and C layer are all that ethylene contents is 0.35wt% with the polypropylene copolymer that contains ethene, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
B layer and D layer use high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, melt index is 3.8g/10min.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 1 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinal stretching multiplying power is 9 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 9 times, and longitudinal stretching multiplying power is 1 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 1 times, and longitudinal stretching multiplying power is 9 times.
A layer, B layer, C layer and D layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 33 μ m, and B layer is 10 μ m, and C layer thickness is 33 μ m, and D layer is 10 μ m, and the thickness of X is 2 μ m, and overall film thickness is 92 μ m.
The performance test results of the film of preparation is listed in table 2.
Embodiment 2:AXBXCXD type structure, layer thickness profile: 38 μ m/2 μ m/30 μ m/2 μ m/38 μ m/2 μ m/30 μ m
A layer and C layer are all that ethylene contents is 0.35wt% with the polypropylene copolymer that contains ethene, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
B layer and D layer are high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, melt index is 3.8g/10min.
A layer, B layer, C layer and D layer all add respectively Petropols, and Petropols addition is 10% weight of each layer of gross weight.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 times.
A layer, B layer, C layer and D layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 38 μ m, and B layer is 30 μ m, and C layer thickness is 38 μ m, and D layer is 30 μ m, and the thickness of X is 2 μ m, and overall film thickness is 142 μ m.
The performance test results of the film of preparation is listed in table 2.
Embodiment 3:AXBXCXD type structure, layer thickness profile: 23 μ m/2 μ m/10 μ m/2 μ m/23 μ m/2 μ m/10 μ m
A layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.C layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.
B layer and D layer are the polypropylene 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 is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
A layer, B layer and C layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt the acid of roll coating model painting polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 23 μ m, and B layer is 10 μ m, and C layer thickness is 23 μ m, and D layer is 10 μ m, and the thickness of X is 2 μ m, and overall film thickness is 72 μ m.
The performance test results of the film of preparation is listed in table 2 as follows.
Embodiment 4:AXBXCXD type structure, layer thickness profile: 43 μ m/2 μ m/20 μ m/2 μ m/43 μ m/2 μ m/20 μ m
A layer is polypropylene homopolymer, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.C layer is the polypropylene copolymer that contains ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.
B layer is LLDPE, and density is 0.915g/cm
3, melt index is 2.8g/10min.
D layer is LLDPE, and density is 0.955g/cm
3, fusing point is 135 ° of C, melt index is 3.8g/10min.
A layer, B layer, C layer and D layer all add respectively Petropols, and Petropols addition is 10% weight of each layer of gross weight.
A layer and C are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
B layer and D layer are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
A layer, B layer, C layer and D layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 43 μ m, and B layer is 20 μ m, and C layer thickness is 43 μ m, and D layer is 20 μ m, and the thickness of X is 2 μ m, and overall film thickness is 132 μ m.
The performance test results of the film of preparation is listed in table 2.
Embodiment 5:AXBXCXD type structure, layer thickness profile: 33 μ m/2 μ m/33 μ m/2 μ m/10 μ m/2 μ m/10 μ m
A layer and B layer are all that ethylene contents is 0.35wt% with the polypropylene copolymer that contains ethene, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
C layer and D layer use high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, melt index is 3.8g/10min.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 2 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 2 times, and longitudinal stretching multiplying power is 8 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 2 times, and longitudinal stretching multiplying power is 8 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 2 times.
A layer, B layer, C layer and D layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 33 μ m, and B layer is 33 μ m, and C layer thickness is 10 μ m, and D layer is 10 μ m, and the thickness of X is 2 μ m, and overall film thickness is 92 μ m.
The performance test results of the film of preparation is listed in table 3.
Embodiment 6:AXBXCXD type structure, layer thickness profile: 38 μ m/2 μ m/30 μ m/2 μ m/38 μ m/2 μ m/30 μ m
A layer and B layer are all that ethylene contents is 0.35wt% with the polypropylene copolymer that contains ethene, and molecular weight distribution is 5.5, and melt index is 2.8g/10min, and isotacticity is 95.6%.
C layer and D layer are high density polyethylene (HDPE), and density is 0.955g/cm
3, fusing point is 135 ° of C, melt index is 3.8g/10min.
A layer, B layer, C layer and D layer all add respectively Petropols, and Petropols addition is 10% weight of each layer of gross weight.
A layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 5 times.
A layer, B layer, C layer and D layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 38 μ m, and B layer is 30 μ m, and C layer thickness is 38 μ m, and D layer is 30 μ m, and the thickness of X is 2 μ m, and overall film thickness is 142 μ m.
The performance test results of the film of preparation is listed in table 3.
Embodiment 7:AXBXCXD type structure, layer thickness profile: 23 μ m/2 μ m/23 μ m/2 μ m/10 μ m/2 μ m/10 μ m
A layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.B layer is low density polyethylene (LDPE), and density is 0.916g/cm
3, melt index is 2.8g/10min.
C layer and D layer are the polypropylene 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 is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 5 times.
B layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 5 times, and longitudinal stretching multiplying power is 8 times.
C layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
D layer is by the processing of plain film method stretch processes, and wherein cross directional stretch multiplying power is 8 times, and longitudinal stretching multiplying power is 8 times.
A layer, B layer and C layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt the acid of roll coating model painting polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 23 μ m, and B layer is 23 μ m, and C layer thickness is 10 μ m, and D layer is 10 μ m, and the thickness of X is 2 μ m, and overall film thickness is 72 μ m.
The performance test results of the film of preparation is listed in table 2 as follows.
Embodiment 8:AXBXCXD type structure, layer thickness profile: 43 μ m/2 μ m/43 μ m/2 μ m/20 μ m/2 μ m/20 μ m
A layer is polypropylene homopolymer, and molecular weight distribution is 5.1, and melt index is 2.8g/10min, and isotacticity is 96.2%.B layer is the polypropylene copolymer that contains ethene, and ethylene contents is 0.35wt%, and molecular weight distribution is 5.5, and melt index is 2.8g/10min.
C layer is LLDPE, and density is 0.915g/cm
3, melt index is 2.8g/10min.
D layer is LLDPE, and density is 0.915g/cm
3, melt index is 2.8g/10min.
A layer, B layer, C layer and D layer all add respectively Petropols, and Petropols addition is 30% weight of each layer of gross weight.
A layer and B are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
C layer and D layer are by the processing of periosteum method stretch processes, and wherein cross directional stretch multiplying power is 7 times, and longitudinally drawing high multiplying power is 7 times.
A layer, B layer, C layer and D layer pass through respectively sided corona treatment, and initial surface tension force is 45 dyne, then adopt roll coating model coating chlorinated polypropylene, are compounded to form composite membrane in process.Wherein A layer thickness is 43 μ m, and B layer is 43 μ m, and C layer thickness is 20 μ m, and D layer is 20 μ m, and the thickness of X is 2 μ m, and overall film thickness is 132 μ m.
The performance test results of the film of preparation is listed in table 3.
The results of property of the multilayer complex films of table 2 embodiment 1-4
The results of property of the multilayer complex films of table 3 embodiment 5-8
Claims (9)
1. a multilayer complex films, it comprises AXBXCXD layer structure, wherein, two-layerly in A layer, B layer, C layer and D layer in described layer structure contain identical or different acrylic polymer, two-layerly in addition contain identical or different ethylene-based polymer, X is adhesive layer, described A layer, B layer, C layer and D layer be biaxial tension and comprise one of following combination:
(1) described in, contain two-layer being inversely proportional to draw ratio in length and breadth of acrylic polymer, described in contain ethylene-based polymer two-layer being inversely proportional to draw ratio in length and breadth;
(2) described in, contain two-layer being inversely proportional to draw ratio in length and breadth of acrylic polymer, described in contain ethylene-based polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical;
(3) described in, contain acrylic polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical, described in contain ethylene-based polymer two-layer being inversely proportional to draw ratio in length and breadth;
(4) described in, contain acrylic polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical, described in contain ethylene-based polymer two-layer in length and breadth to draw ratio be 1 and two-layer stretching ratio identical.
2. multilayer complex films according to claim 1, is characterized in that, the A layer in described multilayer complex films or B layer or C layer or D layer are single layer structure or multi-layer co-extruded structure; Preferably, described A layer, the multi-layer co-extruded structure of B layer or C layer or D layer is at least 2 layers, for example, be 2-15 layer, preferably 3-11 layer, more preferably 5-9 layer, also more preferably 6-8 layer.
3. multilayer complex films according to claim 1 and 2, it is characterized in that, preferably Noblen or propylene copolymer of the acrylic polymer of described A layer or B layer or C layer or D layer, 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 ɑ-alkene, as ethene, butylene, hexene or octene etc.
4. according to the multilayer complex films described in any one in claims 1 to 3, it is characterized in that, the fusing point of the acrylic polymer of described A layer or B layer or C layer or D layer is 148-170 ° 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.
5. according to the multilayer complex films described in any one in claim 1 to 4, it is characterized in that, the ethylene-based polymer of described A layer, B layer or C layer or D layer is high density polyethylene (HDPE), high-pressure process low density polyethylene (LDPE) or low-pressure process LLDPE preferably; Preferably, the fusing point of the ethylene-based polymer of described A layer, B layer or C layer or D layer is 130-150 ° of C, preferably 135-148 ° of C; Melt index is 0.2-50g/10min, preferably 1-45g/10min, more preferably 2-40g/10min.
6. according to the multilayer complex films described in any one in claim 1 to 5, it is characterized in that, in A layer, B layer or C layer or D 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 1-30% weight, preferably 2-20% weight, more preferably 3-15% weight, also more preferably 4-10% weight.
7. a preparation method for the multilayer complex films of any one in claim 1 to 6, it comprises the following steps:
(1) preparation of A layer, B layer, C layer and D layer
Extrude or multi-layer co-extruded by individual layer, prepare polyolefin sheets, then under the temperature environment of 130-185 ° of C, carry out biaxial tension and process A layer, B layer, C layer and D layer, the cross directional stretch multiplying power of each layer and longitudinal stretching multiplying power are set according to the restriction in above-mentioned multilayer complex films;
(2) use rolling method, taking X layer as adhesive, A layer, B layer, C layer and D layer are carried out to gluing, the wherein two-layer single spreading that carries out of the outermost of composite membrane, middle each layer is carried out one or two sides gluing, after gluing, dries for each layer under 40-80 ° of C;
(3) the A layer of gluing, B layer, C layer and D layer are carried out to lamination compound, obtain described composite membrane.
8. an application for the multilayer complex films of any one in claim 1 to 6, it is for bill, marketable securities, printed matter and packaging material.
9. goods, its multilayer complex films face coat and printing by any one in claim 1 to 6 makes, and described goods comprise printed matter (as Front cover of book and periodical or picture album), bill, marketable securities and packaging material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310177288.5A CN104149460B (en) | 2013-05-13 | 2013-05-13 | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310177288.5A CN104149460B (en) | 2013-05-13 | 2013-05-13 | A kind of acrylic polymer-ethylene-based polymer multilayer complex films, its preparation method, purposes and goods thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN104149460A true CN104149460A (en) | 2014-11-19 |
| CN104149460B CN104149460B (en) | 2016-03-23 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251808A (en) * | 1998-09-28 | 2000-05-03 | 可乐丽股份有限公司 | Multi-layer films |
| CN1329981A (en) * | 2001-05-02 | 2002-01-09 | 海南现代企业股份有限公司 | Bidirectionally extensible polypropylene film for cigarettes and its preparing process |
| US20070215610A1 (en) * | 2006-03-14 | 2007-09-20 | Jau-Ming Su | Freezable/microwavable packaging films and venting packages |
| CN102863919A (en) * | 2011-07-04 | 2013-01-09 | 孟孟 | Polypropylene biaxially oriented film without primary coat and preparation method thereof |
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- 2013-05-13 CN CN201310177288.5A patent/CN104149460B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251808A (en) * | 1998-09-28 | 2000-05-03 | 可乐丽股份有限公司 | Multi-layer films |
| CN1329981A (en) * | 2001-05-02 | 2002-01-09 | 海南现代企业股份有限公司 | Bidirectionally extensible polypropylene film for cigarettes and its preparing process |
| US20070215610A1 (en) * | 2006-03-14 | 2007-09-20 | Jau-Ming Su | Freezable/microwavable packaging films and venting packages |
| CN102863919A (en) * | 2011-07-04 | 2013-01-09 | 孟孟 | Polypropylene biaxially oriented film without primary coat and preparation method thereof |
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Inventor after: Chen Dakui Inventor after: Huang Xusheng Inventor after: Zhan Yueqiang Inventor after: Yun Xiaobing Inventor before: Chen Dakui Inventor before: Huang Xusheng Inventor before: Zhan Yueqiang Inventor before: Gu Hanjin Inventor before: Yun Xiaobing |