CN103042791B - Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film and preparation method thereof - Google Patents
Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film and a preparation method thereof. The film comprises a heat-seal layer on the outer surface, an obstruct layer positioned in an inner layer and wrapped by a heat-shrinkable layer, and an external mechanical injury-resistant layer, wherein the heat-seal layer is one or the combination of LDPE (Low-Density Polyethylene), LLDPE (Linear Low-Density Polyethylene) and an m-LLDPE (metallocene-Linear Low-Density Polyethylene); the heat-shrinkable layer is an EVA (Ethylene Vinyl Acetate) copolymer; the obstruct layer is PVDC (Polyvinyl Dichloride) resin; and the external mechanical injury-resistant layer is one or the combination of the LDPE and the LLDPE. Compared with the prior art, the film provided by the invention adopts the EVA copolymer for wrapping and the PVDC resin for extrusion, and the thermal decomposition of the PVDC is reduced to the lowest. The film has anticoagulative function, high lightness and uniform thickness and good puncture-resistant performance. Therefore, the film is suitable for the packaging of dairy products, frozen foods and irregularly-shaped articles, and is particularly suitable for packaging meat products.
Description
Technical field
The present invention relates to a kind of packaging film, be specifically related to a kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, this film is particularly suitable for the packaging of meat products (fresh meat, sausage and poultry meat), dairy products (cheese and butter), frozen food and special-shaped article, belongs to flexible packaging film technical field.
Background technology
Along with the progress of expanding economy, science and technology, the with rapid changepl. never-ending changes and improvements of product, and the life of people is tending towards convenient and leisure more, there has also been higher requirement to the packaging of product.High-isolation film is an important development trend of packing film, and it has the advantages such as the shelf-life of health and prolongation product.Wherein, be different from the high-barrier packing film of shrinkage-void, the shrinkage tensions that high-barrier heat shrinkable package film can utilize its high shrinkage to produce realizes " fit " packaging, makes the commodity after packaging attractive in appearance and saves space; And heat shrinkable package blister-pack technique is simple, as long as to heat-shrinkable film heating, packaging process can be completed instantaneously, improve the production efficiency of commodity packaging.Abroad the main green meat that is applied to by heat shrinkable package film is packed and packaging cheese, and its market potential is huge.
In high-barrier packing film, barrier layer material therefor can choose in ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PEO), polyamide (PA), polyvinylidene chloride (PVDC) or aluminium foil one or more.Wherein, PVDC has symmetrical molecular structure, and intermolecular cohesive force is strong, and oxygen molecule, hydrone are difficult to move in PVDC, therefore have the characteristics such as good barrier and gas barrier properties.And compared with other barrier material, PVDC has more excellent cost performance, and its barrier can not by the impact of ambient humidity as EVOH, PEO and PA, and its pliability also far exceedes aluminium foil.Experiment proves, when humidity is 0 ~ 70%, EVOH(38%) oxygen barrier be better than PVDC; When humidity is greater than 70%, EVOH oxygen barrier declines very fast, not as PVDC; Under the relative humidity of 80%, the oxygen barrier of PVDC is the oxygen barrier more than 3 times of EVOH; Under the relative humidity of 100%, the oxygen barrier of PVDC is then the oxygen barrier more than 13 times of EVOH.Special in packaging of meat products, extraneous relative humidity is 60 ~ 70%, and the relative temperature of meat products inside is 95 ~ 100%, so PVDC is superior more than EVOH in packaging of meat products.Meanwhile, PVDC also has good water preventing ability and fragrance protectiveness.But the poor heat stability of PVDC, adds man-hour excessive shear action and easily causes the thermal decomposition of PVDC.In order to realize PVDC as the barrier layer in PP TYPE, normal needs adds a certain amount of liquid plasticizer or flexibilizer in PVDC resin.Liquid plasticizer can be epoxy soybean wet goods; But liquid plasticizer add the reduction that membership causes thin-film barrier performance, also unavoidably increase the extraction quantity of oiliness food to plasticizer.The flexibilizer of flexibilizer, particularly HMW, can be ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA) and ethylene-methyl acrylate copolymer (EMA) etc.; Being no more than the flexibilizer of 3% weight by adding in PVDC, melt temperature when it not only can reduce process of resin, the decomposition reducing resin, extension of the work cycle, the pliability of goods when low temperature can also being given; And due to flexibilizer molecular weight high, the defect of plasticizer can be overcome to a certain extent.In addition, in order to prevent the thermal decomposition of PVDC, adopt the PVDC resin alloy of different molecular weight to improve the processing characteristics of PVDC, as the GG8 of Japanese Guan Yu company and 880 resins etc. of 2051 resins and Asahi Kasei Corporation.
Grant number is that the Chinese patent literature of CN101306593B discloses a kind of multilayer coextruding pyrocondensation film, and its barrier layer is the PVDC-copolymer-maleic anhydride resin of epoxidized soybean oil plasticising, and the both sides of barrier layer are bonded respectively at top layer and hot sealing layer by tack coat.But hot sealing layer adopts the mixture of the copolymer of poly alpha olefin or the copolymer of poly alpha olefin and polyethylene etc., it adds and easily occurs that melt is broken man-hour, cause heat sealability to decline, and its hot sealing layer does not have anticoagulant functions.
EP2030781A1 disclosed in EUROPEAN PATENT OFFICE discusses a kind of obstruct heat shrink films, and it comprises the heat-sealing polyolefin layer of an outer surface, the PVDC layer of internal layer and another outer resistant to mechanical damage layer; Its outer resistant to mechanical damage layer is PA, and PVDC layer is the copolymer of vinylidene chloride and other unsaturated ethylene thiazolinyl monomers or the mixture of itself and other polyvinyl.But the barrier layer of this film selects modification PVDC, compared to directly using the pure resin of PVDC, more complicated in the production technology of modification PVDC, and its hot sealing layer does not have anticoagulant functions.
Therefore, heat sealability is good, cost performance is high and will be a technical problem urgently to be resolved hurrily with the exploitation of the pure PVDC Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film that is barrier layer.
Summary of the invention
The object of the invention is to overcome the defect existed in prior art, design a kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, its heat sealability is good, and cost performance is high, has anticoagulant functions, and with PVDC resin for barrier layer.
Another object of the present invention is to provide a kind of method preparing above-mentioned film.
For achieving the above object, the technical solution used in the present invention is:
A kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, comprise be positioned at outer surface hot sealing layer, be positioned at internal layer by the barrier layer of at least one deck heat shrink parcel and the outer resistant to mechanical damage layer being positioned at another outer surface;
Wherein, hot sealing layer is one in low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE) and metallocene PE (m-LLDPE) or its mixture; Heat shrink is EVA copolymer; Barrier layer is PVDC; Outer resistant to mechanical damage layer is one in LDPE and LLDPE or its mixture, or is the one in aliphatic PA and aromatic series PA or its mixture.
Preferred technical scheme can be further: in described hot sealing layer, every 100 parts of resins are added with 1 ~ 2 portion of macromolecule anticoagulant containing polar group.A small amount of coagulant can give film anticoagulant functions, to avoid the blood in the packed articles such as meat to solidify, thus ensures the fresh of meat.
Further preferred technical scheme can be: described macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
，
In formula, m+n=1, x are natural number, R
1for H or CH
3, R
2for H or CH
3, R
3for CH
3or
, this coagulant can form chelate with the calcium ion in meat blood, avoids solidifying of blood, thus ensures the fresh of meat.
Further preferred technical scheme can be: in described hot sealing layer, every 100 parts of resins are also added with 1 ~ 2 part of polyamide-based auxiliary agent.A small amount of polyamide-based auxiliary agent can improve thickness evenness and the thickness stability of hot sealing layer, significantly reduce the brilliant point produced in blown film process, stiff block and plasticizing bad phenomenon, eliminate melt flow liner, avoid hot sealing layer easily to occur that melt is broken man-hour adding, improve its heat sealability; In addition, this polyamide-based auxiliary agent also can improve surface smoothness and the brightness of hot sealing layer, improves the paracentesis resistance of film.
Further preferred technical scheme can be: described hot sealing layer is made up of m-LDPE, the LLDPE of 20 ~ 50 parts, the LDPE of 20 ~ 50 parts, the polyamide-based auxiliary agent of 1 ~ 2 part and 1 ~ 2 portion of anticoagulant of 30 ~ 60 parts, wherein, total number of m-LDPE, LLDPE and LDPE is 100 parts, the molecular weight of m-LDPE, LLDPE and LDPE is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C;
Described outer resistant to mechanical damage layer is made up of the PA of 100 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, PA is polyhexamethylene adipamide, or be polycaprolactam, or polyhexamethylene adipamide-polycaprolactam co-polymer, or for the total number be made up of the aromatic series PA of aliphatic PA and 10 ~ 40 part of 60 ~ 90 parts be the mixture of 100 parts, aromatic series PA is the copolymer of aliphatic diamine/isophthalic acid/terephthalic acids;
Or described outer resistant to mechanical damage layer is made up of the LLDPE of 30 ~ 50 parts, the LDPE of 50 ~ 70 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, total number of LLDPE and LDPE is 100 parts, the molecular weight of LLDPE and LDPE is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C;
In described heat shrink, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of EVA copolymer is 0.93 ~ 0.94g/cm
3.
Further preferred technical scheme can be: described outer resistant to mechanical damage layer is or/and be also provided with one deck or two-layer above interior resistant to mechanical damage layer between described hot sealing layer and described heat shrink, interior resistant to mechanical damage layer is one in LDPE and LLDPE or its mixture.The resistant to mechanical damage layer of multilayer is set, comprises interior resistant to mechanical damage layer and outer resistant to mechanical damage layer, the mechanical strength of film can be improved, improve puncture-resistant ability and the barrier of film.
Further preferred technical scheme can be: be provided with tack coat between described outer resistant to mechanical damage layer and described interior resistant to mechanical damage layer, tack coat is EVA copolymer or anhydride modified PE; In EVA copolymer tack coat, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of EVA copolymer is 0.93 ~ 0.94g/cm
3.Particularly, when interior resistant to mechanical damage layer is different with the resin material polarity of outer resistant to mechanical damage layer, tack coat is set between, can bond strength between layers be improved, thus ensure high paracentesis resistance and the high barrier of film.
Further preferred technical scheme can be: described interior resistant to mechanical damage layer is made up of the LDPE of LLDPE and 50 ~ 70 part of 30 ~ 50 parts, total number of LLDPE and LDPE is 100 parts, the molecular weight of LLDPE and LDPE is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Preferred technical scheme can also be: the number of plies of described Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film is more than 5 layers or 6 layers or 7 layers, and the horizontal and vertical shrinkage factor of film is 20 ~ 60%.
A kind of method preparing above-mentioned Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, the method is that coextrusion blow is shaping, and described heat shrink and described barrier layer realize the melting charge of described heat shrink to the parcel of the melting charge of described barrier layer by its respective melting charge through a co-extrusion connector, subsequently by the melting charge after parcel enter co-extrusion die head a runner and with the melting charge coextrusion in other runners and blow molding.
Advantage of the present invention and beneficial effect are: Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film of the present invention adopts EVA copolymer heat shrink parcel PVDC resin extruded, thus is down to minimum by the thermal decomposition of PVDC; In addition, film with the addition of anticoagulant and polyamide-based auxiliary agent in hot sealing layer, imparts film anticoagulant functions, and improves brightness and the smoothness of film, also improves thickness evenness and the thickness stability of film; This film is provided with multilayer resistant to mechanical damage layer, and paracentesis resistance is good.The hot strength of this film can reach more than 25Mpa, and elongation at break can reach more than 300%, and its mist degree is no more than 13%, and light transmittance is higher than 80%, and OTR oxygen transmission rate is no more than 10 cm
3/ m
2dbar, moisture-vapor transmission is no more than 10 g/m
2d, horizontal and vertical shrinkage factor can reach 20 ~ 60%.This film is applicable to the packaging being applied to the dairy products such as cheese and butter, frozen food and special-shaped article, is especially applicable to being applied to the packaging as meat products such as fresh meat, sausage and poultry meats.
Accompanying drawing explanation
Fig. 1 is the cross section structure schematic diagram of the embodiment of the present invention 1;
Fig. 2 is the cross section structure schematic diagram of the embodiment of the present invention 3;
Fig. 3 is the cross section structure schematic diagram of the embodiment of the present invention 4;
Fig. 4 is the cross section structure schematic diagram of the embodiment of the present invention 6;
Fig. 5 is the cross section structure schematic diagram of the embodiment of the present invention 7.
In figure: 1, outer resistant to mechanical damage layer; 2-1 to 2-2, heat shrink; 3, barrier layer; 4, hot sealing layer; 5-1 to 5-2, interior resistant to mechanical damage layer; 6, tack coat.
Detailed description of the invention
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is further described.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Embodiment 1
The present invention is a kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, and as shown in Figure 1, this film is five laminate, and shaping by coextrusion blow, and its transverse and longitudinal shrinkage factor is 20 ~ 60%.The structure expression of this film is: A/B/C/B/D; In formula: from left to right represent each layer that film is laid from top to bottom successively successively, A represents outer resistant to mechanical damage layer, and B represents heat shrink, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer resistant to mechanical damage layer, i.e. A layer are the one in low density polyethylene (LDPE) and LLDPE or its mixture, or are the one in fatty polyamide and aromatic polyamide or its mixture.
Heat shrink, i.e. B layer are ethylene-vinyl acetate copolymer.
Barrier layer, i.e. C layer are polyvinylidene chloride.
Hot sealing layer, i.e. D layer are the one in low density polyethylene (LDPE), LLDPE and metallocene PE or its mixture, and every 100 parts of resins are added with macromolecule anticoagulant and 1 ~ 2 part of polyamide-based auxiliary agent that 1 ~ 2 part contains polar group.Here, macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
，
In formula, m+n=1, x are natural number, R
1for H or CH
3, R
2for H or CH
3, R
3for CH
3or
。
Above-mentioned Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film is shaping by coextrusion blow, and described heat shrink and described barrier layer realize the melting charge of described heat shrink to the parcel of the melting charge of described barrier layer by its respective melting charge through a co-extrusion connector, subsequently by the melting charge after parcel enter co-extrusion die head a runner and with the melting charge coextrusion in other runners and blow molding.
Embodiment 2
On the basis of embodiment 1, the preferred embodiment of the invention is:
Described outer resistant to mechanical damage layer, i.e. A layer, be made up of the LLDPEs of 30 ~ 50 parts, the low density polyethylene (LDPE) of 50 ~ 70 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
In described heat shrink, i.e. B layer, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
Described hot sealing layer, i.e. D layer, be made up of the metallocene PEs of 30 ~ 60 parts, the LLDPE of 20 ~ 50 parts, the low density polyethylene (LDPE) of 20 ~ 50 parts, the polyamide-based auxiliary agent of 1 ~ 2 part and 1 ~ 2 portion of anticoagulant; Wherein, total number of metallocene PE, LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of metallocene PE, LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Embodiment 3
The present invention is a kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, and as shown in Figure 2, this film is six laminate, and shaping by coextrusion blow, and its transverse and longitudinal shrinkage factor is 20 ~ 60%.The structure expression of this film is: A/B/C/B/A*/D; In formula: from left to right represent each layer that film is laid from top to bottom successively successively, A represents outer resistant to mechanical damage layer, and A* represents interior resistant to mechanical damage layer, and B represents heat shrink, and C represents barrier layer, and D represents hot sealing layer.
Outer resistant to mechanical damage layer, i.e. A layer, be made up of the LLDPEs of 30 ~ 50 parts, the low density polyethylene (LDPE) of 50 ~ 70 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent; Wherein, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, and the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Interior resistant to mechanical damage layer, i.e. A* layer, be made up of the low density polyethylene (LDPE) of the LLDPEs of 30 ~ 50 parts and 50 ~ 70 parts, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Heat shrink, namely in B layer, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
Barrier layer, i.e. C layer are polyvinylidene chloride.
Described hot sealing layer, i.e. D layer, be made up of the metallocene PEs of 30 ~ 60 parts, the LLDPE of 20 ~ 50 parts, the low density polyethylene (LDPE) of 20 ~ 50 parts, the polyamide-based auxiliary agent of 1 ~ 2 part and 1 ~ 2 portion of anticoagulant; Wherein, total number of metallocene PE, LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of metallocene PE, LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.Here, macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
,
In formula, m+n=1, x are natural number, R
1for H or CH
3, R
2for H or CH
3, R
3for CH
3or
。
Above-mentioned Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film is shaping by coextrusion blow, and described heat shrink and described barrier layer realize the melting charge of described heat shrink to the parcel of the melting charge of described barrier layer by its respective melting charge through a co-extrusion connector, subsequently by the melting charge after parcel enter co-extrusion die head a runner and with the melting charge coextrusion in other runners and blow molding.
Embodiment 4
The present invention is a kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, and as shown in Figure 3, this film is seven laminate, and shaping by coextrusion blow, and its transverse and longitudinal shrinkage factor is 20-60%.The structure expression of this film is: A/A*/A*/B/C/B/D; In formula: from left to right represent each layer that film is laid from top to bottom successively successively, A represents outer resistant to mechanical damage layer, and A* represents interior resistant to mechanical damage layer, and B represents heat shrink, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer resistant to mechanical damage layer, i.e. A layer are the one in low density polyethylene (LDPE) and LLDPE or its mixture, or are the one in fatty polyamide and aromatic polyamide or its mixture.
Interior resistant to mechanical damage layer, i.e. A* layer are the one in low density polyethylene (LDPE) and LLDPE or its mixture.
Heat shrink, i.e. B layer are ethylene-vinyl acetate copolymer.
Barrier layer, i.e. C layer are polyvinylidene chloride.
Hot sealing layer, i.e. D layer are the one in low density polyethylene (LDPE), LLDPE and metallocene PE or its mixture, and every 100 parts of resins are added with macromolecule anticoagulant and 1 ~ 2 part of polyamide-based auxiliary agent that 1 ~ 2 part contains polar group.Here, macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
，
In formula, m+n=1, x are natural number, R
1for H or CH
3, R
2for H or CH
3, R
3for CH
3or
。
Above-mentioned Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film is shaping by coextrusion blow, and described heat shrink and described barrier layer realize the melting charge of described heat shrink to the parcel of the melting charge of described barrier layer by its respective melting charge through a co-extrusion connector, subsequently by the melting charge after parcel enter co-extrusion die head a runner and with the melting charge coextrusion in other runners and blow molding.
Embodiment 5
On the basis of embodiment 4, the preferred embodiment of the invention is:
Described outer resistant to mechanical damage layer, i.e. A layer, is made up of the LLDPEs of 30 ~ 50 parts, the low density polyethylene (LDPE) of 50 ~ 70 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent; Wherein, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, and the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Described interior resistant to mechanical damage layer, i.e. A* layer, be made up of the low density polyethylene (LDPE) of the LLDPEs of 30 ~ 50 parts and 50 ~ 70 parts, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Described heat shrink, namely in B layer, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
Described hot sealing layer, i.e. D layer, be made up of the metallocene PEs of 30 ~ 60 parts, the LLDPE of 20 ~ 50 parts, the low density polyethylene (LDPE) of 20 ~ 50 parts, the polyamide-based auxiliary agent of 1 ~ 2 part and 1 ~ 2 portion of anticoagulant; Wherein, total number of metallocene PE, LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of metallocene PE, LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Embodiment 6
The present invention is a kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, and as shown in Figure 4, this film is seven laminate, and shaping by coextrusion blow, and its transverse and longitudinal shrinkage factor is 20-60%.The structure expression of this film is: A/A*/B/C/B/A*/D; In formula: from left to right represent each layer that film is laid from top to bottom successively successively, A represents outer resistant to mechanical damage layer, and A* represents interior resistant to mechanical damage layer, and B represents heat shrink, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer resistant to mechanical damage layer, i.e. A layer, be made up of the LLDPEs of 30 ~ 50 parts, the low density polyethylene (LDPE) of 50 ~ 70 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent; Wherein, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, and the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Interior resistant to mechanical damage layer, i.e. A* layer, be made up of the low density polyethylene (LDPE) of the LLDPEs of 30 ~ 50 parts and 50 ~ 70 parts, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Heat shrink, namely in B layer, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
Barrier layer, i.e. C layer are polyvinylidene chloride.
Hot sealing layer, i.e. D layer, be made up of the metallocene PEs of 30 ~ 60 parts, the LLDPE of 20 ~ 50 parts, the low density polyethylene (LDPE) of 20 ~ 50 parts, the polyamide-based auxiliary agent of 1 ~ 2 part and 1 ~ 2 portion of anticoagulant; Wherein, total number of metallocene PE, LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of metallocene PE, LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.Here, macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
，
In formula, m+n=1, x are natural number, R
1for H or CH
3, R
2for H or CH
3, R
3for CH
3or
。
Above-mentioned Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film is shaping by coextrusion blow, and described heat shrink and described barrier layer realize the melting charge of described heat shrink to the parcel of the melting charge of described barrier layer by its respective melting charge through a co-extrusion connector, subsequently by the melting charge after parcel enter co-extrusion die head a runner and with the melting charge coextrusion in other runners and blow molding.
Embodiment 7
The present invention is a kind of Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, and as shown in Figure 5, this film is seven laminate, and shaping by coextrusion blow, and its transverse and longitudinal shrinkage factor is 20-60%.The structure expression of this film is: A/adh/A*/B/C/B/D; In formula: from left to right represent each layer that film is laid from top to bottom successively successively, A represents outer resistant to mechanical damage layer, and A* represents interior resistant to mechanical damage layer, and adh represents tack coat, and B represents heat shrink, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer resistant to mechanical damage layer, i.e. A layer, be made up of the polyamide of 100 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, polyamide is polyhexamethylene adipamide, or be polycaprolactam, or polyhexamethylene adipamide-polycaprolactam co-polymer, or for total number of being made up of the fatty polyamide of 60 ~ 90 parts and the aromatic polyamide of 10 ~ 40 parts be the mixture of 100 parts, aromatic polyamide is the copolymer of aliphatic diamine/isophthalic acid/terephthalic acids.
Interior resistant to mechanical damage layer, i.e. A* layer, be made up of the low density polyethylene (LDPE) of the LLDPEs of 30 ~ 50 parts and 50 ~ 70 parts, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
Tack coat, i.e. adh are ethylene-vinyl acetate copolymer or anhydride modified lldpe; In ethylene-vinyl acetate copolymer tack coat, vinylacetate construction unit accounts for 10 ~ 20 parts, ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
Heat shrink, namely in B layer, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
Barrier layer, i.e. C layer are polyvinylidene chloride.
Hot sealing layer, i.e. D layer, be made up of the metallocene PEs of 30 ~ 60 parts, the LLDPE of 20 ~ 50 parts, the low density polyethylene (LDPE) of 20 ~ 50 parts, the polyamide-based auxiliary agent of 1 ~ 2 part and 1 ~ 2 portion of anticoagulant; Wherein, total number of metallocene PE, LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of metallocene PE, LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, and the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.Here, macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
，
In formula, m+n=1, x are natural number, R
1for H or CH
3, R
2for H or CH
3, R
3for CH
3or
。
Above-mentioned Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film is shaping by coextrusion blow, and described heat shrink and described barrier layer realize the melting charge of described heat shrink to the parcel of the melting charge of described barrier layer by its respective melting charge through a co-extrusion connector, subsequently by the melting charge after parcel enter co-extrusion die head a runner and with the melting charge coextrusion in other runners and blow molding.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film, is characterized in that: comprise be positioned at outer surface hot sealing layer, be positioned at internal layer by the barrier layer of at least one deck heat shrink parcel and the outer resistant to mechanical damage layer being positioned at another outer surface;
Wherein, hot sealing layer is one in low density polyethylene (LDPE), LLDPE and metallocene PE or its mixture; Heat shrink is ethylene-vinyl acetate copolymer; Barrier layer is polyvinylidene chloride; Outer resistant to mechanical damage layer is one in low density polyethylene (LDPE) and LLDPE or its mixture, or is the one in fatty polyamide and aromatic polyamide or its mixture.
2. Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as claimed in claim 1, is characterized in that: in described hot sealing layer, every 100 parts of resins are added with 1 ~ 2 portion of macromolecule anticoagulant containing polar group.
3. Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as claimed in claim 2, it is characterized in that: described macromolecule anticoagulant is acrylic acid esters co-polymer, the general formula of its construction unit is:
，
In formula, m+n=1, x are natural number, R
1for H or CH
3, R
2for H or CH
3, R
3for CH
3or
。
4. Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as claimed in claim 3, is characterized in that: in described hot sealing layer, every 100 parts of resins are also added with 1 ~ 2 part of polyamide-based auxiliary agent.
5. Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as claimed in claim 4, it is characterized in that: described hot sealing layer is by the metallocene PE of 30 ~ 60 parts, the LLDPE of 20 ~ 50 parts, the low density polyethylene (LDPE) of 20 ~ 50 parts, the polyamide-based auxiliary agent of 1 ~ 2 part and 1 ~ 2 part of anticoagulant composition, wherein, metallocene PE, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, metallocene PE, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, fusing point is 88 ~ 96 DEG C,
Described outer resistant to mechanical damage layer is made up of the polyamide of 100 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, polyamide is polyhexamethylene adipamide, or be polycaprolactam, or polyhexamethylene adipamide-polycaprolactam co-polymer, or for total number of being made up of the fatty polyamide of 60 ~ 90 parts and the aromatic polyamide of 10 ~ 40 parts be the mixture of 100 parts, aromatic polyamide is the copolymer of aliphatic diamine/isophthalic acid/terephthalic acids;
Or described outer resistant to mechanical damage layer is made up of the LLDPE of 30 ~ 50 parts, the low density polyethylene (LDPE) of 50 ~ 70 parts, the amide-type slipping agent of 0.05 ~ 0.45 part and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C;
In described heat shrink, vinylacetate construction unit accounts for 10 ~ 20 parts, and ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
6. the Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as described in claim 1 to 5 any one, it is characterized in that: described outer resistant to mechanical damage layer is or/and be also provided with one deck or two-layer above interior resistant to mechanical damage layer between described hot sealing layer and described heat shrink, interior resistant to mechanical damage layer is one in low density polyethylene (LDPE) and LLDPE or its mixture.
7. Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as claimed in claim 6, it is characterized in that: be provided with tack coat between described outer resistant to mechanical damage layer and described interior resistant to mechanical damage layer, tack coat is ethylene-vinyl acetate copolymer or anhydride modified lldpe; In ethylene-vinyl acetate copolymer tack coat, vinylacetate construction unit accounts for 10 ~ 20 parts, ethylene unit unit accounts for 80 ~ 90 parts, and total number of vinylacetate construction unit and ethylene unit unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3.
8. Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as claimed in claim 7, it is characterized in that: described interior resistant to mechanical damage layer is made up of the LLDPE of 30 ~ 50 parts and the low density polyethylene (LDPE) of 50 ~ 70 parts, total number of LLDPE and low density polyethylene (LDPE) is 100 parts, the molecular weight of LLDPE and low density polyethylene (LDPE) is 50,000 ~ 200,000, the melt index of its mixture is 0.3 ~ 10g/10min, and fusing point is 88 ~ 96 DEG C.
9. Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film as claimed in claim 1, it is characterized in that: the number of plies of described Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film is more than 5 layers or 6 layers or 7 layers, the horizontal and vertical shrinkage factor of film is 20 ~ 60%.
10. prepare the method for Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film according to claim 1 for one kind, the method is that coextrusion blow is shaping, it is characterized in that: described heat shrink and described barrier layer realize the melting charge of described heat shrink to the parcel of the melting charge of described barrier layer by its respective melting charge through a co-extrusion connector, subsequently by the melting charge after parcel enter co-extrusion die head a runner and with the melting charge coextrusion in other runners and blow molding.
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| CN105437686A (en) * | 2014-08-26 | 2016-03-30 | 丹东全德高科技包装有限公司 | PA/TIE/PE/EVA/PVDC/EVA/PE seven-layer co-extruded deep-drawing film |
| CN105437687A (en) * | 2014-08-26 | 2016-03-30 | 丹东全德高科技包装有限公司 | PE/TIE/PA/TIE/PE/EVA/PVDC/EVA/PE nine-layer co-extruded deep-drawing film |
| CN105365314A (en) * | 2014-08-26 | 2016-03-02 | 丹东全德高科技包装有限公司 | PE/TIE/PA/TIE/PA/TIE/PE/EVA/PVDC/EVA/PE eleven-layer co-extrusion deep stretch film |
| CN104385565A (en) * | 2014-09-03 | 2015-03-04 | 福建师范大学 | Preparation method for three-layer co-extruded composite high barrier blown film |
| JP6810546B2 (en) * | 2016-07-20 | 2021-01-06 | 株式会社クレハ | Heat shrinkable multilayer film |
| CN106739356B (en) * | 2016-12-14 | 2018-08-17 | 江阴升辉包装材料有限公司 | A kind of multi-layer co-extruded shrink film and production technology |
| CN109824925A (en) * | 2019-01-09 | 2019-05-31 | 江阴宝柏包装有限公司 | A kind of film and preparation method thereof using PCR-PE preparation |
| CN113453897A (en) * | 2019-02-25 | 2021-09-28 | 克里奥瓦克公司 | Abrasion resistant heat shrinkable multilayer film |
| CN113968009A (en) * | 2021-07-30 | 2022-01-25 | 漯河连邦化学有限公司 | PVDC co-extrusion substrate film and preparation method and application thereof |
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