CN103042791A - 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-extruded anticoagulation high-barrier heat-shrinkable film, this film is particularly suitable for being applied to the packing of meat products (fresh meat, sausage and poultry meat), dairy products (cheese and butter), frozen food and special-shaped article, belongs to the flexible packaging film technical field.
Background technology
Along with making rapid progress of progress, the product of expanding economy, science and technology, and people's life is tending towards convenient and leisure more, and the packing of product has also been had higher requirement.High-isolation film is an important development trend of packing film, the advantages such as shelf-life that it has health and prolongs 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 " packing, makes the attractive in appearance and conserve space of commodity after the packing; And heat shrinkable package blister-pack technique is simple, as long as to the heat-shrinkable film heating, can moment finish packaging process, has improved the production efficiency of commodity packaging.Mainly the heat shrinkable package film is applied to green meat packing and packaging cheese abroad, its market potential is huge.
In the high-barrier packing film, the barrier layer material therefor can be chosen one or more in ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PEO), polyamide (PA), polyvinylidene chloride (PVDC) or the aluminium foil.Wherein, PVDC has symmetrical molecular structure, and intermolecular cohesive force is strong, and oxygen molecule, hydrone are difficult in PVDC mobile, so have the characteristics such as good oxygen barrier and gas barrier properties.And compare with other barrier material, PVDC has more excellent cost performance, and its barrier can not be subjected to the impact of ambient humidity as EVOH, PEO and PA, and its pliability also far surpasses aluminium foil.Experiment showed, that when humidity was 0 ~ 70%, oxygen barrier EVOH(38%) was better than PVDC; When humidity greater than 70% the time, the EVOH oxygen barrier descends very fast, not as PVDC; Under 80% relative humidity, the oxygen barrier of PVDC is that the oxygen barrier of EVOH is more than 3 times; Under 100% relative humidity, the oxygen barrier of PVDC then is that the oxygen barrier of EVOH is more than 13 times.For packaging of meat products, extraneous relative humidity is 60 ~ 70% especially, and the relative temperature of meat products inside is 95 ~ 100%, so PVDC is superior more than EVOH in packaging of meat products.Simultaneously, 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 the PP TYPE, often need in the PVDC resin, add a certain amount of liquid plasticizer or flexibilizer.Liquid plasticizer can be the epoxy soybean wet goods; Yet the affiliation that adds of liquid plasticizer causes and has also increased inevitably the extraction quantity of oiliness food to plasticizer by the thin-film barrier reduction of performance.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.; By in PVDC, adding the flexibilizer that is no more than 3% weight, decomposition, the extension of the work cycle of the melt temperature when it not only can reduce process of resin, minimizing resin, can also give the pliability of goods when low temperature; And because the flexibilizer molecular weight is high, can overcome to a certain extent the defective of plasticizer.In addition, in order to prevent the thermal decomposition of PVDC, the PVDC resin alloy that adopts different molecular weight to be improving the processing characteristics of PVDC, such as the GG8 of Japanese Guan Yu company and 880 resins of 2051 resins and Asahi Kasei Corporation etc.
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 bonding respectively at top layer and hot sealing layer by tack coat.But the mixture of the copolymer that hot sealing layer adopts the copolymer of poly alpha olefin or poly alpha olefin and polyethylene etc., it adds and is prone to the melt fragmentation man-hour, cause heat sealability decline, and its hot sealing layer does not have anticoagulant functions.
The disclosed EP2030781A1 of EUROPEAN PATENT OFFICE has discussed a kind of obstruct heat shrink films, and it comprises the heat-sealing polyolefin layer of an outer surface, PVDC layer and another outer anti-mechanical damage layer of internal layer; Its outer anti-mechanical damage layer is PA, and the PVDC layer is the copolymer of vinylidene chloride and other unsaturated ethylene thiazolinyl monomers or the mixture of itself and other polyvinyl.Yet the barrier layer of this film is selected modification PVDC, and is more complicated on the production technology of modification PVDC than directly using the pure resin of PVDC, and its hot sealing layer does not have anticoagulant functions.
Therefore, heat sealability is good, cost performance is high and the exploitation of the multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film take pure PVDC as barrier layer will be a technical problem that needs to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome the defective that exists in the prior art, design a kind of multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, its heat sealability is good, and cost performance is high, has anticoagulant functions, and take the PVDC resin as barrier layer.
Another object of the present invention is to provide a kind of method for preparing said film.
For achieving the above object, the technical solution used in the present invention is:
A kind of multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, comprise the hot sealing layer that is positioned at outer surface, be positioned at internal layer by at least barrier layer of one deck thermal contraction layer parcel and the outer anti-mechanical damage layer that is positioned at another outer surface;
Wherein, hot sealing layer is a kind of or its mixture in low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE) and the metallocene PE (m-LLDPE); The thermal contraction layer is the EVA copolymer; Barrier layer is PVDC; Outer anti-mechanical damage layer is a kind of or its mixture among LDPE and the LLDPE, or is a kind of or its mixture among aliphatic PA and the aromatic series PA.
Further preferred technical scheme can be: per 100 parts of resins are added with 1 ~ 2 portion of macromolecule anticoagulant that contains polar group in the described hot sealing layer.A small amount of coagulant can be given the film anticoagulant functions, solidifies to avoid the blood in the packed article such as meat, thereby guarantees 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 the formula, m+n=1, x are natural number, R
1Be H or CH
3, R
2Be H or CH
3, R
3Be CH
3Or
Further preferred technical scheme can be: per 100 parts of resins also are added with 1 ~ 2 part of polyamide-based auxiliary agent in the described hot sealing layer.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 that produces in the blown film process, stiff piece and plasticizing bad phenomenon, eliminate the melt flow liner, avoid hot sealing layer to be prone to the melt fragmentation 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 comprised of 30 ~ 60 parts m-LDPE, 20 ~ 50 parts LLDPE, 20 ~ 50 parts LDPE, polyamide-based auxiliary agent and 1 ~ 2 portion of anticoagulant of 1 ~ 2 part, wherein, total umber 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 ℃;
Described outer anti-mechanical damage layer is comprised of 100 parts PA, 0.05 ~ 0.45 part amide-type slipping agent 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 copolymer, or the total umber that forms for the aromatic series PA by 60 ~ 90 parts aliphatic PA and 10 ~ 40 parts is 100 parts mixture, and aromatic series PA is the copolymer of aliphatic diamine/isophthalic acid/terephthalic acids;
Or described outer anti-mechanical damage layer is comprised of 30 ~ 50 parts LLDPE, 50 ~ 70 parts LDPE, 0.05 ~ 0.45 part amide-type slipping agent and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, total umber 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 ℃;
In the described thermal contraction layer, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction 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 anti-mechanical damage layer or/and also be provided with one deck between described hot sealing layer and the described thermal contraction layer or two-layer more than interior anti-mechanical damage layer, interior anti-mechanical damage layer is a kind of or its mixture among LDPE and the LLDPE.The anti-mechanical damage layer of multilayer is set, comprises interior anti-mechanical damage layer and outer anti-mechanical damage layer, can improve the mechanical strength of film, improve puncture-resistant ability and the barrier of film.
Further preferred technical scheme can be: be provided with tack coat between described outer anti-mechanical damage layer and the described interior anti-mechanical damage layer, tack coat is EVA copolymer or anhydride modified PE; In the EVA copolymer tack coat, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of EVA copolymer is 0.93 ~ 0.94g/cm
3Particularly, the resin material polarity of interior anti-mechanical damage layer and outer anti-mechanical damage layer not simultaneously, between arranges tack coat, can improve bond strength between layers, thereby guarantees high paracentesis resistance and the high barrier of film.
Further preferred technical scheme can be: described interior anti-mechanical damage layer is comprised of 30 ~ 50 parts LLDPE and 50 ~ 70 parts LDPE, total umber 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 ℃.
Preferred technical scheme can also be: the number of plies of described multi-layer co-extruded anticoagulation high-barrier 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 for preparing above-mentioned multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, the method is the coextrusion blow moulding, and described thermal contraction layer and described barrier layer are realized the melting charge of described thermal contraction layer to the parcel of the melting charge of described barrier layer by its melting charge separately through a co-extrusion connector, subsequently by the melting charge behind the parcel enter co-extrusion die head runner and with other runners in melting charge coextrusion and blow molding.
Advantage of the present invention and beneficial effect are: the multi-layer co-extruded anticoagulation high-barrier of the present invention heat-shrinkable film adopts EVA copolymer thermal contraction layer parcel PVDC resin extruded, thereby is down to the thermal decomposition of PVDC minimum; In addition, film has added anticoagulant and polyamide-based auxiliary agent in hot sealing layer, given the film anticoagulant functions, and has improved brightness and the smoothness of film, has also improved thickness evenness and the thickness stability of film; This film is provided with the anti-mechanical damage layer of multilayer, and paracentesis resistance is good.The hot strength of this film can reach more than the 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 are no more than 10 g/m
2D, horizontal and vertical shrinkage factor can reach 20 ~ 60%.This film is fit to be applied to the packing of dairy products, frozen food and the special-shaped article such as cheese and butter, especially is fit to be applied to the packing such as meat products such as fresh meat, sausage and poultry meats.
Description of drawings
Fig. 1 is the cross section structure schematic diagram of the embodiment of the invention 1;
Fig. 2 is the cross section structure schematic diagram of the embodiment of the invention 3;
Fig. 3 is the cross section structure schematic diagram of the embodiment of the invention 4;
Fig. 4 is the cross section structure schematic diagram of the embodiment of the invention 6;
Fig. 5 is the cross section structure schematic diagram of the embodiment of the invention 7.
Among the figure: 1, outer anti-mechanical damage layer; 2-1 to 2-2, thermal contraction layer; 3, barrier layer; 4, hot sealing layer; 5-1 to 5-2, interior anti-mechanical damage layer; 6, tack coat.
The specific embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is further described.Following examples only are used for technical scheme of the present invention more clearly is described, and can not limit protection scope of the present invention with this.
The present invention is a kind of multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, and as shown in Figure 1, this film is five shape structures layer by layer, and by the coextrusion blow moulding, its transverse and longitudinal shrinkage factor is 20 ~ 60%.The structure expression of this film is: A/B/C/B/D; In the formula: from left to right represent successively each layer that film is laid from top to bottom successively, A represents outer anti-mechanical damage layer, and B represents the thermal contraction layer, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer anti-mechanical damage layer, namely the A layer is a kind of or its mixture in low density polyethylene (LDPE) and the LLDPE, or is a kind of or its mixture in fatty polyamide and the aromatic polyamide.
The thermal contraction layer, namely the B layer is ethylene-vinyl acetate copolymer.
Barrier layer, namely the C layer is polyvinylidene chloride.
Hot sealing layer, namely the D layer is a kind of or its mixture in low density polyethylene (LDPE), LLDPE and the metallocene PE, and per 100 parts of resins are added with 1 ~ 2 part of macromolecule anticoagulant and 1 ~ 2 part of polyamide-based auxiliary agent that contains polar group.Here, the macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
，
In the formula, m+n=1, x are natural number, R
1Be H or CH
3, R
2Be H or CH
3, R
3Be CH
3Or
Above-mentioned multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film is by the coextrusion blow moulding, and described thermal contraction layer and described barrier layer are realized the melting charge of described thermal contraction layer to the parcel of the melting charge of described barrier layer by its melting charge separately through a co-extrusion connector, subsequently by the melting charge behind the parcel enter co-extrusion die head runner and with other runners in melting charge coextrusion and blow molding.
Embodiment 2
On the basis of embodiment 1, the preferred embodiment of the invention is:
Described outer anti-mechanical damage layer, it is the A layer, formed by 30 ~ 50 parts LLDPEs, 50 ~ 70 parts low density polyethylene (LDPE), 0.05 ~ 0.45 part amide-type slipping agent and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, total umber 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 ℃.
In the described thermal contraction layer, be the B layer, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
Described hot sealing layer, namely the D layer is comprised of 30 ~ 60 parts metallocene PEs, 20 ~ 50 parts LLDPE, 20 ~ 50 parts low density polyethylene (LDPE), polyamide-based auxiliary agent and 1 ~ 2 portion of anticoagulant of 1 ~ 2 part; Wherein, total umber 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 ℃.
The present invention is a kind of multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, and as shown in Figure 2, this film is six shape structures layer by layer, and by the coextrusion blow moulding, its transverse and longitudinal shrinkage factor is 20 ~ 60%.The structure expression of this film is: A/B/C/B/A*/D; In the formula: from left to right represent successively each layer that film is laid from top to bottom successively, A represents outer anti-mechanical damage layer, and A* represents interior anti-mechanical damage layer, and B represents the thermal contraction layer, and C represents barrier layer, and D represents hot sealing layer.
Outer anti-mechanical damage layer, i.e. A layer is comprised of 30 ~ 50 parts LLDPEs, 50 ~ 70 parts low density polyethylene (LDPE), 0.05 ~ 0.45 part amide-type slipping agent and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent; Wherein, total umber 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 ℃.
Interior anti-mechanical damage layer, it is the A* layer, low density polyethylene (LDPE) by 30 ~ 50 parts LLDPEs and 50 ~ 70 parts forms, total umber 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 ℃.
The thermal contraction layer, namely in the B layer, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
Barrier layer, namely the C layer is polyvinylidene chloride.
Described hot sealing layer, namely the D layer is comprised of 30 ~ 60 parts metallocene PEs, 20 ~ 50 parts LLDPE, 20 ~ 50 parts low density polyethylene (LDPE), polyamide-based auxiliary agent and 1 ~ 2 portion of anticoagulant of 1 ~ 2 part; Wherein, total umber 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 ℃.Here, the macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
,
In the formula, m+n=1, x are natural number, R
1Be H or CH
3, R
2Be H or CH
3, R
3Be CH
3Or
。
Above-mentioned multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film is by the coextrusion blow moulding, and described thermal contraction layer and described barrier layer are realized the melting charge of described thermal contraction layer to the parcel of the melting charge of described barrier layer by its melting charge separately through a co-extrusion connector, subsequently by the melting charge behind the parcel enter co-extrusion die head runner and with other runners in melting charge coextrusion and blow molding.
The present invention is a kind of multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, and as shown in Figure 3, this film is seven shape structures layer by layer, and by the coextrusion blow moulding, its transverse and longitudinal shrinkage factor is 20-60%.The structure expression of this film is: A/A*/A*/B/C/B/D; In the formula: from left to right represent successively each layer that film is laid from top to bottom successively, A represents outer anti-mechanical damage layer, and A* represents interior anti-mechanical damage layer, and B represents the thermal contraction layer, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer anti-mechanical damage layer, namely the A layer is a kind of or its mixture in low density polyethylene (LDPE) and the LLDPE, or is a kind of or its mixture in fatty polyamide and the aromatic polyamide.
Interior anti-mechanical damage layer, namely the A* layer is a kind of or its mixture in low density polyethylene (LDPE) and the LLDPE.
The thermal contraction layer, namely the B layer is ethylene-vinyl acetate copolymer.
Barrier layer, namely the C layer is polyvinylidene chloride.
Hot sealing layer, namely the D layer is a kind of or its mixture in low density polyethylene (LDPE), LLDPE and the metallocene PE, and per 100 parts of resins are added with 1 ~ 2 part of macromolecule anticoagulant and 1 ~ 2 part of polyamide-based auxiliary agent that contains polar group.Here, the macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
In the formula, m+n=1, x are natural number, R
1Be H or CH
3, R
2Be H or CH
3, R
3Be CH
3Or
Above-mentioned multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film is by the coextrusion blow moulding, and described thermal contraction layer and described barrier layer are realized the melting charge of described thermal contraction layer to the parcel of the melting charge of described barrier layer by its melting charge separately through a co-extrusion connector, subsequently by the melting charge behind the parcel enter co-extrusion die head runner and with other runners in melting charge coextrusion and blow molding.
Embodiment 5
On the basis of embodiment 4, the preferred embodiment of the invention is:
Described outer anti-mechanical damage layer, i.e. A layer is comprised of 30 ~ 50 parts LLDPEs, 50 ~ 70 parts low density polyethylene (LDPE), 0.05 ~ 0.45 part amide-type slipping agent and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent; Wherein, total umber 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 ℃.
Described interior anti-mechanical damage layer, it is the A* layer, low density polyethylene (LDPE) by 30 ~ 50 parts LLDPEs and 50 ~ 70 parts forms, total umber 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 ℃.
Described thermal contraction layer, be in the B layer, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
Described hot sealing layer, namely the D layer is comprised of 30 ~ 60 parts metallocene PEs, 20 ~ 50 parts LLDPE, 20 ~ 50 parts low density polyethylene (LDPE), polyamide-based auxiliary agent and 1 ~ 2 portion of anticoagulant of 1 ~ 2 part; Wherein, total umber 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 ℃.
The present invention is a kind of multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, and as shown in Figure 4, this film is seven shape structures layer by layer, and by the coextrusion blow moulding, its transverse and longitudinal shrinkage factor is 20-60%.The structure expression of this film is: A/A*/B/C/B/A*/D; In the formula: from left to right represent successively each layer that film is laid from top to bottom successively, A represents outer anti-mechanical damage layer, and A* represents interior anti-mechanical damage layer, and B represents the thermal contraction layer, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer anti-mechanical damage layer, i.e. A layer is comprised of 30 ~ 50 parts LLDPEs, 50 ~ 70 parts low density polyethylene (LDPE), 0.05 ~ 0.45 part amide-type slipping agent and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent; Wherein, total umber 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 ℃.
Interior anti-mechanical damage layer, it is the A* layer, low density polyethylene (LDPE) by 30 ~ 50 parts LLDPEs and 50 ~ 70 parts forms, total umber 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 ℃.
The thermal contraction layer, namely in the B layer, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
Barrier layer, namely the C layer is polyvinylidene chloride.
Hot sealing layer, namely the D layer is comprised of 30 ~ 60 parts metallocene PEs, 20 ~ 50 parts LLDPE, 20 ~ 50 parts low density polyethylene (LDPE), polyamide-based auxiliary agent and 1 ~ 2 portion of anticoagulant of 1 ~ 2 part; Wherein, total umber 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 ℃.Here, the macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
In the formula, m+n=1, x are natural number, R
1Be H or CH
3, R
2Be H or CH
3, R
3Be CH
3Or
Above-mentioned multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film is by the coextrusion blow moulding, and described thermal contraction layer and described barrier layer are realized the melting charge of described thermal contraction layer to the parcel of the melting charge of described barrier layer by its melting charge separately through a co-extrusion connector, subsequently by the melting charge behind the parcel enter co-extrusion die head runner and with other runners in melting charge coextrusion and blow molding.
Embodiment 7
The present invention is a kind of multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film, and as shown in Figure 5, this film is seven shape structures layer by layer, and by the coextrusion blow moulding, its transverse and longitudinal shrinkage factor is 20-60%.The structure expression of this film is: A/adh/A*/B/C/B/D; In the formula: from left to right represent successively each layer that film is laid from top to bottom successively, A represents outer anti-mechanical damage layer, and A* represents interior anti-mechanical damage layer, and adh represents tack coat, and B represents the thermal contraction layer, and C represents barrier layer, and D represents hot sealing layer.
Wherein, outer anti-mechanical damage layer, it is the A layer, formed by 100 parts polyamide, 0.05 ~ 0.45 part amide-type slipping agent 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 copolymer, or the total umber that forms for the aromatic polyamide by 60 ~ 90 parts fatty polyamide and 10 ~ 40 parts is 100 parts mixture, and aromatic polyamide is the copolymer of aliphatic diamine/isophthalic acid/terephthalic acids.
Interior anti-mechanical damage layer, it is the A* layer, low density polyethylene (LDPE) by 30 ~ 50 parts LLDPEs and 50 ~ 70 parts forms, total umber 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 ℃.
Tack coat, namely adh is ethylene-vinyl acetate copolymer or anhydride modified lldpe; In the ethylene-vinyl acetate copolymer tack coat, the vinylacetate construction unit accounts for 10 ~ 20 parts, the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
The thermal contraction layer, namely in the B layer, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
Barrier layer, namely the C layer is polyvinylidene chloride.
Hot sealing layer, namely the D layer is comprised of 30 ~ 60 parts metallocene PEs, 20 ~ 50 parts LLDPE, 20 ~ 50 parts low density polyethylene (LDPE), polyamide-based auxiliary agent and 1 ~ 2 portion of anticoagulant of 1 ~ 2 part; Wherein, total umber 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 ℃.Here, the macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
In the formula, m+n=1, x are natural number, R
1Be H or CH
3, R
2Be H or CH
3, R
3Be CH
3Or
。
Above-mentioned multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film is by the coextrusion blow moulding, and described thermal contraction layer and described barrier layer are realized the melting charge of described thermal contraction layer to the parcel of the melting charge of described barrier layer by its melting charge separately through a co-extrusion connector, subsequently by the melting charge behind the parcel enter co-extrusion die head runner and with other runners in melting charge coextrusion and blow molding.
The above only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away 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. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film is characterized in that: comprise the hot sealing layer that is positioned at outer surface, be positioned at internal layer by at least barrier layer of one deck thermal contraction layer parcel and the outer anti-mechanical damage layer that is positioned at another outer surface;
Wherein, hot sealing layer is a kind of or its mixture in low density polyethylene (LDPE), LLDPE and the metallocene PE; The thermal contraction layer is ethylene-vinyl acetate copolymer; Barrier layer is polyvinylidene chloride; Outer anti-mechanical damage layer is a kind of or its mixture in low density polyethylene (LDPE) and the LLDPE, or is a kind of or its mixture in fatty polyamide and the aromatic polyamide.
2. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film as claimed in claim 1, it is characterized in that: per 100 parts of resins are added with 1 ~ 2 portion of macromolecule anticoagulant that contains polar group in the described hot sealing layer.
3. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film as claimed in claim 2, it is characterized in that: described macromolecule anticoagulant is acrylic acid esters co-polymer, and the general formula of its construction unit is:
In the formula, m+n=1, x are natural number, R
1Be H or CH
3, R
2Be H or CH
3, R
3Be CH
3Or
4. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film as claimed in claim 3, it is characterized in that: per 100 parts of resins also are added with 1 ~ 2 part of polyamide-based auxiliary agent in the described hot sealing layer.
5. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film as claimed in claim 4, it is characterized in that: described hot sealing layer is by 30 ~ 60 parts metallocene PE, 20 ~ 50 parts LLDPE, 20 ~ 50 parts low density polyethylene (LDPE), 1 ~ 2 part polyamide-based auxiliary agent and 1 ~ 2 portion of anticoagulant form, wherein, metallocene PE, total umber 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, and fusing point is 88 ~ 96 ℃;
Described outer anti-mechanical damage layer is comprised of 100 parts polyamide, 0.05 ~ 0.45 part amide-type slipping agent 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 copolymer, or the total umber that forms for the aromatic polyamide by 60 ~ 90 parts fatty polyamide and 10 ~ 40 parts is 100 parts mixture, and aromatic polyamide is the copolymer of aliphatic diamine/isophthalic acid/terephthalic acids;
Or described outer anti-mechanical damage layer is comprised of 30 ~ 50 parts LLDPE, 50 ~ 70 parts low density polyethylene (LDPE), 0.05 ~ 0.45 part amide-type slipping agent and 0.05 ~ 0.45 part of silica or talcum powder anti-blocking agent, wherein, total umber 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 ℃;
In the described thermal contraction layer, the vinylacetate construction unit accounts for 10 ~ 20 parts, and the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
6. such as the described multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film of claim 1 to 5 any one, it is characterized in that: described outer anti-mechanical damage layer is or/and also be provided with one deck or two-layer above interior anti-mechanical damage layer between described hot sealing layer and the described thermal contraction layer, interior anti-mechanical damage layer is a kind of or its mixture in low density polyethylene (LDPE) and the LLDPE.
7. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film as claimed in claim 6, it is characterized in that: be provided with tack coat between described outer anti-mechanical damage layer and the described interior anti-mechanical damage layer, tack coat is ethylene-vinyl acetate copolymer or anhydride modified lldpe; In the ethylene-vinyl acetate copolymer tack coat, the vinylacetate construction unit accounts for 10 ~ 20 parts, the ethene construction unit accounts for 80 ~ 90 parts, and total umber of vinylacetate construction unit and ethene construction unit is 100 parts, and the density of ethylene-vinyl acetate copolymer is 0.93 ~ 0.94g/cm
3
8. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film as claimed in claim 7, it is characterized in that: described interior anti-mechanical damage layer is comprised of 30 ~ 50 parts LLDPE and 50 ~ 70 parts low density polyethylene (LDPE), total umber 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 ℃.
9. multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film as claimed in claim 1, it is characterized in that: the number of plies of described multi-layer co-extruded anticoagulation high-barrier 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. method for preparing multi-layer co-extruded anticoagulation high-barrier heat-shrinkable film claimed in claim 1, the method is the coextrusion blow moulding, it is characterized in that: described thermal contraction layer and described barrier layer are realized the melting charge of described thermal contraction layer to the parcel of the melting charge of described barrier layer by its melting charge separately through a co-extrusion connector, subsequently by the melting charge behind the parcel enter co-extrusion die head runner and with other runners in melting charge coextrusion and blow molding.
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