CN101306593B - Multilayer coextruding pyrocondensation film - Google Patents
Multilayer coextruding pyrocondensation film Download PDFInfo
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Abstract
2499. The invention provides a multilayer coextrusion heat shrinking film which comprises a surface layer, a sandwich layer and a heat-sealing layer. The surface layer and the heat-sealing layer are respectively bonded with the sandwich layer through a bonding layer; the sandwich layer comprises a mixture composed of 98Wt% of PVDC resin and 2Wt% of processing aid, wherein, the PVDC resin is a VDC-MA copolymer, the melting point is 150 DEG C, the density is 1.7g/cm<3>, and the processing aid is epoxidized soybean oil or other plasticizing agent systems. The proposal increases the shrinkage factor of the multilayer coextrusion heat shrinking film, and improves the barrier property; the multilayer coextrusion heat shrinking film has excellent heat sealing performance, and is widely applied to the vacuum shrink package.
Description
Technical field
The present invention relates to a kind of heat shrink films, relate in particular to a kind of PVDC multilayer coextruding pyrocondensation film, belong to plastic products, field of packaging material.
Background technology
The packing of commodity for the storage of commodity, transport, guarantee the quality, beautify and have important function.Traditional manner of packing mainly is packed in cases and enlacement packaging.But 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.Based on this, along with the appearance of new material, people begin to adopt polyethylene (PE) heat-shrinkable film to pack to replace packed in cases and tie up.The polyethylene heat-shrinkable film has lot of advantages as packing: economical with materials, reduce cost, protection against the tide, health, easy to use; Attractive in appearance, the conserve space of commodity after the packing.The heat-shrinkable film packing can be accomplished " fit " packing, makes commodity have distinguished outward appearance; The technology of the package of heat-shrinkable film packing is also simple especially, as long as heating just can be finished packaging process to heat-shrinkable film, improved the production efficiency of commodity packaging.
Multilayer coextruding pyrocondensation film has been widely used in vacuum shrink wrapping and MAP field, has good gas barrier property, is used as packaging bag and uses.Difference according to packing machine can be carried out hot cutter heating, PULSE HEATING and high-frequency heating.
The basic structure of multilayer heat shrinkable film comprises: a sandwich layer, a hot sealing layer and a top layer, sandwich layer are gas barrier material, such as PVDC or EVOH; Hot sealing layer is polyolefinic heat-sealable material, such as LDPE, LLDPE, VLDPE, ULDE, SURLYN, EVA etc.; The material that the top layer is wearability, smooth property, processability is good adopts metallocene PE as extexine usually.
The packaging bag of adopting above-mentioned material to make can't be satisfied the environment instructions for use well.For example adopt LDPE to do heat-sealable material, its heat seal strength and hot sticky intensity are all not enough when running into pollution.Select for use LLDPE to do heat-sealable material, its low-temperature heat-sealing is relatively poor.Select for use EVA as heat-sealable material, its heat seal strength is not enough.Under this background, metallocene LLDPE and metallocene VLDPE are used to heat-sealable material, but exposed following problem: add and extrude moment of torsion man-hour and reach pressure more greatly and raise, output can't improve, also can occur melting the body fragmentation, cause heat sealability to descend, the heat-sealing line is bad, transparency is not high, and its outward appearance is not beautiful.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of PVDC multilayer coextruding pyrocondensation film is provided, be intended to effectively solve that present multi-layer co-extruded thermal contraction bag shrinkage factor is low, barrier is poor, technological deficiency such as more crisp under the low temperature.
Purpose of the present invention is achieved through the following technical solutions:
Multilayer coextruding pyrocondensation film, comprise top layer, sandwich layer and hot sealing layer, top layer and hot sealing layer are bonding from the both sides and the sandwich layer of sandwich layer by adhesive layer respectively, characteristics are: described sandwich layer comprises the mixture of being made up of the processing aid of the polyvinylidene chloride resin of 98Wt% and 2Wt%, described polyvinylidene chloride resin is vinylidene chloride-maleic anhydride co-polymer, 150 ℃ of fusing points, density 1.7g/cm
3, described processing aid is an epoxidized soybean oil; Described top layer comprises resin a and resin b, and wherein, the weight content scope of resin a is 0%～60%, and the weight content scope of resin b is 40%～100%; Described resin a density is 0.88～0.917g/cm
3, be the mixture of ethylene-alpha-olefin copolymer or multiple ethylene-alpha-olefin copolymer, the alhpa olefin weight content is 1%～20%; Described resin b is the copolymer of ethene and methacrylic acid, acrylic acid, vinylacetate, butyl acrylate or ethyl acrylate, and wherein carboxylic acid monomer's weight content is 5%～25%; Described alhpa olefin is propylene, butylene, hexene-1 or octene-1; Described hot sealing layer comprises resin c and resin d, and wherein, the weight content scope of resin c is 50%～100%, and the weight content scope of resin d is 0%～50%; The density of described resin c is 0.88～0.917g/cm
3, be the copolymer of ethene and propylene, butylene, hexene-1 or octene-1, wherein the alhpa olefin weight content is 1%～20%; The density of described resin d is 0.90～0.92g/cm
3, the mixture of one or more in anchor line (string) low density polyethylene (LDPE), polyolefin plastomers, ultra-low density polyethylene, the Linear medium-density polyethylene.
Further, above-mentioned multilayer coextruding pyrocondensation film, the thickness range of described sandwich layer are 3～12 microns, and the thickness range on described top layer is 8～10 microns, and the thickness range of described hot sealing layer is 18～25 microns, and the thickness in monolayer of described adhesive layer is 3～5 microns.
Again further, above-mentioned multilayer coextruding pyrocondensation film, described adhesive layer comprises ethylene-vinyl acetate copolymer or maleic anhydride modified ethene polymers, when comprising ethylene-vinyl acetate copolymer, the weight percentage of the vinylacetate of ethylene-vinyl acetate copolymer resin is 5%～25%, and density is 0.93～0.94g/cm
3
Technical solution of the present invention has overcome that general multilayer coextruding pyrocondensation film shrinkage factor is low, barrier is poor, shortcoming such as more crisp under the low temperature.The multilayer coextruding pyrocondensation film of being created has a lot of particular performances, such as the heat sealability of excellence: good antipollution heat sealability, stable heat seal strength, wide heat-sealing scope, low-temperature heat-sealing and hear resistance; Good optical property: transparency is better; Good impact strength: paracentesis resistance, lower temperature resistance, low volatility, good barrier properties for gases, adhesion-resistant slippery and bag, belong to the vacuum shrink wrap material that improves air conditions, be used for the fresh-keeping shrink wrapping of manufactured meat, fresh meat and cheese.Production cost is low, and result of use is better, has brought very considerable economic.
Below in conjunction with accompanying drawing technical solution of the present invention is described further:
Fig. 1: the cross section structure schematic diagram of multilayer coextruding pyrocondensation film of the present invention.
Description of drawings
The implication of each Reference numeral sees the following form among the figure:
The specific embodiment
As shown in Figure 1, multilayer coextruding pyrocondensation film is five-layer structure, and structure is: A//D//B//E//C.Comprise top layer A, sandwich layer B and hot sealing layer C, top layer A is bonding by adhesive layer D and sandwich layer C, and hot sealing layer C is bonding by adhesive layer E and sandwich layer B.The thickness range of top layer A is between 8～10 microns, and the thickness range of sandwich layer B is between 3～12 microns, and the thickness range of hot sealing layer C is between 18～25 microns, and the thickness range of adhesive layer D and adhesive layer E is between 3～5 microns.Have good oxygen and water vapor barrier, high shrinkage factor, good antipollution heat sealability and puncture resistance can be used for the fresh-keeping shrink wrapping of cold fresh meat and cheese.
Sandwich layer B comprises the mixture of being made up of the processing aid of the PVDC resin of 98Wt% and 2Wt%, and described PVDC resin is the VDC-MA co-polymer, 150 ℃ of fusing points, density 1.7g/cm
3, described processing aid is epoxidized soybean oil or other plasticiser system.
Top layer A comprises resin a and resin b, and wherein, the weight content scope of resin a is 0%～60%, and the weight content scope of resin b is 40%～100%; Described resin a density is 0.88～0.917g/cm
3, be the mixture of ethylene-alpha-olefin copolymer or multiple ethylene-alpha-olefin copolymer, the alhpa olefin weight content is 1%～20%; Described resin b is the copolymer of ethene and EMAA, EAA, EVA, EBA or EEA, and wherein carboxylic acid monomer's weight content is 5%～25%.
Hot sealing layer C comprises resin c and resin d, and wherein, the weight content scope of resin c is 50%～100%, and the weight content scope of resin d is 0%～50%; The density of described resin c is 0.88～0.917g/cm
3, be the copolymer of ethene and propylene, butylene, hexene-1 or octene-1, wherein the alhpa olefin weight content is 1%～20%; The density of described resin d is 0.90～0.92g/cm
3, be one or more the mixture among LLDPE, POP, VLDPE, LMDPE, the CEO.
Adhesive layer D and adhesive layer E comprise EVA or maleic anhydride modified ethene polymers, and when comprising EVA, the weight percentage of the VA of EVA resin is 5%～25%, and density is 0.93～0.94g/cm
3
Embodiment 1:
Join each layer raw material earlier, the VDC-MA co-polymer of sandwich layer B:98kg and the epoxidized soybean oil of 2kg.The ethene of the ethylene-alpha-olefin copolymer of top layer A:60kg and 40kg-EMAA copolymer, the density of ethylene-alpha-olefin copolymer are 0.88g/cm
3The ethylene-propylene copolymer of hot sealing layer C:50kg and the LLDPE of 50kg, the density of ethylene-propylene is 0.88g/cm
3, the density of LLDPE is 0.90g/cm
3The EVA of adhesive layer D and adhesive layer E:5kg, density is 0.93g/cm
3
The extruder that each layer raw material is added each layer respectively carries out fusion plastification, thereby enters the circular melt pipe that distribution that a multi-layer co-extruded circular die carries out melt forms a multilayer then; Circular melt pipe carries out entering hot water storgae behind the cooling forming through vacuum sizing and is heated to the suitable temperature that propels the price of, and charges into compressed air and carry out horizontal inflation and longitudinal stretching between two pairs of nip rolls; Carry out rolling after former film after the moulding is heat-treated, carry out radiation treatment then and behind certain dosage, carry out bag.
Embodiment 2:
Join each layer raw material earlier, the VDC-MA co-polymer of sandwich layer B:98kg and the epoxidized soybean oil of 2kg.The multiple ethylene-alpha-olefin copolymer of top layer A:50kg and the ethene of 50kg-EAA copolymer, the density of multiple ethylene-alpha-olefin copolymer is 0.917g/cm
3The ethylene-butene copolymer of hot sealing layer C:60kg and the POP of 40kg, the density of ethylene-butene copolymer is 0.917g/cm
3, the density of POP is 0.92g/cm
3The EVA of adhesive layer D and adhesive layer E:25kg, density is 0.94g/cm
3
Other method and structure is identical with the specific embodiment 1.
Embodiment 3:
Join each layer raw material earlier, the VDC-MA co-polymer of sandwich layer B:98kg and the epoxidized soybean oil of 2kg.The ethene of top layer A:100kg-EVA copolymer.The ethene of hot sealing layer C:100kg--hexene-1 copolymer, the density of ethene--hexene-1 copolymer is 0.90g/cm
3Adhesive layer D and the maleic anhydride modified ethene polymers of adhesive layer E:5kg.
Other method and structure is identical with the specific embodiment 1.
After testing, the multilayer coextruding pyrocondensation film that adopts technical solution of the present invention to obtain, its main performance index sees Table 1.
Table 1
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| In length and breadth to hot strength | 56MPa? | 58MPa? | 50MPa? |
| In length and breadth to elongation at break | 110％? | 115％? | 113％? |
| Sealing-strength | 15N/15mm? | 17N/15mm? | 16N/15mm? |
The invention a kind of heat shrink films of multilayer, overcome that general polyamide multilayer coextruding pyrocondensation film shrinkage factor is low, barrier is poor, shortcoming such as more crisp under the low temperature, have a lot of particular performances, such as the heat sealability of excellence: good antipollution heat sealability, stable heat seal strength, wide heat-sealing scope, low-temperature heat-sealing and hear resistance; Good optical property: transparency is better; Good impact strength: paracentesis resistance, lower temperature resistance, low volatility, good barrier properties for gases, adhesion-resistant slippery and bag belong to the vacuum shrink wrap material that improves air conditions.
This heat shrink films has the advantage of low temperature highly shrinkable; Its preparation method has that difficulty of processing is low, the advantage of non-environmental-pollution.Be used for varieties of food items, meat product, marine product, bird product, life, cooked fresh-keeping packaging, especially cut apart the packing of fresh meat product.Also can be used for the shrink wrapping of all kinds of article, as skin packagings such as handicraft, medicine, commodity, electronic product, chemical products and thermal contractive label, trade marks.
Below only be concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (3)
1. multilayer coextruding pyrocondensation film, comprise top layer, sandwich layer and hot sealing layer, top layer and hot sealing layer are bonding from the both sides and the sandwich layer of sandwich layer by adhesive layer respectively, it is characterized in that: described sandwich layer comprises the mixture of being made up of the processing aid of the polyvinylidene chloride resin of 98Wt% and 2Wt%, described polyvinylidene chloride resin is vinylidene chloride-maleic anhydride co-polymer, 150 ℃ of fusing points, density 1.7g/cm
3, described processing aid is an epoxidized soybean oil;
Described top layer comprises resin a and resin b, and wherein, the weight content scope of resin a is 0%～60%, and the weight content scope of resin b is 40%～100%; Described resin a density is 0.88～0.917g/cm
3, be the mixture of ethylene-alpha-olefin copolymer or multiple ethylene-alpha-olefin copolymer, the alhpa olefin weight content is 1%～20%; Described resin b is the copolymer of ethene and methacrylic acid, acrylic acid, vinylacetate, butyl acrylate or ethyl acrylate, and wherein carboxylic acid monomer's weight content is 5%～25%;
Described alhpa olefin is propylene, butylene, hexene-1 or octene-1;
Described hot sealing layer comprises resin c and resin d, and wherein, the weight content scope of resin c is 50%～100%, and the weight content scope of resin d is 0%～50%; The density of described resin c is 0.88～0.917g/cm
3, be the copolymer of ethene and propylene, butylene, hexene-1 or octene-1, wherein the alhpa olefin weight content is 1%～20%; The density of described resin d is 0.90～0.92g/cm
3, the mixture of one or more in anchor line (string) low density polyethylene (LDPE), polyolefin plastomers, ultra-low density polyethylene, the Linear medium-density polyethylene.
2. multilayer coextruding pyrocondensation film according to claim 1, it is characterized in that: the thickness range of described sandwich layer is 3～12 microns, the thickness range on described top layer is 8～10 microns, and the thickness range of described hot sealing layer is 18～25 microns, and the thickness in monolayer of described adhesive layer is 3～5 microns.
3. multilayer coextruding pyrocondensation film according to claim 1, it is characterized in that: described adhesive layer comprises ethylene-vinyl acetate copolymer or maleic anhydride modified ethene polymers, when comprising ethylene-vinyl acetate copolymer, the weight percentage of the vinylacetate of ethylene-vinyl acetate copolymer resin is 5%～25%, and density is 0.93～0.94g/cm
3
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| CN101913282A (en) * | 2010-08-26 | 2010-12-15 | 河南大有塑业发展有限公司 | High-barrier composite film and production method thereof |
| CN102126322A (en) * | 2011-01-17 | 2011-07-20 | 吴卓彬 | Multilayer heat shrinkable film |
| CN102407969A (en) * | 2011-07-22 | 2012-04-11 | 苏州天加新材料有限公司 | Heat-shrinkable bag for packaging marine products |
| CN102642359A (en) * | 2012-04-28 | 2012-08-22 | 张建岭 | High-separation multilayer joint-extrusion shrink film |
| CN103042791B (en) * | 2012-12-21 | 2015-04-08 | 江阴升辉包装材料有限公司 | Multi-layer co-extrusion anticoagulative high-resistance heat-shrinkable film and preparation method thereof |
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| CN104924713A (en) * | 2015-05-22 | 2015-09-23 | 苏州天加新材料股份有限公司 | Multilayer co-extrusion packaging film with high gas barrier property |
| CN105034504A (en) * | 2015-05-22 | 2015-11-11 | 苏州天加新材料股份有限公司 | High-barrier-property multilayer-co-extrusion packaging film |
| CN105034505A (en) * | 2015-05-22 | 2015-11-11 | 苏州天加新材料科技有限公司 | High-air-barrier-property multilayer-co-extrusion heat-sealing film |
| CN106346926A (en) * | 2016-08-31 | 2017-01-25 | 江阴升辉包装材料有限公司 | High-speed packaged multilayer co-extrusion, thermal forming and drawing bottom film and production process |
| CN108329863A (en) * | 2018-03-28 | 2018-07-27 | 浙江达因包装材料有限公司 | A kind of processing technology of high-performance shrink film |
| CN108516212A (en) * | 2018-03-30 | 2018-09-11 | 浙江众成包装材料股份有限公司 | A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films and preparation method thereof |
| CN110964451B (en) * | 2019-12-03 | 2022-01-04 | 上海辉柯新材料科技有限公司 | Aluminum foil adhesive tape processing technology |
| CN112715637A (en) * | 2020-12-31 | 2021-04-30 | 广东鹰金钱海宝食品有限公司 | Preservation method for preventing tuna white meat from being oxidized |
| CN113968413B (en) * | 2021-10-27 | 2023-03-10 | 雷诺丽特恒迅包装科技（北京）有限公司 | Milk storage bag and preparation method thereof |
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| CN1898086A (en) * | 2003-12-22 | 2007-01-17 | 纳幕尔杜邦公司 | Thermoformable polyester-containing laminates |
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| CN1898086A (en) * | 2003-12-22 | 2007-01-17 | 纳幕尔杜邦公司 | Thermoformable polyester-containing laminates |
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