CN1736812B - Nanometer degradable insulation package membrane and its production method - Google Patents
Nanometer degradable insulation package membrane and its production method Download PDFInfo
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- CN1736812B CN1736812B CN 200510000405 CN200510000405A CN1736812B CN 1736812 B CN1736812 B CN 1736812B CN 200510000405 CN200510000405 CN 200510000405 CN 200510000405 A CN200510000405 A CN 200510000405A CN 1736812 B CN1736812 B CN 1736812B
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Abstract
The invention discloses a production of nanometer degradable high-obstruct packaging film and the method for preparation, specifically a degradable complex film prepared with degradable nanometer polymer as the obstruct material. Said complex film has a layer structure containing at least two outer layers and one interlayer, at least one layer among which is the obstruct layer, the obstruct layerbeing made up of degradable nanometer polymer, and others being made up of degradable polyolefin or polyolefin. The high-obstruct degradable film is transparent and has obstruct to oxygen and aqueousvapor. Modified by nanometer inorganic material, it can prepare 3- 7 layer film, which has high obstruct and makes the article packaged have long shelf retention period and can be degraded after one or two years, and has the same effect with dry complex and coextrusion complex film.
Description
Technical field
The present invention relates to a kind of nanometer degradable insulation package membrane and manufacture method thereof, belong to nanometer plastic cement technical field.
Background technology
In the packaging for foodstuff field, require digestion resistant food package film or bag to meet following requirement usually:
Hot digestion is 40 minutes under 121 ℃ of temperature of √ ability, does not produce distortion inside and outside the packaging bag, and heat-sealing place is not ftractureed, permeated, and layer does not separate.
√ has very high barrier to oxygen, aqueous vapor, food flavor, condiment product fragrance etc.
The √ chemical inertness is good, with soda acid salt solvent, grease chemical reaction does not take place.
The √ mechanical strength is good, heat sealability is good.
√ cooks the ham sausage packing and has meat viscosity.
√ meets the food hygiene requirement, and is nontoxic to human body.
Since the fifties in Europe and developed country exploitation, meat product, high temperature meat product especially as ham sausage etc., mainly uses Vingon (PVDC) as thermophilic digestion and packing.The PVDC film is the film of making through special film-blowing process with the copolymer of vinylidene chloride and vinyl chloride with high obstructing performance, and rejection rate is 8-9cm
3/ m
224h has good mechanical characteristics and heat sealability, and high temperature resistant 140 ℃, low temperature resistant-60 ℃, the higher percent thermal shrinkage that is heated, stable chemical performance is not with various soda acid salt generation chemical reactions, anti-solvent, grease resistance, nontoxic to human body.Classic packaging material for food since the fifties always.The spring in the famous whole nation all, two remittance board ham sausage makes casing with Vingon exactly and make bowel lavage, makes at high temperature sterilization more than 121 ℃.Can guarantee the quality more than six months under the normal temperature.Along with the enhancing of food health consciousness, environmental protection consciousness, in the world some developed countries oneself begin to ban use of the contact packing of the material of chloride ion-containing as food, and advocate the use degradable environment friendly material in various field.Because Vingon (PVDC) can not be degraded, and does not have environmental protection characteristic, reclaim difficulty, so people are constantly studying its substitute.
The problems referred to above at the existence of Vingon PVDC material, it is the package compound film that interlayer is produced that present food flexible packing mainly adopts with the aluminium foil, structure is PET/dam/AL/dam/CPP, has high barrier, high temperature resistant, safe in utilization, but still there are a lot of shortcomings in it, the advantage that lacks PVDC in the use, as:
The √ platinum foil is subjected to the fold frangibility and crackle occurs, makes the barrier forfeiture;
The √ platinum foil is opaque, and the customer can't see inner package, inconvenient purchase of customer;
√ can not use microwave heating;
The √ price is higher.
In order to overcome the above problems, it is the food package film of interlayer with PVDC that Chinese patent ZL99117622.7 discloses a kind of, its cross section structure is PET/adh/PVDC/adh/CPP or BOPP/adh/PVDC/adh/CPP (adh is an adhesive agent), composite methods is successively adopted in this invention, each layer mono-material film is compound one by one, produce the complex film product.When using this kind composite film packaging food, the PVDC rete is direct contact food not, has satisfied the requirement of foodsafety, and having remedied is the shortcoming of the package compound film of interlayer with the aluminium foil, has tangible technological advance.Can finely satisfy the packaging for foodstuff requirement though this kind is the food package film of interlayer with PVDC, still can not solve self can't degrade, discontented sufficient environmental protection requirement problem.
At present, domestic mainly prolonging uses Vingon (PVDC) as food high temperature boiling and packing, and consumption is huge, and only casing film just has nearly 30,000 tons market consumption.Past PVDC pleurodiaphragmatic in terspace material is dependence on import always; at present domestic nearly 2,000,000,000 yuan of the gross investments of building, planning to build 60,000 tons of PVDC resins of production; existing various packaging films all are difficult to satisfy simultaneously above-mentioned various advantages on the market; especially degradable environmental protection characteristic; therefore, suddenly wait to develop and have degradable, meet environmental protection requirement, satisfy the packaging film material of packaging for foodstuff requirement.
Summary of the invention
The object of the present invention is to provide a kind of nanometer degradable insulation package membrane product, a kind of specifically with the degradable complex film of degradable nano poly-mer as the barrier material preparation.
Another object of the present invention provides the manufacture method of above-mentioned nanometer degradable insulation package membrane.
Described complex film has at least two skins and the laminar texture that interlayer constitutes, and wherein one deck is a barrier layer at least, and this barrier layer is the degradable nano poly-mer, and other layer is degradable poly alkene or polyolefin.
In the described laminar texture, can exist one deck to be used for bonded assembly adhesive phase as required between layer and the layer; Facing mutually under the similar situation of two-layer material polarity, also can be without adhesive agent.
No matter be three layers, five layers or seven layers, arbitrarily adjacent two layers of material is if the identical or close material of polarity, and directly coextrusion is compound; If adjacent two layers of material is a polarity material inequality or not close arbitrarily, then must increase one deck tack coat between the two, in order to guarantee the combined strength bination between two layers.
Adhesives is selected " Bai Lao " binder resin of Mitsui ﹠ Co., Ltd. " 528H " or E.I.Du Pont Company for use; Polyolefin can be selected high pressure polyethylene 7042 resins such as grade for use.
Above-mentioned degradable nano poly-mer is through nano imvite or clay, SiO
2, TiO
2, CaCO
3The degradable nano poly-mer that obtains with polymerization or mixing method modification Deng nano inorganic material;
Described poly-mer can be one or more the combination in polyvinyl alcohol (PVA), aliphatic copolyester (APC), poly-second lactones (PCL) and the polyolefins (PO); Be preferably polyvinyl alcohol (PVA).
Can also further contain photodegradable aid in the described poly-mer.
The weight content of described nano inorganic material in poly-mer is 1-10%, and photodegradable aid content is the 0.1-5% of polymer weight, can be according to degradation time and speed adjustment.
Above-mentioned nano inorganic material can be polynite, SiO
2, TiO
2Or CaCO
3Deng the nano inorganic material that can be used for the blend granulation.
Polyolefin resin of the present invention is that homopolymerization does not have or copolymer, the preferred glass transition temperature is 20~100 ℃ a polyolefin resin, melting point resin is 60 ℃---125 ℃, the polyolefin resin of inside and outside both sides will have good heat sealability, impressionability and formability simultaneously.
The preparation method of above-mentioned nanometer polymer comprises: carry out polymerization after inorganic nano material is embedded monomer, or with inorganic nano material and the direct blending of poly-mer, these methods and the poly-mer that obtains are fully open in the prior art, as US4739007, US5385776, US5091462, US5102948, US5552469, and in the Adv.Mater. in 1996 8,29 disclosed silicate nano-composition layering poly-mer; PlasticsTechnology1998, property that the nano-complex of disclosed clay filled provides in 1,21 etc.
Among the present invention, preferably adopt the mode of blend to prepare the nano modification poly-mer.
In the various structures, PO is preferably degradable PO.Be mainly biodegradable polyethylene, polypropylene etc.In order to improve performance, also can be between skin and barrier layer, to increase PO layer or degraded layer.
The preparation method of above-mentioned high-block degradable membrane is: with behind the carbon dioxide resin of said ratio component, maleic acid shortcake, the nano inorganic material mixing granulation (perhaps directly using the carbon dioxide resin), send into the interlayer (being barrier layer) of multi-layer co-extruded equipment, this layer can be respectively: B, C, D layer in three layers of A/B/A, five layers of A/B/C/B/A, the seven layers of A/B/C/D/C/B/A structure; With other material coextrusion; The extrusion temperature of each layer is decided on the material difference, is generally 80-170 ℃; The compound temperature of getting to know of coextrusion is no more than 170 ℃; Other polyolefin resin glass temperature should be less than or equal to 90 ℃; Inflation draft ratio (vertical/horizontal stroke) is no more than 4, is preferably 2-3.
The multi-layer co-extruded technology that the inventive method adopts can be coextrusion blow method, coextrusion casting method, co-extruding biaxial stretched.
Raw MAT'L great majority of the present invention are easy to heat degradation, at first answer the processing temperature of strict control plasticizing extruder, die head during production, and the production and processing temperature is answered≤205 ℃; Fitness for purpose plasticizing extruder, die head temperature range of control:
Plasticizing extruder one district: 80-10 ℃;
Plasticizing extruder two districts: 105-150 ℃;
Plasticizing extruder three districts: 170-205 ℃;
150 ℃≤die head temperature≤205 ℃; Temperature accuracy ± 1.0 ℃ are best.
The plasticizing extruder screw rod is for by variant, and compression ratio is 2.8~3.2, and helical angle should 〉=40 ℃, reduce acute angle or dead angle as far as possible, avoids because of heat degradation or degrades long-time delay of partial material, on machine barrel, screw rod.
Should select linear polyethylene flushing screw rod and machine barrel, die head before unlatching machine, the shutdown for use, cause the material degraded to avoid being heated for a long time.
Described multi-layer co-extruded membrane can be to utilize common co-extrusion film upper blowing method or lower blowing method to make degraded co-extrusion film, or utilizes the double bubble process coextrusion to make degraded co-extrusion shrink film; Or utilize blown film method stretch processes to make the degraded base material film.
According to the goods requirement, can produce transparent type, nontransparent type; Put into the barrier layer in many plasticizing extruders respectively; be respectively B, C, the D layer in three layers of A/B/A, five layers of A/B/C/B/A, the seven layers of A/B/C/D/C/B/A structure; or wherein any one deck; it is respectively the light degradation material of polyolefin class degradative plastics (light/biodegradable master batch), adjustable degradation speed and time that other plasticizing is extruded; it is the inside and outside both sides of multiple-structure, infiltrates in order to protection germ, water and moisture and causes degraded too fast.
In the preparation process, 80-205 ℃ of plasticizing extruder temperature control.
Described polyolefin resinoid glass temperature≤90 ℃ is so that actv. and CO
2The coextrusion of base resin; The polyolefin resinoid can be PE, PP or EVA, also can be poly(lactic acid), poly-own lactones.
According to customer requirement, high-block degradable membrane of the present invention can be made into the film that thickness is 0.01-0.1mm, can be the sheet material of 0.11-0.2mm also, is used to process synthetic goods.
Polyolefin resin of the present invention is homopolymer or copolymer, the preferred glass transition temperature is 20-100 ℃ a polyolefin resin, melting point resin is 60 ℃-125 ℃, and the polyolefin resin of inside and outside both sides will have good heat sealability, impressionability and formability simultaneously.
The present invention is that degraded by erosions such as temperature, bacterium, mould too fast in order to overcome the food package film bag, causes too early degraded, and influence is set by the ratio 70% of the shelf life of bag article.
In addition, according to the requirement of user's barrier property, can select single material or multiple material coextrusion for use.
Another object of the present invention is to provide the production method of above-mentioned packaging film, bag, described method adopts multi-layer co-extruded technology and production technology, and cost is low, technology is simple, one-shot forming.
High-block degradable membrane of the present invention has the good transparency, vapour lock, heat sealability, impressionability, solved the problem that the compound or coextruded plastic food-film bag of existing dry type does not both at home and abroad have the environmental protection characteristics, satisfy the digestion resistant food package film that generally adopts at present, the performance requriements of bag, can be degraded to small molecule material under light and/or biological agent, be a kind of high-performance environment-friendly product.
This high-block degradable membrane transparency is good, oxygen, aqueous vapor had barrier, add biodegradable and/or photodegradative material, as carbon dioxide resin (PPC), polyvinyl alcohol (PVA), aliphatic copolyester (APC), poly-second lactones (PCL) or polyolefins (PO) raw material, adopt multi-layer co-extruded technology to obtain food package film, bag.This high-block degradable membrane is behind the nano grade inorganic material modification, by oneself known PP TYPE, co-extrusion shrink film device fabrication 3-7 tunic are arranged, make product have high barrier, and can guarantee that products to be packaged have long shelf Keeping life, and it was degraded after 1 year or 2 years, it is compound to have dry type, the effect of coextru-lamination plastic film.
Description of drawings
Fig. 1 is nanometer PPC or nanometer PVA three-decker food package film, the bag section drawing as intermediate barrier layer; Structure and consist of PO/ nanometer PPC or nanometer PVA/PO;
Fig. 2 is five-layer structure food package film, bag section drawing;
Fig. 3 is seven-layer structure food package film, bag section drawing
Fig. 4 is a co-extrusion film production process process block scheme;
Fig. 5 is a thermal contraction production technology of stretching film process block scheme.
The specific embodiment
In one embodiment of the present of invention, described packaging film, bag are PO/ nanometer PPC or nanometer PVA/PO three-decker.
In another embodiment of the present invention, described food package film, bag be PO/ nano modification PPC, (PCL) or (APC) at least a or its combination/PVA/PPC, PCL or APC at least a or its combination/POD five-layer structure.The thickness of various embodiment is 5-50um/10-100um/5-50um5-30um/5-30um/10-50um/5-30um/5-30u m.
Referring to accompanying drawing,
The structure of Fig. 1 is PO/ nanometer PPC or nanometer PVA/PO three-decker, and wherein the A layer is PO, and the B layer is a kind of or its combination among nanometer PPC, the nanometer PVA.
Fig. 2 be PO/ nano modification PPC, (PCL) or (APC) at least a or its combination/PVA/PPC, PCL or APC at least a or play combination/POD five-layer structure, wherein the A layer is PO, the B layer be nano modification PPC, (PCL) or (APC) at least a or its combination.
Production method is: select plasticizing extruder according to the number of plies of food package film bag, extrude by co-extrusion die head, batch through air-cooled, water-cooled (on blow or under blow) rear haulage.
The production method of thermal contraction stretch film is: extrude, downward-blowing water-cooling, synchronous bidirectional stretching, thermal finalization, batch and obtain the thermal contraction stretch film by co-extrusion film head through too much platform plasticizing extruder.
The product of the present invention transparency is for being more than 70% at total light transmittance behind the 500nm, and barrier properties for gases is: 23 ℃, 65%RH, 1 standard atmosphere are depressed, and the oxygen transit dose is 20cm
3/ 24H1atm.
The present invention prepares membrane product Performance Detection index
Claims (8)
1. nanometer degradable insulation package membrane, described packaging film is by the degradable complex film of degradable nano poly-mer as the barrier material preparation, described degradable complex film has at least two skins and the laminar texture that interlayer constitutes, wherein one deck is a barrier layer at least, this barrier layer is the degradable nano poly-mer, other layer is degradable poly alkene or polyolefin, it is characterized in that, described degradable nano poly-mer is through nano imvite or clay, SiO
2, TiO
2Or CaCO
3The degradable nano poly-mer that nano inorganic material obtains with polymerization or mixing method modification, described nano inorganic material is polynite, SiO
2, TiO
2Or CaCO
3The nano inorganic material that can be used for the blend granulation, the weight content of described nano inorganic material in described degradable nano poly-mer is 1-10%; Contain photodegradable aid in the described degradable nano poly-mer, photodegradable aid content is the 0.1-5% of degradable nano polymer weight.
2. packaging film according to claim 1 is characterized in that, described degradable nano poly-mer is one or more the combination in polyvinyl alcohol, aliphatic copolyester, poly-second lactones and the polyolefins.
3. packaging film according to claim 2 is characterized in that, described degradable nano poly-mer is a polyvinyl alcohol.
4. according to claim 2 or 3 described packaging films, it is characterized in that, in the described laminar texture, exist one deck to be used for bonded assembly adhesive phase between layer and the layer.
5. packaging film according to claim 4 is characterized in that, described adhesive phase is " 528H " of Mitsui ﹠ Co., Ltd. or " Bai Lao " binder resin of E.I.Du Pont Company; Polyolefin is high pressure polyethylene 7042 resins.
6. the manufacture method of the described nanometer degradable insulation package membrane of claim 1, it is characterized in that, described nanometer degradable insulation package membrane is co-extrusion film or stretch film, the preparation method of described co-extrusion film is: the number of plies according to packaging film is selected plasticizing extruder, extrude by co-extrusion die head, batch through air-cooled or water-cooled rear haulage and obtain the co-extrusion film; The preparation method of described stretch film is: through too much platform plasticizing extruder by co-extrusion die head extrude, downward-blowing water-cooling, synchronous bidirectional stretching, thermal finalization and batch and obtain stretch film.
7. manufacture method according to claim 6 is characterized in that, the processing temperature of described plasticizing extruder, die head, production and processing temperature≤205 ℃.
8. manufacture method according to claim 6, it is characterized in that, the screw rod of described plasticizing extruder is for pursuing variant, compression ratio is 2.8~3.2, helical angle 〉=40 °, reduce acute angle or dead angle as far as possible, avoid being detained and degrade, on machine barrel, screw rod because of heat degradation or partial material are long-time.
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Cited By (1)
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CN104364081A (en) * | 2011-12-15 | 2015-02-18 | 蒂帕有限责任公司 | Biodegradable sheet |
Families Citing this family (8)
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DE112007001518T5 (en) * | 2006-06-27 | 2009-05-07 | Sumitomo Chemical Co., Ltd. | Process for producing a polyolefin resin film |
ES2365640T3 (en) * | 2006-12-29 | 2011-10-07 | Dow Global Technologies Llc | FILMS, ARTICLES PREPARED FROM THEM, AND METHODS OF OBTAINING. |
CN101195694B (en) * | 2007-12-22 | 2011-01-19 | 西北师范大学 | Degradable composite plastics and method for producing the same |
CN102729563B (en) * | 2012-06-01 | 2015-01-07 | 朝阳佛瑞达科技有限公司 | Easily degradable paper-like novel high-barrier packaging film for UHT liquid milk |
CN104149406A (en) * | 2014-07-17 | 2014-11-19 | 上海唐科新型包装材料有限公司 | Degradable plastic film |
CN108773140B (en) * | 2018-06-05 | 2024-04-05 | 洛阳兴瑞新型膜材料有限公司 | Nano modified high-barrier composite film and production method thereof |
CN109233232A (en) * | 2018-08-21 | 2019-01-18 | 昆明理工大学 | A method of preparing high barrier polylactic acid nano packaging film |
CN113524642A (en) * | 2021-08-02 | 2021-10-22 | 浙江大成新材料科技有限公司 | High-barrier degradable composite film for food packaging and manufacturing method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN2457074Y (en) * | 2000-12-18 | 2001-10-31 | 平湖市比例包装材料有限公司 | Composite film for packaging food |
CN1355753A (en) * | 1999-06-14 | 2002-06-26 | 国际纸业公司 | Multilayer rein/paper laminate structrue containing at least polymer/nanoclay composite layer and packaging materials made thereof |
JP2003001771A (en) * | 2001-06-22 | 2003-01-08 | Morinaga Milk Ind Co Ltd | Thermoplastic resin multilayered laminated sheet and multilayered laminated container |
-
2005
- 2005-01-07 CN CN 200510000405 patent/CN1736812B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1355753A (en) * | 1999-06-14 | 2002-06-26 | 国际纸业公司 | Multilayer rein/paper laminate structrue containing at least polymer/nanoclay composite layer and packaging materials made thereof |
CN2457074Y (en) * | 2000-12-18 | 2001-10-31 | 平湖市比例包装材料有限公司 | Composite film for packaging food |
JP2003001771A (en) * | 2001-06-22 | 2003-01-08 | Morinaga Milk Ind Co Ltd | Thermoplastic resin multilayered laminated sheet and multilayered laminated container |
Non-Patent Citations (1)
Title |
---|
JP 2003001771 A,全文. |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104364081A (en) * | 2011-12-15 | 2015-02-18 | 蒂帕有限责任公司 | Biodegradable sheet |
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