CN102390148A - High-separation multi-layer co-extrusion bio-based blow moulding film and preparation method thereof - Google Patents
High-separation multi-layer co-extrusion bio-based blow moulding film and preparation method thereof Download PDFInfo
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- CN102390148A CN102390148A CN2011101956610A CN201110195661A CN102390148A CN 102390148 A CN102390148 A CN 102390148A CN 2011101956610 A CN2011101956610 A CN 2011101956610A CN 201110195661 A CN201110195661 A CN 201110195661A CN 102390148 A CN102390148 A CN 102390148A
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Abstract
The invention relates to a high-separation multi-layer co-extrusion bio-based blow moulding film and a preparation method thereof. The high-separation multi-layer co-extrusion bio-based blow moulding film comprises at least one separation layer, wherein at least one plastic film layer is arranged on the inner side and outer side of the separation layer respectively; and the separation layer is a poly(propylene carbonate) layer. The high-separation multi-layer co-extrusion bio-based blow moulding film provided by the invention has good separation property and high inter-layer strength and ensures that the layers are not easily separated; the film has excellent toughness; and moreover, the physicochemical properties and biological properties reach the standard according to tests, and the leftover materials and wastes can be degraded and recycled, thus the film is non-toxic and harmless to the environment.
Description
Technical field
The present invention relates to multi-layer co-extruded bio-based blown film of a kind of high barrier and preparation method thereof, belong to technical field of polymer materials.
Background technology
The transfusion package container mainly contains vial, soft infusion bottle (PP (polypropylene) or PE (polyethylene)), soft three types of the infusion bag (PVC (polyvinyl chloride) and non-PVC) of moulding of moulding at present.Initial transfusion package is a vial, improves though experienced several times, has broken away from not the general character defective of glass all the time, as frangible, the bottleneck sealing is poor, puncture is prone to produce exfoliation and increase problem such as air secondary pollution when using.Therefore, plastic containers (plastic bottle and PVC infusion bag) occurred, at the beginning of the nineties, developed the non-PVC composite membrane transfusion bag again in the sixties in 20th century.Novel soft transfusion package and the traditional glass packing of moulding is compared, at cost, safe and sanitary and easy-to-use etc. all have significant advantage aspect several, but at barrier, sealing and transparently show deficiency aspect several.Especially, the most outstanding with the influence that barrier was brought.Oxygen is the principal element that causes injection rotten, if the oxygen-barrier property of transfusion package container does not pass a test, then possibly cause medicine to lose efficacy in advance or rotten, thereby cause serious consequence.The Obstruct membrane that packaging field is commonly used at present is PVDC (polyvinylidene chloride) film and EVOH (ethylene-vinyl alcohol copolymer) film.Wherein the PVDC film has higher barrier, but because the leftover pieces of PVDC film and discarded object are difficult to recycle, emits HCl gas during burning disposal, can cause environmental pollution.The EVOH film has the advantage of nontoxic and nonpollution environment, but it is to prepare through rubbing method, thus complicated operation, and production efficiency is low.Along with the extensive use of flexible packaging infusion bag, increasing to the demand of flexible packaging infusion bag, the white pollution that causes will be serious day by day.Therefore, the low pollution of development of new high-barrier infusion bag packaging material are extremely urgent.
Summary of the invention
In view of this, the object of the present invention is to provide the multi-layer co-extruded bio-based blown film of a kind of high barrier, it has the good barrier property to steam and oxygen, is suitable for preparing the bio-based thin-film material of medical infusion bags.
For realizing above-mentioned purpose; The present invention provides a kind of high barrier multi-layer co-extruded bio-based blown film; The multi-layer co-extruded bio-based blown film of said high barrier comprises one deck barrier layer at least, has the plastic film layers of one deck at least respectively in the inboard and the outside of said barrier layer; Said barrier layer is the poly (propylene carbonate) layer.
Preferably, the mean molecule quantity of wherein said poly (propylene carbonate) is 6～140,000, and vitrification point is 10～40 ℃, and heat decomposition temperature is 210 ℃.
Preferably, be provided with the adhesive phase that one deck is used to bond between wherein said barrier layer and the adjacent plastic film layers.
Preferably, adhesive-free layer between wherein said barrier layer and the adjacent plastic film layers.
Preferably, wherein said plastic sheeting is one or more in polypropylene screen, density polyethylene film with high, LLDPE film, PA membrane, PETG film, polycarbonate membrane or the polybutylene terephthalate (PBT) film.
Preferably, wherein said adhesive is one or both in vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, maleic anhydride modified polypropylene, maleic anhydride modified polyethylene or the acrylic acid ester.
Preferably, the thickness of wherein said barrier layer is 3～10 μ m.
Preferably, the thickness of wherein said plastic film layers is 5～20 μ m.
Preferably, the thickness of wherein said adhesive phase is 1～10 μ m.
The preparation method of the multi-layer co-extruded bio-based blown film of described high barrier is: the number of plies according to the infusion bag film is selected the coextrusion film blowing machine, extrudes through co-extrusion die head, batches through air-cooled, water-cooled rear haulage, can obtain the multi-layer co-extruded bio-based blown film of high barrier.
In addition; PPC (poly (propylene carbonate)) conduct is the environmentally-friendly plastic of the synthetic a kind of Wholly-degradable property of raw material with carbon dioxide and expoxy propane; Comparing oxygen barrier property (being similar to nylon resin) and the relatively cheap price with excellence with other degradation material, is a kind of desirable barrier material; Also possessed excellent processability simultaneously, directly blowing film forming in inflation film manufacturing machine.Compare advantages such as having production technology is simple, production efficiency is high, the variation of product size scale with the coating film forming mode of PVA.According to These characteristics, be a kind of bio-based thin-film material with PPC as the composite membrane that barrier layer and other plastic film layers co-extrusion obtain with high barrier, extensive market prospects is arranged.
The multi-layer co-extruded bio-based blown film of high barrier provided by the present invention, barrier property is good, and interlaminar strength is high, and each layer is not easily separated; Has excellent flexibility; Physical and chemical performance and biological property test are up to standard, and be good to the barrier property of steam and oxygen, and leftover pieces and discarded object degradable are recycled, and be nontoxic to environment.
Description of drawings
Fig. 1 is the structural representation of the embodiment of the invention 1;
Fig. 2 is the structural representation of the embodiment of the invention 2;
Fig. 3 is a co-extrusion film production process process block diagram.
The specific embodiment
Below will combine concrete embodiment that the present invention is done further detailed description.
For the convenience of explaining, the following noun of specific justice:
The inboard of barrier layer is meant the side that the coextrusion blow film contacts with packing material, and the outside of barrier layer is meant the opposite side that the coextrusion blow film contacts with environment.
With the one deck that intercepts inboard next-door neighbour is interior one deck, with interior one deck next-door neighbour be interior two layers, with interior two layers of next-door neighbour be interior three layers; With the one deck that intercepts outside next-door neighbour be outer one deck, with outer one deck next-door neighbour be outer two layers, with outer two layers of next-door neighbour be outer three layers.
Difference according to the packing material demand; Plastic film layers also can be different; Common said plastic sheeting can be PP (polypropylene) film, HDPE (high density polyethylene (HDPE)) film, LLDPE (LLDPE) film, PA (polyamide) film, one or more in PET (PETG) film, PC (Merlon) film or PBT (polybutylene terephthalate (PBT)) film.
In order to improve the adhesive strength of each layer of the present invention, can also between barrier layer and adjacent plastic film layers, be provided with layer of adhesive layer (what play is the effect of solubilizer).At this moment, interior one deck is an adhesive phase with outer one deck, and interior two layers, interior three layers, outer two layers, outer three layers is plastic film layers.Under the similar situation of adjacent two layers material polarity (because of two kinds of close not phase-splittings of material blend uniformly of polarity), also can be without adhesive.
Please refer to Fig. 1.In the present embodiment, the multi-layer co-extruded bio-based blown film of said high barrier by outer 1, barrier layer 2, internal layer 3 totally three layers constitute.Barrier layer 2 is PPC, and its thickness is 6 μ m, and outer one deck is the PET film of 5 μ m, and interior one deck is the PET film of 5 μ m.
The specific embodiment is following, and what present embodiment adopted is three-layer co-extruded inflation film manufacturing machine.
| T 1(℃) | T 2(℃) | T 3(℃) | T 4(℃) | |
| Outer 1 (PET) | 245 | 260 | 275 | 290 |
| Barrier layer 2 (PPC) | 100 | 115 | 130 | 150 |
| Internal layer 3 (PET) | 245 | 260 | 275 | 290 |
According to hauling speed and the extruded velocity of the needed thickness adjustment layers of material of each layer in each screw rod.
Present embodiment gained blown film product gas barrier is: oxygen transit dose≤18cm
2/ m
224H0.1Mpa (ASTMD3985), steam penetrating capacity≤4g/m
224H (JISE0208).
Please refer to Fig. 2.In the present embodiment, the multi-layer co-extruded bio-based blown film of high barrier by outer two layer 4, outer one deck 1, barrier layer 2, interior one deck 3 and interior two layer 5 totally five layers constitute.Outer two layer 4 is plastic film layers with interior two layer 5, and outer one deck 1 is an adhesive phase with interior one deck 3.Barrier layer 2 is PPC, and its thickness is 10 μ m.Outer two layer 4 is the PP film of 13 μ m, and interior two layer 5 is the PE film of 10 μ m.Outer one deck 1 is the EEA of 1 μ m, and interior one deck 3 also is the EEA of 1 μ m.Present embodiment needs five extruders to extrude five layers blown film.
The practical implementation method is following, and present embodiment need adopt the five-layer co-squeezing inflation film manufacturing machine.
| T 1(℃) | T 2(℃) | T 3(℃) | T 4(℃) | |
| Outer two layer 4 (PP) | 140 | 160 | 180 | 220 |
| Outer one deck 1 (EAA) | 150 | 170 | 185 | 210 |
| Barrier layer 2 (PPC) | 110 | 125 | 140 | 160 |
| Interior one deck 3 (EAA) | 150 | 170 | 185 | 210 |
| Interior two layer 5 (PE) | 120 | 140 | 160 | 180 |
According to hauling speed and the extruded velocity of the needed thickness adjustment layers of material of each layer in each screw rod.
Present embodiment gained blown film product gas barrier is: oxygen transit dose≤18cm
2/ m
224H0.1Mpa (ASTMD3985), steam penetrating capacity≤4g/m
224H (JISE0208).
The difference of present embodiment and embodiment 2 is that outer two layer 4 is the PET film of 8 μ m, and outer one deck 1 is the EVA of 1 μ m, and other layers of materials and thickness are identical with embodiment 2.Present embodiment needs five extruders to extrude five layers blown film.
The practical implementation method is following, and present embodiment need adopt the five-layer co-squeezing inflation film manufacturing machine.
| T 1(℃) | T 2(℃) | T 3(℃) | T 4(℃) | |
| Outer two layer 4 (PET) | 245 | 260 | 275 | 290 |
| Outer one deck 1 (EVA) | 120 | 140 | 160 | 180 |
| Barrier layer 2 (PPC) | 110 | 125 | 140 | 160 |
| Interior one deck 3 (EAA) | 150 | 170 | 185 | 210 |
| Interior two layer 5 (PE) | 120 | 140 | 160 | 180 |
According to hauling speed and the extruded velocity of the needed thickness adjustment layers of material of each layer in each screw rod.
Present embodiment gained blown film product gas barrier is: oxygen transit dose≤10cm
2/ m
224H0.1Mpa (ASTMD3985), steam penetrating capacity≤5g/m
224H (JISE0208).
In embodiments of the invention 1-3; The preparation method of the multi-layer co-extruded bio-based blown film of said high barrier is: the number of plies according to the infusion bag film is selected the coextrusion film blowing machine; Extrude through co-extrusion die head, batch (see figure 3) through air-cooled, water-cooled (on blow or under blow) rear haulage.
The multi-layer co-extruded bio-based blown film of high barrier of the present invention through long term test, all has excellent waterproof property and gas barrier property, and preparation is simple, nontoxic pollution-free.
The above is merely preferred embodiment of the present invention, and protection scope of the present invention is not constituted any limitation, and scope of patent protection of the present invention is as the criterion with the content of claims.
Claims (10)
1. the multi-layer co-extruded bio-based blown film of high barrier is characterized in that, the multi-layer co-extruded bio-based blown film of said high barrier comprises one deck barrier layer at least, has the plastic film layers of one deck at least respectively in the inboard and the outside of said barrier layer; Said barrier layer is the poly (propylene carbonate) layer.
2. the multi-layer co-extruded bio-based blown film of high barrier according to claim 1 is characterized in that the mean molecule quantity of said poly (propylene carbonate) is 6～140,000, and vitrification point is 10～40 ℃, and heat decomposition temperature is 210 ℃.
3. the multi-layer co-extruded bio-based blown film of high barrier according to claim 1 is characterized in that, is provided with the adhesive phase that one deck is used to bond between said barrier layer and the adjacent plastic film layers.
4. the multi-layer co-extruded bio-based blown film of high barrier according to claim 1 is characterized in that, adhesive-free layer between said barrier layer and the adjacent plastic film layers.
5. the multi-layer co-extruded bio-based blown film of high barrier according to claim 1; It is characterized in that said plastic sheeting is one or more in polypropylene screen, density polyethylene film with high, LLDPE film, PA membrane, PETG film, polycarbonate membrane or the polybutylene terephthalate (PBT) film.
6. the multi-layer co-extruded bio-based blown film of high barrier according to claim 3; It is characterized in that said adhesive is one or both in vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, maleic anhydride modified polypropylene, maleic anhydride modified polyethylene or the acrylic acid ester.
7. the multi-layer co-extruded bio-based blown film of high barrier according to claim 1 and 2 is characterized in that, the thickness of said barrier layer is 3～10 μ m.
8. the multi-layer co-extruded bio-based blown film of high barrier according to claim 1 and 2 is characterized in that, the thickness of said plastic film layers is 5～20 μ m.
9. the multi-layer co-extruded bio-based blown film of high barrier according to claim 3 is characterized in that, the thickness of said adhesive phase is 1～10 μ m.
10. the preparation method of the multi-layer co-extruded bio-based blown film of the described high barrier of claim 1; It is characterized in that; Said preparation method is: the number of plies according to the infusion bag film is selected the coextrusion film blowing machine; Extrude through co-extrusion die head, batch, can obtain the multi-layer co-extruded bio-based blown film of high barrier through air-cooled, water-cooled rear haulage.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103950257A (en) * | 2014-05-08 | 2014-07-30 | 武汉华丽生物材料有限公司 | High-barrier bio-based composite membrane and preparation method thereof |
| CN104890332A (en) * | 2015-05-30 | 2015-09-09 | 汕头市金品塑胶实业有限公司 | High-barrier coated sheet and production method thereof |
| CN105365317A (en) * | 2015-12-07 | 2016-03-02 | 武汉华丽生物股份有限公司 | Biologic high-barrier compound membrane and preparation method thereof |
| CN105383133A (en) * | 2015-12-17 | 2016-03-09 | 武汉华丽生物股份有限公司 | Bio-based high-barrier sheet material and preparation method thereof |
| CN105419351A (en) * | 2015-12-23 | 2016-03-23 | 刘家容 | Composite membrane medical soft plastic infusion bag and preparation method thereof |
| CN105838046A (en) * | 2016-05-16 | 2016-08-10 | 久裕电子科技（江苏）有限公司 | Three-layer co-extrusion high-temperature-resistant glue blocking release film and production process thereof |
| CN108909114A (en) * | 2018-06-14 | 2018-11-30 | 深圳市通产丽星股份有限公司 | A kind of carbon dioxide-base composite material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103950257A (en) * | 2014-05-08 | 2014-07-30 | 武汉华丽生物材料有限公司 | High-barrier bio-based composite membrane and preparation method thereof |
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| CN108909114A (en) * | 2018-06-14 | 2018-11-30 | 深圳市通产丽星股份有限公司 | A kind of carbon dioxide-base composite material and preparation method |
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Application publication date: 20120328 |