CN103205045A - Preparation method for oxygen separating degradable plastic thin film - Google Patents
Preparation method for oxygen separating degradable plastic thin film Download PDFInfo
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- CN103205045A CN103205045A CN2013101110894A CN201310111089A CN103205045A CN 103205045 A CN103205045 A CN 103205045A CN 2013101110894 A CN2013101110894 A CN 2013101110894A CN 201310111089 A CN201310111089 A CN 201310111089A CN 103205045 A CN103205045 A CN 103205045A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention relates to a preparation method for an oxygen separating degradable plastic thin film. The method comprises the following steps of: (1) preparing a PBM (Plastic Master Batch) degradable material which is composited by full degradable natural high polymer material synthesized by main raw materials such as starch, plant grease and the like through special treatment with water soluble high polymer material and small amount of resin for later use; (2) mixing low density polyethylene, Pulullan and an antioxygen and an ultraviolet light absorber in a high speed mixer for 25-35 minutes; then, extruding and prilling in a twin-screw extruder to obtain master batch; and (3) mixing the master batch obtained by the step (1) with the PBM degradable material, and extruding and blowing by a plastic film blowing machine to obtain the product. According to the preparation method of the oxygen separating degradable plastic thin film, marketed mature modified starch degradable plastic master batch PBM and Pullulan and thin film grade LDPE are co-mixed, extruded and blown, so that the thin film has good mechanical property and degradability, and meanwhile has higher oxygen separating property.
Description
Technical field
The invention belongs to the plastic film material field, the preparation method of especially a kind of oxygen barrier and degradable plastic film.
Background technology
Flourish along with food, medicine trade, more more urgent than in the past to the demand of novel oxygen barrier wrapping material, exploitation and the novel oxygen barrier material for food, drug packaging of research are important and urgent strategic tasks.Current, the wrapping material problem of environmental pollution has caused the great attention of countries in the world, and the environment friendly of realizing wrapping material has become one of the most attractive and challenging direction of Materials science research.
Biodegradable plastic is one of effective way of administering plastic refuse environmental pollution and buffering petroleum resources contradiction, from the packing bag of food to agricultural film, arrive shells of electronics again, from non-returnable container, edible products to product durable in use, biodegradable plastic just progressively replaces the conventional plastic material, and market outlook are very wide.It is reported, the biodegradable plastic kind of global development is existing tens kinds at present, principal item has: the polyhydroxyalkanoate (PHA, PHB, PHBV etc.) that microbial fermentation is synthetic, the poly(lactic acid) of chemosynthesis (PLA), polycaprolactone, dibasic alcohol dicarboxylic acid aliphatic polyester (PBS), aliphatic/aromatic copolyesters, CO2/ epoxy compound composition copolymer (APC), polycaprolactone (PCL), polyvinyl alcohol (PVA) etc., natural polymer starch plastics and biodegradable plastic blend, polyblend etc.The kind that has entered at present pilot scale or batch process has starch plastics, PHA (PHB, PHBV, PHBH-HX etc.), PLA, PBS, APC, modified PVA, starch/PVA, polyblend such as PLA, PCL and blend etc.
Starch is a kind of abundant, cheap natural macromolecular material of originating, it also is a kind of inexhaustible renewable resources, it can be by biological degradation under multiple envrionment conditions, final degraded product CO2 and H2O can carry out recirculation by photosynthesis of plants, can not cause any pollution to environment.Therefore, starch is widely used in research and the product development of degradable plastics, and has obtained great progress.
At present, the domestic biodegradable packaging film that adopts the starch preparation of having developed, the pertinent literature report is more.For example, POL biodegradable plastic and the preparation technology [CN1624034] thereof of Anlishan Green Environment Science ﹠ Technology Co., Ltd., Shenyang's invention; A kind of biodegradable poly (propylene carbonate) matrix material of CNOOC's invention and preparation method thereof [CN101962470]; The poly lactic acid nano composite material of a kind of complete biodegradable of Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences's invention and preparation method thereof [CN101735583]; Sichuan Food Fermentative Industry Design Academy is about the development of fruits and vegetables nano preservative film and the applied research [Yu Wenhua in green pepper is fresh-keeping thereof, Li Jiezhi etc. the development of fruits and vegetables nano preservative film and the applied research in green pepper is fresh-keeping thereof. Sichuan food and fermentation, 2008 (5): 28-31]; Fujian Province industries under Ministry of the Second Light Industry institute about starch/cerium stearate cooperate the degraded LDPE packaging film of system research [Zhang Huaji. starch/cerium stearate cooperates the research of the degraded LDPE packaging film of system. Chinese plastics, 1999 (2): 60-65]; Institute of Hua Zhong Agriculture University is about the polyethylene/mechanical property of mineral powder composite degradation film and the research [Wang Jinling of light degradation property, Yin Yeping, Deng. mechanical property and the light degradation property of polyethylene/mineral powder composite degradation film. print 2006 (3): 6-10 during chemical industry].
Current starch plastic has experienced three generation products: first-generation product is with the blend preparation of 6%～20% starch and polyolefine (as PE, PP), belong to starch filled plastic, stay the porous polymer that the next one can not degrade again behind the starch degradation and can not recycle.Its fragment causes more severe contamination to soil, so these kind of starch base plastics are called as " false degradative plastics " or " disintegration plastics ".S-generation product carries out the blend preparation with content greater than 50% starch and hydrophilic polymer, stronger physics and chemical action take place between starch and the hydrophilic polymer, and exist with external phase, this material has shown biological degradability, workability, economy, practicality preferably, technology comparative maturity.Third generation product is that thermoplastic starch, native starch, amylose starch or high amylose starch are not being added polymkeric substance, all biological degradation type plastic material that extrusion molding or injection moulding obtain under high temperature, high pressure and super-humid conditions, but still be in conceptual phase at present.
But, the Plastic Packaging Materials that adopts starch to prepare at present, the size of biodegradability depends on the height of starch content in the system.The plastic film material that starch content is high, although biodegradability is better, thin film material mechanics performance shortcoming, and the film oxygen barrier is bad is when being used in packaging field such as food, medicine, because having the quality that in various degree ventilation property has a strong impact on packing.Therefore, good, the mechanical property of development new bio degradation property can satisfy the attention that the packing plastics film of packing service requirements, having a good oxygen barrier is subjected to the countries in the world height.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, provide a kind of treated starch degradable plastics masterbatch PBM through maturation and Propiram (Pullulan) polysaccharide films level Low Density Polyethylene (LDPE) blend to extrude oxygen barrier that blown film obtains and the preparation method of degradable plastic film.
The object of the present invention is achieved like this:
The preparation method of a kind of oxygen barrier and degredation plastic film is:
⑴ mixed Low Density Polyethylene, pulullan polysaccharide and oxidation inhibitor, UV light absorber 25-35 minute in high-speed mixer, extruding pelletization in twin screw extruder obtains master batch then,
⑵ mix master batch with the PBM degradable material, adopt plastic film blowing machine to extrude blown film, namely gets product.
And, the parts by weight difference that feeds intake of described Low Density Polyethylene, pulullan polysaccharide, oxidation inhibitor, UV light absorber and PBM degradable material:
And the described twin screw extruder tube of step ⑴ back segment temperature is divided four sections controls, controls respectively at 180～200 ℃, and the barrel front-end temperature divides four sections controls, controls respectively at 200～230 ℃, and head temperature divides two sections controls, controls respectively at 220～240 ℃
And, the described inflation film manufacturing machine barrel of step ⑵ back segment temperature is divided four sections controls, control respectively at 180～200 ℃, the barrel front-end temperature divides four sections controls, controls respectively at 210～230 ℃, and head temperature divides two sections controls, control respectively at 220～240 ℃, blow-up ratio is 1.5～2.0, screw speed 20～40r/min, pulling speed 10～50m/min.
And described oxidation inhibitor is antioxidant 1010 or oxidation inhibitor 168.
And described UV light absorber is salol or ultraviolet absorbent UV-531.
And, described PBM degradable material will adopt starch, Vegetable oil lipoprotein etc. for the synthetic fully-degradable natural macromolecular material of main raw material after special processing, be composited with water-soluble high-molecular material and low amounts of resin, this PBM degradable material is the commercial goods.
Advantage of the present invention and positively effect are:
1, oxygen barrier provided by the invention and degradable plastic film select for use ripe in the market treated starch degradable plastics masterbatch PBM and Pullulan polysaccharide and film-grade LDPE blend to extrude blown film in the preparation method, utilize the characteristics of LDPE, guarantee film good mechanical performance; Utilize the degradability of PBM and Pullulan, realize the environment friendly of thin-film material; Utilize the high oxygen barrier of Pullulan, improve the oxygen barrier of thin-film material; Utilize starch and Pullulan as glucide similarity structurally, improve the consistency of plastic film material integral body; Blend proportioning by control LDPE/PBM/Pullulan system can realize the regulation and control to oxygen barrier and degradability etc.
2, oxygen barrier provided by the invention and degradable plastic film can decompose under oxygen enrichment and action of microorganisms automatically, film after discarded can be by the digestion of degrading fully of occurring in nature microorganism, final carbonic acid gas and the water of generating can improve 40% than the ldpe film oxygen barrier performance of same thickness.Preparation method's technology of the present invention is simple, production efficiency is high, industrializing implementation is easy, available common plastics inflation film manufacturing machine is produced.
Embodiment
Be described in detail embodiments of the invention below; Need to prove that present embodiment is narrative, is not determinate, can not limit protection scope of the present invention with this.
Related PBM degradable material is to utilize agro-ecology matter resource to be the biodegradable material of main material production among the present invention, be to adopt fully-degradable natural macromolecular material that starch, Vegetable oil lipoprotein etc. synthesize for main raw material after special processing, be composited with water-soluble high-molecular material and low amounts of resin, be the commercial goods.
Embodiment 1:
A kind of oxygen barrier and degradable plastic film, its preparation method may further comprise the steps:
⑴ take by weighing LDPE, 100Kg; The PBM degradable material, 50Kg; Propiram (Pullulan) polysaccharide, 40Kg; Antioxidant 1010,4 Kg; Salol, 0.5Kg;
⑵ ⑴ prescription set by step mixes LDPE, Pullulan polysaccharide and antioxidant 1010, salol etc. 30 minutes in conventional high-speed mixer, and extruding pelletization in twin screw extruder forms master batch; Four sections temperature of extruding granulator barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, and four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 230 ℃, and two sections temperature of head are respectively 230 ℃, 230 ℃;
⑶ mix master batch among the step ⑵ with the PBM degradable material, plastic film blowing machine is extruded blown film, four sections temperature of inflation film manufacturing machine barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 220 ℃, and two sections temperature of head are respectively 230 ℃, 230 ℃.Blow-up ratio 1.5, screw speed 40r/min, pulling speed 30m/min namely gets product.
Embodiment 2:
A kind of oxygen barrier and degradable plastic film, its preparation method may further comprise the steps:
⑴ take by weighing LDPE, 100Kg; The PBM degradable material, 70Kg; Propiram (Pullulan), polysaccharide 40Kg; Antioxidant 1010,4 Kg; Salol, 1Kg;
⑵ ⑴ prescription set by step mixes LDPE, Pullulan polysaccharide and antioxidant 1010, salol etc. 30 minutes in conventional high-speed mixer, and extruding pelletization in twin screw extruder forms master batch; Four sections temperature of extruding granulator barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, and four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 230 ℃, and two sections temperature of head are respectively 230 ℃, 230 ℃;
⑶ mix master batch among the step ⑵ with the PBM degradable material, plastic film blowing machine is extruded blown film, four sections temperature of inflation film manufacturing machine barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 220 ℃, and two sections temperature of head are respectively 230 ℃, 230 ℃.Blow-up ratio 1.5, screw speed 40r/min, pulling speed 30m/min namely gets product.
Embodiment 3:
A kind of oxygen barrier and degradable plastic film, its preparation method may further comprise the steps:
⑴ take by weighing LDPE, 100Kg; The PBM degradable material, 60Kg; Propiram (Pullulan), polysaccharide 30Kg; Antioxidant 1010,3 Kg; Salol, 1Kg;
⑵ ⑴ prescription set by step mixes LDPE, Pullulan polysaccharide and antioxidant 1010, salol etc. 25 minutes in conventional high-speed mixer, and extruding pelletization in twin screw extruder forms master batch; Four sections temperature of extruding granulator barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, and four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 230 ℃, and two sections temperature of head are respectively 230 ℃, 240 ℃;
⑶ mix master batch among the step ⑵ with the PBM degradable material, plastic film blowing machine is extruded blown film, four sections temperature of inflation film manufacturing machine barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 220 ℃, and two sections temperature of head are respectively 230 ℃, 240 ℃.Blow-up ratio 1.5, screw speed 40r/min, pulling speed 30m/min namely gets product.
Embodiment 4:
A kind of oxygen barrier and degradable plastic film, its preparation method may further comprise the steps:
⑴ take by weighing LDPE, 100Kg; The PBM degradable material, 50Kg; Propiram (Pullulan), polysaccharide 40Kg; Antioxidant 1010,4 Kg; Salol, 0.5Kg;
⑵ ⑴ prescription set by step mixes LDPE, Pullulan polysaccharide and oxidation inhibitor 168, ultraviolet absorbent UV-531 etc. 25 minutes in conventional high-speed mixer, and extruding pelletization in twin screw extruder forms master batch.Four sections temperature of extruding granulator barrel back segment are respectively 190 ℃, 190 ℃, 200 ℃, 200 ℃, and four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 230 ℃, and two sections temperature of head are respectively 240 ℃, 240 ℃;
⑶ mix master batch among the step ⑵ with the PBM degradable material, plastic film blowing machine is extruded blown film, four sections temperature of inflation film manufacturing machine barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 220 ℃, and two sections temperature of head are respectively 240 ℃, 240 ℃.Blow-up ratio 1.5, screw speed 40r/min, pulling speed 50m/min namely gets product.
Embodiment 5:
A kind of oxygen barrier and degradable plastic film, its preparation method may further comprise the steps:
⑴ take by weighing LDPE, 100Kg; The PBM degradable material, 70Kg; Propiram (Pullulan), polysaccharide 40Kg; Antioxidant 1010,4 Kg; Salol, 1Kg;
⑵ ⑴ prescription set by step mixes LDPE, Pullulan polysaccharide and oxidation inhibitor 168, ultraviolet absorbent UV-531 etc. 35 minutes in conventional high-speed mixer, and extruding pelletization in twin screw extruder forms master batch.Four sections temperature of extruding granulator barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, and four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 230 ℃, and two sections temperature of head are respectively 240 ℃, 240 ℃;
⑶ mix master batch among the step ⑵ with the PBM degradable material, plastic film blowing machine is extruded blown film, four sections temperature of inflation film manufacturing machine barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 220 ℃, and two sections temperature of head are respectively 230 ℃, 230 ℃.Blow-up ratio 1.5, screw speed 20r/min, pulling speed 10m/min namely gets product.
Embodiment 6:
A kind of oxygen barrier and degradable plastic film, its preparation method may further comprise the steps:
⑴ take by weighing LDPE, 100Kg; The PBM degradable material, 60Kg; Propiram (Pullulan), polysaccharide 30Kg; Oxidation inhibitor 168,3 Kg; Salol, 1Kg;
⑵ ⑴ prescription set by step mixes LDPE, Pullulan polysaccharide and oxidation inhibitor 168, ultraviolet absorbent UV-531 etc. 35 minutes in conventional high-speed mixer, and extruding pelletization in twin screw extruder forms master batch.Four sections temperature of extruding granulator barrel back segment are respectively 180 ℃, 190 ℃, 190 ℃, 200 ℃, and four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 210 ℃, 230 ℃, and two sections temperature of head are respectively 230 ℃, 240 ℃;
⑶ mix master batch among the step ⑵ with PBM degradable material in the step, plastic film blowing machine is extruded blown film, four sections temperature of inflation film manufacturing machine barrel back segment are respectively 190 ℃, 190 ℃, 190 ℃, 200 ℃, four sections temperature of barrel leading portion are respectively 200 ℃, 210 ℃, 220 ℃, 220 ℃, and two sections temperature of head are respectively 230 ℃, 240 ℃.Blow-up ratio 2, screw speed 30r/min, pulling speed 40m/min namely gets product.
Claims (7)
1. the preparation method of an oxygen barrier and degredation plastic film is characterized in that: the steps include:
⑴ mixed Low Density Polyethylene, pulullan polysaccharide and oxidation inhibitor, UV light absorber 25-35 minute in high-speed mixer, extruding pelletization in twin screw extruder obtains master batch then,
⑵ mix master batch with the PBM degradable material, adopt plastic film blowing machine to extrude blown film, namely gets product.
2. the preparation method of oxygen barrier according to claim 1 and degredation plastic film is characterized in that:
The parts by weight difference that feeds intake of described Low Density Polyethylene, pulullan polysaccharide, oxidation inhibitor, UV light absorber and PBM masterbatch:
3. the preparation method of oxygen barrier according to claim 1 and degredation plastic film, it is characterized in that: the described twin screw extruder tube of described step ⑴ back segment temperature is divided four sections controls, control respectively at 180～200 ℃, the barrel front-end temperature divides four sections controls, control respectively at 200～230 ℃, head temperature divides two sections controls, controls respectively at 220～240 ℃.
4. the preparation method of oxygen barrier according to claim 1 and degredation plastic film, it is characterized in that: the described inflation film manufacturing machine barrel of described step ⑵ back segment temperature is divided four sections controls, control respectively at 180～200 ℃, the barrel front-end temperature divides four sections controls, controls respectively at 210～230 ℃, and head temperature divides two sections controls, control respectively at 220～240 ℃, blow-up ratio is 1.5～2.0, screw speed 20～40r/min, pulling speed 10～50m/min.
5. the preparation method of oxygen barrier according to claim 2 and degredation plastic film, it is characterized in that: described oxidation inhibitor is antioxidant 1010 or oxidation inhibitor 168.
6. the preparation method of oxygen barrier according to claim 2 and degredation plastic film, it is characterized in that: described UV light absorber is salol or ultraviolet absorbent UV-531.
7. the preparation method of oxygen barrier according to claim 1 and 2 and degredation plastic film, it is characterized in that: described PBM degradable material will adopt starch, Vegetable oil lipoprotein etc. for the synthetic fully-degradable natural macromolecular material of main raw material after special processing, be composited with water-soluble high-molecular material and low amounts of resin, this PBM degradable material is the commercial goods.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483850A (en) * | 2013-09-22 | 2014-01-01 | 苏州市湘园特种精细化工有限公司 | Biodegradable plastic |
| CN103483664A (en) * | 2013-09-22 | 2014-01-01 | 苏州市湘园特种精细化工有限公司 | Degradable plastic film |
| CN103554788A (en) * | 2013-11-08 | 2014-02-05 | 苏州新颖新材料科技股份有限公司 | Bacteriostat composite resin film and preparation method thereof |
| CN104861246A (en) * | 2014-11-27 | 2015-08-26 | 天津市金盛昱塑料制品有限公司 | Preparation method for degradable plastic composite film with oxygen separation performance |
| CN104859237A (en) * | 2014-11-27 | 2015-08-26 | 天津市金盛昱塑料制品有限公司 | Degradable three-layer co-extrusion plastic composite film with oxygen separation performance |
| CN110227036A (en) * | 2019-05-21 | 2019-09-13 | 南京神奇科技开发有限公司 | A kind of raw material used for cosmetic and preparation method thereof |
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| GB1494253A (en) * | 1974-02-28 | 1977-12-07 | Hayashibara Biochem Lab | Composition of pullulan and thermoplastics |
| CN1418906A (en) * | 2002-11-28 | 2003-05-21 | 玉环县星光环卫薄膜厂 | Double degradation plastic film and production method thereof |
| CN101717533A (en) * | 2009-11-19 | 2010-06-02 | 深圳市新纶科技股份有限公司 | Anti-electrostatic degradable film material and preparation method thereof |
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2013
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| GB1494253A (en) * | 1974-02-28 | 1977-12-07 | Hayashibara Biochem Lab | Composition of pullulan and thermoplastics |
| CN1418906A (en) * | 2002-11-28 | 2003-05-21 | 玉环县星光环卫薄膜厂 | Double degradation plastic film and production method thereof |
| CN101717533A (en) * | 2009-11-19 | 2010-06-02 | 深圳市新纶科技股份有限公司 | Anti-electrostatic degradable film material and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483850A (en) * | 2013-09-22 | 2014-01-01 | 苏州市湘园特种精细化工有限公司 | Biodegradable plastic |
| CN103483664A (en) * | 2013-09-22 | 2014-01-01 | 苏州市湘园特种精细化工有限公司 | Degradable plastic film |
| CN103483850B (en) * | 2013-09-22 | 2016-08-10 | 苏州市湘园特种精细化工有限公司 | A kind of biodegradable plastic |
| CN103554788A (en) * | 2013-11-08 | 2014-02-05 | 苏州新颖新材料科技股份有限公司 | Bacteriostat composite resin film and preparation method thereof |
| CN104861246A (en) * | 2014-11-27 | 2015-08-26 | 天津市金盛昱塑料制品有限公司 | Preparation method for degradable plastic composite film with oxygen separation performance |
| CN104859237A (en) * | 2014-11-27 | 2015-08-26 | 天津市金盛昱塑料制品有限公司 | Degradable three-layer co-extrusion plastic composite film with oxygen separation performance |
| CN104859237B (en) * | 2014-11-27 | 2017-06-06 | 天津市金盛昱塑料制品有限公司 | It is a kind of with barrier degradable three-layer co-extruded composite plastic film |
| CN104861246B (en) * | 2014-11-27 | 2017-09-12 | 天津市金盛昱塑料制品科技股份有限公司 | A kind of preparation method with barrier degradation plastic laminated film |
| CN110227036A (en) * | 2019-05-21 | 2019-09-13 | 南京神奇科技开发有限公司 | A kind of raw material used for cosmetic and preparation method thereof |
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Application publication date: 20130717 |