CN102407644A - Biodegradable multilayer composite polyethylene film and preparation method thereof - Google Patents
Biodegradable multilayer composite polyethylene film and preparation method thereof Download PDFInfo
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- CN102407644A CN102407644A CN2011102076482A CN201110207648A CN102407644A CN 102407644 A CN102407644 A CN 102407644A CN 2011102076482 A CN2011102076482 A CN 2011102076482A CN 201110207648 A CN201110207648 A CN 201110207648A CN 102407644 A CN102407644 A CN 102407644A
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- 239000004698 Polyethylene Substances 0.000 title claims abstract description 120
- -1 polyethylene Polymers 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 38
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
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- 244000226021 Anacardium occidentale Species 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
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- 235000019438 castor oil Nutrition 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 239000000944 linseed oil Substances 0.000 claims description 4
- 235000021388 linseed oil Nutrition 0.000 claims description 4
- 239000010466 nut oil Substances 0.000 claims description 4
- 230000002207 retinal effect Effects 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a biodegradable multilayer composite polyethylene film and a preparation method thereof. The film comprises the following three layers: (1) a polyethylene internal layer containing an inorganic filling material; (2) a polyethylene middle layer containing a compatibilizer; (3) a polyethylene external layer containing starch, grease and metallocene polyethylene. The preparation method provided in the invention comprises the following steps: (1) respectively mixing master batch components in each layer of the composite film and subjecting an obtained mixture to melt plasticization at a temperature of 70 to 200 DEG C; (2) allowing raw materials in each layer after melt plasticization to enter into a same die and carrying out co-extrusion to obtain the multilayer composite film. The biodegradable multilayer composite polyethylene film provided in the invention can maintain its inherent physical and mechanical properties for a long time under normal storage and usage conditions; once the film turns into waste, under the action of the factors of water, microbes and the like, the strength of the film decreases in a short time, the film undergoes fragmentation and returns back to nature, thereby posing no harm to environment, and a fast degradation speed and a good degradation effect are achieved.
Description
Technical field
The invention belongs to plastic package material, be specifically related to a kind of biodegradable MULTILAYER COMPOSITE polyethylene film and preparation method thereof.
Background technology
Be accompanied by the fast development of Chinese commodity economy, the demand cumulative year after year of plastic package material.Wherein, polyethylene (PE) is as most important plastic raw materials, and its goods are widely used in fields such as agricultural mulching and packaging material.Yet its pollution problem to environment also highlights thereupon.This is that its discarded object long-term existence out of doors will cause " white pollution " because polyethylene is difficult to by daylight and microbial degradation, and " white pollution " become harmful in harmless, has become the task of top priority.The biodegradable complexity of polyethylene is relevant with molecular weight, and the above alkane of side chain and 20 carbon is difficult to by biodegradation.Therefore polyethylene is carried out modification and make it become the degradable materials minimizing, have very major and immediate significance the load that environment produces.
The modified poly ethylene product has had wide application market in the packaging material field.Yet, also have many technical problems that needs to be resolved hurrily.For example the direct mechanical blend will cause lacking bonding force between separation system two phases; When coextrusion prepares multilayer Polyethylene film; Often owing to melt viscosity between layer and the layer does not match; The fluidity and the melt viscosity of interlayer do not match, and make that the one deck in the film partial cross section a certain section is easy to squeezed out by other one deck, and have caused brilliant point.
After U.S. Pat 4133784 is used ethylene-acrylic acid copolymer and starch blending polyethylene is carried out modification, but, cause the thin film physics performance to descend because modified material is too much.Chinese patent CN 200810011021 uses bio-based materials PLA and polyethylene blend to carry out modification, but cost is higher, complex process.
Summary of the invention
The objective of the invention is to overcome the deficiency of above prior art, a kind of structure and stable performance are provided, and the biodegradable MULTILAYER COMPOSITE polyethylene film in discarded back.
Another object of the present invention provides the preparation method of above-mentioned film.
Biodegradable MULTILAYER COMPOSITE polyethylene film of the present invention comprises following three layers:
(1) contains the polyethylene inner layer of inorganic filler;
(2) contain the polyethylene middle level of bulking agent;
(3) contain the outer layer of polyethene of starch, grease and metallocene PE.
Said polyethylene inner layer has only a surface adhesion in this structure and one deck of contact packing object.Two first type surfaces in said polyethylene middle level all directly adhere in this structure.Said outer layer of polyethene is to have only in this structure and not one deck of contact packing object of a surface adhesion.
Said polyethylene inner layer master batch raw material consists of: inorganic filler 5～35%, all the other are polyethylene.The granularity of inorganic filler is 800～2000 orders generally speaking.
Said polyethylene middle level master batch raw material consists of: bulking agent 10～60%, all the other are polyethylene.
Said outer layer of polyethene master batch raw material consists of: starch 20～50%, grease 15～25%, metallocene PE 15～30%, all the other are polyethylene.
Further, said inorganic filler is one or more the mixture in calcium carbonate, talcum powder or the zinc stearate.
Further, said bulking agent is one or several the mixture in ethylene-acrylic acid copolymer, acrylic acid, maleic anhydride, maleimide, the ethyl acrylate.
Further, said grease is a kind of in epoxidized soybean oil, castor oil, retinal, epoxy linseed oil or the cashew nut oil.
Further, the thickness of said MULTILAYER COMPOSITE polyethylene film is 25～50 microns.
Except metallocene PE, all the other polyethylene can be in high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), the LLDPE (LLDPE) any one among the present invention.
The polyethylene inner layer of biodegradable multilayer composite plastic film of the present invention, the effect of inorganic filler are to improve the light sensitivity of polyethylene layer, promote light degradation, and have improved additive extinction efficient.In macromolecular material, add sensitising agents such as transition metal complex, utilize action of ultraviolet radiation generation free radical, can further impel the polymer molecular chain fracture and cause it to lose mechanical strength, change structure.
The effect that the bulking agent that polyethylene middle level described in the invention is contained plays is to make blend that compatibility preferably arranged, and the cohesive force of two-phase interface strengthens, and has both played the effect of thermograde and stress gradient, plays the effect of bonding coat again.For example: ethylene-acrylic acid copolymer (EAA) and starch have very strong affinity, its carboxyl can with the hydroxyl generation association of starch, the chain structure of EAA composites of starch is similar with poly chain structure on the other hand.The moulding temperature difference of having avoided the melt temperature difference and having produced; Enough cohesivenesses are arranged between each layer; Each layer hybrid resin rheological property is roughly the same, under head temperature and shear rate, has identical or similar viscosity, forms more consistent viscosity combination and makes blend that compatibility is preferably arranged like this; And the bonding force of two-phase interface increases mechanical property and obviously improvement of the transparency.
Outer layer of polyethene described in the invention contains starch and grease, and wherein grease is a kind of in epoxidized soybean oil, castor oil, retinal, epoxy linseed oil, the cashew nut oil.Starch and oily blend can promote the degraded of polyethylene layer, and starch is not participated in the degraded of polymer directly, but the mixture of adding starch and oil can promote the deterioration of polymer, and its result shows as carbonyl increase, oxidizing temperature decline, variation of melting.
The preparation method of biodegradable MULTILAYER COMPOSITE polyethylene packaging film of the present invention comprises following two steps:
(1) the master batch raw material components of each layer of composite membrane is mixed respectively is incorporated in the extruder separately in 70～200 ℃ of fusion plastifications; This can carry out according to any method of the prior art, for example in double screw extruder, carries out blend.
(2) each layer raw materials melt plasticizing back gets in the same mouthful of mould, and co-extrusion gets multi-layer compound film.The multi-layer co-extruded technology of the present invention's employing is through each layer component of this composite membrane of design, and the moulding temperature difference that has reduced between layer and the layer satisfies the technological requirement that co-extrusion modling is processed.
Biodegradable MULTILAYER COMPOSITE polyethylene film described in the invention is under normal storage, service condition, but its intrinsic physical and mechanical property of long preservation, and in case become discarded object; Under effect of factors such as water and microorganism; Intensity reduces more in a short time, fragmentation and back to nature, therefore unlikely harm environment; Degradation speed is fast, good degrading effect.Preparation method of the present invention has low, the advantage of simple technology of cost.
The specific embodiment
Embodiment 1
A kind of biodegradable MULTILAYER COMPOSITE polyethylene film; Comprise following three layers: percentage meter by weight, polyethylene inner layer master batch raw material consists of: polyethylene inner layer master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 89%, calcium carbonate and talcum powder mixture (wherein carbonated calcium 7%) 10.7%, zinc stearate 0.3%; Polyethylene middle level master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 50%, ethylene-acrylic acid copolymer 47%, maleic anhydride 3%; Outer layer of polyethene master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 35%, starch 35%, epoxidized soybean oil 15%, metallocene PE (trade mark 1018, Co., Ltd of ExxonMobil Chemical) 15%.
The biodegradable MULTILAYER COMPOSITE polyethylene film preparation method of present embodiment comprises the steps:
(1) with polyethylene inner layer master batch component, polyethylene middle level master batch component, outer layer of polyethene master batch component is mixed the back respectively and is dropped in the double screw extruder separately
Preparation polyethylene inner layer master batch double screw extruder parameter is provided with as follows:
Screw speed: 80rpm vacuum: 0.5kPa draw ratio: 48 rate of feeding: 1.75kg/h
Machine barrel is respectively distinguished temperature and is provided with as follows:
I district: 80 ℃ of II districts: 130 ℃ of III districts: 180 ℃ of IV districts: 190 ℃ of V districts: 190 ℃
The double screw extruder parameter of preparation polyethylene middle level master batch is provided with as follows:
Screw speed: 80rpm vacuum: 0.5kPa draw ratio: 48 rate of feeding: 1.75kg/h
Machine barrel is respectively distinguished temperature and is provided with as follows:
I district: 80 ℃ of II districts: 130 ℃ of III districts: 180 ℃ of IV districts: 190 ℃ of V districts: 190 ℃
The double screw extruder parameter of preparation outer layer of polyethene master batch is provided with as follows:
Screw speed: 80rpm vacuum: 0.5kPa draw ratio: 48 rate of feeding: 1.0kg/h
Machine barrel is respectively distinguished temperature and is provided with as follows:
I district: 80 ℃ of II districts: 130 ℃ of III districts: 180 ℃ of IV districts: 190 ℃ of V districts: 190 ℃
(2) in same mouthful of mould of master batch entering that each layer master batch component obtains behind the double screw extruder fusion plastification, co-extrusion gets multi-layer compound film.
Each master batch converges master batch in the cylindrical shell of the concetrated pipe through extrusion die, and together through die head, wherein the die head size can be regulated according to the film thickness needs under the condition of streamline flow.Obtaining thickness through up-coiler is 30 microns film.
The properties of product testing result (detects according to standard GB 13022-91 " film stretching method for testing performance ") as follows: hot strength (Mpa): horizontal 32, vertical 45; Elongation at break: horizontal 245, vertical 215, shock resistance: impact damaged quality 170g.The shop film experiment of carrying out in THE LOWER YANGTZE VALLEY area, the west and south, Jiangsu Province: after 3 months, film begins to burst apart, and is broken into 2～3cm after 6 months
2, can only see tiny filiform after 12 months.
Embodiment 2
A kind of biodegradable MULTILAYER COMPOSITE polyethylene film; Comprise following three layers: percentage meter by weight; Polyethylene inner layer master batch raw material consists of: polyethylene (LD100AC visits in Shanghai than getting plastics Co., Ltd) 85%, calcium carbonate and talcum powder mixture 14.7% (by weight, calcium carbonate accounts for 10%), zinc stearate 0.3%; Polyethylene middle level master batch raw material consists of: polyethylene (trade mark LD100AC visits in Shanghai than getting plastics Co., Ltd) 40%, ethylene-acrylic acid copolymer 57%, maleic anhydride 3%; Outer layer of polyethene master batch raw material consists of: polyethylene (trade mark LD100AC visits in Shanghai than getting plastics Co., Ltd) 25%, starch 35%, epoxidized soybean oil 25%, metallocene PE (trade mark 1018 Co., Ltds of ExxonMobil Chemical) 15%.
Adopt the composition of present embodiment, the film thickness of preparation is 30 microns, and the properties of product testing result (detects according to standard GB 13022-91 " film stretching method for testing performance ") as follows:
Hot strength (Mpa): horizontal 33, vertical 46; Elongation at break: horizontal 230, vertical 220, shock resistance: impact damaged quality 160g.The shop film experiment of carrying out in THE LOWER YANGTZE VALLEY area, the west and south, Jiangsu Province: after 3 months, film begins to burst apart, and is broken into 2～3cm after 6 months
2, can only see tiny filiform after 12 months.
Embodiment 3
A kind of biodegradable MULTILAYER COMPOSITE polyethylene film; Comprise following three layers: percentage meter by weight, polyethylene inner layer master batch raw material consists of: polyethylene inner layer master batch raw material consists of: polyethylene (PE BT 100K Brazil Braskem) 95%, calcium carbonate 5%; Polyethylene middle level master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 90%, acrylic acid 10%; Outer layer of polyethene master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 47%, starch 20%, cashew nut oil 15%, metallocene PE (trade mark 1018, Co., Ltd of ExxonMobil Chemical) 18%.
Adopt the composition of present embodiment, the film thickness of preparation is 30 microns, and the properties of product testing result (detects according to standard GB 13022-91 " film stretching method for testing performance ") as follows:
Hot strength (Mpa): horizontal 34, vertical 48; Elongation at break: horizontal 240, vertical 235, shock resistance: impact damaged quality 185g.The shop film experiment of carrying out in THE LOWER YANGTZE VALLEY area, the west and south, Jiangsu Province: after 3 months, film begins to burst apart, and is broken into 2～3cm after 6 months
2, can only see tiny filiform after 12 months.
Embodiment 4
A kind of biodegradable MULTILAYER COMPOSITE polyethylene film; Comprise following three layers: percentage meter by weight, polyethylene inner layer master batch raw material consists of: polyethylene inner layer master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 65%, talcum powder 35%; Polyethylene middle level master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 55%, maleic anhydride 45%; Outer layer of polyethene master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 10%, starch 40%, castor oil 25%, metallocene PE (trade mark 1018, Co., Ltd of ExxonMobil Chemical) 25%.
Adopt the composition of present embodiment, the film thickness of preparation is 30 microns, and the properties of product testing result (detects according to standard GB 13022-91 " film stretching method for testing performance ") as follows:
Hot strength (Mpa): horizontal 30, vertical 38; Elongation at break: horizontal 200, vertical 190, shock resistance: impact damaged quality 145g.The shop film experiment of carrying out in THE LOWER YANGTZE VALLEY area, the west and south, Jiangsu Province: after 3 months, film begins to burst apart, and is broken into 2～3cm after 6 months
2, can only see tiny filiform after 12 months.
Embodiment 5
A kind of biodegradable MULTILAYER COMPOSITE polyethylene film; Comprise following three layers: percentage meter by weight, polyethylene inner layer master batch raw material consists of: polyethylene inner layer master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 80%, zinc stearate 20%; Polyethylene middle level master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 85%, maleimide 15%; Outer layer of polyethene master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 28%, starch 20%, retinal 22%, metallocene PE (trade mark 1018, Co., Ltd of ExxonMobil Chemical) 30%.
Adopt the composition of present embodiment, the film thickness of preparation is 30 microns, and the properties of product testing result (detects according to standard GB 13022-91 " film stretching method for testing performance ") as follows:
Hot strength (Mpa): horizontal 34, vertical 48; Elongation at break: horizontal 230, vertical 220, shock resistance: impact damaged quality 160g.The shop film experiment of carrying out in THE LOWER YANGTZE VALLEY area, the west and south, Jiangsu Province: after 3 months, film begins to burst apart, and is broken into 2～3cm after 6 months
2, can only see tiny filiform after 12 months.
Embodiment 6
A kind of biodegradable MULTILAYER COMPOSITE polyethylene film; Comprise following three layers: percentage meter by weight, polyethylene inner layer master batch raw material consists of: polyethylene inner layer master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 80%, zinc stearate 20%; Polyethylene middle level master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 70%, ethyl acrylate 30%; Outer layer of polyethene master batch raw material consists of: polyethylene (trade mark PE BT 100K Brazil Braskem) 16%, starch 50%, epoxy linseed oil 18%, metallocene PE (trade mark 1018, Co., Ltd of ExxonMobil Chemical) 16%.
Adopt the composition of present embodiment, the film thickness of preparation is 30 microns, and the properties of product testing result (detects according to standard GB 13022-91 " film stretching method for testing performance ") as follows:
Hot strength (Mpa): horizontal 33, vertical 46; Elongation at break: horizontal 220, vertical 210, shock resistance: impact damaged quality 155g.The shop film experiment of carrying out in THE LOWER YANGTZE VALLEY area, the west and south, Jiangsu Province: after 3 months, film begins to burst apart, and is broken into 2～3cm after 6 months
2, can only see tiny filiform after 12 months.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and distortion, these improvement and distortion also should be regarded as protection scope of the present invention.
Claims (10)
1. a biodegradable MULTILAYER COMPOSITE polyethylene film is characterized in that, comprises following three layers:
(1) contains the polyethylene inner layer of inorganic filler;
(2) contain the polyethylene middle level of bulking agent;
(3) contain the outer layer of polyethene of starch, grease and metallocene PE.
2. biodegradable MULTILAYER COMPOSITE polyethylene film according to claim 1 is characterized in that, percentage meter by weight, and said polyethylene inner layer master batch raw material consists of: inorganic filler 5～35%, all the other are polyethylene.
3. biodegradable MULTILAYER COMPOSITE polyethylene film according to claim 1 is characterized in that, percentage meter by weight, and said polyethylene middle level master batch raw material consists of: bulking agent 10～60%, all the other are polyethylene.
4. biodegradable MULTILAYER COMPOSITE polyethylene film according to claim 1; It is characterized in that; Percentage meter by weight, said outer layer of polyethene master batch raw material consists of: starch 20～50%, grease 15～25%, metallocene PE 15～30%, all the other are polyethylene.
5. according to claim 2 or 3 or 4 described biodegradable MULTILAYER COMPOSITE polyethylene films, it is characterized in that, percentage meter by weight, said polyethylene inner layer master batch raw material consists of: inorganic filler 5～35%, all the other are polyethylene; Said polyethylene middle level master batch raw material consists of: bulking agent 10～60%, and all the other are polyethylene; Said outer layer of polyethene master batch raw material consists of: starch 20～50%, grease 15～25%, metallocene PE 15～30%, all the other are polyethylene.
6. biodegradable MULTILAYER COMPOSITE polyethylene film according to claim 2 is characterized in that, said inorganic filler is one or more the mixture in calcium carbonate, talcum powder or the zinc stearate.
7. biodegradable MULTILAYER COMPOSITE polyethylene film according to claim 3; It is characterized in that said bulking agent is one or several the mixture in ethylene-acrylic acid copolymer, acrylic acid, maleic anhydride, maleimide, the ethyl acrylate.
8. biodegradable MULTILAYER COMPOSITE polyethylene film according to claim 4 is characterized in that, said grease is a kind of in epoxidized soybean oil, castor oil, retinal, epoxy linseed oil or the cashew nut oil.
9. according to each described biodegradable MULTILAYER COMPOSITE polyethylene film of claim 1-7, it is characterized in that the thickness of said MULTILAYER COMPOSITE polyethylene film is 25～50 microns.
10. the preparation method of each described biodegradable MULTILAYER COMPOSITE polyethylene film of claim 1-8 is characterized in that, may further comprise the steps:
(1) the master batch raw material components with each layer of composite membrane mixes respectively, then respectively in the extruder separately in 70～200 ℃ of fusion plastifications;
(2) each layer raw materials melt plasticizing back gets in the same mouthful of mould, and co-extrusion gets multi-layer compound film.
Priority Applications (1)
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| CN103707586A (en) * | 2013-12-06 | 2014-04-09 | 蚌埠蓝天塑料包装有限公司 | High-barrier puncture resistant recyclable food packaging bag |
| WO2014169448A1 (en) * | 2013-04-17 | 2014-10-23 | 香港格林天使科技有限公司 | Environmentally friendly stone paper and preparation method therefor |
| CN105109163A (en) * | 2015-09-11 | 2015-12-02 | 杨洋 | Multi-layer environment-friendly composite polyethylene film and preparation method thereof |
| CN105173383A (en) * | 2015-08-07 | 2015-12-23 | 江苏红太阳新材料有限公司 | Polycaprolactone multi-layer composite degradable packaging film |
| WO2016090799A1 (en) * | 2014-12-11 | 2016-06-16 | 昆山市张浦彩印厂 | Degradable po foamed and co-extruded composite film |
| CN107107541A (en) * | 2014-12-29 | 2017-08-29 | 陶氏环球技术有限责任公司 | Multilayer film, its manufacture method and the product comprising it |
| CN108903542A (en) * | 2018-06-06 | 2018-11-30 | 安徽永豪日用品有限公司 | A kind of preparation method of self-adhesion degradable disponsable tablecloth |
| CN110774712A (en) * | 2019-11-08 | 2020-02-11 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material sheet and plastic uptake tray manufactured by sheet |
| CN110843296A (en) * | 2019-09-30 | 2020-02-28 | 黑龙江幸福人生态农业开发股份有限公司 | Bio-based composite material film and rice brick bag made of same |
| CN112274688A (en) * | 2020-10-12 | 2021-01-29 | 南京江北新区生物医药公共服务平台有限公司 | Multi-layer composite dressing material with anti-inflammatory effect |
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| WO2014169448A1 (en) * | 2013-04-17 | 2014-10-23 | 香港格林天使科技有限公司 | Environmentally friendly stone paper and preparation method therefor |
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| WO2016090799A1 (en) * | 2014-12-11 | 2016-06-16 | 昆山市张浦彩印厂 | Degradable po foamed and co-extruded composite film |
| CN107107541A (en) * | 2014-12-29 | 2017-08-29 | 陶氏环球技术有限责任公司 | Multilayer film, its manufacture method and the product comprising it |
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| CN105109163A (en) * | 2015-09-11 | 2015-12-02 | 杨洋 | Multi-layer environment-friendly composite polyethylene film and preparation method thereof |
| CN108903542A (en) * | 2018-06-06 | 2018-11-30 | 安徽永豪日用品有限公司 | A kind of preparation method of self-adhesion degradable disponsable tablecloth |
| CN110843296A (en) * | 2019-09-30 | 2020-02-28 | 黑龙江幸福人生态农业开发股份有限公司 | Bio-based composite material film and rice brick bag made of same |
| CN110774712A (en) * | 2019-11-08 | 2020-02-11 | 黑龙江幸福人生态农业开发股份有限公司 | Preparation method of bio-based composite material sheet and plastic uptake tray manufactured by sheet |
| CN112274688A (en) * | 2020-10-12 | 2021-01-29 | 南京江北新区生物医药公共服务平台有限公司 | Multi-layer composite dressing material with anti-inflammatory effect |
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