CN1297599C - Utterly biodegradable packaging film and mulch film - Google Patents
Utterly biodegradable packaging film and mulch film Download PDFInfo
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- CN1297599C CN1297599C CNB2004100376092A CN200410037609A CN1297599C CN 1297599 C CN1297599 C CN 1297599C CN B2004100376092 A CNB2004100376092 A CN B2004100376092A CN 200410037609 A CN200410037609 A CN 200410037609A CN 1297599 C CN1297599 C CN 1297599C
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Abstract
The present invention relates to a film which can be biodegraded completely, and relates to a method for forming the film by using an electromagnetic dynamic extruder or a common blow molding machine in a blow molding way. Concretely, components of starch-olycaprolactone-EAA which can be biodegraded completely are utilized, and a ternary composite plasticizer of glycerol, EVA compatilizer and polyester polyol frost resisting agents and reinforcing agents are used as auxiliary materials. The modification is carried out through the reaction in a blending way, and after the granulation is carried out, the film is formed in a blow molding way. The present invention has the mechanical properties of a common polyethylene film, and the temperature resistance, the weather resistance and the water resistance of the film are better than the temperature resistance, the weather resistance and the water resistance of the original Italy Meter-Bi. The film can be degraded completely under the action of microbes within a half year, and the use range is approximate to the use range of the polyethylene film. The film can be used as packing materials which can be degraded completely, such as shopping bags, refuse bags, other packing or padding films and mulching films.
Description
Technical field
The present invention relates to film of a kind of fully biodegradable and preparation method thereof, belong to International Classification of Patents C08J5/18 " manufacturing of film or sheet material " technical field.
Background technology
People seek polyethylene that degradable mulch film and wrapping material are on the rise with redemption, polypropylene, polystyrene, polyvinyl chloride etc. not the degradative plastics waste brought " white pollution " time, initial exploration is exactly biodegradable starch and organic acid or ester to be incorporated into go in the common polyethylene film or approach by photoxidation reaches this purpose.Because be that photodegradation, biological degradation or light/bio-degradable all are the processes of an oxidation, its finally be become acid or ester and be decomposed into carbonic acid gas and water with back to nature.So polyethylene/polycaprolactone/polyethylene type, starch-polyethylene propylene acid copolymer-polyethylene degradative membrane and Light ?lysis Film are come out one after another.But find, this class film only starch can be degraded and polyethylene can not be by microbiological degradation, therefore this class film has experienced the process of cooling, and generation is the research and development of a series of organic acids or ester, as Biopol, this is the multipolymer of hydroxybutyric acid and hydroxypentanoic acid, for another example the ester of poly(lactic acid) (PLA), polycaprolactone (PCL), polycarbonate and aliphatic dicarboxylic acid and dibasic alcohol polycondensation, come out one after another as Japan " Bionolle " etc., also very effective really.Unique weak point is too expensive, can not be used for general wrapping material and mulch film.
U.S. F, H, Otey etc. have developed the film (Ind of a kind of polyvinyl alcohol-starch-polyvinyl chloride type, Eng, Chem, Prod, Res, Dev, 1980,19,592-595), this film is starch-containing 60%, and polyvinyl alcohol about 15% improves polyvinyl chloride colloidal sol coated the water-resistant capacity of film on polyethylene-starch film.This film almost do not have wet tenacity, and the introducing of polyvinyl chloride is disadvantageous to degraded under the situation of coated polyvinyl chloride not.It is that (MPI 1991 for the Biodegradable films for preparing of the modified polyvinyl alcohol of 70% starch and 30% that Italy Novamont company uses its relative quantity, 100,9, P7), be called Meter-Bi, have the ability of degraded fully, and price is relatively low, be listed in one of three famous in the world big fully biodegradable plastics brands, two classes are the Biopol of Britain ICI in addition, the Novon of the U.S. (being close to full starch).But it is temperature tolerance that Meter-Bi has the weakness of a maximum, weathering resistance and water tolerance have limited its use range inadequately and seriously, can not be beyond 0-50 ℃ as it, use under low temperature, high temperature and the high humidity environment condition beyond the relative humidity 30-80% (degradative plastics communication: NO2, P32 1993).
Summary of the invention
Purpose of the present invention, be to overcome mulch film that prior art manufactures weather-proof, heatproof and water-fast aspect defective, and provide a kind of range of application wide, at short notice the packing film of fully biodegradable and mulch film.
Another object of the present invention provides that a kind of use Electromagnetic Dynamic is extruded or the film forming method of common blow moulding machine blowing.
Technical scheme of the present invention is as follows.
The packing film of fully biodegradable of the present invention and mulch film, comprise starch-polycaprolactone-EAA ternary system Biodegradable films and the film forming method of blowing, it is the component starch-polycaprolactone-ethylene acrylic acid co polymer that utilizes fully biodegradable, be aided with glycerine and EVA (ethene-acetate ethylene copolymer) compatilizer, ternary composite elasticizer system with polyester polyols alcohols cold-resistant agent composition, and strengthening agent, through blending reaction, be blow molded into film after the granulation.Be to use electromagnetic dynamic plasticizing extruder or the film forming method of common blow moulding machine blowing.
A kind of packing film of fully biodegradable and mulch film, its prescription contains (weight percent):
Starch 3060%; Polycaprolactone 5-10%;
Ethylene acrylic acid co polymer 20-30%; Polyethylene 0-3%;
The composite softening agent 10-20% of glycerine-ethylene vinyl acetate-polyester polyol combination; Ethylene vinyl acetate 1-3%;
Strengthening agent is below 0.4%; Dispersion agent is less than 0.4%.
Described starch is W-Gum, tapioca (flour), potato starch, lotus root starch or high amylose starch.In described ethylene acrylic acid co polymer, the content of AA accounts for 10%-30%.
Described polyethylene is IF7B type LDPE..In described ethylene vinyl acetate, the content of VA is 28-33%, and described polyester polyol is the polycondensate of adipate glycol.Described strengthening agent is selected from potassium aluminium sulfate, borax, water glass.Described dispersion agent is tributyl phosphate or triphenylphosphate or silicone oil.
A kind of packing film of fully biodegradable or the preparation method of mulch film may further comprise the steps:
1) starch and the strengthening agent and the defoamer that are dissolved in the suitable quantity of water are stirred evenly in mixer;
2) ethene-acrylic copolymer, polycaprolactone are joined in the composite softening agent of forming by glycerine-ethylene vinyl acetate-polyester polyol, again in mixer with above-mentioned starch mixture mixing and stirring, compound is used for granulation;
3) granulation in single screw extrusion machine, prilling temperature be---machine barrel: one section 60-70 degree centigrade, two sections 100-110 degree centigrade, three sections 120-130 degree centigrade, the film head is taken over 110-115 degree centigrade, 95-105 degree centigrade on film head;
4) material grain blowing film forming on electromagnetic dynamic plasticizing extruder or common blow moulding machine, or on T shape head film extrusion; Mold temperature is---machine barrel: and one section 125-130 degree centigrade, two sections 130-140 degree centigrade, three sections 135-145 degree centigrade; The film head is taken over to 110-120 degree centigrade; The film head is 100-118 degree centigrade.
5) film of making bag on bag machine, its sealing machine bag temperature is 150-160 degree centigrade, pressure 2KG/ square centimeter; Described extruder screw length-to-diameter ratio is 20-25: 1.
The present invention overcome existing Meter-Bi method weather-proof, heatproof and water-fast aspect defective, to widen the use range of such film, provide a kind of its use range wide more than Meter-Bi, the film of complete biodegradable in a short time again, and provide a kind of use Electromagnetic Dynamic to extrude or the film forming method of common blow moulding machine blowing.
The invention scheme is specially:
The present invention prescription contains starch, ethylene acrylic acid co polymer EAA, polycaprolactone and by plasticiser system that glycerine-EVA (compatilizer)-polyester polyol (cold-resistant agent) is formed, strengthening agent and lubricant etc. are through blending reaction, granulation, the blowing film forming also can be passed through the T connector film extrusion.
Starch-EAA in this-polycaprolactone is the main body of film, and starch is biodegradable inductor, and with EAA good consistency is arranged, and can increase the content of starch in film, and can make polycaprolactone compatible with starch.Starch EAA and polycaprolactone all have good biodegradation character, but pure starch film wet tenacity is poor, water tolerance is bad, the introducing of EAA and polycaprolactone mainly is in order to improve the water tolerance of film, high temperature water tolerance particularly, and adopt glycerine-EVA-adipate glycol polyester (cold-resistant agent) ternary built plasticiser system that three effects are greatly arranged, and the one, play the plasticising lubrication; The 2nd, in order to improve the weathering resistance of film; The 3rd, in order to improve the kindliness of film, strengthen starch, the consistency of EAA and polycaprolactone ternary system.And the introducing of strengthening agent is greatly improved the tensile strength of film, and its tensile strength can reach more than the 20Mpa, than the 12Mpa height of former Meter-Bi.More than the realization of these measures, make no matter this film is improved at the former Meter-Bi of ratio aspect wet fastness, weathering resistance and the water tolerance, make it can be near the use range of polyethylene film.
The starch that the present invention uses is W-Gum, potato starch, tapioca (flour), lotus root starch or high amylose starch; AA content 10-30% among the employed EAA; Employed polyester is a polycaprolactone; Employed softening agent is glycerine-EVA-polyester polyol (the particularly ester of adipate glycol polycondensation) ternary plasticiser system; Employed strengthening agent is potassium aluminium sulfate, borax, water glass etc.; Employed defoamer is tributyl phosphate or triphenylphosphate, silicone oil etc.; Employed tablets press is short 45 types or 65 type list screw pelletizers of length-to-diameter ratio.
Blow moulding machine used in the present invention is the dynamic forcing machine of electromagnet or common three sections screw rod blow moulding machines.Electromagnetic dynamic plasticizing extruder has the characteristics of length-to-diameter ratio weak point and homogeneous heating owing to its special type of heating, makes it be more suitable for the processing of starch based degradative plastics, and is prepared membranous even, beautiful.Also can use T connector processing film forming or sheet material.
The present invention is prepared by the following method film:
Blend → granulation → blowing → goods
When blend, add starch earlier, suitable quantity of water, mixings such as strengthening agent, add EAA, polycaprolactone again in the softening agent of the glycerine-EVA-polyester polyol that disposes by a certain percentage, this mixture and above-mentioned starch mixture are mixed in mixer, blend composition granulation in 45 types or 65 type single screw extrusion machines, each section temperature is roughly as follows:
Barrel zone temperature: one section 50-60 ℃
Two sections 110-120 ℃
Three sections 120-130 ℃
Die head is taken over 110-120 ℃
Die head 95-105 ℃
Pellet can be blown film forming on common blow moulding machine, mold temperature is roughly:
Barrel zone temperature: one section 120-125 ℃
Two sections 130-140 ℃
Three sections 140-150 ℃
Die head is taken over 110--120 ℃
Die head 105-118 ℃
Prepared film bag on bag machine, the sealing temperature of its sealing machine are 150-160 ° of C, and pressure is 2Kg/cm
2
The prepared film of the present invention, mechanical property be tensile strength at 20Mpa-30Mpa, extension at break is 140-200%; Young's modulus is 130-400Mpa.
This class film is when starch content is 30% left and right sides, measure through the carbon dioxide releasing amount assay method, biological degradation rate in the time of four months reaches as high as more than 85%, and starch content is about 50% the film degradation experiment by the world and domestic standard, and its biological degradation rate is best in all kinds of degradative membranes in the whole nation.This class film is through in examination shop, field, and its surface is corroded by bacterium and Institute of Micro-biology and blackening decomposes about half a year substantially fully in the time of two months.
The prepared film of the present invention mainly can be used as shopping bag, refuse bag and packing bag, and can be used as mulch film.
Meter-Bi generally can not be beyond 0-50 ℃, relative temperature is used under low temperature, high temperature and high humidity environment beyond the 30-80%, and film of the present invention generally can use under the envrionment conditions that the PE film can be used, and its water tolerance, temperature tolerance and weathering resistance are better than Meter-Bi.
Embodiment
Embodiment 1: take by weighing W-Gum and place in the mixer for 500 parts, in 100 parts of water, add 3 parts of potassium aluminium sulfates, 3 parts of tributyl phosphates, under agitation with the starch mixing, take by weighing EAA250 part again, 50 parts of polycaprolactones join 170 parts of glycerine with it, in 30 parts of EVA and the 20 parts of polyester polyols (being mainly the polycondensate of adipate glycol), this glycerine mixed solution is with above-mentioned starch mixture, stir evenly in mixer, high-speed stirring 2 minutes is granulation in 25: 1 the 45 type single screw extrusion machines in length-to-diameter ratio, barrel zone temperature is one section 50--60 ℃, two sections 100--110 ℃, three sections 115--120 ℃, die head is taken over 105--110C, granulation under the head 95-100 ℃ condition, blowing film forming on electromagnetic dynamic plasticizing extruder or common three sections blow moulding machines, mold temperature are one section 120--125 ℃ of machine barrel, two sections 125--135 ℃, three sections 135--150 ℃, die head is taken over 110--120 ℃, and head 105--118 ℃, prepared film is used for bag.
Embodiment 2: take by weighing 580 parts of potato starches in mixer, in 120 parts of water, add 3 parts of boraxs, 3 parts of triphenylphosphates, under agitation with the starch mixing, take by weighing EAA260 part again, 40 parts of polycaprolactones, it is joined 180 parts of glycerine, in 30 parts of EVA and the 10 parts of polyester polyols, this glycerol mixture stirs in mixer with above-mentioned starch mixture, high-speed stirring is 2 minutes again, in length-to-diameter ratio is granulation in 25: 1 the 65 type single screw extrusion machines, and other operational condition is with example one, the blowing film forming.
Embodiment 3: take by weighing 500 parts of tapioca (flour)s, in 120 parts of water, add 3 parts of boraxs, 3 parts of defoamer tributyl phosphates, under agitation with this aqueous solution and starch mixing, take by weighing EAA280 part again, 30 parts of polycaprolactones join it and contain 170 parts of glycerine, in the composite softening agent of 30 parts of EVA and 20 parts of polyester polyols, and adding 0.5 part of lauric monoglyceride, this glycerol mixture stirs in mixer with above-mentioned starch mixture, high-speed stirring is 2 minutes again, in length-to-diameter ratio is granulation in 25: 1 the single screw extrusion machine, blowing film forming in electromagnetic dynamic plasticizing extruder, and its granulation and blow molding operation parameter are with example one.
Embodiment 4: take by weighing 500 parts of W-Gums, place in the mixer, add 3 parts of boraxs in 100 parts of water, Wet Strength Resin PAE10 part, 3 parts of triphenylphosphates are under agitation with this aqueous solution and starch mixing, take by weighing EAA260 part again, 30 parts of polycaprolactones, IF7B type LDPE20 part joins it and contains 180 parts of glycerine, in EVA30 part and the 20 parts of polyester polyols, this glycerol mixture stirs in mixer with above-mentioned starch mixture, and high-speed stirring is 2 minutes again.Film forming equipment of its granulation and blowing and operating parameters are with example one.
Claims (8)
- The packing film of 1 one kinds of fully biodegradables or mulch film, its prescription and weight percent are:Starch 30-60%; Polycaprolactone 5-10%;Ethylene acrylic acid co polymer 20-30%; Polyethylene 0-3%;The composite softening agent 10-20% that glycerine-ethylene vinyl acetate-polyester polyol is formed; Ethylene vinyl acetate 1-3%;Strengthening agent is below 0.4%; Dispersion agent is less than 0.4%.
- 2 films as claimed in claim 1 is characterized in that: described starch is W-Gum, tapioca (flour), potato starch, lotus root starch or high amylose starch.
- 3 films as claimed in claim 1 is characterized in that: in described ethylene acrylic acid co polymer, the content of AA accounts for 10%-30%.
- 4 films as claimed in claim 1 is characterized in that: in described ethylene vinyl acetate, the content of VA is 28-33%, and described polyester polyol is the polycondensate of adipate glycol.
- 5 films as claimed in claim 1 is characterized in that: described strengthening agent is selected from potassium aluminium sulfate, borax, water glass.
- 6 films as claimed in claim 1 is characterized in that: described dispersion agent is tributyl phosphate or triphenylphosphate or silicone oil.
- 7 one kinds of packing film of fully biodegradable or preparation methods of mulch film according to claim 1 may further comprise the steps:1) starch and the strengthening agent and the defoamer that are dissolved in the suitable quantity of water are stirred evenly in mixer;2) ethene-acrylic copolymer and polycaprolactone are joined in the composite softening agent of glycerine-ethylene vinyl acetate-polyester polyol, again in mixer with above-mentioned starch mixture mixing and stirring, compound is used for granulation;3) granulation in single screw extrusion machine, prilling temperature be---machine barrel: one section 60-70 degree centigrade, two sections 100-110 degree centigrade, three sections 120-130 degree centigrade, die head is taken over 110-115 degree centigrade, die head 95-105 degree centigrade;4) material grain blowing film forming on electromagnetic dynamic plasticizing extruder or common blow moulding machine, or on T shape head film extrusion;Mold temperature is---machine barrel: and one section 125-130 degree centigrade, two sections 130-140 degree centigrade, three sections 135-145 degree centigrade; Die head is taken over to 110-120 degree centigrade; Die head is 100-118 degree centigrade;5) film of making bag on bag machine, its sealing machine bag temperature is 150-160 degree centigrade, pressure 2KG/ square centimeter.
- 8 preparation methods according to claim 7 is characterized in that: described extruder screw length-to-diameter ratio is 20-25: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100376092A CN1297599C (en) | 2004-04-27 | 2004-04-27 | Utterly biodegradable packaging film and mulch film |
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| CNB2004100376092A CN1297599C (en) | 2004-04-27 | 2004-04-27 | Utterly biodegradable packaging film and mulch film |
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| CN1569937A CN1569937A (en) | 2005-01-26 |
| CN1297599C true CN1297599C (en) | 2007-01-31 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102131855B (en) * | 2008-07-31 | 2015-04-08 | 特里斯塔诺私人有限公司 | Compositions comprising thermoplastic starch |
| CN105237813A (en) * | 2014-07-08 | 2016-01-13 | 蒋永清 | Formula of degradable mulching film for paddy field and preparation method for formula |
| JP2023506481A (en) * | 2019-12-10 | 2023-02-16 | ティコナ・エルエルシー | Cellulose ester compositions containing anti-bloom or bio-based plasticizers |
| CN112011097B (en) * | 2020-09-03 | 2022-03-08 | 湖南工业大学 | Starch-based fully-degradable film with waterproofness and high strength |
| CN112321902A (en) * | 2020-09-14 | 2021-02-05 | 惠州市环美盛新材料有限公司 | Biodegradable functional material and preparation method thereof |
Citations (6)
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|---|---|---|---|---|
| US5254607A (en) * | 1991-06-26 | 1993-10-19 | Tredegar Industries, Inc. | Biodegradable, liquid impervious films |
| CN1099399A (en) * | 1993-08-24 | 1995-03-01 | 北京华新淀粉降解树脂制品有限公司 | Biodegradable composition containing starch and its producing method and its use |
| US5422387A (en) * | 1991-06-26 | 1995-06-06 | The Proctor & Gamble Company | Biodegradable, liquid impervious films |
| CN1239725A (en) * | 1999-06-22 | 1999-12-29 | 沈阳南阳经贸集团有限公司 | Polynary degradable resin composition and its preparation process |
| CN1357563A (en) * | 2001-12-29 | 2002-07-10 | 中国科学院长春应用化学研究所 | Prepn of biodegradable film of ternary starch-PVA-polyester system material |
| CN1478808A (en) * | 2002-08-26 | 2004-03-03 | 兰州凯翔科技有限公司 | Starch base trielement system complete biodegradation film and blow moulding film forming method |
-
2004
- 2004-04-27 CN CNB2004100376092A patent/CN1297599C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254607A (en) * | 1991-06-26 | 1993-10-19 | Tredegar Industries, Inc. | Biodegradable, liquid impervious films |
| US5422387A (en) * | 1991-06-26 | 1995-06-06 | The Proctor & Gamble Company | Biodegradable, liquid impervious films |
| CN1099399A (en) * | 1993-08-24 | 1995-03-01 | 北京华新淀粉降解树脂制品有限公司 | Biodegradable composition containing starch and its producing method and its use |
| CN1239725A (en) * | 1999-06-22 | 1999-12-29 | 沈阳南阳经贸集团有限公司 | Polynary degradable resin composition and its preparation process |
| CN1357563A (en) * | 2001-12-29 | 2002-07-10 | 中国科学院长春应用化学研究所 | Prepn of biodegradable film of ternary starch-PVA-polyester system material |
| CN1478808A (en) * | 2002-08-26 | 2004-03-03 | 兰州凯翔科技有限公司 | Starch base trielement system complete biodegradation film and blow moulding film forming method |
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