CN1181123C - Biologically degradable starch film and its prepn - Google Patents
Biologically degradable starch film and its prepn Download PDFInfo
- Publication number
- CN1181123C CN1181123C CNB021157766A CN02115776A CN1181123C CN 1181123 C CN1181123 C CN 1181123C CN B021157766 A CNB021157766 A CN B021157766A CN 02115776 A CN02115776 A CN 02115776A CN 1181123 C CN1181123 C CN 1181123C
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- Prior art keywords
- film
- starch
- water
- hydrolysate
- polyvinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to a full biodegradable starch film and a preparation method thereof. The film is composed of the components by weight: 5 to 70% starch polysaccharide hydrolysate, 0.2 to 3% of natural rubber hydrolysate, 18 to 85% of polyvinyl alcohol, 0.2 to 0.3% of crosslinking agent and 8 to 14% of water. The preparation method comprises the following steps: 1) starch polysaccharide, natural rubber and the water are proportionally and uniformly mixed, and a proper amount of polysaccharidase is added for hydrolyzation so as to obtain a polysaccharide hydrosol solution; 2) the polyvinyl alcohol and a proper amount of water are mixed and dissolved by water bath, and thus, a polyvinyl alcohol hydrosol solution is obtained; 3) the polysaccharide hydrosol solution and the polyvinyl alcohol hydrosol solution are uniformly mixed, and besides, a proper quantity of crosslinking agent is added for mixing so as to form mixed sol; 4) a film is formed in a drooling way by the mixed sol with a dry method, and then, the film is dried, stretched and treated by heat setting so that the final water content of the film is 8 to 14% of the weight of the film. The film has various kinds of excellent performance existing in chemical plastic films and can be completely decomposed and quickly absorbed by microorganisms in the soil. Meanwhile, the manufacturing cost of the full biodegradable starch film is very low.
Description
Technical field
The present invention relates to a kind of substitute of Xylonite film, refer to a kind of biologically degradable starch film and preparation method thereof particularly.
Background technology
The birth of Xylonite once was described as the revolution of twentieth century, but its widespread use has also formed the white pollution of generally acknowledging.Studies show that: the Xylonite waste all was difficult to degraded through 70 years in physical environment, this has caused serious pollution for rivers and lakes and land, and physical environment has been caused great harm.Be accumulated in the field year in year out as depleted agrochemicals plastics film, can destroy the structure of farm crop soil, influence the growth of farm crop root system, cause the significantly underproduction of farm crop.The Xylonite mulch film was used in continuous 5 years in the farmland after tested, and residual mulch film plastics waste residue will reach more than 20 kilograms in every mu of farmland, can cause crop production reduction about 20 percent.In order to solve the pollution problem of above-mentioned Xylonite film, people are striving to find the substitute that can effectively replace it always.Some scientific worker is based on the principle that the paper product that with the Mierocrystalline cellulose are main production raw material can be degraded by microorganisms fully at occurring in nature, once imagines with paper product to replace the Xylonite film article.Yet the production of paper will consume a large amount of timber, causes the forest big area to be cut down, and causes Ecological environment worsening; The production of paper also can produce a large amount of organic waste water, pollutes rivers,lakes and seas.And strength of paper is low, and cost height, particularly light transmission are too poor, replaces the Xylonite film not satisfy the requirement of purposes and quantitative aspects with it.Also some researchist designs with polyethylene, treated starch and intact quick material and produces half degradable film as stopping composition, accelerates rotting of film and decomposes with the biodegradation character that utilizes component such as treated starch.But because the polyethylene in this film can be by biological degradation, its residual white pollution that causes still can not be eradicated, thereby the use of this half degradable film also has been subjected to very big restriction.Also some R﹠D institution selects for use treated starch and polyvinyl alcohol mixing, producing with treated starch and polyvinyl alcohol mixture is the degradable films of major ingredient, but starch material and the easy phase-splitting of polyvinyl alcohol raw material in process of production, make that this type of finished film rate is lower, quality is also very unstable, and its mechanics of machinery intensity is relatively poor, does not often reach practical requirement.And countries such as U.S., Europe utilize the method for artificial cultivation to produce macromolecular compound such as xanthan gum, poly-beta-hydroxy-butanoic acid etc. earlier, utilize these macromolecular compounds to come the small serial production biological whole degrading film again.Though this method can accomplish to eradicate white pollution, its investment cost is huge, production cost is expensive, makes us being deeply aware of one's own helplessness when faced with a great task.
Summary of the invention
Purpose of the present invention will overcome the deficiencies in the prior art exactly, a kind of biologically degradable starch film and preparation method thereof is provided, the feasible film of preparing with this method had both had the various premium propertiess of Xylonite film, can be decomposed rapid absorption fully by the microorganism in the soil again, its cost of manufacture is very cheap simultaneously.
For realizing this purpose, the biologically degradable starch film that the present invention developed is made up of 5～70% starch-polysaccharides hydrolysate, 0.2～3% natural gum hydrolysate, 18～85% polyvinyl alcohol, 0.2～0.3% linking agent and 8～14% moisture content by weight.Above-mentioned starch-polysaccharides hydrolysate and natural gum hydrolysate can preferred starch polysaccharide and natural gum formed incomplete hydrolysates under the α-Dian Fenmei effect.The raw material of above-mentioned starch-polysaccharides hydrolysate is corn or wheat starch preferably, and the raw material of natural gum hydrolysate is carrageenin or sodium alginate or xanthan gum preferably, and linking agent is glutaraldehyde or oxalic dialdehyde or propylene oxide preferably.
The preparation method of above-mentioned biologically degradable starch film comprises the steps:
1) in proportion starch-polysaccharides, natural gum and water are mixed, add an amount of polysaccharidase and be hydrolyzed, obtain the water-soluble glue of polysaccharide;
2) polyvinyl alcohol and an amount of water are mixed, the water-bath dissolving obtains the water-soluble glue of polyvinyl alcohol;
3) water-soluble glue of above-mentioned polysaccharide and the water-soluble glue of polyvinyl alcohol are mixed, the adding proper amount of cross-linking agent is mixing, forms mixed sols;
4) above-mentioned mixed sols is passed through dry method hydrostomia film forming, handle through super-dry, stretching and heat setting type, making its final water content is that 8～14% of film weight gets final product.
Wherein, can in step 1), preferred α-Dian Fenmei be hydrolyzed, when the viscosity of sampling detection hydrolyzed solution under 35 ℃ condition reaches 26PaS, stop hydrolysis reaction, obtain the water-soluble glue of polysaccharide of incomplete hydrolysis.
The invention has the advantages that: the starch-polysaccharides hydrolysate that filmogen adopted has than without much smaller molecular structure of the high molecular starch-polysaccharides of hydrolysis and much higher molecular size equilibrium degree, be very beneficial for auxiliary material crosslinkedly, overcome the deficiency that the direct film forming fragility of starch-polysaccharides is big, transparency is low; The polyvinyl alcohol auxiliary material that is adopted has good water gel-formation power, and it and starch-polysaccharides hydrolysate be crosslinked to strengthen film forming physical strength, improves film forming heat sealability; The natural gum hydrolysate that is adopted has good synergy with the starch-polysaccharides hydrolysate in film process, also can promote the raising of film forming machinery mechanical strength; And the linking agent that is adopted can be crosslinked together securely with starch-polysaccharides hydrolysate and natural gum hydrolysate and polyvinyl alcohol, form tridimensional network, avoided the said hydrolyzed product to mix the easily defective of phase-splitting of back with polyvinyl alcohol, not only distribution of material is even to make formed film, and its mechanics of machinery intensity also can significantly improve.Simultaneously, select that corn or wheat starch equal yield line are huge, cheap, the natural polysaccharide that is easy to obtain is as hydrolysis material, can significantly reduce the production cost of film.Select cheap and high-temperature resistant alpha-amylase carries out incomplete hydrolysis to raw material, hydrolytic process is easy to control, obtain the comparatively balanced oligosaccharides hydrolysate of molecular weight size easily, hydrolysis can not take place to be controlled improper and problem formation monose, can guarantee that quality of forming film is intact, production cost further reduces.And different linking agents such as selection glutaraldehyde can adapt to the needs that film is used for different field such as food product pack, agricultural mulching.Show after testing: above-mentioned starch-polysaccharides hydrolysate and natural gum hydrolysate have very approaching three-D space structure and the very little oligosaccharides side chain of difference, and these sugar chains have many hydrophilic radicals, and its hydrophilicity is extremely strong, can be degraded by nature microorganism fully.Above-mentioned polyvinyl alcohol is the macromolecular compound of chemosynthesis, also has the good hydrophilicity energy, can be by the quick and complete decomposition of nature microorganism, and nontoxic to human body.Thereby biologically degradable starch film of the present invention had both had the various premium propertiess of polyethylene kind Xylonite film, can be decomposed absorption fast by the microorganism in the soil again.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment:
Embodiment 1: a kind of biologically degradable starch film, form by 5% W-Gum polysaccharide hydrolysate, 0.2% carrageenin hydrolysate, 0.229% glutaraldehyde, 80.571% polyvinyl alcohol and 14% moisture content by weight.
Embodiment 2: a kind of biologically degradable starch film, by weight by 70% W-Gum polysaccharide hydrolysate, 3% sodium alginate hydrolysate, 0.245% oxalic dialdehyde, 18.755% polyvinyl alcohol and 8% moisture content forms.
Embodiment 3: a kind of biologically degradable starch film, form by 35% wheat starch polysaccharide hydrolysate, 0.75% xanthan gum hydrolysate, 0.235% propylene oxide, 54.015% polyvinyl alcohol and 10% moisture content by weight.
The preparation method of above-mentioned biologically degradable starch film comprises the steps:
1) in ratio extracting corn starch or wheat starch among the embodiment, carrageenin or sodium alginate or xanthan gum mix with water, add an amount of α-Dian Fenmei again, are hydrolyzed under 37～90 ℃ temperature.When the viscosity of sampling detection hydrolyzed solution under 35 ℃ condition reaches 26PaS, be warming up to 100 ℃ and end hydrolysis reaction, and filter by 100 order mesh screens, obtain the water-soluble glue of polysaccharide of incomplete hydrolysis.
2) 18-99 type polyvinyl alcohol and an amount of water are mixed, 100 ℃ of water-bath dissolvings obtain the water-soluble glue of polyvinyl alcohol.
3) water-soluble glue of the polysaccharide of above-mentioned incomplete hydrolysis and the water-soluble glue of polyvinyl alcohol are mixed, add glutaraldehyde or oxalic dialdehyde or propylene oxide solution in the ratio among the embodiment, insulation is crosslinked 24 hours under 40 ℃ temperature, forms mixed sols.
4),, be coated on the bright and clean film former of Stainless Steel Band for no reason that siliconizing is crossed warm air drying film forming under 80 ℃ temperature by spray lip hydrostomia with behind the above-mentioned mixed sols vacuum deaerator.Handle through two-way stretch in length and breadth again behind the demoulding, quick xeothermic typing under 150 ℃ temperature, making its final water content is that 8～14% of film weight gets final product.
Also can or eat materials such as cured as required, form the film of various different purposes at the poly-butyric acid fourth diester of one-tenth's film surface spraying.
As stated above, by controlling the consumption of corresponding component, can obtain the biologically degradable starch film of other component content
Embodiment 4: earlier in 1000 gram W-Gums or wheat starch, add 50 gram carrageenin or sodium alginates, mix, add 6500 milliliters of the α-Dian Fenmei aqueous solution containing 1,000 ten thousand activity units, stirring and evenly mixing, be hydrolyzed under 60 ℃ temperature, the control hydrolysis time is 100 minutes, obtains thickness syrupy shape glue.This glue filters through 100 order mesh screens, removes impurity wherein, obtains the water-soluble glue of major ingredient polysaccharide.
Secondly add 3600 ml waters in 450 gram polyvinyl alcohol, 100 ℃ of water-baths are dissolved fully until polyvinyl alcohol, obtain the water-soluble glue of auxiliary material polyvinyl alcohol.
With water-soluble glue of above-mentioned major ingredient polysaccharide and the water-soluble glue thorough mixing of auxiliary material polyvinyl alcohol, be cooled to 40 ℃ then, add 8 milliliters of weightmeasurement ratios and be 50% glutaraldehyde solution, mix, 40 ℃ of insulations 24 hours obtain mixed sols.
With the mixed sols vacuum deaerator, through spray lip metering ejection, hydrostomia blasts 80 ℃ warm air drying film forming on the bright and clean film former of Stainless Steel Band for no reason, film forming water content is controlled between 15～18% again.Demoulding is after two-way stretch in length and breadth, and 150 ℃ of heat setting types are moments later air-cooled fast, and its final water content is controlled between 8～14%.
Last difference according to thin film application is selected to spray poly-butyric acid fourth diester or eat method do surface processing such as cured, to increase its waterproof and dampproof ability.Film is involved on the spool, and pressure roller flattens, and packing gets product.
For film is stripped down at easy Stainless Steel Band for no reason from film former after the drying, Stainless Steel Band should adopt the silication agent to handle before coming into operation for no reason.Concrete treatment process is as follows: with after Stainless Steel Band is fit into film former for no reason of film former, with width be 10 centimetres scrubbing brush with commercially available silication liquid laterally brushing in steel strip surface, painting way is 10 centimetres of per 10 centimetres of wide intervals, can use 100 ℃ of following oven dry.Formed film both can be subjected to the certain stretching action of steel band on the Stainless Steel Band like this, stripped down from it easily again, can be optimized to film quality.
Claims (7)
1. biologically degradable starch film, form by 5～70% starch-polysaccharides hydrolysate, 0.2～3% natural gum hydrolysate, 18～85% polyvinyl alcohol, 0.2～0.3% linking agent and 8～14% moisture content by weight, wherein: starch-polysaccharides hydrolysate and natural gum hydrolysate are that starch-polysaccharides and natural gum are in hydrolytic process, when reaching 26PaS, the viscosity of sampling detection hydrolyzed solution under 35 ℃ condition stops hydrolysis reaction, and the incomplete hydrolysate that obtains.
2. biologically degradable starch film according to claim 1 is characterized in that: said starch-polysaccharides hydrolysate and natural gum hydrolysate are the incomplete hydrolysates that starch-polysaccharides and natural gum form under the α-Dian Fenmei effect.
3. biologically degradable starch film according to claim 1 and 2 is characterized in that: the raw material of said starch-polysaccharides hydrolysate is selected corn or wheat starch for use, and the raw material of said natural gum hydrolysate is selected carrageenin or sodium alginate or xanthan gum for use.
4. biologically degradable starch film according to claim 1 and 2 is characterized in that: said linking agent is selected glutaraldehyde or oxalic dialdehyde or propylene oxide for use.
5. biologically degradable starch film according to claim 3 is characterized in that: said linking agent is selected glutaraldehyde or oxalic dialdehyde or propylene oxide for use.
6. the preparation method of the described biologically degradable starch film of claim 1 comprises the steps:
1) in proportion starch-polysaccharides, natural gum and water are mixed, add an amount of polysaccharidase and be hydrolyzed, when the viscosity of sampling detection hydrolyzed solution under 35 ℃ condition reaches 26PaS, stop hydrolysis reaction, obtain the water-soluble glue of polysaccharide of incomplete hydrolysis;
2) polyvinyl alcohol and an amount of water are mixed, the water-bath dissolving obtains the water-soluble glue of polyvinyl alcohol;
3) water-soluble glue of above-mentioned polysaccharide and the water-soluble glue of polyvinyl alcohol are mixed, the adding proper amount of cross-linking agent is mixing, forms mixed sols;
4) above-mentioned mixed sols is passed through dry method hydrostomia film forming, handle through super-dry, stretching and heat setting type, making its final water content is that 8～14% of film weight gets final product.
7. the preparation method of biologically degradable starch film according to claim 6 is characterized in that: select for use α-Dian Fenmei to be hydrolyzed in the said step 1).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157766A CN1181123C (en) | 2002-04-28 | 2002-04-28 | Biologically degradable starch film and its prepn |
| AU2003236166A AU2003236166A1 (en) | 2002-04-28 | 2003-04-25 | Fully-biodegradable film and its preparation process |
| PCT/CN2003/000306 WO2003093361A1 (en) | 2002-04-28 | 2003-04-25 | Fully-biodegradable film and its preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021157766A CN1181123C (en) | 2002-04-28 | 2002-04-28 | Biologically degradable starch film and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1453303A CN1453303A (en) | 2003-11-05 |
| CN1181123C true CN1181123C (en) | 2004-12-22 |
Family
ID=29256956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021157766A Expired - Fee Related CN1181123C (en) | 2002-04-28 | 2002-04-28 | Biologically degradable starch film and its prepn |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1181123C (en) |
| AU (1) | AU2003236166A1 (en) |
| WO (1) | WO2003093361A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100554330C (en) * | 2006-08-31 | 2009-10-28 | 陕西师范大学 | The preparation method of polyvinyl alcohol beta-cyclodextrin multipolymer |
| CN101585932B (en) * | 2008-05-22 | 2013-04-17 | 深圳市环之源生物科技有限公司 | Full biodegradable package film and preparation method thereof |
| CN101914223B (en) * | 2010-08-06 | 2012-01-25 | 西北师范大学 | Preparation method of modified starch-polyvinyl alcohol-based composite plastic film |
| CN103554553B (en) * | 2013-10-25 | 2016-01-13 | 中南林业科技大学 | A kind of Starch rice based, biodegradable packing film and preparation method thereof |
| CN104260990B (en) * | 2014-08-06 | 2016-12-07 | 宁波华丰包装有限公司 | A kind of medical device package film and manufacture method thereof |
| CN106084310A (en) * | 2016-06-22 | 2016-11-09 | 福州大学 | Biodegradable plastics based on Sargassum polysaccharides and preparation method thereof |
| CN108219330A (en) * | 2017-12-30 | 2018-06-29 | 姜向军 | A kind of degradable mulch |
| CN109881533A (en) * | 2019-02-15 | 2019-06-14 | 滁州卷烟材料厂 | A kind of preparation method of environment-friendly degradable waterproof aluminium-foil paper |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3949145A (en) * | 1975-02-27 | 1976-04-06 | The United States Of America As Represented By The Secretary Of Agriculture | Degradable starch-based agricultural mulch film |
| DE3939721C2 (en) * | 1988-12-05 | 2002-08-01 | Nippon Synthetic Chem Ind | Polyvinyl alcohol-starch film |
| JPH05320397A (en) * | 1992-05-19 | 1993-12-03 | Nippon Synthetic Chem Ind Co Ltd:The | Degradable foamed molding |
| JP3344760B2 (en) * | 1993-03-19 | 2002-11-18 | 日本合成化学工業株式会社 | Collapsed molded foam |
-
2002
- 2002-04-28 CN CNB021157766A patent/CN1181123C/en not_active Expired - Fee Related
-
2003
- 2003-04-25 WO PCT/CN2003/000306 patent/WO2003093361A1/en not_active Application Discontinuation
- 2003-04-25 AU AU2003236166A patent/AU2003236166A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003093361A1 (en) | 2003-11-13 |
| AU2003236166A1 (en) | 2003-11-17 |
| CN1453303A (en) | 2003-11-05 |
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