CA2079768C - Starch-containing biodegradable plastic and method of producing same - Google Patents

Starch-containing biodegradable plastic and method of producing same Download PDF

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Publication number
CA2079768C
CA2079768C CA002079768A CA2079768A CA2079768C CA 2079768 C CA2079768 C CA 2079768C CA 002079768 A CA002079768 A CA 002079768A CA 2079768 A CA2079768 A CA 2079768A CA 2079768 C CA2079768 C CA 2079768C
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Canada
Prior art keywords
starch
aliphatic polyester
polyester resin
gelatinized starch
biodegradable
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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CA002079768A
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French (fr)
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CA2079768A1 (en
Inventor
Yutaka Tokiwa
Sigeyuki Takagi
Masatoshi Koyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chuo Kagaku Co Ltd
National Institute of Advanced Industrial Science and Technology AIST
New Energy and Industrial Technology Development Organization
Original Assignee
Agency of Industrial Science and Technology
Chuo Kagaku Co Ltd
Research Institute of Innovative Technology for the Earth RITE
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Priority claimed from JP28384791A external-priority patent/JPH05331315A/en
Application filed by Agency of Industrial Science and Technology, Chuo Kagaku Co Ltd, Research Institute of Innovative Technology for the Earth RITE filed Critical Agency of Industrial Science and Technology
Publication of CA2079768A1 publication Critical patent/CA2079768A1/en
Application granted granted Critical
Publication of CA2079768C publication Critical patent/CA2079768C/en
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Classifications

    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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

Abstract

A biodegradable plastic composition, which may be in the form of a molded body, includes gelatinized starch and a biodegradable, aliphatic polyester resin having a melting point of 45-130 °C. The plastic is produced by kneading a blend containing a starchy substance selected from non-gelatinized, granular starch and gelatinized starch and the aliphatic polyester resin at a temperature higher than the melting point of the aliphatic polyester in the presence of water in an amount of 1-45 % based on the weight of the starchy substance.

Description

STARCH-CONTAINING BIODEGRADABLE PLASTIC AND
METHOD OF PRODUCING SAME
This invention relates to a biodegradable plastic material and a method of preparing same.
There is an increasing demand for a plastic material which is decomposed by the action of microorganisms (bacteria, yeast, fungi, etc.) or enzymes, thereby to lose the original shape.
One well know biodegradable plastic material includes a mixture of starch with a synthetic polymer such as a polyethylene (Maddever and Chapman, "Modified Starch Based Biodegradable Plastics", ANTEC '89, Soc. Plastics Eng.
Conference Proceedings pp. 1351-1355 (May 1-4, 1989)), an ethylene/acrylic acid copolymer (US-A-4,138,784 and 4,337,181) or an ethylene/vinyl alcohol copolymer (JP-A-Hei-3-31333).
In the above polyethylene-containing plastic material, the starch is present as a filler within a matrix of the polyethylene which is not biodegradable. Thus, the biodegradability of this material is not satisfactory. While the plastic material containing the ethylene/acrylic acid copolymer has superior water resistance and mechanical properties as compared with the polyethylene-containing plastic material, the biodegradability is less satisfactory.
Regarding the ethylene/vinyl alcohol copolymer-containing plastic material, the composition of the copolymer is not disclosed so that it is not clear whether or not the copolymer is biodegradable. This material has a problem that pin holes are apt to be formed in films obtained therefrom because bubbles are unavoidably formed by vaporization of water during kneading of the raw materials.
The present invention has been made with the foregoing problems of the conventional plastic materials in view.

CA 02079768 2002-07-31 w.
Other aspects of this invention are as follows:
A biodegradable plastic material comprising a mixture of gelatinized starch with a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C.
A method of producing a biodegradable plastic material comprising the steps of:
providing a blend containing gelatinized starch and a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C;
and kneading said blend at a temperature higher than the melting point of said aliphatic polyester but lower than the decomposition temperature of said gelatinized starch in the presence of water in an amount of 1-45 % based on the weight of said gelatinized starch.
A biodegradable plastic material comprising a matrix of a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C;
and gelatinized starch dispersed in said matrix, wherein said gelatinized starch is present in an amount of 30-90~ based on the total weight of said aliphatic polyester resin and said gelatinized starch.
A process for producing a biodegradable plastic molding, comprising the steps of:
providing a molten mixture containing a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C, and gelatinized starch, wherein the weight ratio of said polyester resin to said gelatinized starch is 10:90 to 70:30; and extruding said mixture through a die under the conditions satisfying the following expressions:
100 > ns / ne > 0.8 ne > 600 wherein r~ and ns stand for the viscosity, in terms of poise, of the aliphatic polyester resin and the gelatinized starch, respectively, at the extrusion temperature.

-2a-A method of producing a biodegradable plastic material comprising the steps of:
providing a blend containing a non-gelatinized, granular starch and a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C;
and kneading said blend at a temperature higher than the melting point of said aliphatic polyester but lower than the decomposition temperature of said l0 starch in the presence of water in an amount of 1-45% based on the weight of said starch to gelatinize said starch.
The present invention will now be described in detail below.
The term "starch" as used herein is intended to refer to any type of non-modified and modified starches and includes starches or starch-containing materials of natural, vegetable origin composed mainly of amylose and/or amylopectin, and modified starch products. lllustrative of suitable starches and t a 207~~~~
starch-containing materials are potato starch, corn starch, wheat starch, tapioca starch, rice starch, sweat potato starch, sago starch, waxy corns, high amylose corns, wheat flour and rice flour. Polysaccharides such as guar gum, chitin and chitosan may also be usable. Examples of modified starch products include starches onto which a monomer such as an acrylate, a methacrylate, an olefin or styrene is grafted;
products obtained by reaction of starches with a fatty acid; and starches modified by dextrinization, oxidation, acidification, alphanization, etherification, esterification and cross-linking.
In addition, destructurized starches obtained by heat-treating water-containing starch at a temperature of 105-190 °C (EP-A-0327505) are included within the scope of the modified starches.
The term "gelatinized starches" as used herein is intended to refer to products obtained by treating the above starches by any known gelatinization method such as by heating in the presence of water at a temperature of about 40 °C or more. Gelatinization may also be effected by kneading starch granules in the presence of 1-45 $ by weight of water for a period of time sufficient to disrupt the granules.
The term "plastic material" as used herein is intended to refer both to a plastic composition to be used as raw material for the production of shaped or molded articles and to a plastic molding or shaped body obtained from the composition.
The aliphatic polyester resin used in the present invention should be biodegradable. Illustrative of suitable biodegradable polyester resin are polyethylene adipate, polyethylene suberate, polyethylene azelate, polyethylene decamethylate, polytetramethylene succinate, polytetramethylene adipate, polypropiolactone, polycaprolactone and block copolymers of the above esters with polyamide. The use of polycaprolactone is especially preferred. It is also important that the aliphatic polyester resin have a melting point of 45-130 °C, preferably 50-120 °C. When the melting point is lower than 45 °C, the resulting molded product tends to thermally deform at room temperature. Too high a melting point in excess 20~~7~
- - 4 _ of 130 °C is disadvantageous because vaporization of water considerably occurs to cause the formation of bubbles in the molded product.
The biodegradable plastic material according to the present invention comprises a mixture of the above gelatinized starch with the above biodegradable, aliphatic polyester. The amount of the gelatinized starch is generally 2-98 ~, preferably 10-95 ~, more preferably 30-90 ~, most preferably 40-85 ~, based on the total weight of the gelatinized starch and the aliphatic pplyester.
In addition to the above mixture, the plastic material of this invention may contain various additives such as a biodegradable plasticizes, a weatherability improving agent (e.g. UV stabilizer), a germicide, a herbicide, a fertilizer, an anti-oxidation agent, a surfactant, a filler, a starch stabilizer and a pigment. Illustrative of suitable plasticizers are ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol with a number average molecular weight of 200-4000, glycerin and sorbitol. The plasticizes is used in an-amount of 0.5-100 ~ based on the weight of the gelatinized starch.
The plastic material may be prepared by kneading a blend of ungelatinized or gelatinized starch, an aliphatic polyester resin and an additive (optional) in the presence of water at a temperature higher than the melting point of the aliphatic polyester resin but lower than the decomposition point of the starch. When polycaprolactone is used as the aliphatic polyester resin, the kneading is generally performed at a temperature of 70-130 °C, preferably 80-110 °C. Ungelatinized starch is gelatinized as a result of the kneading. The amount of the water is generally 1-45 $, preferably 12-45 ~, based on the weight of the starch on dry basis. The water to be present in the kneading system may be derived from that contained in the raw material starch and/or that added at the start of the kneading operation. The kneaded mixture is then shaped into any desired shape such as a pellet, sheet, film, plate, rod, pipe or ' - 5 -receptacle. In one preferred embodiment according to the present invention, gelatinization of starch, kneading and molding are simultaneously performed using an extruder.
The plastic material according to the present invention preferably has a structure in which the aliphatic polyester resin, which exhibits good resistance to water, forms a matrix and the gelatinized starch, which is poor in water resistance, is dispersed in the matrix. Such a plastic material exhibits satisfactory resistance to water since the gelatinized starch which is poor in water resistance is covered with the matrix of the aliphatic polyester resin which has good resistance to water.
The plastic material in which the polyester resin forms a matrix may be suitably obtained extruding a molten mixture of an aliphatic polyester and gelatinized starch through a die under the conditions satisfying the following expressions:
100 > ns/ne > 0.8, preferably 50 > ns/ne > 0.8, and ne > 600, preferably ne > 900 wherein ne and ns stand for the viscosities, in terms of poise, of the aliphatic polyester resin and the gelatinized starch, respectively, at the extrusion temperature. The above conditions can be achieved by suitably selecting the kind and/or the molecular weight of the aliphatic polyester resin and/or by suitably selecting the water content of the gelatinized starch.
As described previously, ungelatinized starch may be fed as such to an extruder since gelatinization thereof occurs before extrusion through the die.
The plastic material of this invention is capable of being consumed by microorganisms in an environment suitable for the growth of the microorganisms to cause reduction of the weight and volume of the plastic material with time. Thus, the plastic material may be used as daily necessaries such as disposable packages in the form of a case, a bottle or the like receptacle, as agricultural materials such as a green house construction film, a soil cover sheet, a nursery pot, a fertilizer bag or a pesticidal carrier, as a leisure goods such 2p"~~'~6~
_' - 6 -as a bag, a packing material for fishing equipments and as a material for drug delivery systems.
The following examples will further illustrate the present invention. Percentages are by weight.
Preparation of Plastic Materials:
Example 1 Granular cornstarch (9217 g) having a water content of 13.2 ~ was placed into a kneader, over which were sprayed 783 g of water. The total water content is 25 ~ based on the weight of the starch on dry basis. After the contents in the kneader had been kneaded for about 1 hour, 2000 g of polycaprolactone (PCL) were added and the mixture was kneaded for about 30 minutes. The resulting mixture was charged into a hopper of a biaxial extruder and extruded through a T-die at a feed rate of 10 kg/hour, a screw revolution speed of 100 rpm and a barrel temperature gradient of 30-80-95 °C to obtain a uniform film free of air bubbles. The ne and ns values measured at 95 °C
with a flow tester (orifice diameter: 1 mm) are found to be 113,000 poises and 1,600,000 poises, respectively, so that ns/ne is 14.2.
Examples 2-4 Example 1 was repeated in the same manner as described except that the amount of water sprayed was changed to 1183 g (total water content: 30 ~), 1983 g (total water content: 40 ~) and 0 g (total water content: 15.2 ~). The films thus obtained were uniform and free of air bubbles.
Example 5 Granular cornstarch having a water content of 13.2 was placed into an oven and maintained at 110 °C until the water content of 6 ~ was reached. The resulting cornstarch (8511 g) was kneaded together with 2000 g of PCL for about 1 hour. The resulting mixture was then extruded in the same manner as that in example 1 to give a uniform film free of air bubbles.

_ 7 _ Comparative Example 1 Example 1 was repeated in the same manner as described except that no PCL was used.
Examples 6-9 Example 1 was repeated in the same manner as described except that the amount of PCL was changed to 889 g (Example 6), 3429 g (Example 7), 8000 g (Example 8) and 18667 g (Example 9).
Water Resistance:
Example 10 Each of the films (0.1 g) obtained in Examples 1-9 and Comparative Example 1 was sliced to a thickness of about 100 ~um.
The sliced sample was placed into a flask containing 20 ml of water at 30 °C and shaken for 16 hours while maintaining at that temperature. The mixture was then filtered and the filtrate was measured for its total organic carbon concentration (TOC). The results are summarized in Table 1 below.
Biodecrradabilit Example 11 Each of the films (0.1 g) obtained in Examples 1-9 and Comparative Example 1 was sliced to a thickness of about 100 ~Zm.
The sliced sample was placed into a flask containing 20 ml of water containing alpha-amylase and lipase and shaken for 16 hours while maintaining at 30 °C. The mixture was then filtered and the filtrate was measured for its total organic carbon concentration (TOC). The results are summarized in Table 1 below.
In Table 1, the term "total water content" refers to percentage of water based on the weight of starch on dry basis and the term "content of gelatinized starch" refers to percentage of the weight of the starch on dry basis based on the total weight of the starch and PCL.

"' _ 8 _ Table 1 Example Total Content of ns/ne Water Biodegra-No. Water Gelatinized Resistance dability Content Starch TOC (ppm) TOC (ppm) 1 25 80 14.2 24 1747 2 30 80 3.2 28 1877 3 40 80 0.9 34 1970 4 15.2 80 43.5 4 1624 5 6 80 93.7 4 1451 6 25 90 14.2 30 1710 7 25 70 14.2 22 1045 8 25 50 14.2 10 650 9 25 30 14.2 6 443 Comp.l 25 100 - 700 1510 From the results shown in Table 1, it will be appreciated that the TOC values in the water resistance test of the films of Examples 1-9 are much lower than that of Comparative Example 1. This indicates that the dissolution of starch in water was reduced in the case of the films of this invention. Especially, the films of Examples 4, 5, 8 and 9 in which PCL forms a matrix exhibit excellent water resistance.
The results of the biodegradability test summarized in Table 1 show that the films of this invention have satisfactory biodegradability. The TOC value of a film formed only of PCL is found to be 350 ppm.
Preparation of Plastic Materials:
Example 12 Acid-treated starch (9281 g) having a water content of 13.8 ~ was placed into a kneader, over which was sprayed a mixed liquid consisting of 719 g of water and 800 g of glycerin. The total water content is 25 ~ based on the weight of the starch on dry basis. The glycerin content is 10 ~ based on the weight of _. -the starch on dry basis. After the contents in the kneader had been kneaded for about 1 hour, 2000 g of polypropiolactone were added and the mixture was kneaded for about 30 minutes. The resulting mixture was charged into a hopper of a biaxial extruder and extruded through a T-die at a feed rate of 15 kg/hour, a screw revolution speed of 60 rpm and a barrel temperature gradient of 30-85-105 °C to obtain a uniform, flexible film free of air bubbles. The ns/ne value was found to be 14.2. The film was tested for water resistance and biodegradability in the same manner as above to reveal that the TOC values in water resistance test and biodegradability test are 81 ppm and 2211 ppm, respectively.
Example 13 Example 12 was repeated in the same manner as described except that white dextrin and polyethylene adipate were substituted for the acid treated starch and the polypropiolactone, respectively. The ns/ne value was found to be 81.3. The film obtained was tested for water resistance and biodegradability in the same manner as above to reveal that the TOC values in water resistance test and biodegradability test are 70 ppm and 1300 ppm, respectively.

Claims (11)

1 THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A biodegradable plastic material comprising a mixture of gelatinized starch with a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C.
2. A biodegradable plastic material as claimed in Claim 1, wherein the amount of said gelatinized starch is 2-98% based on the total weight of said aliphatic polyester resin and said gelatinized starch.
3. A biodegradable plastic material as claimed in Claim 1, wherein said aliphatic polyester resin is a polycaprolactone.
4. A method of producing a biodegradable plastic material comprising the steps of:
providing a blend containing gelatinized starch and a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C; and kneading said blend at a temperature higher than the melting point of said aliphatic polyester but lower than the decomposition temperature of said gelatinized starch in the presence of water in an amount of 1-45% based on the weight of said gelatinized starch.
5. A method as claimed in Claim 4, further comprising molding said kneaded blend into a desired shape.
6. A biodegradable plastic material comprising a matrix of a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C; and gelatinized starch dispersed in said matrix, wherein said gelatinized starch is present in an amount of 30-90% based on the total weight of said aliphatic polyester resin and said gelatinized starch.
7. A biodegradable plastic material as claimed in Claim 6, wherein said aliphatic polyester resin is a polycaprolactone.
8. A process for producing a biodegradable plastic molding, comprising the steps of:
providing a molten mixture containing a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C, and gelatinized starch, wherein the weight ratio of said polyester resin to said gelatinized starch is 10:90 to 70:30; and extruding said mixture through a die under the conditions satisfying the following expressions:
100 > n s / n e ~ 0.8 n e ~ 600 wherein n e and n s stand for the viscosity, in terms of poise, of the aliphatic polyester resin and the gelatinized starch, respectively, at the extrusion temperature.
9. A process as claimed in Claim 8, wherein said molten mixture further contains water in an amount of 1-45% based on the weight of said gelatinized starch.
10. A method of producing a biodegradable plastic material comprising the steps of:
providing a blend containing a non-gelatinized, granular starch and a biodegradable, aliphatic polyester resin having a melting point of 45°-130°C;
and kneading said blend at a temperature higher than the melting point of said aliphatic polyester but lower than the decomposition temperature of said starch in the presence of water in an amount of 1-45% based on the weight of said starch to gelatinize said starch.
11. A method as claimed in Claim 10, further comprising molding said kneaded blend into a desired shape.
CA002079768A 1991-10-04 1992-10-02 Starch-containing biodegradable plastic and method of producing same Expired - Lifetime CA2079768C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP3-283,847 1991-10-04
JP28384791A JPH05331315A (en) 1991-10-04 1991-10-04 Biodegradable plalstic composition containing gelatinized starch and production thereof
JP3319899A JP2631050B2 (en) 1991-10-04 1991-11-07 Biodegradable plastic molded article containing gelatinized starch and method for producing the same
JP3-319,899 1991-11-07

Publications (2)

Publication Number Publication Date
CA2079768A1 CA2079768A1 (en) 1993-04-05
CA2079768C true CA2079768C (en) 2002-11-19

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EP (1) EP0535994B1 (en)
CA (1) CA2079768C (en)
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Families Citing this family (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4136694C2 (en) * 1991-11-07 1996-10-10 Inventa Ag Starch fiber or starch-modified fiber, process for its production and its use
US5709827A (en) 1992-08-11 1998-01-20 E. Khashoggi Industries Methods for manufacturing articles having a starch-bound cellular matrix
US5618341A (en) 1992-08-11 1997-04-08 E. Khashoggi Industries Methods for uniformly dispersing fibers within starch-based compositions
US5582670A (en) 1992-08-11 1996-12-10 E. Khashoggi Industries Methods for the manufacture of sheets having a highly inorganically filled organic polymer matrix
US5928741A (en) 1992-08-11 1999-07-27 E. Khashoggi Industries, Llc Laminated articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix
US5800647A (en) 1992-08-11 1998-09-01 E. Khashoggi Industries, Llc Methods for manufacturing articles from sheets having a highly inorganically filled organic polymer matrix
US5660903A (en) 1992-08-11 1997-08-26 E. Khashoggi Industries Sheets having a highly inorganically filled organic polymer matrix
US5506046A (en) 1992-08-11 1996-04-09 E. Khashoggi Industries Articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix
US5662731A (en) 1992-08-11 1997-09-02 E. Khashoggi Industries Compositions for manufacturing fiber-reinforced, starch-bound articles having a foamed cellular matrix
US5830548A (en) 1992-08-11 1998-11-03 E. Khashoggi Industries, Llc Articles of manufacture and methods for manufacturing laminate structures including inorganically filled sheets
US5810961A (en) 1993-11-19 1998-09-22 E. Khashoggi Industries, Llc Methods for manufacturing molded sheets having a high starch content
US5580624A (en) 1992-08-11 1996-12-03 E. Khashoggi Industries Food and beverage containers made from inorganic aggregates and polysaccharide, protein, or synthetic organic binders, and the methods of manufacturing such containers
US5679145A (en) 1992-08-11 1997-10-21 E. Khashoggi Industries Starch-based compositions having uniformly dispersed fibers used to manufacture high strength articles having a fiber-reinforced, starch-bound cellular matrix
US5830305A (en) 1992-08-11 1998-11-03 E. Khashoggi Industries, Llc Methods of molding articles having an inorganically filled organic polymer matrix
US5783126A (en) 1992-08-11 1998-07-21 E. Khashoggi Industries Method for manufacturing articles having inorganically filled, starch-bound cellular matrix
US5658603A (en) 1992-08-11 1997-08-19 E. Khashoggi Industries Systems for molding articles having an inorganically filled organic polymer matrix
US5683772A (en) 1992-08-11 1997-11-04 E. Khashoggi Industries Articles having a starch-bound cellular matrix reinforced with uniformly dispersed fibers
US5851634A (en) 1992-08-11 1998-12-22 E. Khashoggi Industries Hinges for highly inorganically filled composite materials
US5545450A (en) 1992-08-11 1996-08-13 E. Khashoggi Industries Molded articles having an inorganically filled organic polymer matrix
US5508072A (en) 1992-08-11 1996-04-16 E. Khashoggi Industries Sheets having a highly inorganically filled organic polymer matrix
US5844023A (en) 1992-11-06 1998-12-01 Bio-Tec Biologische Naturverpackungen Gmbh Biologically degradable polymer mixture
US5716675A (en) 1992-11-25 1998-02-10 E. Khashoggi Industries Methods for treating the surface of starch-based articles with glycerin
DK169728B1 (en) 1993-02-02 1995-01-23 Stein Gaasland Process for releasing cellulose-based fibers from each other in water and molding for plastic molding of cellulosic fiber products
DE4317694A1 (en) * 1993-05-27 1994-12-01 Biotec Biolog Naturverpack Molded part made of starch foam
US5602188A (en) 1993-07-13 1997-02-11 Suzuki Sogyo Co., Ltd. Biodegradable resin foam and method and apparatus for producing same
US5462983A (en) * 1993-07-27 1995-10-31 Evercorn, Inc. Biodegradable moldable products and films comprising blends of starch esters and polyesters
CN1055940C (en) * 1993-07-28 2000-08-30 生物技术生物自然包装有限两合公司 Reinforced biodegradable polymer
US5738921A (en) 1993-08-10 1998-04-14 E. Khashoggi Industries, Llc Compositions and methods for manufacturing sealable, liquid-tight containers comprising an inorganically filled matrix
US6083586A (en) 1993-11-19 2000-07-04 E. Khashoggi Industries, Llc Sheets having a starch-based binding matrix
US5736209A (en) 1993-11-19 1998-04-07 E. Kashoggi, Industries, Llc Compositions having a high ungelatinized starch content and sheets molded therefrom
US5565407A (en) * 1993-12-27 1996-10-15 University Of Kansas Center For Research, Inc. Biologically active agent encapsulated in biodegradable starch/polymer matrices
AU1442095A (en) * 1993-12-27 1995-07-17 University Of Kansas Center For Research, Inc., The Biologically active agent encapsulated in biodegradable starch/polymer matrices
US5843544A (en) 1994-02-07 1998-12-01 E. Khashoggi Industries Articles which include a hinged starch-bound cellular matrix
US5776388A (en) 1994-02-07 1998-07-07 E. Khashoggi Industries, Llc Methods for molding articles which include a hinged starch-bound cellular matrix
US5705203A (en) 1994-02-07 1998-01-06 E. Khashoggi Industries Systems for molding articles which include a hinged starch-bound cellular matrix
US5500465A (en) * 1994-03-10 1996-03-19 Board Of Trustees Operating Michigan State University Biodegradable multi-component polymeric materials based on unmodified starch-like polysaccharides
DE4437792A1 (en) 1994-10-21 1996-04-25 Inventa Ag Molding compounds based on aliphatic polyesters
US5759569A (en) * 1995-01-10 1998-06-02 The Procter & Gamble Company Biodegradable articles made from certain trans-polymers and blends thereof with other biodegradable components
DE19513237A1 (en) * 1995-04-07 1996-12-05 Biotec Biolog Naturverpack Bio-degradable polymer mixt. for adhesive, hygiene articles etc.
ATE242295T1 (en) 1995-04-07 2003-06-15 Biotec Biolog Naturverpack BIODEGRADABLE POLYMER BLEND
FR2735483B1 (en) * 1995-06-13 1997-08-08 Potency Sarl TOTALLY BIODEGRADABLE COMPOSITE MATERIAL AND PROCESS FOR PRODUCING THE SAME
EP0837902B1 (en) * 1995-07-12 2004-03-17 Valtion Teknillinen Tutkimuskeskus Thermoplasticized starch component and process for the preparation thereof
US6025417A (en) * 1996-02-28 2000-02-15 Biotechnology Research & Development Corp. Biodegradable polyester compositions with natural polymers and articles thereof
US5861216A (en) * 1996-06-28 1999-01-19 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer laminates
US5665786A (en) * 1996-05-24 1997-09-09 Bradley University Biodegradable polyester and natural polymer compositions and expanded articles therefrom
US5821286A (en) * 1996-05-24 1998-10-13 The United States Of America As Represented By The Secretary Of The Agriculture Biodegradable polyester and natural polymer compositions and films therefrom
US5852078A (en) * 1996-02-28 1998-12-22 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester compositions with natural polymers and articles thereof
US6168857B1 (en) 1996-04-09 2001-01-02 E. Khashoggi Industries, Llc Compositions and methods for manufacturing starch-based compositions
AU3227297A (en) * 1996-06-13 1998-01-07 Regents Of The University Of Minnesota Method of grafting functional groups to synthetic polymers for making biodegradable plastics
DE19624641A1 (en) 1996-06-20 1998-01-08 Biotec Biolog Naturverpack Biodegradable material consisting essentially of or based on thermoplastic starch
US6893527B1 (en) 1996-06-28 2005-05-17 William M. Doane Biodegradable polyester and natural polymer laminates
CN1098303C (en) * 1997-07-22 2003-01-08 张蕾 Fully degradeable foamed material
TW506894B (en) * 1997-12-15 2002-10-21 Ykk Corp A biodegradable resin composition
DE19757147A1 (en) * 1997-12-20 1999-06-24 Buna Sow Leuna Olefinverb Gmbh Derivatized starch based polymer blend
CN1099439C (en) * 1998-10-29 2003-01-22 孙国榆 Process for making fully-biodegradable containers of food or beverage with potato
US6383246B1 (en) * 1999-08-06 2002-05-07 Nisshin Flour Milling Inc. Composting accelerator for plant-derived material
US6515054B1 (en) 1999-11-02 2003-02-04 Nippon Shokubai Co., Ltd. Biodegradable resin composition and its molded product
US6231970B1 (en) 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
US20090123682A1 (en) * 2007-11-08 2009-05-14 Weder Donald E Floral packaging formed of renewable or biodegradable polymer materials
US7625994B2 (en) 2002-07-30 2009-12-01 E.I. Du Pont De Nemours And Company Sulfonated aliphatic-aromatic copolyetheresters
DE10258227A1 (en) * 2002-12-09 2004-07-15 Biop Biopolymer Technologies Ag Biodegradable multilayer film
CN1230466C (en) * 2003-02-25 2005-12-07 丁少忠 Fully bio-degradable plastic master batch and preparing process thereof
ITMI20041150A1 (en) * 2004-06-09 2004-09-09 Novamont Spa PEARL PROCESS PRODUCTION OF BIODEGRADABLE FILMS HAVING IMPROVED MECHANICAL PROPERTIES
US7629405B2 (en) * 2004-11-19 2009-12-08 Board Of Trustees Of Michigan State University Starch-polyester biodegradable graft copolyers and a method of preparation thereof
US20090160095A1 (en) * 2004-11-19 2009-06-25 Board Of Trustees Of Michigan State University Biodegradable thermoplasticized starch-polyester reactive blends for thermoforming applications
CN101151349B (en) * 2005-03-31 2011-04-13 三菱化学株式会社 Deterioration preventing agent
US20070021515A1 (en) * 2005-07-19 2007-01-25 United States (as represented by the Secretary of Agriculture) Expandable starch-based beads and method of manufacturing molded articles therefrom
US7989524B2 (en) * 2005-07-19 2011-08-02 The United States Of America, As Represented By The Secretary Of Agriculture Fiber-reinforced starch-based compositions and methods of manufacture and use
ITMI20061845A1 (en) * 2006-09-27 2008-03-28 Novamont Spa STYLE BIODEGRADABLE POLYPHASIC COMPOSITIONS BASED ON STARCH
FR2927084B1 (en) * 2008-02-01 2011-02-25 Roquette Freres PROCESS FOR THE PREPARATION OF THERMOPLASTIC COMPOSITIONS BASED ON PLASTICIZED STARCH AND COMPOSITIONS THUS OBTAINED
FR2927088B1 (en) * 2008-02-01 2011-02-25 Roquette Freres PLASTICIZED STARCH THERMOPLASTIC COMPOSITIONS AND PROCESS FOR THE PREPARATION OF SUCH COMPOSITIONS.
FR2934272B1 (en) * 2008-07-24 2013-08-16 Roquette Freres PROCESS FOR THE PREPARATION OF COMPOSITIONS BASED ON AMYLACEOUS MATERIAL AND SYNTHETIC POLYMER
US8466337B2 (en) * 2009-12-22 2013-06-18 Kimberly-Clark Worldwide, Inc. Biodegradable and breathable film
US8586821B2 (en) * 2009-12-23 2013-11-19 Kimberly-Clark Worldwide, Inc. Melt-processed films of thermoplastic cellulose and microbial aliphatic polyester
GB201104263D0 (en) * 2011-03-14 2011-04-27 Biome Bioplastics Ltd Bio-resins
TWI445755B (en) 2012-06-27 2014-07-21 Ind Tech Res Inst Flame-retardant thermoplastic starch material, bio-composite and manufacturing method thereof
EP3019547B1 (en) 2013-03-05 2020-07-22 The Penn State Research Foundation Composite materials
GB2522492B (en) 2014-06-02 2020-07-15 York Potash Ltd Dry powder processing
GB2530757B (en) * 2014-09-30 2019-04-24 York Potash Ltd Pelletising process

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850863A (en) * 1972-07-28 1974-11-26 Union Carbide Corp Blends of a biodegradable thermoplastic oxyalkanoyl polymer and a naturally occurring biodegradable product
GB1582341A (en) 1976-05-03 1981-01-07 Nat Res Dev Printed circuit board
US4133784A (en) * 1977-09-28 1979-01-09 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable film compositions prepared from starch and copolymers of ethylene and acrylic acid
US4337181A (en) * 1980-01-17 1982-06-29 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable starch-based blown films
GB2214918B (en) * 1988-02-03 1992-10-07 Warner Lambert Co Polymeric materials made from starch and at least one synthetic thermoplastic polymeric material
IT1233599B (en) 1989-05-30 1992-04-06 Butterfly Srl POLYMERIC COMPOSITIONS FOR THE PRODUCTION OF BIODEGRADABLE PLASTIC ITEMS AND PROCEDURES FOR THEIR PREPARATION
DE69125965T2 (en) * 1990-02-28 1997-09-25 Agency Ind Science Techn Process for the production of a biodegradable, moldable material
US5108807A (en) * 1990-03-14 1992-04-28 First Brands Corporation Degradable multilayer thermoplastic articles

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CA2079768A1 (en) 1993-04-05
DE69212557T2 (en) 1997-01-02
DE69212557D1 (en) 1996-09-05

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