US20070043148A1 - Biodegradable resin composition - Google Patents
Biodegradable resin composition Download PDFInfo
- Publication number
- US20070043148A1 US20070043148A1 US11/489,841 US48984106A US2007043148A1 US 20070043148 A1 US20070043148 A1 US 20070043148A1 US 48984106 A US48984106 A US 48984106A US 2007043148 A1 US2007043148 A1 US 2007043148A1
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- US
- United States
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- resin composition
- biodegradable resin
- biodegradable
- composition according
- cellulose diacetate
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- Abandoned
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- 229920006167 biodegradable resin Polymers 0.000 title claims abstract description 61
- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 238000000465 moulding Methods 0.000 claims abstract description 30
- 229920001747 Cellulose diacetate Polymers 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical group CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 18
- 239000004014 plasticizer Substances 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 12
- 239000001087 glyceryl triacetate Substances 0.000 claims description 9
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229960002622 triacetin Drugs 0.000 claims description 9
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 7
- 229920000704 biodegradable plastic Polymers 0.000 claims description 7
- 239000001069 triethyl citrate Substances 0.000 claims description 7
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000013769 triethyl citrate Nutrition 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002734 clay mineral Substances 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims description 4
- 235000019504 cigarettes Nutrition 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 241000251468 Actinopterygii Species 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 239000002361 compost Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 235000019325 ethyl cellulose Nutrition 0.000 claims 1
- 229920001249 ethyl cellulose Polymers 0.000 claims 1
- 238000011109 contamination Methods 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 14
- 229920002678 cellulose Polymers 0.000 description 13
- 239000001913 cellulose Substances 0.000 description 13
- 229920002301 cellulose acetate Polymers 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000010421 standard material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 241001599832 Agave fourcroydes Species 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- PTOAARAWEBMLNO-KVQBGUIXSA-N Cladribine Chemical compound C1=NC=2C(N)=NC(Cl)=NC=2N1[C@H]1C[C@H](O)[C@@H](CO)O1 PTOAARAWEBMLNO-KVQBGUIXSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
Classifications
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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
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic 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
Definitions
- the present invention relates to a biodegradable resin composition and a biodegradable molding using the same and more particularly, it relates to a biodegradable resin composition comprising cellulose diacetate as a main component, which can not only satisfy the biodegradability, processability and properties required for a biodegradable resin but also lower manufacturing costs and prevent environmental contamination by producing the biodegradable resin by reusing a cause factor of environmental contamination and a biodegradable molding using the same.
- U.S. Pat. Nos. 5,234,977, 5,256,711, 5,264,030, 5,292,782, 5,334,634, 5,461,093, 5,461,094, 5,569,692, 5,616,671, 5,696,186, 5,869,647, and 5,874,486 disclose methods of preparing biodegradable plastics by mixing a starch which is inexpensive and easily biodegradable with common resins such as polyethylene, polypropylene and polystyrene, and polyester-based matrix resins.
- common resins such as polyethylene, polypropylene and polystyrene, and polyester-based matrix resins.
- a plasticizer is to be added, which causes discoloring and bad fume during processing and the properties of the plastics are remarkably deteriorated.
- U.S. Pat. Nos. 4,133,784 and 4,337,181 disclose methods of preparing films by adding pregelatinized starches to ethylene-acrylic acid copolymers.
- the ethylene-acrylic acid copolymers are expensive and the properties of the produced films are extremely fragile for practical use, and their biodegradability is not good.
- U.S. Pat. Nos. 5,254,607, 5,256,711 and 5,258,430 disclose the use of a pregelatinized starch, but they require a separate apparatus for adding water and a plasticizer in a large amount so as to pregelatinize starch and also, the degradability of the ethylene-vinyl alcohol copolymers which are synthetic resins used to increase properties and dimension stability has not been verified.
- Korean Patent Laid-Open Nos. 1994-0011542, 1994-0011556, and 1994-0011558 attempted reaction extrusion by use of an organic acid catalyst and binding agent to induce the chemical binding of starch and polyethylene.
- unreacted coarse monomers are likely to remain, and in the case that the content of the starch is more than 30%, mechanical properties are remarkably reduced, and the polyethylene which is used as a matrix resin is not degraded and remains.
- the cellulose acetate a conversion form into an acetic ester of cellulose, has been known to be inherently biodegradable but in fact, its biodegradability is not good.
- molding products comprising the cellulose acetate are laid under the grounds, they maintain the prototype of the molding products until 1 or 2 years and it takes considerably long time for the molding products to be completely biodegraded.
- the molding products are sometimes landfilled as wastes, or left in nature environment, not being recovered as wastes.
- Japanese Patent Laid Open No. 6-199901 discloses a method of regulating the biodegradability of the cellulose acetate by adding an acid compound having a higher acid dissociation constant than acetic acid to the cellulose acetate.
- the acid compound is added to the cellulose acetate, the cellulose acetate is chemically hydrolyzed by the influence of the acid compound and this hydrolysis reaction generates acetic acid, which gives strong acetic acid odor to the cellulose acetate products.
- biodegradable resin composition comprising a cellulose (di)acetate as a main component, which satisfies the biodegradability, processability and properties required for a biodegradable resin and from which acetic acid odor is removed, and a biodegradable molding using the same.
- biodegradable resin composition which can lower the manufacturing costs of the biodegradable resin composition to be produced and prevent environmental contamination in advance by reusing a cause factor inducing environmental contamination and a biodegradable molding using the same.
- the present invention provides a biodegradable resin composition comprising a cellulose diacetate as a main component.
- the molecular weight of the cellulose diacetate is 10,000 to 500,000.
- the biodegradable resin composition comprises:
- the invention provides a biodegradable molding prepared by kneading and extruding the biodegradable resin composition.
- FIG. 1 is a graph showing of the biodegradability of a biodegradable film prepared by using an embodiment of the invention comprising cellulose diacetate, comparing with that of cellulose which is a standard material.
- FIG. 2 is a graph showing the biodegradability of PLA which is a commonly used biodegradable material, comparing with that of cellulose which is a standard material.
- a cellulose diacetate can be biodegraded and it has a remarkably low melting point and thus has an excellent processability while possessing superior properties and accordingly, they have completed the invention.
- the biodegradable resin composition of the invention is characterized by comprising a cellulose diacetate that is a biodegradable resin, as a main component.
- the biodegradable resin composition of the invention comprises a cellulose diacetate and plasticizer, and biodegradable moldings can be prepared by evenly mixing the biodegradable resin composition and kneading and extruding the mixed composition.
- the cellulose diacetate is contained in the biodegradable resin composition preferably in an amount of 50 to 90 parts by weight. Within the above ranges, satisfactory processability as a biodegradable resin composition as well as the properties of moldings can be obtained.
- the cellulose diacetate can be obtained from a waste cigarette filter which is a cause factor of environmental contamination, and the manufacturing costs of the biodegradable resin compositions can be remarkably lowered by preparing the biodegradable resin compositions by recycling the cellulose diacetate of the waste cigarette filters and environmental contamination can be prevented in advance.
- the plasticizer used in the invention makes molding, injection, etc. easy when the biodegradable moldings are prepared and it improves glass transition temperature (Tg), tensile strength, Young's modulus, etc. of the cellulose diacetate.
- triacetin TA
- TEC triethyl citrate
- glycerin epoxidized soybean oil
- ESO epoxidized soybean oil
- the plasticizer is contained in the biodegradable resin composition of the invention preferably in an amount of 10 to 50 parts by weight, and the above range is preferable in aspect of the easiness of molding and injection when the moldings are prepared.
- the biodegradable resin composition comprising the above components may further comprise clay minerals such as montmorillonite and bentonite, additives such as a degradation catalyst or processing aid, etc. if necessary and their amount is preferably 0.1 to 10 parts by weight.
- a latent heat catalyst can be used to cause the ring opening polymerization of epoxidized soybean when the epoxidized soybean is contained as a plasticizer.
- the clay minerals have excellent hygroscopic property due to their laminated structure and accordingly, they render the moldings prepared with the biodegradable resin composition of the invention to be readily degraded even in the water.
- the montmorillonite is preferably used as a clay mineral.
- the clay minerals are used in the biodegradable resin composition of the invention, it is preferable to mix the clay minerals with the plasticizer and disperse them using an ultrasonic machine before they are added to the biodegradable resin composition.
- the invention may further comprise a natural vegetable fiber as a filling agent within the biodegradable resin composition in the preparation of the biodegradable resin composition.
- a natural vegetable fiber are coconut fiber, hemp fiber, ramie fiber, sisal fiber, henequen fiber, pineapple leaf fiber, cotton fiber, coier fiber, rice straw, etc. and it is preferable to have an average diameter of 10 to 500 ⁇ m or so.
- the filling agent is contained preferably in an amount of 1 to 50 parts by weight of 100 parts by weight of the biodegradable resin composition, and in this case, it is advisable to maintain the content of the plasticizer in at least 10% by weight of the biodegradable resin composition. If the filling agent is used, mechanical strength can be complemented and the use of the natural vegetable fibers that are inexpensive can much lower the manufacturing costs of the biodegradable resin composition.
- the invention provides a biodegradable molding characterized in that it is prepared by kneading and extruding the biodegradable resin composition comprising the aforementioned components.
- kneading and extrusion conventional methods used to knead and extrude biodegradable resin compositions can be applied and for example, a twin screw extruder or batch mixer can be used.
- the temperature during the kneading process is 25 ⁇ 120° C. as the melting point of the cellulose diacetate is low and more preferably, it is 25 ⁇ 100° C.
- the biodegradable moldings prepared by the aforementioned method can be applied to films for semiconductor packaging, disposable products such as a variety of containers, cups, spoons, forks, knives, toothbrushes and straws, paper cups, melty coatings such as paper coatings for the manufacture of paper plates, mulching films, agriculture and gardening supplies such as plant ports, clips, etc. garbage bags, compost bags, shrink wrap films, wrapping films, medical supplies such as syringes for animal injection, mouthpieces for endoscope, modifiers for hard biodegradable plastics, golf tee, fish net, fishing line, bottles, a variety of stationery and so on.
- the biodegradable resin composition in accordance with the invention is melted at a melting point remarkably lower than the melting point required in the manufacture of cellulose derivatives used as a substance of prior biodegradable plastics so that it is easy to be prepared into moldings and at the same time, it has properties equal to those of the moldings prepared by using the prior biodegradable resins.
- it can in advance prevent environmental contamination by reusing a cause factor of environmental contamination and remarkably lower the manufacturing costs of the biodegradable resin compositions.
- the biodegradable moldings prepared by using the biodegradable resin compositions of the invention can be degraded under the ground or in the air within a short period when landfilled after their use, they have an advantage in that they can prevent environmental contamination.
- CDA 1 Cellulose (Di)Acetate(Mn ca. 202,332 g ⁇ mol ⁇ 1 , 54.5 wt. % acetyl content, Tg 188° C., Eastman Co., Ltd)
- CDA 2 Recycling fabric
- CDA 3 Recycling fiber CDA (SK) CA: Cellulose acetate(Mn ca. 50,000 g ⁇ mol ⁇ 1 , 39.7 wt.
- PP Polypropylene (grade H1500, Hyundai)
- PLA Polylacetic acid (Mn 83,000 g ⁇ mol ⁇ 1 , Mw 153000 g ⁇ mol ⁇ 1 Cargill-Dow Co., Ltd.)
- TA Triacetin(Mw. 218.21), Dae Shin Chemical Ind. Co., Ltd.
- TEC Triethyl citrate(Mw. 276.29), Aldrich Co., Ltd.
- ESO ShinDongBang Coroperation GC: Glycerin
- the blending mixtures prepared by melting the biodegradable resin composition in Haake rheocord system in Examples 1 to 9 were extruded for 10 minutes at the melting points of the blending mixtures using Carver laboratory press equipped with a temperature control device thereby to prepare initial films having a width of 10 cm, a height of 10 cm and a thickness of 300 ⁇ m.
- the prepared films were cut into ones having a width of 0.5 cm and a height of 4 cm and their glass transition temperature and modulus were measured by Dynamic Mechanical Analyzer. The results are shown in Table 2 below.
- TABLE 2 Glass transition temperature (Tg) and Young's modulus measured from MDA Young's modulus EX./COM. EX. Tg (° C.) (GPa) EX.
- tensile specimen were prepared according to ASTM D1708 and ASTM D638, wherein the injection pressure was 750-900 psi, injection time was 3 seconds, the temperature of cylinder was 180-200° C. and cycle time was 2 min.
- the mechanical strength of the films prepared above was measured by the machine named LR30K-plus from LLOYD, Inc. 10 Specimen in each example were fabricated and then tested. The average value was taken and the results are shown in Table 3 below. TABLE 3 Young's Tensile Strength Elongation modulus EX. (MPa) (%) (MPa) EX. 1 72 8 2300 EX. 2 131 8 3671 EX. 4 90 5 2964 EX. 9 73 6 2254 COM. EX. 5 84 5 2633
- biodegradable resin compositions of the inventions showed properties similar to Comparative Example 5 in which the prior biodegradable resin was used.
- the biodegradable resin composition of Example 2 was subject to experiment according to KS M 3100-1 (ISO 14855) provision, and the biodegradability test was carried out in composting conditions.
- the composition of Comparative Example 5 was tested likewise. As of cellulose which is a standard material and Example 2 and Comparative Example 5, their aerobic biodegradability and collapse rate were measured in the composting conditions and the quantity of the generated carbon dioxide was measured by titration.
- FIG. 1 showed the biodegradability of Example 2 of the invention and cellulose which is a standard material over time and FIG. 2 showed the biodegradability of Comparative Example 5 and the cellulose which is a standard material over time.
- the biodegradable resin composition of the invention showed biodegradability almost equal to that of Comparative Example 5 wherein the commonly used biodegradable resin composition was used.
- the biodegradable resin composition in accordance with the invention can remarkably lower the manufacturing costs when compared with the cellulose acetate which has been used as biodegradable plastic materials, can prevent environmental contamination by reusing the cause factor of environmental contamination, remarkably improves the properties, is easy to be prepared into moldings at a low temperature due to its low melting point, and has considerably improved properties when compared with prior biodegradable moldings using starch.
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This invention provides a biodegradable resin composition and a biodegradable molding using the same and in particular, it not only have satisfactory biodegradability, processability and properties required for biodegradable resins by comprising cellulose diacetate as a main component but also can lower manufacturing costs and prevent environmental contamination by preparing the biodegradable resins by reusing a cause factor of environmental contamination.
Description
- 1. Field of the Invention
- The present invention relates to a biodegradable resin composition and a biodegradable molding using the same and more particularly, it relates to a biodegradable resin composition comprising cellulose diacetate as a main component, which can not only satisfy the biodegradability, processability and properties required for a biodegradable resin but also lower manufacturing costs and prevent environmental contamination by producing the biodegradable resin by reusing a cause factor of environmental contamination and a biodegradable molding using the same.
- 2. Description of Related Art
- As plastics are light and strong and they are easy to be processed and not easily degraded, their consumption from industrial materials to disposable products and wrapping materials is continuously increasing. Hard wastes including such plastics are disposed by landfill or incineration after their use, or reused by recycling them. However, the disposal of wastes by landfill, incineration, etc. gives rise to environmentally severe damage. Accordingly, to solve the environment issue, various biodegradable plastics that keep their function and structure during their use but can be degraded into water and carbon dioxide by microorganism once wasted are being produced.
- For example, U.S. Pat. Nos. 5,234,977, 5,256,711, 5,264,030, 5,292,782, 5,334,634, 5,461,093, 5,461,094, 5,569,692, 5,616,671, 5,696,186, 5,869,647, and 5,874,486 disclose methods of preparing biodegradable plastics by mixing a starch which is inexpensive and easily biodegradable with common resins such as polyethylene, polypropylene and polystyrene, and polyester-based matrix resins. However, as the starch is added, a plasticizer is to be added, which causes discoloring and bad fume during processing and the properties of the plastics are remarkably deteriorated.
- Further, U.S. Pat. Nos. 4,133,784 and 4,337,181 disclose methods of preparing films by adding pregelatinized starches to ethylene-acrylic acid copolymers. However, the ethylene-acrylic acid copolymers are expensive and the properties of the produced films are extremely fragile for practical use, and their biodegradability is not good.
- Further, U.S. Pat. Nos. 5,254,607, 5,256,711 and 5,258,430 disclose the use of a pregelatinized starch, but they require a separate apparatus for adding water and a plasticizer in a large amount so as to pregelatinize starch and also, the degradability of the ethylene-vinyl alcohol copolymers which are synthetic resins used to increase properties and dimension stability has not been verified.
- Also, Korean Patent Laid-Open Nos. 1994-0011542, 1994-0011556, and 1994-0011558 attempted reaction extrusion by use of an organic acid catalyst and binding agent to induce the chemical binding of starch and polyethylene. However, unreacted coarse monomers are likely to remain, and in the case that the content of the starch is more than 30%, mechanical properties are remarkably reduced, and the polyethylene which is used as a matrix resin is not degraded and remains.
- Hence, researches about methods of preparing biodegradable resins using cellulose derivatives have been conducted and especially, the researches about the biodegradable resins using cellulose acetate among the cellulose derivatives have been mainly performed.
- The cellulose acetate, a conversion form into an acetic ester of cellulose, has been known to be inherently biodegradable but in fact, its biodegradability is not good. Thus, although molding products comprising the cellulose acetate are laid under the grounds, they maintain the prototype of the molding products until 1 or 2 years and it takes considerably long time for the molding products to be completely biodegraded. Also, the molding products are sometimes landfilled as wastes, or left in nature environment, not being recovered as wastes.
- Accordingly, researches about methods for improving the biodegradability of the cellulose acetate are in progress. Japanese Patent Laid Open No. 6-199901 discloses a method of regulating the biodegradability of the cellulose acetate by adding an acid compound having a higher acid dissociation constant than acetic acid to the cellulose acetate. However, in this method, at the point when the acid compound is added to the cellulose acetate, the cellulose acetate is chemically hydrolyzed by the influence of the acid compound and this hydrolysis reaction generates acetic acid, which gives strong acetic acid odor to the cellulose acetate products.
- Therefore, studies about methods of preparing biodegradable plastics using different kinds of cellulose derivatives other than the cellulose acetate have been incessantly conducted and more progressive studies are in need.
- In order to solve the problems of the prior arts, it is an object of the invention to provide a biodegradable resin composition comprising a cellulose (di)acetate as a main component, which satisfies the biodegradability, processability and properties required for a biodegradable resin and from which acetic acid odor is removed, and a biodegradable molding using the same.
- Also, it is another object of the invention to provide a biodegradable resin composition which can lower the manufacturing costs of the biodegradable resin composition to be produced and prevent environmental contamination in advance by reusing a cause factor inducing environmental contamination and a biodegradable molding using the same.
- It is still another object of the invention to provide a biodegradable resin composition capable of preventing environmental contamination because the container is degraded under the ground or in the air within a short period when landfilled after its use, a method of preparing a biodegradable molding using the same and the biodegradable molding.
- To achieve the aforementioned objects, the present invention provides a biodegradable resin composition comprising a cellulose diacetate as a main component.
- Preferably, the molecular weight of the cellulose diacetate is 10,000 to 500,000.
- Also, more preferably, the biodegradable resin composition comprises:
- a) 50 to 90 parts by weight of a cellulose diacetate; and
- b) 10 to 50 parts by weight of a plasticizer.
- Further, the invention provides a biodegradable molding prepared by kneading and extruding the biodegradable resin composition.
-
FIG. 1 is a graph showing of the biodegradability of a biodegradable film prepared by using an embodiment of the invention comprising cellulose diacetate, comparing with that of cellulose which is a standard material. -
FIG. 2 is a graph showing the biodegradability of PLA which is a commonly used biodegradable material, comparing with that of cellulose which is a standard material. - This invention is further described in detail.
- The inventors found that a cellulose diacetate can be biodegraded and it has a remarkably low melting point and thus has an excellent processability while possessing superior properties and accordingly, they have completed the invention.
- The biodegradable resin composition of the invention is characterized by comprising a cellulose diacetate that is a biodegradable resin, as a main component.
- Preferably, the biodegradable resin composition of the invention comprises a cellulose diacetate and plasticizer, and biodegradable moldings can be prepared by evenly mixing the biodegradable resin composition and kneading and extruding the mixed composition.
- The cellulose diacetate is contained in the biodegradable resin composition preferably in an amount of 50 to 90 parts by weight. Within the above ranges, satisfactory processability as a biodegradable resin composition as well as the properties of moldings can be obtained.
- Preferably, the cellulose diacetate can be obtained from a waste cigarette filter which is a cause factor of environmental contamination, and the manufacturing costs of the biodegradable resin compositions can be remarkably lowered by preparing the biodegradable resin compositions by recycling the cellulose diacetate of the waste cigarette filters and environmental contamination can be prevented in advance.
- The plasticizer used in the invention makes molding, injection, etc. easy when the biodegradable moldings are prepared and it improves glass transition temperature (Tg), tensile strength, Young's modulus, etc. of the cellulose diacetate.
- For the plasticizers, triacetin (TA), triethyl citrate (TEC), or glycerin can be suitably used, epoxidized soybean oil (ESO) as a secondary plasticizer can be added thereto and preferably, it is preferable to use triacetin.
- The plasticizer is contained in the biodegradable resin composition of the invention preferably in an amount of 10 to 50 parts by weight, and the above range is preferable in aspect of the easiness of molding and injection when the moldings are prepared.
- The biodegradable resin composition comprising the above components may further comprise clay minerals such as montmorillonite and bentonite, additives such as a degradation catalyst or processing aid, etc. if necessary and their amount is preferably 0.1 to 10 parts by weight.
- For the catalysts, a latent heat catalyst can be used to cause the ring opening polymerization of epoxidized soybean when the epoxidized soybean is contained as a plasticizer.
- The clay minerals have excellent hygroscopic property due to their laminated structure and accordingly, they render the moldings prepared with the biodegradable resin composition of the invention to be readily degraded even in the water. In particular, the montmorillonite is preferably used as a clay mineral.
- Also, when the clay minerals are used in the biodegradable resin composition of the invention, it is preferable to mix the clay minerals with the plasticizer and disperse them using an ultrasonic machine before they are added to the biodegradable resin composition.
- Further, the invention may further comprise a natural vegetable fiber as a filling agent within the biodegradable resin composition in the preparation of the biodegradable resin composition. Specific examples of the natural vegetable fiber are coconut fiber, hemp fiber, ramie fiber, sisal fiber, henequen fiber, pineapple leaf fiber, cotton fiber, coier fiber, rice straw, etc. and it is preferable to have an average diameter of 10 to 500 μm or so. Also, the filling agent is contained preferably in an amount of 1 to 50 parts by weight of 100 parts by weight of the biodegradable resin composition, and in this case, it is advisable to maintain the content of the plasticizer in at least 10% by weight of the biodegradable resin composition. If the filling agent is used, mechanical strength can be complemented and the use of the natural vegetable fibers that are inexpensive can much lower the manufacturing costs of the biodegradable resin composition.
- Further, the invention provides a biodegradable molding characterized in that it is prepared by kneading and extruding the biodegradable resin composition comprising the aforementioned components.
- For the kneading and extrusion, conventional methods used to knead and extrude biodegradable resin compositions can be applied and for example, a twin screw extruder or batch mixer can be used.
- Preferably, the temperature during the kneading process is 25˜120° C. as the melting point of the cellulose diacetate is low and more preferably, it is 25˜100° C.
- Also, after kneaded at the above temperature, it can be molded into moldings preferably at the temperature of 160˜220° C. using a common extruder.
- The biodegradable moldings prepared by the aforementioned method can be applied to films for semiconductor packaging, disposable products such as a variety of containers, cups, spoons, forks, knives, toothbrushes and straws, paper cups, melty coatings such as paper coatings for the manufacture of paper plates, mulching films, agriculture and gardening supplies such as plant ports, clips, etc. garbage bags, compost bags, shrink wrap films, wrapping films, medical supplies such as syringes for animal injection, mouthpieces for endoscope, modifiers for hard biodegradable plastics, golf tee, fish net, fishing line, bottles, a variety of stationery and so on.
- The biodegradable resin composition in accordance with the invention is melted at a melting point remarkably lower than the melting point required in the manufacture of cellulose derivatives used as a substance of prior biodegradable plastics so that it is easy to be prepared into moldings and at the same time, it has properties equal to those of the moldings prepared by using the prior biodegradable resins. In addition, it can in advance prevent environmental contamination by reusing a cause factor of environmental contamination and remarkably lower the manufacturing costs of the biodegradable resin compositions. Also, as the biodegradable moldings prepared by using the biodegradable resin compositions of the invention can be degraded under the ground or in the air within a short period when landfilled after their use, they have an advantage in that they can prevent environmental contamination.
- For better understanding of the present invention, preferred embodiments follow. The following examples are intended to merely illustrate the invention without limiting the scope of the invention.
- After 70 parts by weight of cellulose diacetate having a molecular weight of 202,332 (Eastman Co., Ltd.), and 30 parts by weight of triacetin (Mw. 218.21, major component C9H14O6), Dae Shin Chemical Ind. Co., Ltd.) as a plasticizer were evenly mixed, the mixture was kneaded for 3 hours at the temperature of 100° C. and melted in Haake rheocord system of 200° C. thereby to prepare a blending mixture.
- With the exception that the compositions and ratios as shown in Table 1 below were used, blending mixtures were prepared by carrying out the same method as above Example 1.
TABLE 1 Cellulose (Parts by Plasticizer Weight) TA TEC GC ESO BET EX. 1 CDA 1 7030 EX. 2 CDA 1 8020 EX. 3 CDA 1 8020 EX. 4 CDA 1 8020 EX. 5 CDA 1 8010 10 EX. 6 CDA 2 8020 EX. 7 CDA 2 7020 10 EX. 8 CDA 3 8020 EX. 9 CDA 3 7030 COM. EX. 1 CA 9010 COM. EX. 2 CA 8020 COM. EX. 3 CA 7030 COM. EX. 4 pure PP COM. EX. 5 pure PLA
Note
CDA1: Cellulose (Di)Acetate(Mn ca. 202,332 g · mol−1, 54.5 wt. % acetyl content, Tg 188° C., Eastman Co., Ltd)
CDA2: Recycling fabric CDA (SK)
CDA3: Recycling fiber CDA (SK)
CA: Cellulose acetate(Mn ca. 50,000 g · mol−1, 39.7 wt. % acetyl content, Tg 188° C., Aldrich Co., Ltd.)
PP: Polypropylene (grade H1500, Hyundai)
PLA: Polylacetic acid (Mn 83,000 g · mol−1 , Mw 153000 g · mol−1 Cargill-Dow Co., Ltd.)
TA: Triacetin(Mw. 218.21), Dae Shin Chemical Ind. Co., Ltd.
TEC: Triethyl citrate(Mw. 276.29), Aldrich Co., Ltd.
ESO: ShinDongBang Coroperation
GC: Glycerin
- The blending mixtures prepared by melting the biodegradable resin composition in Haake rheocord system in Examples 1 to 9 were extruded for 10 minutes at the melting points of the blending mixtures using Carver laboratory press equipped with a temperature control device thereby to prepare initial films having a width of 10 cm, a height of 10 cm and a thickness of 300 μm. The prepared films were cut into ones having a width of 0.5 cm and a height of 4 cm and their glass transition temperature and modulus were measured by Dynamic Mechanical Analyzer. The results are shown in Table 2 below.
TABLE 2 Glass transition temperature (Tg) and Young's modulus measured from MDA Young's modulus EX./COM. EX. Tg (° C.) (GPa) EX. 1 97 1.50 EX. 2 108 1.55 EX. 3 138.5 1.72 EX. 4 146.9 1.64 EX. 5 141.9 1.91 EX. 6 89.9 1.34 EX. 8 92.8 1.34 COM. EX. 2 206.3 2.51 - As shown in Table 2 above, the working Examples of the invention had remarkably lower Tg and Young's modulus than Comparative Example in which cellulose acetate was used and thus they could be very easily processed.
- In addition, to measure mechanical properties of the working Examples of the invention and Comparative Examples, tensile specimen were prepared according to ASTM D1708 and ASTM D638, wherein the injection pressure was 750-900 psi, injection time was 3 seconds, the temperature of cylinder was 180-200° C. and cycle time was 2 min. The mechanical strength of the films prepared above was measured by the machine named LR30K-plus from LLOYD, Inc. 10 Specimen in each example were fabricated and then tested. The average value was taken and the results are shown in Table 3 below.
TABLE 3 Young's Tensile Strength Elongation modulus EX. (MPa) (%) (MPa) EX. 1 72 8 2300 EX. 2 131 8 3671 EX. 4 90 5 2964 EX. 9 73 6 2254 COM. EX. 5 84 5 2633 - As shown in Table 3 above, the biodegradable resin compositions of the inventions showed properties similar to Comparative Example 5 in which the prior biodegradable resin was used.
- Also, in order to examine the biodegradability of the biodegradable resin compositions of the invention, the biodegradable resin composition of Example 2 was subject to experiment according to KS M 3100-1 (ISO 14855) provision, and the biodegradability test was carried out in composting conditions. The composition of Comparative Example 5 was tested likewise. As of cellulose which is a standard material and Example 2 and Comparative Example 5, their aerobic biodegradability and collapse rate were measured in the composting conditions and the quantity of the generated carbon dioxide was measured by titration.
-
FIG. 1 showed the biodegradability of Example 2 of the invention and cellulose which is a standard material over time andFIG. 2 showed the biodegradability of Comparative Example 5 and the cellulose which is a standard material over time. - As shown in
FIG. 1 andFIG. 2 , the biodegradable resin composition of the invention showed biodegradability almost equal to that of Comparative Example 5 wherein the commonly used biodegradable resin composition was used. - The biodegradable resin composition in accordance with the invention can remarkably lower the manufacturing costs when compared with the cellulose acetate which has been used as biodegradable plastic materials, can prevent environmental contamination by reusing the cause factor of environmental contamination, remarkably improves the properties, is easy to be prepared into moldings at a low temperature due to its low melting point, and has considerably improved properties when compared with prior biodegradable moldings using starch.
Claims (9)
1. A biodegradable resin composition comprising a cellulose diacetate as a main component.
2. The biodegradable resin composition according to claim 1 wherein the cellulose diacetate is an ethyl cellulose having a molecular weight of 10,000 to 500,000.
3. The biodegradable resin composition according to claim 1 wherein the biodegradable resin composition comprises:
a) 50 to 90 parts by weight of a cellulose diacetate; and
b) 10 to 50 parts by weight of a plasticizer.
4. The biodegradable resin composition according to claim 1 wherein the plasticizer is selected from the group consisting of triacetin (TA), triethyl citrate (TEC), glycerin and a mixture thereof.
5. The biodegradable resin composition according to claim 1 wherein the cellulose diacetate is obtained from a waste cigarette filter.
6. The biodegradable resin composition according to claim 1 wherein the biodegradable resin composition further comprises a clay mineral, degradation catalyst or processing aid.
7. The biodegradable resin composition according to claim 1 wherein the biodegradable resin composition further comprises a natural vegetable fiber.
8. A biodegradable molding prepared by kneading, extruding and injecting the biodegradable resin composition of claim 1 .
9. The biodegradable molding according to claim 8 wherein the biodegradable molding is a film for semiconductor packaging, container, cup, spoon, fork, knife, toothbrush, straw, paper cup, paper coating for the manufacture of paper plates, mulching film, plant port, clip, garbage bag, compost bag, shrink wrap film, wrapping film, syringe for animal injection, mouthpiece for endoscope, modifier for hard biodegradable plastics, golf tee, fish net, fishing line, bottles or stationery.
Applications Claiming Priority (2)
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KR10-2005-0065780 | 2005-07-20 | ||
KR1020050065780A KR20070010837A (en) | 2005-07-20 | 2005-07-20 | Biodegradable composition |
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US11/489,841 Abandoned US20070043148A1 (en) | 2005-07-20 | 2006-07-20 | Biodegradable resin composition |
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US (1) | US20070043148A1 (en) |
KR (1) | KR20070010837A (en) |
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US20100230405A1 (en) * | 2009-03-11 | 2010-09-16 | Nuvision Bioplastics, Llc | Biodegradable Resin Composition Utilized in the Manufacture of Biodegradable Containers, Biodegradable Containers, and Method of Manufacture |
WO2011102940A1 (en) * | 2010-02-21 | 2011-08-25 | Innovative Bottles, Llc | Disposable items made from bioplastic resins |
US20120328828A1 (en) * | 2011-06-24 | 2012-12-27 | Mcinturff Richard Alexander | Tear resistent and eco friendly disposable visor protective sheets |
US20130225731A1 (en) * | 2011-02-28 | 2013-08-29 | Jiangsu Jinhe Hi-Tech Co., Ltd | Degradable plastic and manufacturing method thereof |
US8852157B2 (en) | 2010-02-21 | 2014-10-07 | Innovative Bottles, Llc | Disposable items made from bioplastic resins |
US9282769B2 (en) | 2011-03-15 | 2016-03-15 | Altria Client Services Llc | Biodegradable cigar tip |
CN108059734A (en) * | 2016-11-08 | 2018-05-22 | 四川普什醋酸纤维素有限责任公司 | Environment-friendly type cellulose diacetate micelle and preparation method thereof |
JP2022545133A (en) * | 2019-09-03 | 2022-10-25 | アールジェイソルター,リミティド ライアビリティ カンパニー | Biodegradable article and manufacturing method |
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KR20110035215A (en) * | 2009-09-30 | 2011-04-06 | 성균관대학교산학협력단 | Biodegradable thermoplastic composition comprising cellulose derivatives and natural fiber processed by additive |
ITMI20112181A1 (en) * | 2011-11-30 | 2013-05-31 | Es Laminati Estrusi Termoplasti Ci S P A | BIODEGRADABLE PLASTIC MATERIAL BASED ON CELLULOSE ACETATE AND RELATED ARTICLES |
KR101449466B1 (en) * | 2013-02-25 | 2014-10-14 | 재단법인대구경북과학기술원 | Cellulose ester based composition for eyeglass frame using complex plasticizers, method of preparing eyeglass temple using the same, and eyeglass temple prepared from the same |
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KR20070010837A (en) | 2007-01-24 |
WO2007011119A1 (en) | 2007-01-25 |
TW200708554A (en) | 2007-03-01 |
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