Classifications

• • 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.
• 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.
• US Patent 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.
• US Patent No. 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.
• 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.
• 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.
• TA triacetin
• 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 um 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.
• the invention provides a biodegradable molding characterized in that it is prepared by kneading and extruding the biodegradable resin composition comprising the aforementioned components.
• the temperature during the kneading process is 25 ⁇ 120 0 C as the melting point of the cellulose diacetate is low and more preferably, it is 25 ⁇ 100 0 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.
• 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.
• 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.
• EXAMPLE 1 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 C H O ), Dae Shin Chemical Ind. Co., Ltd.) as a plasticizer were evenly mixed, the mixture was kneaded for 3 hours at the temperature of 100 0 C and melted in Haake rheocord system of 200 0 C thereby to prepare a blending mixture.
• tensile specimen were prepared according to ASTM D 1708 and ASTM D638, wherein the injection pressure was 750 - 900 psi, injection time was 3 seconds, the temperature of cylinder was 180 - 200 0 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.
• 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 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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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Mechanical Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Biological Depolymerization Polymers (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2005
  • 2005-07-20 KR KR1020050065780A patent/KR20070010837A/ko not_active Application Discontinuation
• 2006
  • 2006-07-05 WO PCT/KR2006/002617 patent/WO2007011119A1/en active Application Filing
  • 2006-07-11 TW TW095125240A patent/TW200708554A/zh unknown
  • 2006-07-20 US US11/489,841 patent/US20070043148A1/en not_active Abandoned

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