WO2011145899A2 - 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품 - Google Patents
폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품 Download PDFInfo
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- 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
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Definitions
- the present invention relates to a polylactic acid resin and a copolymerized polyester resin blend and a molded article using the same, and more particularly, to a polylactic acid resin and a copolymer polyester resin blend having excellent impact resistance and heat resistance and a molded article using the same. .
- Polylactic acid (PLA) resin is a plant-derived resin obtained from plants such as corn, and has biodegradable properties.
- Polystyrene resin, polyvinyl chloride (PVC) resin, and polyethylene (Polyethylene) Unlike petroleum-based resins such as), it is possible to reduce the environmental pollution, which is a disadvantage of petroleum-based plastic products, because it is effective in preventing the exhaustion of petroleum resources and suppressing carbon dioxide emissions. Accordingly, as the environmental pollution problem caused by waste plastics has emerged as a social problem, efforts are being made to expand the scope of application to general plastics (petroleum resins) such as food packaging materials, containers, and electronic product cases.
- polylactic acid resins are limited in application range compared to conventional petroleum resins because of their low impact resistance and heat resistance.
- Korean Patent Publication No. 10-2005-0056021 discloses a method of improving the low impact resistance of polylactic acid by blending polylactic acid and polycarbonate resin.
- the specific gravity of the petroleum-based plastic resin increases, resulting in a violation of the purpose of using the polylactic acid resin. .
- An object of the present invention is to provide a polylactic acid resin and a copolyester resin blend having a ratio of a biomaterial maintained at a predetermined amount or more and excellent in impact resistance and heat resistance, and a molded product using the same.
- polylactic acid resin 5 to 95% by weight; And an acid component comprising terephthalic acid and a diol component containing 5 to 99 mol% of 1,4-cyclohexanedimethanol, 1 to 60 mol% isosorbide, to form an acid moiety derived from the acid component, and
- a polylactic acid resin and a copolyester resin blend comprising 5 to 95% by weight of a copolyester resin having a repeating structure of a diol moiety derived from a diol component are provided.
- the present invention also provides a molded product produced by molding the polylactic acid resin and the copolymerized polyester resin blend.
- the polylactic acid resin and the copolyester resin blend according to the present invention are blended with a polylactic acid resin and a copolyester resin containing an isosorbide (bio monomer), thereby increasing the content of the copolyester resin even if the bio of the blend is increased. It is environmentally friendly by maintaining the content of the material (polylactic acid resin and isosorbide) more than a certain amount, it is possible to improve the low impact resistance and heat resistance of the polylactic acid resin. In addition, unlike the case of blending other petroleum-based resin, the polylactic acid resin and the copolyester resin blend of the present invention can prevent the generation of bubbles during thermoforming, and thus, a separate drying process is additionally required when manufacturing a molded product. There is no time and economic benefit as it is not included.
- the polylactic acid resin and the copolyester resin blend according to the present invention include a copolyester resin comprising a polylactic acid (PLA) resin and an isosorbide (bio monomer).
- PLA polylactic acid
- bio monomer bio monomer
- polylactic acid resin used in the present invention a conventional polylactic acid resin can be used without limitation, and a commercialized polylactic acid resin can be used.
- the polylactic acid resin is typically prepared from a monomer derived from L-lactic acid and / or D-lactic acid, and L-lactic acid and D- in a range that does not impair the effects of the present invention. It may also contain a certain amount of other monomers not derived from lactic acid.
- There are many methods for producing the polylactic acid resin but the most known method is ring-opening polymerization of lactide prepared from lactic acid. However, the polycondensation reaction may be carried out directly without being limited thereto.
- Polylactic acid resins prepared from monomers derived from L- and D-lactic acids, respectively, are crystalline and have a high melting point.
- L-lactide, D-lactide and meso-lactide derived from L-lactic acid, D-lactic acid the content of L-lactide, D-lactide and meso-lactide Crystallinity and melting point can be freely adjusted according to the requirements, each component content can be adjusted according to the application.
- the number average molecular weight of the polylactic acid resin used in the present invention is 10,000 to 500,000, preferably 10,000 to 300,000.
- the number average molecular weight of the polylactic acid resin is less than 10,000, mechanical properties such as impact resistance may not be sufficiently expressed, and when the number average molecular weight exceeds 500,000, processing may be difficult due to excessive molecular weight.
- the copolyester resin used in the present invention is for improving the impact resistance and heat resistance of the polylactic acid resin and the copolyester resin blend, and maintaining a biomaterial content of the blend in a predetermined amount or more, and includes an acid component containing terephthalic acid and Acid moieties and diols derived from the acid component are copolymerized with diol components comprising 5 to 99 mole% of 1,4-cyclohexanedimethanol and 1 to 60 mole% isosorbide (see Formula 1).
- the diol moiety derived from the component has a repeating structure.
- the acid component includes terephthalic acid as a main component. That is, the acid component is a total acid component is a terephthalic acid component, or in order to improve the physical properties of the polyester resin, in addition to the terephthalic acid component, aromatic dicarboxylic acid component having 8 to 14 carbon atoms and aliphatic dicarboxylic acid component having 4 to 12 carbon atoms It may include some of the copolymerized acid component (copolymerization monomer) selected from the group consisting of.
- the content of the copolymerized acid component for improving the physical properties is preferably 0 to 50 mol%, for example, 0.1 to 40 mol%, more preferably 0.1 to 10 mol% based on the total acid component.
- the aromatic dicarboxylic acid component having 8 to 14 carbon atoms is selected from polyester resins such as naphthalenedicarboxylic acid such as isophthalic acid and 2,6-naphthalenedicarboxylic acid and diphenyl dicarboxylic acid except for terephthalic acid component.
- Aromatic dicarboxylic acid component commonly used in the preparation wherein the aliphatic dicarboxylic acid component having 4 to 12 carbon atoms is 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Linear, branched or the like commonly used in the preparation of polyester resins such as cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, isodecyl succinic acid, maleic acid, fumaric acid, adipic acid, glutaric acid, azelaic acid, and the like. Cyclic aliphatic dicarboxylic acid components. The acid component may be used alone or in combination of two or more thereof.
- terephthalic acid component terephthalic acid
- alkyl esters thereof lower alkyl esters having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester
- acid anhydrides thereof acid anhydride
- an acid moiety and a diol moiety include a residue remaining after hydrogen, a hydroxy group or an alkoxy group is removed when an acid component and a diol component are subjected to a conventional polyester polymerization reaction.
- the diol component is (i) 5 to 99 mol, preferably 5 to 95 mol%, more preferably 8 to 91 mol% of 1,4-cyclohexanedimethanol with respect to the total diol component and (ii) 1 to 60 mol%, preferably in a range not exceeding 60 mol%, including isosorbide in a range corresponding to the following Equation 1, more preferably 4 to 40 mol% (in Equation 1 below) , ISB mol% is isosorbide, CHDM mol% is 1,4-cyclohexanedimethanol).
- Equation 1 0.0012 (CHDM mol%) 2 -0.2401 (CHDM mol%) +14.136 ⁇ ISB mol% ⁇ 0.0049 (CHDM mol%) 2 -0.2255 (CHDM mol%) +71.176
- the diol component in addition to the (i) 1,4-cyclohexane dimethanol and (ii) isosorbide, the other diol component, (iii) ethylene glycol and (iv) other for improving the physical properties of the polyester resin
- the copolymerized diol (monomer) component diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4-butanediol, pentanediol, hexanediol (1,6 -Hexanediol, etc.), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1 , 3-cyclohexanedimethanol, tetra
- the main component of the remaining diol component is preferably (iii) ethylene glycol, and besides ethylene glycol (Iv)
- the content of the other copolymerized diol component for improving physical properties is, for example, preferably 0 to 50 mol%, for example 0.1 to 40 mol%, more preferably 0.1 to the total diol component. To 10 mol%.
- 1,4-cyclo by adjusting the content of 1,4-cyclohexanedimethanol and isosorbide (1,4: 3,6- dianhydroglucinitol) as described above As the content of hexanedimethanol increased, it was confirmed that the impact strength rapidly increased. That is, in the present invention, 1,4-cyclohexanedimethanol and isosorbide are used for improving physical properties such as moldability of homopolymers using only terephthalic acid and ethylene glycol as raw materials.
- the content of the 1,4-cyclohexane dimethanol is less than 5 mol% there is a fear that the impact strength is insufficient, if it exceeds 99 mol% isosorbide content is less than 1 mol% there is a fear that the heat resistance is lowered have.
- the content of the isosorbide is less than 1 mol%, there is a fear that the heat resistance rise is insufficient, and when the content of the isosorbide exceeds 60 mol%, the product may be yellowed.
- the notch Izod impact strength (ASTM D256 method, measuring temperature: 23 °C) is measured, the impact strength of 50J / m or more preferably Indicates.
- the notched Izod impact strength of the polyester resin copolymerized only with ethylene glycol and isosorbide usually shows a value of 50 J / m or less.
- the polyester resin according to the present invention was dissolved in orthochlorophenol (OCP) at a concentration of 1.2 g / dl, and when the intrinsic viscosity was measured at 35 ° C., 0.35 dl / g or more, preferably 0.40 dl / g or more, more preferably 0.45 dl / g. Since the polyester resin is excellent in heat resistance and impact resistance, blending with the polylactic acid resin may compensate for the low impact resistance and heat resistance of the polylactic acid resin.
- OCP orthochlorophenol
- the copolyester resin may be prepared through an esterification reaction (first step) and a polycondensation reaction (second step).
- the first step, the esterification reaction may be performed in a batch or continuous manner, and each raw material (acid component and diol component) may be separately added, but the acid component is added to the diol component in a slurry form. Most preferred.
- the content of 1,4-cyclohexanedimethanol is 10 to 90 parts by weight, preferably 20 to 80 parts by weight based on 100 parts by weight of the acid component If possible, the total acid component and the diol component are added, and 200 to 300 ° C, preferably 240 to 260 ° C, more preferably 245 to 255 ° C and 0.1 to 3.0 kg / cm 2 , preferably 0.2 to 3.0 kg /
- the esterification reaction is carried out under a pressurized pressure condition of cm 2 .
- the esterification reaction time (average residence time) is usually about 100 minutes to 10 hours, preferably about 2 hours to 500 minutes, and may vary depending on the reaction temperature, pressure, and content of the diol component relative to the acid component to be used.
- a polycondensation reaction (second step) is carried out, and before the start of the polycondensation reaction (second step), a polycondensation catalyst, stabilizer is added to the product of the esterification reaction. , Colorants and the like can be added.
- a polycondensation catalyst one or more of conventional titanium, germanium, antimony, aluminum, tin compound, and the like may be appropriately selected and used.
- Useful titanium-based catalysts include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate , Triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide / silicon dioxide copolymer, titanium dioxide / zirconium dioxide copolymer, etc. can be illustrated. .
- useful germanium crab catalysts include germanium dioxide and copolymers using the same.
- phosphorus compounds such as phosphoric acid, trimethyl phosphate and triethyl phosphate can be generally used, and the amount of the additive is 10 to 100 ppm relative to the weight of the final polymer based on the amount of phosphorus element. If the amount of the stabilizer is less than 10 ppm, the stabilization effect is insufficient, and the color of the polymer may change to yellow. If the amount of the stabilizer exceeds 100 ppm, the polymer of the desired high polymerization degree may not be obtained.
- the polycondensation reaction is carried out under reduced pressure conditions of 260 to 290 ° C, preferably 260 to 280 ° C, more preferably 265 to 275 ° C and 400 to 0.1 mmHg.
- the decompression condition of 400 to 0.1mmHg is to remove glycol which is a by-product of the polycondensation reaction.
- the polycondensation reaction is carried out for the required time until reaching the desired intrinsic viscosity, for example, for an average residence time of 1 to 10 hours.
- the polylactic acid resin and the copolyester resin blend according to the present invention are 5 to 95% by weight of the polylactic acid resin, preferably 10 to 90% by weight and 5 to 95% by weight of the polyester resin, preferably 5 to 90%. Wt%, more preferably 10 to 85 wt%.
- the content of the polylactic acid resin when the content of the polylactic acid resin is less than 5% by weight or the content of the copolyester resin is more than 90% by weight, the biodegradable properties of the polylactic acid resin, preventing the exhaustion of petroleum resources, suppressing carbon dioxide emissions
- the effect of the polylactic acid resin is more than 95% by weight, or the content of the copolyester resin is less than 5% by weight, the impact resistance and heat resistance of the blend are poor and various molded products It may not be used for
- 0 to 40 parts by weight for example, 1 to 30 parts by weight of other resin components may be further included with respect to 100 parts by weight of the total blend.
- the blend may be extruded or injected directly by simple blending, or cooled and pelletized while blended and compounded by extrusion, and then crystallized and reused for the purpose of extrusion or injection again using the obtained blended pellet-type blend chips. .
- the notched Izod impact strength (ASTM D256 method, measurement temperature: 23 ° C.) was measured, and more than 30 J / m, preferably 50 J / m or more. It shows the impact strength.
- the polylactic acid resin and the copolyester resin blend according to the present invention are molded through conventional molding processes such as injection, extrusion, extrusion blow, injection blow, and profile extrusion known in the art, and post-processing such as thermoforming processes using the same. It can be made into a molded product (sheet or the like) of a suitable shape as needed.
- Tg Heat resistance: With glass-rubber transition temperature (Tg), the polymer (blend) is annealed at 300 ° C. for 5 minutes, cooled to room temperature, and then heated up to 10 ° C./min. Measure the Tg temperature at the second scan.
- thermoforming machine visually observe the presence / absence of a plate-shaped bubble with thermoforming at 130 ° C. and a mark of “SK” type.
- the reactor was firstly depressurized to 50 mmHg at atmospheric pressure while increasing the internal temperature of the reactor from 240 ° C to 275 ° C, and ethylene glycol was removed by low vacuum for 40 minutes. Then, the mixture was slowly depressurized to 0.1 mmHg and subjected to polycondensation reaction under high vacuum until the desired intrinsic viscosity was obtained, thereby preparing a copolymerized polyester resin.
- Copolymerization was carried out in the same manner as in Preparation Example 1, except that 640 g of 1,4-cyclohexanedimethanol, 150 g of ethylene glycol and 850 g of isosorbide were used based on 6 moles of terephthalic acid and 6 moles of terephthalic acid as the diol component. Polyester resins were prepared.
- a polylactic acid resin in the form of pellets was prepared in the same manner as in Example 1 except that the copolyester resin was not used. Using the method described above, the glass transition temperature, notched Izod impact strength, the presence / absence of bubbles and the presence of harmful substances after thermoforming, and the results are shown in Table 1 below.
- the polylactic acid resin and the copolyester resin blend according to the present invention have excellent heat resistance at a glass transition temperature of 67 to 90 ° C. and a notch Izod impact strength of 50 to 110 J / m and excellent impact resistance. It can be seen.
- bubbles do not occur after thermoforming, a separate drying process is not additionally included in the manufacture of molded products (sheets, etc.), and thus, there is a time and an economic advantage, and eco-friendly because no harmful substances (such as bisphenol-A) are leaked out. .
- the polylactic acid resin and the copolyester resin blend according to the present invention are useful as materials of environmentally friendly molded products (sheets, packaging materials, containers, interiors or exteriors for electronics, interiors or exteriors for automobiles, interiors or exteriors for construction, etc.).
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Abstract
Description
Claims (9)
- 폴리유산 수지 5 내지 95중량%; 및테레프탈산을 포함하는 산 성분 및 5 내지 99몰%의 1,4-사이클로헥산디메탄올, 1 내지 60몰%의 아이소소바이드를 포함하는 디올 성분이 공중합되어, 상기 산 성분으로부터 유도된 산 부분 및 디올 성분으로부터 유도된 디올 부분이 반복되는 구조를 가지는 공중합 폴리에스테르 수지 5 내지 95중량%를 포함하는 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드.
- 제1항에 있어서, 상기 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드의 노치 아이조드 충격강도는 30J/m 이상인 것인, 폴리유산 수지 및 공중합 폴리에스테르 수지.
- 제1항에 있어서, 상기 폴리유산 수지의 수평균 분자량은 10,000 내지 500,000인 것인, 폴리유산 수지 및 공중합 폴리에스테르 수지.
- 제1항에 있어서, 상기 산 성분(acid component)은 (i) 테레프탈산 외에, 공중합 산 성분으로서, (ii) 탄소수 8 내지 14의 방향족 디카르복실산 성분 및 탄소수 4 내지 12의 지방족 디카르복실산 성분으로 이루어진 군으로부터 선택된 산 성분을, 전체 산 성분에 대하여, 0 내지 50몰% 포함하는 것인 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드.
- 제1항에 있어서, 상기 아이소소바이드의 함량(ISB mol%) 및 1,4-사이클로헥산디메탄올의 함량(CHDM mol%)은 하기 수학식 1로 표현되는 범위인 것인, 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드.[수학식 1] 0.0012(CHDM mol%)2-0.2401(CHDM mol%)+14.136 ≤ ISB mol% ≤ 0.0049(CHDM mol%)2-0.2255(CHDM mol%)+71.176
- 제1항에 있어서, 상기 디올 성분은 (i) 8 내지 91몰%의 1,4-사이클로헥산 디메탄올 및 (ii) 4 내지 40몰%의 아이소소바이드를 포함하는 것인, 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드.
- 제1항에 있어서, 상기 디올 성분(diol component)은, (i) 1,4-사이클로헥산디메탄올 및 (ii) 아이소소바이드 외에 나머지 디올 성분으로서, (iii) 에틸렌 글리콜 및 전체 디올 성분에 대하여, 0 내지 50몰%의 (iv) 디에틸렌글리콜, 트리에틸렌글리콜, 프로판디올, 1,4-부탄디올, 펜탄디올, 헥산디올, 네오펜틸 글리콜(2,2-디메틸-1,3-프로판디올), 1,2-사이클로헥산디올, 1,4-사이클로헥산디올, 1,2-사이클로헥산디메탄올, 1,3-사이클로헥산디메탄올, 테트라메틸사이클로부탄디올 및 이들의 혼합물로 이루어진 군으로부터 선택되는 디올 성분을 더욱 포함하는 것인 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드.
- 제1항에 있어서, 상기 1,4-사이클로헥산디메탄올의 함량은 상기 산 성분 100중량부에 대하여, 10 내지 90중량부인 것인, 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드.
- 제1항 내지 제8항 중 어느 한 항에 따른 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드를 성형하여 제조된 성형제품.
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CN201180035440.5A CN103025828B (zh) | 2010-05-20 | 2011-05-19 | 聚乳酸树脂和共聚聚酯树脂的共混物及使用其的模塑制品 |
US13/698,930 US8633295B2 (en) | 2010-05-20 | 2011-05-19 | Blend of polylactic acid resin and copolyester resin, and molded product using same |
ES11783781.5T ES2599413T3 (es) | 2010-05-20 | 2011-05-19 | Mezcla de resina de ácido poliláctico y resina de copoliéster, y producto moldeado que utiliza la misma |
EP11783781.5A EP2573136B1 (en) | 2010-05-20 | 2011-05-19 | Blend of polylactic acid resin and copolyester resin, and molded product using same |
JP2013511118A JP2013526645A (ja) | 2010-05-20 | 2011-05-19 | ポリ乳酸樹脂および共重合ポリエステル樹脂ブレンドおよびこれを利用した成型製品 |
HK13106178.6A HK1179288A1 (en) | 2010-05-20 | 2013-05-24 | Blend of polylactic acid resin and copolyester resin, and molded product using same |
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KR1020100047231A KR101650923B1 (ko) | 2010-05-20 | 2010-05-20 | 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품 |
KR10-2010-0047231 | 2010-05-20 |
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US (1) | US8633295B2 (ko) |
EP (1) | EP2573136B1 (ko) |
JP (1) | JP2013526645A (ko) |
KR (1) | KR101650923B1 (ko) |
CN (1) | CN103025828B (ko) |
ES (1) | ES2599413T3 (ko) |
HK (1) | HK1179288A1 (ko) |
TW (1) | TWI494367B (ko) |
WO (1) | WO2011145899A2 (ko) |
Cited By (1)
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EP2759569A1 (en) | 2013-01-24 | 2014-07-30 | So.F.Ter. Tecnopolimeri Srl | A polyactic acid-based composition, a process for processing a polylactic acid based composition into a moulded article |
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KR20110028696A (ko) * | 2009-09-14 | 2011-03-22 | 에스케이케미칼주식회사 | 아이소소바이드와 1,4-사이클로헥산디메탄올이 공중합된 폴리에스테르 수지 및 그 제조방법 |
CN102918078B (zh) * | 2010-06-02 | 2015-02-25 | 科学与工业研究委员会 | 乳酸-异山梨醇共聚酯及其制备方法 |
KR101801703B1 (ko) * | 2011-11-18 | 2017-11-28 | 에스케이케미칼주식회사 | 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품 |
KR101952941B1 (ko) * | 2012-06-05 | 2019-02-27 | 에스케이케미칼 주식회사 | 폴리에스테르 수지 및 이의 제조 방법 |
KR20160065275A (ko) | 2014-11-28 | 2016-06-09 | 링크가가(주) | 블루투스 신호를 이용한 통신신호 자동선택 분실방지 시스템 및 방법 |
KR101929308B1 (ko) * | 2015-12-17 | 2018-12-17 | 주식회사 삼양사 | 폴리락트산 수지 조성물의 사출 성형품 제조방법 |
FR3054551B1 (fr) * | 2016-07-29 | 2019-08-02 | Roquette Freres | Composition polymere comprenant un polyester thermoplastique |
WO2018105823A1 (ko) * | 2016-12-06 | 2018-06-14 | 주식회사 삼양사 | 폴리락트산 공중합체 및 그 제조방법 |
CN109280167B (zh) * | 2018-09-28 | 2020-12-08 | 湖北茂盛生物有限公司 | 一种复合天冬氨酸聚合物及其制备方法和应用 |
KR20200089585A (ko) * | 2019-01-17 | 2020-07-27 | 에스케이케미칼 주식회사 | 폴리에스테르 필름 및 이의 제조 방법 |
WO2020149472A1 (ko) | 2019-01-17 | 2020-07-23 | 에스케이케미칼 주식회사 | 폴리에스테르 필름 및 이의 제조 방법 |
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- 2011-05-19 TW TW100117623A patent/TWI494367B/zh active
- 2011-05-19 WO PCT/KR2011/003710 patent/WO2011145899A2/ko active Application Filing
- 2011-05-19 JP JP2013511118A patent/JP2013526645A/ja active Pending
- 2011-05-19 CN CN201180035440.5A patent/CN103025828B/zh active Active
- 2011-05-19 US US13/698,930 patent/US8633295B2/en active Active
- 2011-05-19 EP EP11783781.5A patent/EP2573136B1/en active Active
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Also Published As
Publication number | Publication date |
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WO2011145899A3 (ko) | 2012-03-22 |
JP2013526645A (ja) | 2013-06-24 |
EP2573136A2 (en) | 2013-03-27 |
TW201144380A (en) | 2011-12-16 |
HK1179288A1 (en) | 2013-09-27 |
KR20110127795A (ko) | 2011-11-28 |
TWI494367B (zh) | 2015-08-01 |
EP2573136A4 (en) | 2014-03-26 |
CN103025828A (zh) | 2013-04-03 |
CN103025828B (zh) | 2014-11-05 |
EP2573136B1 (en) | 2016-07-20 |
US8633295B2 (en) | 2014-01-21 |
KR101650923B1 (ko) | 2016-08-25 |
US20130072642A1 (en) | 2013-03-21 |
ES2599413T3 (es) | 2017-02-01 |
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