KR0156892B1 - The method of preparation for biodegradable resin - Google Patents

The method of preparation for biodegradable resin Download PDF

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KR0156892B1
KR0156892B1 KR1019950025906A KR19950025906A KR0156892B1 KR 0156892 B1 KR0156892 B1 KR 0156892B1 KR 1019950025906 A KR1019950025906 A KR 1019950025906A KR 19950025906 A KR19950025906 A KR 19950025906A KR 0156892 B1 KR0156892 B1 KR 0156892B1
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ethylene
biodegradable resin
acid
biodegradable
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KR970010870A (en
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임대우
김순식
김대진
이창수
이영춘
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박홍기
제일합섬주식회사
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016Plasticisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • C08K5/103Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853Vinylacetate
    • C08L23/0861Saponified vinylacetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
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Abstract

본 발명의 생분해성 수지는 지방족 폴리에스테르 30∼85중량%, 폴리비닐알코올 5∼20중량%, 에틸렌-비닐 알코올 5∼25중량% 및 에틸렌-비닐 아세테이트 5∼25중량%를 혼합하여 얻은 합성수지 1∼99중량%와 전분 99∼1중량%를 가소제, 윤활제 및 물과 함께 트윈·익스트루더에 투입하고 90∼230℃, 스크류RPM 80∼150, 토오크 40∼60의 조건으로 가공하여 사용후 토양중의 미생물에 의하여 완전분해가 되어 환경오염을 유발하지 않으며, 우수한 기계적 및 물리적 성질을 갖춘 생분해성 수지의 제조방법을 제공하는데 있다.The biodegradable resin of the present invention is a synthetic resin obtained by mixing 30 to 85% by weight of aliphatic polyester, 5 to 20% by weight of polyvinyl alcohol, 5 to 25% by weight of ethylene-vinyl alcohol and 5 to 25% by weight of ethylene-vinyl acetate. -99% by weight and starch 99 ~ 1% by weight together with plasticizer, lubricant and water are added to twin extruder and processed under conditions of 90 ~ 230 ℃, screw RPM 80 ~ 150, torque 40 ~ 60 The present invention provides a method for producing a biodegradable resin having excellent mechanical and physical properties by being completely decomposed by microorganisms in which it does not cause environmental pollution.

Description

생분해성 수지의 제조방법Manufacturing method of biodegradable resin

본 발명은 사용후 폐기시 토양중에 존재하는 미생물에 의하여 분해되는 생분해성 수지에 관한 것으로, 천연물질과 합성수지로 이루어져 환경오염을 유발하지 않는 생분해성 수지의 제조방법에 관한 것이다.The present invention relates to a biodegradable resin that is decomposed by microorganisms present in the soil at the time of disposal after use, and relates to a method for producing a biodegradable resin which is composed of natural materials and synthetic resins and does not cause environmental pollution.

일반적으로 합성수지는 내약품성, 투명성, 유연성 및 강도등 물성이 우수하여 여러분야에 걸쳐 광범위하게 사용되고 있으나, 사용후 자체적으로 분해되지 않기 때문에 폐기 플라스틱에 의한 환경오염이 사회적인 문제로 대두되면서 최근 포장용 필름을 비롯한 일회용 제품에 분해성이 있는 수지의 사용이 점차 확대되고 있다.In general, synthetic resins are widely used throughout the field because of their excellent physical properties such as chemical resistance, transparency, flexibility and strength, but since they do not decompose themselves after use, environmental pollution caused by waste plastics has become a social problem. The use of degradable resins in disposable products, including, is gradually expanding.

분해성 수지는 토양중에 존재하는 미생물에 의하여 분해되는 생분해성 수지와 태양광의 자외선에 의하여 분해되는 광분해성 수지로 구분할 수 있다. 광분해성 수지는 토양에 매립시 빛을 받지 못하여 분해가 되지 않는 단점을 가지고 있으므로 생분해성 수지가 주로 사용된다. 생분해성 수지로는 미생물의 생체내에서 합성되는 폴리하이드록시아릴레이트계 수지와 합성고분자계 생분해성 수지인 폴리카프로락톤, 폴리락티드 및 디올과 디 애시드의 축중합에 의하여 합성된 지방족 폴리에스테르 등이 있으나 이들은 생분해성은 우수하지만 가격이 비싼 단점이 있다.Degradable resins can be classified into biodegradable resins decomposed by microorganisms present in the soil and photodegradable resins decomposed by ultraviolet rays of sunlight. Biodegradable resins are mainly used because they do not receive light when they are buried in soil. Examples of biodegradable resins include polyhydroxyarylate resins synthesized in vivo by microorganisms and polycaprolactones, polylactides, which are synthetic polymer biodegradable resins, and aliphatic polyesters synthesized by condensation polymerization of diols and diacids. Although there are excellent biodegradability, but the price is disadvantageous.

이와 같은 문제점을 해결하기 위하여 열가소성 수지인 폴리에틸렌, 폴리스틸렌, 폴리프로필렌, 폴리에틸렌테레프탈레이트 등과 같은 비분해성 수지에 분해성을 부여하기 위하여 천연 고분자 물질인 전분과 가소제를 첨가하고 적절한 온도와 압력하에서 혼련, 압출하여 생분해성 수지를 제조하는 방법이 유럽특허 제535,994호, 제32,802호, 제327,505호, 제400,532호, 제404,728호 등에 개시되어 있으나, 전분은 쉽게 분해되나 열가소성 수지는 분해가 되지 않고 미세한 조각으로 토양중에 잔존하여 2차적 환경오염을 유발하는 단점이 있다.In order to solve this problem, starch and plasticizer, which is a natural polymer, is added, kneaded and extruded under an appropriate temperature and pressure to impart degradability to non-degradable resins such as thermoplastic resins such as polyethylene, polystyrene, polypropylene, and polyethylene terephthalate. Although methods for preparing biodegradable resins are disclosed in European Patent Nos. 535,994, 32,802, 327,505, 400,532, and 404,728, starch is easily decomposed, but thermoplastic resins are not decomposed but are finely divided into soil. There is a disadvantage of remaining in the environment causing secondary environmental pollution.

따라서, 본 발명의 목적은 사용후 폐기시 토양중의 미생물에 의하여 완전 분해되어 환경오염을 유발하지 않으며, 우수한 물성을 갖는 생분해성 수지의 제조 방법을 제공하는데 있다.Accordingly, it is an object of the present invention to provide a method for producing a biodegradable resin having excellent physical properties by being completely decomposed by microorganisms in soil upon disposal after use.

본 발명은 천연물질과 합성수지를 혼합한것으로, 천연물질로는 전분, 합성 수지로는 폴리에스테르, 폴리비닐알코올, 에틸렌-비닐 알코올 및 에틸렌-비닐 아세테이트, 첨가제로는 가공성 향상제와 물을 투입하여 고온, 고압에서 혼련 압출하여 생분해성 수지를 제조함으로써 상기한 분해성 수지의 단점을 개선하였다.The present invention is a mixture of natural materials and synthetic resins, starch as a natural material, polyester, polyvinyl alcohol, ethylene-vinyl alcohol and ethylene-vinyl acetate as a synthetic resin, and additives to improve the workability and water as a high temperature, By kneading extrusion at high pressure to produce a biodegradable resin, the disadvantages of the above-described degradable resins are improved.

이하 본 발명을 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명 생분해성 수지는 합성수지로서 지방족 폴리에스테르 30∼85중량% 폴리비닐알코올 5∼20중량%, 에틸렌-비닐 알코올 5∼25중량% 및 에틸렌-비닐 아세테이트 공중합체 5∼25중량%를 혼합하여 얻은 합성수지 1∼99중량%와 천연 물질인 전분 99∼1중량%를 가소제, 윤활제 및 물과 함께 트윈·익스트루더에 투입하고 90∼230℃, 스크류 RPM 80∼150, 토오크 40∼60의 조건으로 혼련, 압출하여 제조한다.The biodegradable resin of the present invention is obtained by mixing 30 to 85% by weight of polyvinyl alcohol, 5 to 25% by weight of ethylene-vinyl alcohol, and 5 to 25% by weight of ethylene-vinyl acetate copolymer as synthetic resins. 1 to 99% by weight of synthetic resin and 99 to 1% by weight of natural starch are added to the twin extruder together with a plasticizer, lubricant and water, and the conditions are 90 to 230 ° C, screw RPM 80 to 150 and torque 40 to 60. It is prepared by kneading and extruding.

본 발명에서의 천연물질은 감자, 쌀, 고구마, 옥수수 등에서 추출되는 전분으로 직쇄형의 아밀로오스 및 분지형 구조를 가지는 아밀로펙틴으로 구성되며 각 전분은 단독 또는 2종 이상을 혼합하여 사용할 수 있다.Natural substances in the present invention is a starch extracted from potatoes, rice, sweet potatoes, corn and the like is composed of amylopectin having a straight amylose and branched structure, each starch can be used alone or in combination of two or more.

본 발명에서의 합성수지는 2가 알코올 및 지방족 2가 카르복시산을 주성분으로 하여 생분해성을 가지며 퇴비화가 가능할뿐 아니라 성형가공성 및 경제성이 우수한 폴리에스테르를 주로하여 폴리비닐알코올, 에틸렌-비닐 알코올 공중합체 및 에틸렌-비닐 아세테이트 공중합체를 혼합 사용한다.In the present invention, the synthetic resin is mainly composed of a dihydric alcohol and an aliphatic dicarboxylic acid, and is mainly biodegradable and compostable. Use a mixed vinyl acetate copolymer.

본 발명에 사용되는 폴리에스테르는 하기 일반식(I)과 같은 구조를 갖는 것을 특징으로 한다.The polyester used in the present invention is characterized by having the same structure as the following general formula (I).

(상기식에서 X는 0.1∼80몰%의 페닐렌잔기와 20∼99.9몰%의 지방족 디카르복시산 잔기로 이루어져 있으며, Y는 탄소수가 6 이하인 알킬렌글리콜 잔기가 주성분이고 나머지는 X를 구성하는 전체 산성분의 0.1∼3몰%의 3관능 이상의 말단 히드록시기를 갖는 화합물의 잔기로 구성된다.)(Wherein X is composed of 0.1 to 80 mol% of phenylene residues and 20 to 99.9 mol% of aliphatic dicarboxylic acid residues, Y is an alkylene glycol residue having 6 or less carbon atoms as a main component, and the rest is the total acidic acid constituting X) It consists of the residue of the compound which has a trifunctional or more than trifunctional terminal hydroxyl group of 0.1-3 mol% of a minute.)

본 발명에 사용되는 산성분중에서 페닐렌잔기를 구성하는 원료성분은 테레프탈산, 이소프탈산, 디메틸테레프탈레이트, 디메틸이소프탈레이트 중에서 선택 된 1종 또는 2종 이상의 혼합구성을 의미하며 그 사용량은 식(I)의 전체 산성분 X의 0.1∼80몰% 정도가 적당하다. 페닐렌 잔기가 80몰% 이상인 경우에는 형성된 폴리에스테르의 분해 및 퇴비화가 매우 어렵게 된다. 본 발명에서 사용된 지방족 디카르복시산 잔기를 구성하는 원료성분으로는 석신산, 아디프산, 세바식산, 아제라익산 등이 사용 가능하다.Among the acid components used in the present invention, a raw material component constituting a phenylene residue means one or two or more mixed configurations selected from terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl isophthalate, and the amount thereof is represented by Formula (I). About 0.1-80 mol% of all the acid component X of is suitable. When the phenylene residue is 80 mol% or more, decomposition and composting of the formed polyester becomes very difficult. As a raw material constituting the aliphatic dicarboxylic acid residue used in the present invention, succinic acid, adipic acid, sebacic acid, azeraic acid and the like can be used.

본 발명에서 식(I)의 성분 Y를 구성하는 물질은 탄소수 6 이하인 알킬렌글리콜의 잔기로서 사용 원료로는 에틸렌글리콜, 1,2-프로판디올, 1,3-프로판디올, 1,4-부탄디올, 1,6-헥산디올 중에서 선택된 1성분 또는 2종 이상의 혼합 사용이 가능하다. 또 성분 X의 3관능 이상의 말단 히드록시기를 갖는 화합물로는 트리메틸롤에탄, 트리메틸롤프로판, 펜타에리스리톨, 디펜타에리스리톨 중에서 선택된 1 성분 또는 2종 이상의 혼합 사용도 가능하다. 3관능 이상의 말단 히드록시기를 갖는 화합물의 사용량은 성분 X의 0.1∼3몰%정도 사용하는 것이 좋다. 사용량이 3몰% 이상인 경우에는 생성된 폴리에스테르에 가교가 발생하여 겔이 형성되어 기계적 물성이 매우 불량하게 된다.In the present invention, the material constituting the component Y of formula (I) is a residue of alkylene glycol having 6 or less carbon atoms. As a raw material, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol , 1, 6- hexanediol selected from one component or a mixture of two or more may be used. Moreover, as a compound which has a trifunctional or more than trifunctional terminal hydroxyl group of component X, the 1 component chosen from trimethylol ethane, a trimethylol propane, pentaerythritol, and dipentaerythritol, or a mixture of 2 or more types can also be used. As for the usage-amount of the compound which has a trifunctional or more than trifunctional terminal hydroxyl group, it is good to use about 0.1-3 mol% of component X. If the amount of use is more than 3 mol% crosslinking occurs in the resulting polyester to form a gel, the mechanical properties are very poor.

본 발명에서 공중합 폴리에스터를 제조하는 방법은 식(I)의 X와 Y를 구성하는 모노머 성분을 가열 및 교반 가능한 용기에 촉매와 같이 투입하고 220℃이상, 1mmHg 이하의 고온 고진공하에서 축중합 반응을 시킨다. 이때 사용된 축중합 촉매로는 주석 화합물이나 티탄 화합물이 좋다. 주석화합물로는 산화제일주석, 산화제이주석 등의 산화주석류, 염화제일주석, 염화제이주석, 황화제일주석 등의 할로겐주석류, 모노부틸산화주석, 디부틸산화주석, 산화모노부틸히드록시주석, 이염화디부틸주석, 테트라페닐주석, 테트라부틸주석과 같은 유기주석화합물류가 있으며, 티탄계 화합물로는 테트라부틸티타네이트, 테트라메틸티타네이트, 테트라이소프로필티타네이트, 테트라(2-에틸헥실) 티타네니트 등을 사용할 수 있다.In the present invention, the method for preparing the copolyester is carried out in a container capable of heating and stirring the monomer components constituting X and Y of the formula (I) together with a catalyst and subjected to a condensation polymerization reaction under high temperature and high vacuum of 220 ° C or higher and 1 mmHg or lower. Let's do it. The condensation polymerization catalyst used at this time is preferably a tin compound or a titanium compound. Examples of the tin compound include tin oxides such as tin oxide and tin oxide, halogenated tin salts such as tin oxide, tin chloride, and monosulfide, monobutyl tin oxide, dibutyl tin oxide, monobutyl hydroxy tin oxide, Organotin compounds such as dibutyltin dichloride, tetraphenyltin, and tetrabutyltin are included, and titanium-based compounds include tetrabutyl titanate, tetramethyl titanate, tetraisopropyl titanate, and tetra (2-ethylhexyl) Tannetite etc. can be used.

본 발명에서 사용된 열안정제로는 인화합물이 가능하며, 예를 들면 인산 모노에틸인산, 트리메틸인산, 트리부틸인산, 트리옥틸인산, 모노페닐인산, 트리페닐 인산 및 그 유도체, 아인산, 트리페닐아인산, 트리메틸아인산 및 그 유도체, 이가녹스 1010, 이가녹스 1222, 이가포스 168, 페닐포스폰산등이 있으며, 특히 인산, 트리메틸인산, 트리페닐인산 등이 그 효과가 우수하다.The thermal stabilizer used in the present invention may be a phosphorus compound, for example, monoethyl phosphate, trimethyl phosphate, tributyl phosphate, trioctyl phosphate, monophenyl phosphate, triphenyl phosphate and derivatives thereof, phosphorous acid, triphenyl phosphite , Trimethylphosphoric acid and its derivatives, Iganox 1010, Iganox 1222, Igafos 168, Phenylphosphonic acid, and the like. Phosphoric acid, trimethyl phosphoric acid, triphenyl phosphoric acid and the like are excellent in effect.

본 발명에서 사용한 폴리비닐알코올은 검화도가 50∼99%인 것으로 함유량은 전체 합성수지의 총량의 5∼20중량%가 좋다. 또한 전분, 폴리에스터 및 폴리비닐알코올 이외에 에틸렌-비닐알코올 공중합체 및 에틸렌-비닐아세테이트 공중합체를 혼합하여 사용할 수 있다. 에틸렌-비닐알코올 공중합체는 에틸렌 함량이 44몰%를 초과하지 않는 고융점 화합물로 전체 합성수지 총량의 5∼25중량%가 좋으며, 에틸렌-비닐아세테이트 공중합체는 초산비닐함량은 2∼20몰%이며 함량은 전체 합성수지 총량의 5∼25중량%인 것을 특징으로 한다.The polyvinyl alcohol used in the present invention has a saponification degree of 50 to 99%, and the content thereof is preferably 5 to 20% by weight of the total amount of the total synthetic resin. In addition to starch, polyester and polyvinyl alcohol, an ethylene-vinyl alcohol copolymer and an ethylene-vinylacetate copolymer may be used in combination. Ethylene-vinyl alcohol copolymer is a high melting point compound having an ethylene content of not more than 44 mol%, preferably 5 to 25% by weight of the total amount of the synthetic resin. The ethylene-vinylacetate copolymer has a vinyl acetate content of 2 to 20 mol%. The content is characterized in that 5 to 25% by weight of the total amount of the synthetic resin.

또한 생분해성수지 제조시 가공성을 향상시키기 위하여 가소제, 윤활제 등을 첨가할 수 있다. 가소제로는 물, 글리세린 에틸렌디글리콜, 폴리에틸렌글리콜, 1,4-부탄디올 등을 단독 또는 2종 이상을 혼합하여 사용할 수 있으며, 윤활제로는 트리글리세롤모노스테 어레이트, 트리글리세롤디스테 어레이트, 트리글리세롤트리스테 어레이트를 단독 또는 혼합하여 첨가한다. 가소제의 첨가량은 물의 경우는 전분에 대하여 10∼50중량%, 기타 가소제는 전체 생분해성수지에 대하여 1∼5중량%가 좋으며, 윤활제는 전체 조성물에 대하여 1∼5중량%를 첨가하는 것이 바람직하다.In addition, a plasticizer, a lubricant, and the like may be added to improve processability in the manufacture of biodegradable resins. As a plasticizer, water, glycerin ethylene diglycol, polyethylene glycol, 1,4-butanediol, or the like may be used alone or as a mixture of two or more thereof.As a lubricant, triglycerol monoester array, triglycerol distea array, tri Glycerol triste array is added alone or in combination. The amount of plasticizer added is preferably 10 to 50% by weight relative to starch in water, 1 to 5% by weight relative to total biodegradable resin, and 1 to 5% by weight relative to the total composition.

본 발명에서의 생분해성수지 제조방법은 트윈-스크류 압출기 내의 밀폐공 간에 전분을 호화시키기 충분한 물을 공급하면서 상기 조성물을 투입하여 열을 가하여 용융, 압출한다. 압출시 다이를 통하여 토출되는 수지의 수분함량은 전체 생분해수지에 대하여 10∼30%가 되도록 물의 투입량을 조절한다. 배럴내의 온도는 90∼230℃ , 스크류 RPM은 80∼150, 토오크는 40∼60등의 조건으로 용융, 혼합하여 생분해성수지를 제조한다. 이와같이 제조된 생분해성수지는 사출성형품, 압출성형품, 시트, 필름 등의 여러가지 성형가공이 가능하다.The biodegradable resin manufacturing method according to the present invention is supplied to the composition while supplying enough water to gelatinize the starch between the closed pores in the twin-screw extruder to melt and extrude by applying heat. The water content of the resin discharged through the die during extrusion is adjusted to 10-30% of the total biodegradable resin. The biodegradable resin is produced by melting and mixing in a barrel at a temperature of 90 to 230 ° C., a screw RPM of 80 to 150, and a torque of 40 to 60. The biodegradable resins prepared in this way are capable of various molding processes such as injection molded articles, extruded molded articles, sheets, and films.

이와같이 제조된 분해성수지의 분해성은 필름상태로 컴포스트방법으로 측정하였다. 컴포스트법의 매질로는 국내에서 발생되는 쓰레기의 구성비율과 같이 다음 표 1과 같이 조성하였으며 내부환경은 표 2와 같이 조절하여 시료를 매립하여 10주 동안 무게감소를 측정하여 분해도를 평가하였다.The degradability of the degradable resin thus prepared was measured in a film state by the compost method. The composition of the compost method was composed as shown in the following Table 1 as the composition ratio of waste generated in Korea, and the internal environment was adjusted as shown in Table 2, and the sample was buried to measure the weight loss for 10 weeks to evaluate the degree of decomposition.

이하, 실시예에서 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail in the Examples.

[합성예 1]Synthesis Example 1

교반기 및 콘덴서가 부착된 반응기에 에틸렌글리콜 1310.7g(21.218몰), 석신산 857g(7.257몰), 디메틸테레프탈레이트 1,143g(5.888몰) 및 트리메틸롤프로판 5g(0.037몰)을 투입하고 촉매로서 망간아세테이트 1.0g을 첨가하여 반응기 내의 온도를 상온으로 부터 30분에 걸쳐 120℃까지 승온시키고 교반하면서 120분 간에 걸쳐 220℃까지 승온 반응시켰다. 이때 생성된 부반응물인 메탄올과 물은 콘덴서를 통하여 완전히 유출시킨다. 이어서 촉매로서 테트라부톡시티타네이트를 1.5g, 열안정제로서 인산 0.4g을 투입하고 45분간에 걸쳐 관내압력을 0.5mmHg까지 서서히 감압시킴과 동시에 관내온도를 280℃까지 승온시키면서 180분 동안 교반 반응을 진행한 다음 교반을 중단하고 관내로 질소를 주입하여 중합체를 가압, 토출하여 목적하는 폴리에스테르를 얻었다.1310.7 g (21.218 mole) of ethylene glycol, 857 g (7.257 mole) of succinic acid, 1,143 g (5.888 mole) of dimethyl terephthalate and 5 g (0.037 mole) of trimethylolpropane were added to a reactor equipped with a stirrer and a condenser and manganese acetate as a catalyst. 1.0g was added, the temperature in the reactor was heated up to 120 degreeC over 30 minutes from normal temperature, and it heated up to 220 degreeC over 120 minutes, stirring. At this time, the side reaction product, methanol and water, is completely discharged through the condenser. Subsequently, 1.5 g of tetrabutoxy titanate as a catalyst and 0.4 g of phosphoric acid as a heat stabilizer were added, and the pressure was gradually reduced to 0.5 mmHg over 45 minutes, and the reaction was stirred for 180 minutes while the temperature was raised to 280 ° C. After proceeding, the stirring was stopped and nitrogen was injected into the tube to pressurize and discharge the polymer to obtain a desired polyester.

[합성예 2]Synthesis Example 2

교반기 및 콘덴서가 부착된 반응기에 1,4-부탄디올 1,187g(19.124몰), 아디프산 649g(4.441몰), 디메틸테레프탈레이트 862g(4.440몰) 및 펜타에리스리톨 5g(0.037몰)을 투입하고 촉매로서 망간아세테이트 1.0g을 첨가하여 반응기 내의 온도를 상온으로 부터 30분에 걸쳐 120℃까지 승온시키고 교반하면서 120분에 걸쳐서 220℃까지 승온 반응시킨다. 이어서 촉매로서 테트라부톡시티타네이트를 1.5g, 열안정제로서 인산 0.4g을 투입하고 45분간에 걸쳐 관내 압력을 0.5mmHg까지 서서히 감압시킴과 동시에 관내온도를 245℃까지 승온시키면서 180분 동안 교반반응을 진행한 다음 교반을 중단하고 관내로 질소를 주입하여 중합체를 가압, 토출하여 목적하는 폴리에스테르를 얻었다.1,187 g (19.124 moles) of 1,4-butanediol, 649 g (4.441 moles) of adipic acid, 862 g (4.440 moles) of dimethyl terephthalate and 5 g (0.037 moles) of pentaerythritol were added to a reactor equipped with a stirrer and a condenser. 1.0 g of manganese acetate is added to increase the temperature in the reactor to 120 ° C. over 30 minutes from room temperature and to a temperature of 220 ° C. over 120 minutes with stirring. Subsequently, 1.5 g of tetrabutoxy titanate as a catalyst and 0.4 g of phosphoric acid as a heat stabilizer were added, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, and the reaction was stirred for 180 minutes while the temperature was raised to 245 ° C. After proceeding, the stirring was stopped and nitrogen was injected into the tube to pressurize and discharge the polymer to obtain a desired polyester.

[실시예 1]Example 1

옥수수 전분 20중량%, 합성수지 80중량%를 혼합한 것으로, 합성수지는 합성예 1에서 합성한 폴리에스테르 46중량%, 검화도 80%인 폴리비닐알코올 18중량%, 에틸렌-비닐알코올 공중합체(에틸렌 함량 44몰%) 20중량%, 에틸렌-비닐 아세테이트 공중합체 10중량% 및 윤활제로 트리글리세롤노스테러레이트 2중량%를 혼합하여 투입하고 가소제로 글리세린 4중량% 및 물을 전분에 대하여 10%로 투입하여 압출기에서 다음 조건으로 용융, 혼합, 압출시켜 생분해성 수지 펠렛을 제조하였다.20% by weight of corn starch, 80% by weight of synthetic resin, synthetic resin 46% by weight of polyester synthesized in Synthesis Example 1, 18% by weight of polyvinyl alcohol having a saponification degree of 80%, ethylene-vinyl alcohol copolymer (ethylene content 44 mol%) 20% by weight, 10% by weight of ethylene-vinyl acetate copolymer and 2% by weight of triglycerol nosterate were mixed with a lubricant, and 4% by weight of glycerin and 10% of water were added as a plasticizer. Biodegradable resin pellets were prepared by melting, mixing and extruding in the extruder under the following conditions.

● 압출조건● Extrusion condition

- 스크류 속도 : 80Screw Speed: 80

- 토오크 : 40Torque: 40

- 베럴 온도 : 110/150/190/210/180/160℃-Barrel temperature: 110/150/190/210/180/160 ℃

[실시예 2]Example 2

실시예 1과 비교하여 합성예 1에서 합성한 폴리에스테르 대신 합성예 2에서 합성한 폴리에스테르를 사용한 것 이외에는 실시예 1과 같다.It is the same as Example 1 except having used the polyester synthesize | combined by the synthesis example 2 instead of the polyester synthesize | combined by the synthesis example 1 with respect to Example 1.

[실시예 3]Example 3

실시예 1과 비교하여 합성수지 함량은 폴리에스테르 40중량%, 검화도 80%인 폴리비닐알코올 8중량%, 에틸렌-비닐 알코올 공중합체(에틸렌 함량 44몰%) 20중량%, 에틸렌-비닐아세테이트 20중량%를 첨가한 것 이외에는 실시예 1과 같다.Compared to Example 1, the synthetic resin content was 40% by weight of polyester, 8% by weight of polyvinyl alcohol having a saponification degree of 80%, 20% by weight of ethylene-vinyl alcohol copolymer (44% by mole of ethylene), and 20% by weight of ethylene-vinylacetate. It is the same as Example 1 except having added%.

[실시예 4]Example 4

실시예 2에 비교하여 합성수지 함량은 지방족 폴리에스테르 50중량%, 검화도 80%인 폴리비닐알코올 16중량%, 에틸렌-비닐알코올 공중합체 8중량%, 에틸렌-비닐아세테이트 20중량%를 첨가한 것 이외에는 실시예 1과 같다.Compared to Example 2, the synthetic resin content was 50% by weight of aliphatic polyester, 16% by weight of polyvinyl alcohol having a saponification degree of 80%, 8% by weight of ethylene-vinyl alcohol copolymer, and 20% by weight of ethylene-vinylacetate. Same as Example 1.

[실시예 5]Example 5

옥수수 전분 15중량부, 합성수지 85중량부로 합성수지 중 합성예 1에서 합성한 폴리에스테르 65중량%, 검화도 80%인 폴리비닐알코올 5중량%, 에틸렌-비닐 알코올(에틸렌 함량 44몰%) 10중량%, 에틸렌-비닐아세테이트 공중합체 14중량%를 사용한 것 이외에는 실시예 1과 같다.15 parts by weight of corn starch, 85 parts by weight of synthetic resin, 65% by weight of polyester synthesized in Synthesis Example 1, 5% by weight of polyvinyl alcohol having a degree of saponification of 80%, and 10% by weight of ethylene-vinyl alcohol (44% by mole of ethylene) It is the same as Example 1 except having used 14 weight% of ethylene-vinylacetate copolymers.

[실시예 6]Example 6

실시예 5와 비교하여 합성예 1에서 합성한 폴리에스테르 대신에 합성예 2에서 합성한 폴리에스테르를 사용한 것 이외에는 동일하게 실시하였다.It carried out similarly to Example 5 except having used the polyester synthesize | combined by the synthesis example 2 instead of the polyester synthesize | combined by the synthesis example 1.

실시예에서 제조한 펠렛을 블로운 필름으로 제조하여 강신도 및 분해성을 평가하여 표 3과 같은 결과를 얻었다.The pellets prepared in Examples were prepared as a blown film to evaluate the elongation and degradability to obtain the results shown in Table 3.

Claims (9)

폴리에스테르 공중합체를 주성분으로 하는 분해성 합성수지와 전분 및 가소제를 함유하는 생분해성 수지를 제조함에 있어서, 하기 일반식(I)의 구조를 가지는 폴리에스테르와 폴리비닐알코올, 에틸렌-비닐 알코올 공중합체, 에틸렌-비닐 아세테이트를 공중합체를 함께 혼합하여 얻은 분해성 합성수지를 1∼99중량%, 옥수수, 감자, 쌀, 고구마 등에서 추출한 전분 99∼1중량%와 가소제, 유화제를 첨가하고 용융, 혼련시킴을 특징으로 하는 생분해성 수지의 제조방법.In preparing a biodegradable resin containing a polyester copolymer as a main component, a starch and a plasticizer, a polyester having a structure of the following general formula (I), polyvinyl alcohol, ethylene-vinyl alcohol copolymer, ethylene 1 to 99% by weight of the decomposable synthetic resin obtained by mixing the copolymer together with vinyl acetate, 99 to 1% by weight of starch extracted from corn, potato, rice, sweet potato, etc., and a plasticizer and an emulsifier are added, followed by melting and kneading. Method of producing biodegradable resins. (상기식에서 X는 0.1∼80몰%의 페닐렌잔기와 20∼99.9몰%의 지방족 디카르복시산 잔기로 이루어져 있으며, Y는 탄소수가 6 이하인 알킬렌글리콜 잔기가 주성분이고 나머지는 X를 구성하는 전체 산성분의 0.1∼3몰%의 3관능 이상의 말단 히드록시기를 갖는 화합물의 잔기로 구성된다.)(Wherein X is composed of 0.1 to 80 mol% of phenylene residues and 20 to 99.9 mol% of aliphatic dicarboxylic acid residues, Y is an alkylene glycol residue having 6 or less carbon atoms as a main component, and the rest is the total acidic acid constituting X) It consists of the residue of the compound which has a trifunctional or more than trifunctional terminal hydroxyl group of 0.1-3 mol% of a minute.) 제1항에 있어서, X성분중 페닐렌잔기는 테레프탈산, 이소프탈산, 디메틸테레프탈레이트, 디메틸이소프탈레이트이고, 지방족 디카르복시산 잔기는 석신산, 아디프산, 세바식산, 아제라익산중에서 선택된 1성분 또는 2종 이상을 혼합하여 사용함을 특징으로 하는 생분해성 수지의 제조방법.The phenylene residue in X component is terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, and the aliphatic dicarboxylic acid residue is one or two selected from succinic acid, adipic acid, sebacic acid, azeraic acid. A method for producing a biodegradable resin, characterized in that used by mixing more than one species. 제1항에 있어서, Y성분중 알킬렌글리콜 잔기는 에틸렌글리콜, 1,2-프로판디올, 1,3-프로판디올, 1,4-부탄디올, 1,6-헥산디올 중에서 선택된 1성분 또는 2종 이상을 혼합하여 사용함을 특징으로 하는 생분해성 수지의 제조방법.The method of claim 1, wherein the alkylene glycol residues in the Y component is one or two selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol A method for producing a biodegradable resin, characterized by using a mixture of the above. 제1항에 있어서, 3관능 이상의 말단 히드록시기를 갖는 화합물로는 트리메틸롤에탄, 트리메틸롤프로판, 펜타에리스리톨, 디펜타에리스리톨 중에서 1종 또는 2종 이상을 혼합하여 사용함을 특징으로 하는 생분해성 수지의 제조방법.The method of claim 1, wherein the compound having a tri- or higher functional terminal hydroxyl group is used in the production of biodegradable resins, characterized in that one or two or more of trimethylol ethane, trimethylolpropane, pentaerythritol, and dipentaerythritol are used in combination. Way. 제1항에 있어서, 폴리비닐알코올은 검화도가 50∼99%이고, 사용량은 전체 합성수지에 대해 5∼20중량%임을 특징으로 하는 생분해성 수지의 제조 방법.The method for producing a biodegradable resin according to claim 1, wherein the polyvinyl alcohol has a degree of saponification of 50 to 99% and the amount of the polyvinyl alcohol used is 5 to 20% by weight based on the total synthetic resin. 제1항에 있어서, 에틸렌-비닐알코올 공중합체는 에틸렌함량이 27∼44몰%이고, 사용량은 전체 합성수지에 대해 5∼25중량%임을 특징으로 하는 생분해성 수지의 제조방법.The method of claim 1, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 27 to 44 mol%, and the amount of the ethylene-vinyl alcohol copolymer is 5 to 25 wt% with respect to the total synthetic resin. 제1항에 있어서, 에틸렌-비닐아세테이트는 비닐아세테이트의 함량이 2∼20몰%이고, 사용량은 전체 합성수지에 대해 5∼25중량%임을 특징으로 하는 생분해성 수지의 제조방법.The method for producing a biodegradable resin according to claim 1, wherein the ethylene-vinylacetate has a vinyl acetate content of 2 to 20 mol% and an amount of 5 to 25 wt% with respect to the total synthetic resin. 제1항에 있어서, 가소제는 물을 전분에 대해 10-50중량% 첨가하고 글리세린, 에틸렌디글리콜, 폴리에틸렌글리콜 및 1,4-부탄디올 중에서 1종 또는 2종 이상 혼합한 것을 전체 생분해성 수지에 대해 1∼5중량% 첨가함을 특징으로 하는 생분해성 수지의 제조방법.The plasticizer according to claim 1, wherein 10 to 50% by weight of water is added to the starch and a mixture of one or two or more of glycerin, ethylene diglycol, polyethylene glycol, and 1,4-butanediol is added to the total biodegradable resin. A method for producing a biodegradable resin, characterized in that 1 to 5% by weight is added. 제1항에 있어서, 윤활제는 트리글리세롤모노스테아레이트, 트리글리세롤디스테아레이트, 트리글리세롤트리스테아레이트 중에서 1종 또는 2종 이상을 혼합하여 전체 생분해성 수지에 대해 1∼5중량% 첨가함을 특징으로 하는 생분해성 수지의 제조방법.According to claim 1, The lubricant is triglycerol monostearate, triglycerol distearate, triglycerol tristearate is mixed with one or two or more kinds of 1 to 5% by weight based on the total biodegradable resin, characterized in that The manufacturing method of biodegradable resin made into.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020029050A (en) * 2002-03-29 2002-04-17 주식회사 나선하이테크 Disasemble resin and the manufacturing method for thereof
KR20020037119A (en) * 2000-11-13 2002-05-18 윤진산 Paste composition for a disposable and bio-degradable bowl and method of preparing the bowl using same
KR100466965B1 (en) * 2002-05-20 2005-01-24 박태표 Manufacturing process of resolvability wire and the wire
KR100503763B1 (en) * 1998-01-23 2005-10-27 주식회사 새 한 Biodecomposable resin composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000059820A (en) * 1999-03-09 2000-10-05 한형수 Composition of the biodecomposable resin with the high melting viscosity

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100503763B1 (en) * 1998-01-23 2005-10-27 주식회사 새 한 Biodecomposable resin composition
KR20020037119A (en) * 2000-11-13 2002-05-18 윤진산 Paste composition for a disposable and bio-degradable bowl and method of preparing the bowl using same
KR20020029050A (en) * 2002-03-29 2002-04-17 주식회사 나선하이테크 Disasemble resin and the manufacturing method for thereof
KR100466965B1 (en) * 2002-05-20 2005-01-24 박태표 Manufacturing process of resolvability wire and the wire

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