KR20210158454A - Biodegradable sheet for food packaging container to prevent the elution of ingredients in the packaging container and food container using the same - Google Patents

Biodegradable sheet for food packaging container to prevent the elution of ingredients in the packaging container and food container using the same Download PDF

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KR20210158454A
KR20210158454A KR1020200076572A KR20200076572A KR20210158454A KR 20210158454 A KR20210158454 A KR 20210158454A KR 1020200076572 A KR1020200076572 A KR 1020200076572A KR 20200076572 A KR20200076572 A KR 20200076572A KR 20210158454 A KR20210158454 A KR 20210158454A
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weight
parts
base layer
packaging container
coating layer
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KR1020200076572A
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Korean (ko)
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홍승회
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(주)제영산업
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • B65D65/466Bio- or photodegradable packaging materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • 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
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • 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
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • 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
    • C08L23/06Polyethene
    • 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • 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
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06Waxes

Abstract

A biodegradable sheet for a food packaging container which prevents elution of substances in a packaging container of the present invention comprises: a base layer; and a coating layer which is integrally laminated on an upper surface of the base layer, and prevents elution of substances in a packaging container, wherein the base layer is formed in oxidative biodegrading agent base layer pellets by extruding a compound comprising plant biomass, wax, linear low density polyethylene (LLDPE), maleic acid, dicumyl peroxide, ethylene vinyl alcohol, sodium bicarbonate, calcium stearate, linoleic acid, myristoleic acid, and calcium carbonate, by using a double extruder; a coating layer is formed in coating layer pellets by mixing a PP resin or a PE resin with starch and extrusion molding the same; and the base layer pellets and the coating layer pellets are respectively mixed and heated to integrate the base layer and the coating layer through co-extrusion. According to the present invention, a food packaging container having biodegradability can be manufactured while preventing substances of the packaging container from eluting.

Description

포장용기의 성분 용출을 방지하는 식품포장용기용 생분해성 시트 및 이를 이용한 식품 용기{Biodegradable sheet for food packaging container to prevent the elution of ingredients in the packaging container and food container using the same}Biodegradable sheet for food packaging container to prevent the elution of ingredients in the packaging container and food container using the same

본 발명은 식품 포장 용기의 성분의 용출을 방지할 수 있는 생분해성 시트 및 이를 이용하여 제조된 다층 식품 포장용기에 관한 것으로, 보다 상세하게는 식품 포장용기로는 합성수지재가 많이 사용되며, 최근에는 환경 오염을 예방하기 위하여 생분해성 첨가제를 포함하는 생분해성 수지를 이용하여 식품 포장용기를 제조하고 있다.The present invention relates to a biodegradable sheet capable of preventing the elution of components of a food packaging container and a multi-layered food packaging container manufactured using the same, and more particularly, a synthetic resin material is widely used as a food packaging container, and recently In order to prevent contamination, food packaging containers are manufactured using biodegradable resins containing biodegradable additives.

이렇게 사용되는 식품 포장용기는 생분해성을 부여하기 위하여 첨가되는 성분이 식품을 수용한 용기 내에 용출되어 인간의 건강에 위험을 초래할 수 있으므로 이러한 용출을 방지하는 것은 매우 중요하다. In the food packaging container used in this way, it is very important to prevent such elution because ingredients added to impart biodegradability may be eluted in the container containing the food and may pose a risk to human health.

식품 포장용기는 소비자의 국민 소득 증가와 식품 위생에 대한 인식의 변화로 고기능 고품질의 제품을 소비자가 요구하고 있고, 지구의 온난화 등에 따른 기후 및 계절적 요인과 소비자의 식품 기호 등의 급격한 변화와 즉석 조리 가공식품의 다양화 및 과일 생선 및 육류 등의 포장 대상물의 특성에 따라, 각종 식품의 포장방식과 수요 패턴이 급속하게 변화되고 있다.As for food packaging, consumers are demanding high-performance, high-quality products due to the increase in national income and changes in the perception of food hygiene. According to the diversification of food and the characteristics of packaging objects such as fruits, fish and meat, packaging methods and demand patterns of various foods are rapidly changing.

이러한 식품 포장방식과 수요패턴에 변화에 따라 식품의 포장용기는 종래의 식품에 대한 단순한 포장에 대한 개념을 넘어 포장 대상물의 특성에 대응하여 식품의 신선도 유지기간의 증대를 통한 신선 식품의 공급 및 식품 폐기물의 저감과, 즉석 가공 조리 및 고온 식품의 포장을 위한 내열성의 확보, 포장용기의 폐기에 따른 환경 오염 발생을 저감하기 위한 항균, 탈취, 항산화 등의 기능성을 구비하고, 각종 즉석 가공식품과 고온의 식품 포장을 위한 내열성을 확보하며, 포장용기의 폐기시 친환경성을 갖는 식품 포장용기의 개발이 절실히 요구되고 있는 실정이다.According to these changes in food packaging methods and demand patterns, food packaging containers go beyond the conventional concept of simple packaging for food, and respond to the characteristics of the packaging object to supply fresh food and food by increasing the period of maintaining the freshness of the food. It is equipped with functions such as antibacterial, deodorizing, and antioxidant to reduce waste, secure heat resistance for instant processing cooking and packaging of high-temperature foods, and reduce environmental pollution caused by disposal of packaging containers. There is an urgent need to develop a food packaging container that secures heat resistance for food packaging and has eco-friendliness when the packaging container is disposed of.

다음으로, 내열성이 개선된 생분해성 폴리유산 다층시트와 관련된 선행기술로는, 한국 공개특허공보 제10-2012-0039866호(2012. 04. 26 공개)의 "내열성이 우수한 생분해성 다층시트"에 개시된 바와 같이,『D-이소머의 함량이 3몰% 또는 이를 넘지 않는 폴리유산(PLA) 10 내지 40 중량부로 이루어진 외층(B, 상,하층)과, D-이소머의 함량이 8몰% 또는 이를 넘지 않는 폴리유산(PLA) 60 내지 90 중량부로 이루어진 내층(A, 중간층)이 상기 상,하 외층(B) 사이에 형성된 구조의 층으로 이루어진 것임을 특징으로 하는 내열성이 우수한 생분해성 폴리유산 다층시트』가 개시되어 있다.Next, as a prior art related to a biodegradable polylactic acid multilayer sheet with improved heat resistance, in “biodegradable multilayer sheet with excellent heat resistance” of Korean Patent Application Laid-Open No. 10-2012-0039866 (published on April 26, 2012) As disclosed, "The outer layer (B, upper and lower layers) consisting of 10 to 40 parts by weight of polylactic acid (PLA) having a D-isomer content of 3 mol% or not exceeding it, and a D-isomer content of 8 mol% Or a biodegradable polylactic acid multilayer with excellent heat resistance, characterized in that the inner layer (A, middle layer) consisting of 60 to 90 parts by weight of polylactic acid (PLA) not exceeding this is composed of a layer having a structure formed between the upper and lower outer layers (B) sheet' is disclosed.

이렇게 다양한 기능과 생분해성을 식품 용기에 부여하기 위해서는 용기의 제조 공정에 다양한 기능별 첨가제를 사용하게 되는데, 이러한 첨가제가 식품을 수용하거나 보관하고 있는 용기 내에서 용출되어 인간이 섭취하게 되는 문제가 발생할 수 있으므로 건강에 위협이 되고 있다. In order to impart such diverse functions and biodegradability to food containers, various functional additives are used in the manufacturing process of the container. Therefore, it is a threat to health.

한국 공개특허공보 제10-2012-0039866호(2012. 04. 26 공개) "내열성이 우수한 생분해성 다층시트"Korean Patent Application Laid-Open No. 10-2012-0039866 (published on April 26, 2012) "Biodegradable multi-layer sheet with excellent heat resistance"

본 발명은 전술한 바와 같은 문제점을 해결하기 위해 안출된 것으로, 본 발명의 제1의 목적은 식품과 접촉하는 코팅층에 내산성, 내유성 고분자 수지를 함유시켜, 산성 식품의 수용 또는 보관 중에도 식품 용기의 분해를 방지하고자 하는 것이다. The present invention has been devised to solve the above-described problems, and a first object of the present invention is to contain an acid-resistant and oil-resistant polymer resin in a coating layer in contact with food, thereby decomposing a food container even during storage or accommodation of acidic food. is to prevent

본 발명의 제2의 목적은 식품 수용용기의 코팅층에 추가적으로 생분해성 성분을 포함하여 사용후 폐기시에 식품 포장용기가 산화생분해성을 가지도록 하는 것이다. A second object of the present invention is to provide a food packaging container with oxidative biodegradability upon disposal after use by including an additional biodegradable component in the coating layer of the food container.

본 발명의 포장용기의 성분 용출을 방지하는 식품 포장용기용 생분해성 시트는 총중량에 대하여 80 내지 90 중량%로 이루어진 베이스층과; 상기 베이스층의 상면에 일체로 적층되며, 상기 포장용기의 성분 용출을 방지하는 코팅층이 한 산화 생분해성 시트의 총중량에 대하여 10 내지 20 중량%로 이루어지고, 상기 베이스층은 베이스층의 총중량에 대하여, 식물체 바이오매스 10~50 중량부; 왁스 1~5 중량부; 선형저밀도폴리에틸렌 (LLDPE) 15~75 중량부; 말레산 0.2~5 중량부; 디큐밀 퍼옥사이드 0.01~1 중량부; 에틸렌비닐알코올, 0.5~5 중량부; 중탄산소다 2.5~7.5 중량부; 스테아린산칼슘 0.5~5 중량부; 리놀레산 0.1~3 중량부; 미리스트올레산 0.1~3 중량부; 및 탄산칼슘 10~65 중량부;가 포함된 화합물을 이중 압출기를 이용하여 압출하여 산화생분해제 베이스층 펠릿으로 형성되고, 상기 코팅층은 PP수지 또는 PE수지 100 중량부에 대하여 전분 1 내지 25 중량부를 혼합하여 압출성형되어 코팅층 펠릿으로 형성되고, 펠릿 형상의 베이스층 펠릿과 상기 코팅층 펠릿을 각각 혼합하여 가열하고 베이스층과 상기 코팅층을 일체로 형성되도록 동시압출하여 형성되는 것을 특징으로 하는 포장용기의 성분 용출을 방지하는 식품 포장용기용 생분해성 시트를 제공한다. The biodegradable sheet for food packaging for preventing the dissolution of components of the packaging container of the present invention comprises: a base layer composed of 80 to 90% by weight based on the total weight; The coating layer, which is integrally laminated on the upper surface of the base layer, and prevents the elution of components of the packaging container, consists of 10 to 20 wt% based on the total weight of one oxidative biodegradable sheet, and the base layer is based on the total weight of the base layer. , 10-50 parts by weight of plant biomass; 1 to 5 parts by weight of wax; 15 to 75 parts by weight of linear low density polyethylene (LLDPE); 0.2 to 5 parts by weight of maleic acid; 0.01 to 1 part by weight of dicumyl peroxide; ethylene vinyl alcohol, 0.5-5 parts by weight; 2.5 to 7.5 parts by weight of sodium bicarbonate; 0.5-5 parts by weight of calcium stearate; 0.1 to 3 parts by weight of linoleic acid; 0.1 to 3 parts by weight of myristic oleic acid; and 10 to 65 parts by weight of calcium carbonate; extruded using a double extruder to form oxidative biodegradant base layer pellets, and the coating layer is 1 to 25 parts by weight of starch based on 100 parts by weight of PP resin or PE resin Mixed and extruded to form a coating layer pellet, each of the pellet-shaped base layer pellets and the coating layer pellets are mixed and heated, and the base layer and the coating layer are co-extruded so as to be integrally formed. Components of a packaging container To provide a biodegradable sheet for food packaging that prevents dissolution.

상기 베이스층의 두께는 0.6mm이며, 상기 코팅층의 두께는 0.2mm인 것을 특징으로 하는 식품 포장용기의 성분 용출을 방지하는 식품 포장용기용 생분해성 시트를 제공한다.The thickness of the base layer is 0.6mm, and the thickness of the coating layer provides a biodegradable sheet for food packaging to prevent the dissolution of components of the food packaging container, characterized in that 0.2mm.

또한 상기 포장용기의 성분 용출을 방지하는 식품 포장용기용 생분해성 시트를 이용한 식품 저장용기를 제공한다.In addition, there is provided a food storage container using a biodegradable sheet for a food packaging container to prevent the dissolution of the components of the packaging container.

본 발명은 식품과 접촉하는 코팅층에 내산성, 내유성 고분자 수지를 함유시켜, 산성 식품의 수용 또는 보관 중에도 식품 용기의 분해를 방지하여 포장용기의 성분이 용출되지 않도록 하면서도 생분해성을 가지는 식품 포장용기를 제조할 수 있다. The present invention contains an acid-resistant and oil-resistant polymer resin in a coating layer in contact with food to prevent decomposition of the food container even during storage or accommodation of acidic food, thereby preventing the components of the packaging from eluting and manufacturing a food packaging container having biodegradability can do.

본 발명은 식품 수용용기의 코팅층에 추가적으로 생분해성 성분을 포함하여 사용 후 폐기시에 식품 포장용기가 자연상태에서 용이하게 분해될 수 있다.According to the present invention, the food packaging container can be easily decomposed in its natural state upon disposal after use by including an additional biodegradable component in the coating layer of the food container.

이하, 도면을 참조한 실시 예들의 상세한 설명을 통하여 본 발명에 따른 포장용기의 성분 용출을 방지하는 식품 포장용기용 생분해성 시트 및 이를 이용하여 제조되는 식품 포장용기에 대해 보다 상세하게 기술하기로 한다. 본 발명을 설명함에 있어서, 관련된 공지기술 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그에 대한 상세한 설명은 생략될 것이다. 그리고 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로서 사용자의 의도 또는 관례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다. 또한, 어떤 구성 요소를 '포함'한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수도 있다는 것을 의미한다.Hereinafter, a biodegradable sheet for a food packaging container for preventing the dissolution of components of the packaging container according to the present invention and a food packaging container manufactured using the same will be described in detail through the detailed description of the embodiments with reference to the drawings. In describing the present invention, if it is determined that a detailed description of a related known technology or configuration may unnecessarily obscure the gist of the present invention, a detailed description thereof will be omitted. And the terms to be described later are terms defined in consideration of functions in the present invention, and may vary according to the intention or custom of the user. Therefore, the definition should be made based on the content throughout this specification. In addition, 'including' a certain component means that other components may be further included, rather than excluding other components, unless otherwise stated.

상기 포장 용기의 성분 용출을 방지하는 산화생분해성 시트 총중량에 대하여 80 내지 90 중량%로 이루어진 베이스층과 상기 베이스층의 상면에 일체로 적층되며, 상기 포장용기의 성분 용출을 방지하는 코팅층이 상기 산화 생분해성 시트의 총 중량에 대하여 10 내지 20 중량 %로 이루어진 것이다. A base layer composed of 80 to 90% by weight based on the total weight of the oxidative biodegradable sheet for preventing the dissolution of components of the packaging container and the upper surface of the base layer are integrally laminated, and the coating layer for preventing the dissolution of the components of the packaging container is the oxidation It is composed of 10 to 20% by weight based on the total weight of the biodegradable sheet.

상기 베이스층은 베이스층의 총중량에 대하여, 식물체 바이오매스 10~50 중량부; 왁스 1~5 중량부; 선형저밀도폴리에틸렌 (LLDPE) 15~75 중량부; 말레산 0.2~5 중량부; 디큐밀 퍼옥사이드 0.01~1 중량부; 에틸렌비닐알코올, 0.5~5 중량부; 중탄산소다 2.5~7.5 중량부; 스테아린산칼슘 0.5~5 중량부; 리놀레산 0.1~3.0 중량부; 미리스트올레산 0.1~3.0 중량부; 및 탄산칼슘 10~65 중량부;가 포함된 화합물을 이중 압출기를 이용하여 압출하여 산화생분해제 베이스층 펠릿으로 형성된다. The base layer is based on the total weight of the base layer, 10-50 parts by weight of plant biomass; 1 to 5 parts by weight of wax; 15 to 75 parts by weight of linear low density polyethylene (LLDPE); 0.2 to 5 parts by weight of maleic acid; 0.01 to 1 part by weight of dicumyl peroxide; ethylene vinyl alcohol, 0.5-5 parts by weight; 2.5 to 7.5 parts by weight of sodium bicarbonate; 0.5-5 parts by weight of calcium stearate; 0.1 to 3.0 parts by weight of linoleic acid; 0.1 to 3.0 parts by weight of myristic oleic acid; and 10 to 65 parts by weight of calcium carbonate; extruding the compound containing the compound using a double extruder to form oxidative biodegradant base layer pellets.

상기 왁스는 식물체 바이오매스 분말의 코팅에 의한 수분 재흡수 방지 기능과 더불어, 저분자량 및 저융점에 기인하여 활제 보조제 역할도 함께 수행하는 성분이다. 또한 상기 왁스는 저분자 물질로서 생분해가 가능하다는 장점을 지닌다.The wax is a component that serves as a lubricant adjuvant due to its low molecular weight and low melting point as well as a function of preventing water reabsorption by coating of plant biomass powder. In addition, the wax has the advantage of being biodegradable as a low molecular weight material.

상기 왁스로는 파라핀 왁스, 유동 파라핀 왁스, 밀납, 몰다 왁스, 이멀시파잉 왁스, 칸데릴라 왁스, PE 왁스, PP 왁스 등 당분야에서 통상적으로 사용되는 종류를 특별한 제한 없이 사용할 수 있다. 상기 왁스는 식물체 바이오매스 분말 100 중량부에 대하여 1~20 중량부, 더욱 상세하게는 1~5 중량부 사용되는 것이 바람직하다. 왁스의 함량이 1 중량부 미만이면 코팅 기능 및 활제 보조제 역할이 미약해 질 수 있으며, 20 중량부를 초과하면 추후 생산설비 다이스에 이물질 등 찌꺼기 발생하거나 제조원가가 상승할 수 있다.As the wax, paraffin wax, liquid paraffin wax, beeswax, molda wax, emulsifying wax, candelilla wax, PE wax, PP wax, etc. commonly used in the art may be used without particular limitation. The wax is preferably used in an amount of 1 to 20 parts by weight, more specifically 1 to 5 parts by weight, based on 100 parts by weight of the plant biomass powder. If the content of wax is less than 1 part by weight, the coating function and the role of lubricant adjuvant may be weak, and if it exceeds 20 parts by weight, debris such as foreign matter may be generated in the dies of the production equipment or the manufacturing cost may increase.

상기 선형저밀도폴리에틸렌(Linear Low Density PolyEthylene; LLDPE)은 [0026] 조성물을 구성하는 분말이 서로 엉켜 붙게 하는 바인더의 역할을 하는 플라스틱 수지 성분이다.The Linear Low Density PolyEthylene (LLDPE) is a plastic resin component that serves as a binder for the powders constituting the composition to entangle with each other.

상기 선형저밀도폴리에틸렌(LLDPE)은 15~75 중량부의 함량으로 포함되는 것이 바람직하다. 선형저밀도폴리에틸렌(LLDPE)의 함량이 15 중량부 미만이면 결착력이 부족해 완성된 펠릿이 깨어지거나 분말이 생길 우려가 있으며, 75 중량부를 초과하면 필요한 정도를 넘어 불필요한 제조비용 상승을 불러올 수 있다.The linear low-density polyethylene (LLDPE) is preferably included in an amount of 15 to 75 parts by weight. If the content of linear low-density polyethylene (LLDPE) is less than 15 parts by weight, there is a risk that the finished pellet may be broken or powder may be generated due to insufficient binding force, and if it exceeds 75 parts by weight, it may cause unnecessary increase in manufacturing cost beyond the required level.

상기 말레산(Maleic acid)은 과산화물이 절단시킨 고분자 말단기에 식물체 바이오매스를 결합시키기 위한 중간체 역할 및 산화분해제 역할을 하는 유기산 성분이다. 상기 말레산은 0.2~5.0 중량부의 함량으로 포함되는 것이 바람직하다. 말레산의 함량이 0.2 중량부 미만이면 플라스틱 수지의 산화분해 기능이 약해질 수 있으며, 5.0 중량부를 초과하면 필요한 정도를 넘어 불필요한 제조비용 상승을 불러올 수 있다.The maleic acid is an organic acid component serving as an intermediate for binding plant biomass to the end groups of the polymer cut by the peroxide and serving as an oxidative decomposition agent. The maleic acid is preferably included in an amount of 0.2 to 5.0 parts by weight. If the content of maleic acid is less than 0.2 parts by weight, the oxidative decomposition function of the plastic resin may be weakened, and if it exceeds 5.0 parts by weight, it may cause unnecessary increase in manufacturing cost beyond the required level.

상기 디큐밀 퍼옥사이드는 플라스틱 수지의 고분자 체인을 화학적으로 절단하여 식물체 바이오매스 분말 및 플라스틱 수지의 그라프트 결합 구조체가 원활히 생성되도록 하는 과산화물 성분이다. 상기 디큐밀 퍼옥사이드는 전체 혼합물 100 중량부 기준으로 0.01~1.0 중량부, 또는 상기 LLDPE 100 중량부 기준으로 0.01~5.0 중량부 포함되는 것이 바람직하다. 디큐밀 퍼옥사이드의 함량이 전체 혼합물 100 중량부 기준으로 0.01 중량부 미만이면 고분자 체인 절단에 의한 수지 고분자 말단기 생성이 적어 고분자와의 그라프트 결합 기능을 기대하기 어렵거나 최종 제품의 식물체 바이오매스 분말 함량이 줄어들게 되거나 플라스틱 수지의 자연분해 및 산화 효과가 감소하여 최종 자연분해 기간이 길어지는 문제가 생길 수 있으며, 1.0 중량부를 초과하면 필요한 정도를 넘어 불필요한 제조비용 상승을 불러올 수 있다.The dicumyl peroxide is a peroxide component that chemically cuts the polymer chain of the plastic resin so that the graft bonding structure of the plant biomass powder and the plastic resin is smoothly generated. The dicumyl peroxide is preferably included in an amount of 0.01 to 1.0 parts by weight based on 100 parts by weight of the total mixture, or 0.01 to 5.0 parts by weight based on 100 parts by weight of the LLDPE. If the content of dicumyl peroxide is less than 0.01 parts by weight based on 100 parts by weight of the total mixture, it is difficult to expect a graft binding function with the polymer or the plant biomass powder of the final product because the generation of end groups of the resin polymer by polymer chain cleavage is small. If the content is reduced or the natural decomposition and oxidation effect of the plastic resin is reduced, there may be a problem that the final biodegradation period is prolonged.

상기 상용화제(Compatibilizer)는 극성인 식물체 바이오매스와 비극성인 바인더(LLDPE)간의 이형성을 제거하여 서로 잘 섞이도록 상용성을 부여하는 성분이다. 상기 상용화제로는 글리시딜메타크릴레이트, 에틸렌비닐알코올, 폴리비닐알코올 및 에틸렌비닐아세테이트 등 당업계에서 통상적으로 사용되는 것을 특별한 제한없이 사용할 수 있다. 바람직하게는, 하기 화학식 1의 폴리올레핀계 또는 하기 화학식 2의 폴리올레핀 유도 중합체를 사용하며, 예를 들어 ADPOLY PH-200, EM-200, SMS-554(롯데케미칼(주)) 등을 사용할 수 있다.The compatibilizer is a component that imparts compatibility to mix well with each other by removing the releasability between the polar plant biomass and the non-polar binder (LLDPE). As the compatibilizer, those commonly used in the art, such as glycidyl methacrylate, ethylene vinyl alcohol, polyvinyl alcohol, and ethylene vinyl acetate, may be used without particular limitation. Preferably, a polyolefin-based polymer of the following formula (1) or a polyolefin-derived polymer of the following formula (2) is used, for example, ADPOLY PH-200, EM-200, SMS-554 (Lotte Chemical Co., Ltd.), etc. may be used.

상기 상용화제는 0.5~5 중량부의 함량으로 포함되는 것이 바람직하다. 상용화제의 함량이 0.5 중량부 미만이면 상용성이 충분치 못해 층간 분리현상이 발생할 수 있으며, 5 중량부를 초과하면 필요한 정도를 넘어 불필요한 제조비용 상승을 불러올 수 있다.The compatibilizer is preferably included in an amount of 0.5 to 5 parts by weight. If the content of the compatibilizer is less than 0.5 parts by weight, compatibility may not be sufficient, and interlayer separation may occur.

상기 중탄산소다(NaHCO3)는 옥수수대 등 본 발명에 사용되는 식물체 바이오매스(셀룰로오스)를 가소화시키는 가소제 성분이다. 최종 제품의 식물성 바이오매스 함량이 높으면 그만큼 이산화탄소 배출이 적게 되는 측면에서 바람직한데, 일반 식물체는 신장률, 강도, 흐름성 등 물성이 나빠 완제품에 많은 양을 첨가할 수 없다. 따라서 부족한 식물체 바이오매스 함량을 높이는 작용으로서 식물체의 가소화가 매우 중요하며, 이를 위해 본 발명에서는 가소제로서 중탄산소다를 사용한다. 그 결과 식물체 바이오매스의 가소화를 통해 제품의 기계적 물성이 크게 향상됨을 확인하였다.The bicarbonate of sodium (NaHCO 3 ) is a plasticizer component that plasticizes plant biomass (cellulose) used in the present invention, such as cornstalks. A higher content of plant biomass in the final product is desirable in terms of lowering carbon dioxide emission. Therefore, plasticization of plants is very important as an action to increase the content of insufficient plant biomass, and for this purpose, sodium bicarbonate is used as a plasticizer in the present invention. As a result, it was confirmed that the mechanical properties of the product were greatly improved through the plasticization of plant biomass.

상기 중탄산소다는 25~75 중량부의 함량으로 포함되는 것이 바람직하다. 중탄산소다의 함량이 25 중량부 미만이면 기계적 물성 향상 효과가 미미해지거나 식물체 바이오매스의 함량을 원하는 수준까지 높이는데 제약이 가해질 수 있으며, 75 중량부를 초과하면 필요한 정도를 넘어 불필요한 제조비용 상승을 불러올 수 있다.The sodium bicarbonate is preferably included in an amount of 25 to 75 parts by weight. If the content of sodium bicarbonate is less than 25 parts by weight, the effect of improving mechanical properties may be insignificant or restrictions may be placed on increasing the content of plant biomass to a desired level. have.

상기 스테아린산칼슘은 식물체 바이오매스 원료의 흐름성을 좋게 하여 펠릿의 원활한 생산을 가능하게 하는 활제 성분으로서, 환경친화도가 높은 천연물이다. 상기 스테아린산칼슘은 0.5~5 중량부의 함량으로 포함되는 것이 바람직하다. 스테아린산칼슘의 함량이 0.5 중량부 미만이면 활제의 첨가에 따른 원하는 효과를 거두기 어려워질 수 있으며, 5 중량부를 초과하면 사용시 다이스에 이물질 등 찌꺼기가 발생하거나 제조비용이 상승할 수 있다.The calcium stearate is a natural product with high environmental friendliness as a lubricant component that enables smooth production of pellets by improving the flowability of plant biomass raw materials. The calcium stearate is preferably included in an amount of 0.5 to 5 parts by weight. If the content of calcium stearate is less than 0.5 parts by weight, it may be difficult to obtain the desired effect according to the addition of the lubricant, and if it exceeds 5 parts by weight, residues such as foreign substances may be generated on the dice during use or the manufacturing cost may increase.

상기 리놀레산 및 미리스트올레산은 플라스틱 수지 등과 같은 고분자 물질의 분해를 가속화하고 열분해 및 광분해를 촉진하기 위한 불포화 지방산 성분이다. 특히, 본 발명은 리놀레산과 더불어 미리스트올레산을 함께 사용하는바, 미리스트올레산은 이중결합을 가진 불포화 지방산으로서 자동산화에 의한 고분자 분해 기능을 더욱 촉진하게 하는 장점을 지닌다. 상기 리놀레산 및 미리스트올레산은 각각 0.1~3 중량부, 합계 0.2~6 중량부의 함량으로 포함되는 것이 바람직하다. 이들의 함량이 0.1 중량부 미만이면 고분자 물질의 원활한 분해를 기대하기 어려울 수 있으며, 3 중량부를 초과하면 필요한 정도를 넘어 불필요한 제조비용 상승을 불러올 수 있다.The linoleic acid and myristoleic acid are unsaturated fatty acid components for accelerating the decomposition of polymer materials such as plastic resins and promoting thermal decomposition and photolysis. In particular, the present invention uses myristic oleic acid together with linoleic acid. Myristic oleic acid is an unsaturated fatty acid having a double bond and has the advantage of further accelerating the decomposition of polymers by auto-oxidation. The linoleic acid and myristoleic acid are preferably included in an amount of 0.1 to 3 parts by weight, respectively, and 0.2 to 6 parts by weight in total. If their content is less than 0.1 parts by weight, it may be difficult to expect smooth decomposition of the polymer material, and if it exceeds 3 parts by weight, it may cause unnecessary increase in manufacturing cost beyond the required level.

상기 탄산칼슘으로는 나노 크기의 분체가 1~50 중량%의 양으로 포함된 것을 사용하는 것이 물성 향상 측면에서 바람직한바, 더욱 상세하게는 80~100 나노 크기의 분체가 10~30 중량%의 양으로 포함된 것을 사용하는 것이 좋다. 상기 탄산칼슘은 10~65 중량부의 함량으로 포함되는 것이 바람직하다. 탄산칼슘의 함량이 10 중량부 미만이면 이의 첨가에 따른 내구성 강화 및 원가 절감 효과를 기대하기 어려울 수 있으며, 65 중량부를 초과하면 제품의 압축강도, 신장률 등의 물성이 저하될 수 있다.As the calcium carbonate, it is preferable to use a nano-sized powder in an amount of 1 to 50% by weight in terms of improving physical properties, and more specifically, an amount of 10 to 30% by weight of 80-100 nano-sized powder. It is better to use what is included. The calcium carbonate is preferably included in an amount of 10 to 65 parts by weight. If the content of calcium carbonate is less than 10 parts by weight, it may be difficult to expect the effect of strengthening durability and reducing cost according to its addition, and if it exceeds 65 parts by weight, physical properties such as compressive strength and elongation of the product may be reduced.

(( 1)산화생분해제1) Oxidative biodegradant 베이스층base layer 펠릿의 제조 Preparation of pellets

옥수수대, 코코넛 부산물 및 거대억새 중에서 선택된 식물체 바이오매스를 80~300 메쉬의 미립자로 분쇄하여 식물체 바이오매스 분말을 생성하는 하고, 상기 식물체 바이오매스 분말을 50~150℃에서 05~24시간 동안 가열 건조하여 수분을 제거한다. 상기 가열 건조된 식물체 바이오매스 분말에 왁스를 투입하고, 교반속도 300~800RPM으로 고속 교반하여 식물체 바이오매스 분말의 표면을 코팅한 후에 상기 표면 코팅된 식물체 바이오매스 분말에 선형저밀도폴리에틸렌(LLDPE), 말레산, 디큐밀 퍼옥사이드, 상용화제, 중탄산소다, 스테아린산칼슘, 리놀레산, 미리스트올레산, 및 탄산칼슘을 투입하고 교반하여 혼합물을 생성한다. To produce plant biomass powder by pulverizing plant biomass selected from cornstalk, coconut by-product and giant pampas grass into fine particles of 80 to 300 mesh, and heating and drying the plant biomass powder at 50 to 150° C. for 05 to 24 hours to remove moisture. Wax is added to the heat-dried plant biomass powder, and the surface of the plant biomass powder is coated by high-speed stirring at a stirring speed of 300 to 800 RPM, and then linear low-density polyethylene (LLDPE), male to the surface-coated plant biomass powder. Acid, dicumyl peroxide, compatibilizer, sodium bicarbonate, calcium stearate, linoleic acid, myristoleic acid, and calcium carbonate are added and stirred to form a mixture.

상기 혼합물을 이축 압출기를 이용하여 선형저밀도폴리에틸렌(LLDPE) 가소화된 식물체 바이오매스의 그라프트 결합이 이루어지도록 하고, 토출구를 통해 토출시킨 다음, 토출된 스트랜드를 컨베이어 벨트를 통하여 이송 하면서 송풍 건조 후 커팅 또는 다이페이스 핫 커팅하여 산화생분해제 베이스층 펠릿을 형성한다. The mixture is subjected to graft bonding of linear low-density polyethylene (LLDPE) plasticized plant biomass using a twin-screw extruder, discharged through a discharge port, and then blow-dried while transporting the discharged strand through a conveyor belt, followed by cutting Alternatively, die face hot cutting is performed to form oxidative biodegradant base layer pellets.

(2) 포장용기 성분 용출을 방지하는 생분해성 시트 제조(2) Manufacture of biodegradable sheet to prevent dissolution of packaging container components

펠릿 형상으로 식물체 바이오매스 8 KG; 왁스 0.5 KG; 선형저밀도폴리에틸렌 (LLDPE) 70 KG; 말레산 1 KG; 디큐밀 퍼옥사이드 1 KG; 에틸렌비닐알코올, 3 KG; 중탄산소다 3 KG; 스테아린산칼슘 1 KG; 리놀레산 1 KG; 미리스트올레산 1 KG; 및 탄산칼슘 10.5 KG;가 포함된 화합물을 이중 압출기를 이용하여 압출하여 산화생분해제 베이스층 펠릿으로 형성되고, 베이스층(110)용 혼합물을 형성하고, 펠릿 형태의 PP수지 10KG, 전분 포함 기능성 마스터 배치 펠릿 2Kg 코팅층을 형성하였다. 8 KG of plant biomass in pellet form; Wax 0.5 KG; Linear Low Density Polyethylene (LLDPE) 70 KG; 1 kg of maleic acid; 1 KG of dicumyl peroxide; ethylene vinyl alcohol, 3 KG; 3 kg of bicarbonate of soda; 1 KG of calcium stearate; 1 kg of linoleic acid; 1 KG of myristic oleic acid; and 10.5 KG of calcium carbonate; extruded using a double extruder to form oxidative biodegradant base layer pellets, a mixture for the base layer 110 is formed, and PP resin in pellet form 10KG, starch-containing functional master A 2Kg coating layer of batch pellets was formed.

상기 베이스층용 혼합물과 코팅층용 혼합물을 각각의 사일로(SILO)에 충진하였다. 그리고 상기 사일로로부터 공급되는 베이스층용 혼합물과 코팅층용 혼합물의 각각을 170℃의 온도로 가열하여 용융 시키고 각각의 압출기 스크루를 이용하여 베이스층용 혼합물의 상부에 코팅층용 혼합물이 적층되도록 연속 압출하며, 압출되는 베이스층용 혼합물과 코팅층용 혼합물을 냉각롤러로 압력을 가하여 베이스층의 두께가 0.6mm이고, 코팅층의 두께가 0.2mm인 평판 시트 형태의 포장용기의 성분의 용출을 방지하는 생분해성 시트를 제조하였다. 상기 냉각롤러로 성형된 평판 시트 형태의 식품 포장용기의 성분 용출을 방지하는 생분해성 시트를 열풍 또는 히터 건조기로 건조하여 베이스층의 상부에 코팅층이 일체로 형성된 포장용기의 성분 용출을 방지하는 생분해성 시트의 제조가 완성되었다.The mixture for the base layer and the mixture for the coating layer were filled in each silo (SILO). Then, each of the mixture for the base layer and the mixture for the coating layer supplied from the silo is heated to a temperature of 170° C. and melted, and the mixture for the coating layer is continuously extruded so that the mixture for the coating layer is laminated on the top of the mixture for the base layer using each extruder screw. By applying pressure to the mixture for the base layer and the mixture for the coating layer with a cooling roller, the thickness of the base layer was 0.6 mm and the thickness of the coating layer was 0.2 mm. A biodegradable sheet preventing the elution of the components of the packaging container in the form of a flat sheet was prepared. A biodegradable sheet that prevents the dissolution of ingredients in a flat sheet food packaging container molded with the cooling roller is dried with hot air or a heater dryer to prevent the dissolution of components of the packaging container in which the coating layer is integrally formed on the top of the base layer The production of the sheet was completed.

또한 상기 완성된 포장용기의 성분 용출을 방지하는 생분해성 시트를 100×100mm 및 100×150mm를 포함하는 다양한 크기로 절단하여 본 발명의 코팅층)을 구비한 시트 시료를 제조하였다.In addition, the biodegradable sheet for preventing the dissolution of components of the completed packaging container was cut into various sizes including 100 × 100 mm and 100 × 150 mm to prepare a sheet sample having the coating layer of the present invention).

Claims (3)

포장 용기의 성분 용출을 방지하는 산화생분해성 시트 총중량에 대하여 80 내지 90 중량%로 이루어진 베이스층과;
상기 베이스층의 상면에 일체로 적층되며, 상기 포장용기의 성분 용출을 방지하는 코팅층이 산화 생분해성 시트의 총중량에 대하여 10 내지 20 중량%로 이루어지고,
상기 베이스층은 베이스층의 총중량에 대하여, 식물체 바이오매스 10~50 중량부; 왁스 1~5 중량부; 선형저밀도폴리에틸렌 (LLDPE) 15~75 중량부; 말레산 0.2~5 중량부; 디큐밀 퍼옥사이드 0.01~1 중량부; 에틸렌비닐알코올, 0.5~5 중량부; 중탄산소다 2.5~7.5 중량부; 스테아린산칼슘 0.5~5 중량부; 리놀레산 0.1~3 중량부; 미리스트올레산 0.1~3 중량부; 및 탄산칼슘 10~65 중량부;가 포함된 화합물을 이중 압출기를 이용하여 압출하여 산화생분해제 베이스층 펠릿으로 형성되고,
상기 코팅층은 PP수지 또는 PE수지 100 중량부에 대하여 전분 1 내지 25 중량부를 혼합하여 압출성형되어 코팅층 펠릿으로 형성되고,
펠릿 형상의 베이스층 펠릿과 상기 코팅층 펠릿을 각각 혼합하여 가열하고 베이스층과 상기 코팅층을 일체로 형성되도록 동시압출하여 형성되는 것을 특징으로 하는 포장용기의 성분 용출을 방지하는 식품 포장용기용 생분해성 시트.
a base layer composed of 80 to 90% by weight based on the total weight of the oxidative biodegradable sheet for preventing the dissolution of components in the packaging container;
The coating layer, which is integrally laminated on the upper surface of the base layer, and prevents the dissolution of the components of the packaging container, consists of 10 to 20% by weight based on the total weight of the oxidative biodegradable sheet,
The base layer is based on the total weight of the base layer, 10-50 parts by weight of plant biomass; 1 to 5 parts by weight of wax; 15 to 75 parts by weight of linear low density polyethylene (LLDPE); 0.2 to 5 parts by weight of maleic acid; 0.01 to 1 part by weight of dicumyl peroxide; ethylene vinyl alcohol, 0.5-5 parts by weight; 2.5 to 7.5 parts by weight of sodium bicarbonate; 0.5-5 parts by weight of calcium stearate; 0.1 to 3 parts by weight of linoleic acid; 0.1 to 3 parts by weight of myristic oleic acid; and 10 to 65 parts by weight of calcium carbonate; extruded using a double extruder to form oxidative biodegradant base layer pellets,
The coating layer is extruded by mixing 1 to 25 parts by weight of starch with respect to 100 parts by weight of PP resin or PE resin to form coating layer pellets,
A biodegradable sheet for food packaging to prevent dissolution of components in a packaging container, characterized in that it is formed by mixing and heating the pellet-shaped base layer pellets and the coating layer pellets, respectively, and simultaneously extruding the base layer and the coating layer to form integrally.
제1항에 있어서
상기 베이스층의 두께는 0.6mm이며, 상기 코팅층의 두께는 0.2mm인 것을 특징으로 하는 포장용기의 성분 용출을 방지하는 식품 포장용기용 생분해성 시트.
2. The method of claim 1
The thickness of the base layer is 0.6mm, the thickness of the coating layer is a biodegradable sheet for food packaging to prevent the dissolution of components of the packaging container, characterized in that 0.2mm.
제1항 또는 제2항의 포장용기의 성분 용출을 생분해성 시트로 제조되는 식품 용기.

A food container prepared by dissolving the components of the packaging container of claim 1 or 2 into a biodegradable sheet.

KR1020200076572A 2020-06-23 2020-06-23 Biodegradable sheet for food packaging container to prevent the elution of ingredients in the packaging container and food container using the same KR20210158454A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120039866A (en) 2010-10-18 2012-04-26 도레이첨단소재 주식회사 Polylactic sheet retaining biodegradability and heat-resistant property and preparing process thereof

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