KR20240040516A - Biodegradable polymer coating composition with excellent softness and solubility and method for preparing coating solution comprising the same - Google Patents
Biodegradable polymer coating composition with excellent softness and solubility and method for preparing coating solution comprising the same Download PDFInfo
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- KR20240040516A KR20240040516A KR1020220119552A KR20220119552A KR20240040516A KR 20240040516 A KR20240040516 A KR 20240040516A KR 1020220119552 A KR1020220119552 A KR 1020220119552A KR 20220119552 A KR20220119552 A KR 20220119552A KR 20240040516 A KR20240040516 A KR 20240040516A
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- South Korea
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- biodegradable polymer
- pla
- polymer coating
- coating composition
- peroxide
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- 238000000576 coating method Methods 0.000 title claims abstract description 66
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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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
- C08L29/00—Compositions 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
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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Abstract
본 발명은 생분해성 고분자 코팅 조성물 및 이를 포함하는 코팅액 제조방법에 관한 것으로서, 보다 상세하게는 생분해성 고분자 PLA의 표면 경도를 낮추어 연질성을 향상시키고, 과산화물을 통해 PLA의 분자량을 낮추어 용해도를 향상시킴으로써, 종이류 또는 단일소재 비닐 포장재의 코팅 작업효율을 극대화시킬 수 있을 뿐만 아니라 내수성, 내유성, 열 접착성 및 산소 차단성이 우수한 생분해성 고분자 코팅 조성물 및 이를 포함하는 코팅액 제조방법에 관한 것이다. The present invention relates to a biodegradable polymer coating composition and a method for producing a coating liquid containing the same. More specifically, the present invention relates to a method of manufacturing a biodegradable polymer coating composition and a coating solution containing the same. More specifically, the softness is improved by lowering the surface hardness of the biodegradable polymer PLA, and the solubility is improved by lowering the molecular weight of PLA through peroxide. It relates to a biodegradable polymer coating composition that can maximize the coating efficiency of paper or single-material vinyl packaging materials and has excellent water resistance, oil resistance, heat adhesiveness, and oxygen barrier properties, and a method of manufacturing a coating solution containing the same.
Description
본 발명은 생분해성 고분자 코팅 조성물 및 이를 포함하는 코팅액 제조방법에 관한 것으로서, 보다 상세하게는 생분해성 고분자 PLA의 표면 경도를 낮추어 연질성을 향상시키고, 과산화물을 통해 PLA의 분자량을 낮추어 용해도를 향상시킴으로써, 종이류 또는 단일소재 비닐 포장재의 코팅 작업효율을 극대화시킬 수 있을 뿐만 아니라 내수성, 내유성, 열 접착성 및 산소 차단성이 우수한 생분해성 고분자 코팅 조성물 및 이를 포함하는 코팅액 제조방법에 관한 것이다.The present invention relates to a biodegradable polymer coating composition and a method for producing a coating liquid containing the same. More specifically, the present invention relates to a method of manufacturing a biodegradable polymer coating composition and a coating solution containing the same. More specifically, the softness is improved by lowering the surface hardness of the biodegradable polymer PLA, and the solubility is improved by lowering the molecular weight of PLA through peroxide. It relates to a biodegradable polymer coating composition that can maximize the coating efficiency of paper or single-material vinyl packaging materials and has excellent water resistance, oil resistance, heat adhesiveness, and oxygen barrier properties, and a method of manufacturing a coating solution containing the same.
플라스틱 포장재 쓰레기는 배달음식 문화의 발전과 1인 가구 증가로 소포장의 증가로 식품 포장재 쓰레기의 증가는 심각한 사회 문제로 대두되고 있다.The increase in food packaging waste is emerging as a serious social problem due to the development of delivery food culture and the increase in small packaging due to the increase in single-person households.
식품 포장재 쓰레기는 음식물 오염 및 포장재 재질의 복합화로 인해 소각로에서 처리되는 것이 상당하다. 따라서, 재생·재활용의 극대화를 위해서는 기존의 다층 복합재질의 포장재 대신에 단일재질의 기능성 필름 및 종이 포장재의 개발이 시급하다.A significant portion of food packaging waste is processed in incinerators due to food contamination and complexity of packaging materials. Therefore, in order to maximize recycling, it is urgent to develop single-material functional film and paper packaging materials instead of existing multi-layer composite packaging materials.
이에 따라, 종이 재질 포장재로의 대체가 급속히 진행되고 있으나, 기존의 종이 재질 포장재의 기능적 한계인 내수성, 내유성 및 기체 차단성이 취약하다는 문제가 존재한다.Accordingly, replacement with paper-based packaging materials is rapidly progressing, but there are problems with existing paper-based packaging materials being weak in water resistance, oil resistance, and gas barrier properties, which are functional limitations.
그에 따라, 종이 포장 패키지 내부를 폴리에틸렌 필름 합지 또는 내수성 코팅제로 코팅하여 사용하는데, 폴리에틸렌 합지는 재생이 불가하고 내수성(PVA, 아크릴 수지) 코팅 종이 포장재의 경우 일정 시간이 지나면 수분이 흡수되어 상용성이 떨어지고 포장재 봉투로 가공 시 개구성이 떨어져 상용화가 어렵다는 한계가 있었다. Accordingly, the inside of the paper packaging package is coated with polyethylene film or water-resistant coating. However, polyethylene film is not recyclable, and water-resistant (PVA, acrylic resin) coated paper packaging material absorbs moisture after a certain period of time, making it non-compatible. There were limitations that made commercialization difficult due to poor openness when processed into packaging bags.
아울러, 기존 PLA 생분해성 필름을 22 내지 40㎛ 두께로 필름 압출하여 종이에 합지공정을 통해 생분해성 필름이 복합화된 비닐 대체 종이 포장재를 상용화하였으나 필름의 두께가 합지한 종이 포장재 총 두께의 30% 이상을 상회하므로 사용 후 폐기 시 해리 공정에서 필름 이물로 추출되어 친환경 포장재의 재생 재활용성이 결여되었고, 필름의 경도가 너무 높아 포장재 완제품 가공 후 접착면 및 접지에 크랙이 발생하여 주요기능인 내수, 발수, 내유, 산소차단 기능이 저하되는 문제점이 있었다.In addition, an alternative vinyl paper packaging material in which the existing PLA biodegradable film is extruded to a thickness of 22 to 40㎛ and the biodegradable film is composited through a lamination process has been commercialized. However, the thickness of the film is more than 30% of the total thickness of the laminated paper packaging material. Since it exceeds There was a problem in that oil resistance and oxygen blocking functions were deteriorated.
그리고 기존 식품 포장재 대부분을 차지하는 다층복합 비닐 포장재는 산소차단, 진공, 멸균 및 포장재 가공 시 열 접착성 극대화를 위해 다층화를 통해 상기 문제를 해결하고자 하였으나, 사용 후 폐기 시 재활용성이 어렵다는 문제로 인해, 최근에는 기존 다층복합 비닐 포장재 대신에 단일재질 다층화를 통하여 재사용율을 높이는 방향으로 변화하고 있다. 그러나, 다층 복합재질 구성의 포장 폐기물은 용융·압출 방법으로 각각의 재질별 용융 온도가 상이하여 재생 플라스틱 소재 펠릿 제조가 매우 어렵다는 한계가 있었다.In addition, multi-layer composite vinyl packaging materials, which make up most of the existing food packaging materials, were attempted to solve the above problems through multi-layering to maximize heat adhesiveness during oxygen blocking, vacuum, sterilization, and packaging material processing. However, due to the problem of difficulty in recycling when discarded after use, Recently, there has been a change in the direction of increasing the reuse rate through multi-layering of single materials instead of existing multi-layer composite vinyl packaging materials. However, packaging waste composed of multi-layer composite materials had a limitation in that it was very difficult to manufacture recycled plastic material pellets because the melting temperature for each material was different using the melting/extrusion method.
본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로서, 생분해성 고분자 PLA의 표면 경도를 낮추어 연질성을 향상시키고, 과산화물을 통해 PLA의 분자량을 낮추어 용해도를 향상시켜, 종이류 또는 단일소재 비닐 포장재의 코팅 작업효율을 극대화할 뿐만 아니라, 내수성, 내유성, 열 접착성 및 산소차단성이 우수하고, 해리공정을 통해 재생펄프화하여 포장재의 재사용이 가능한 생분해성 고분자 코팅 조성물 및 이를 포함하는 코팅액 제조방법을 제공하는 목적이 있다.The present invention was developed to solve the above problems. It improves softness by lowering the surface hardness of biodegradable polymer PLA, and improves solubility by lowering the molecular weight of PLA through peroxide, so that it can be used as a paper or single-material vinyl packaging material. A biodegradable polymer coating composition that not only maximizes coating work efficiency, but also has excellent water resistance, oil resistance, heat adhesion, and oxygen barrier properties, and can be converted into recycled pulp through a dissociation process to reuse packaging materials, and a coating liquid manufacturing method containing the same. There is a purpose for providing it.
본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 기술적 과제로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 아래의 기재로부터 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.
이러한 목적을 달성하기 위하여, 본 발명에 따른 생분해성 고분자 코팅 조성물은 과산화물로 개질한 생분해성 고분자 PLA와, 규산염 용액 및 다가 알코올로 이루어진 군으로부터 하나 이상 선택되는 연질부여제를 반응시켜 제조되는 것을 특징으로 한다.In order to achieve this purpose, the biodegradable polymer coating composition according to the present invention is manufactured by reacting a biodegradable polymer PLA modified with peroxide and a softening agent selected from the group consisting of silicate solution and polyhydric alcohol. Do it as
상기 규산염은 규산나트륨, 규산칼륨을 포함하는 규산금속착화합물일 수 있다.The silicate may be a silicate metal complex containing sodium silicate and potassium silicate.
상기 연질부여제는 규산염 용액 또는 다가 알코올을 폴리비닐알코올(PVA)과 반응시킨 것일 수 있다.The softening agent may be a silicate solution or a polyhydric alcohol reacted with polyvinyl alcohol (PVA).
상기 과산화물은 구연산, 과산화 수소, 개미산, 라디칼 생성 반응형 개질제, 그라프트 반응형 개질제로 이루어진 군으로부터 하나 이상 선택되는 것일 수 있다.The peroxide may be one or more selected from the group consisting of citric acid, hydrogen peroxide, formic acid, radical generation reactive modifier, and graft reactive modifier.
또 다른 본 발명인 포장재는 상기 코팅 조성물로 코팅처리된 것을 특징으로 한다.Another packaging material of the present invention is characterized by being coated with the coating composition.
상기 포장재는 종이류 또는 필름류일 수 있으며, 상기 필름류는 단일소재 필름일 수 있다.The packaging material may be paper or film, and the film may be a single material film.
이러한 목적을 달성하기 위한 또 다른 본 발명인 생분해성 고분자 코팅액 제조방법은 생분해성 고분자 PLA; 금속규산염 용액 및 다가 알코올로 이루어진 군으로부터 하나 이상 선택되는 연질부여제; 및 과산화물을 배합기에 넣고 70 내지 100 ℃온도로 교반시켜 개질 생분해성 고분자 컴파운드를 제조하는 제1단계; 극성 유기용매에 상기 개질 생분해성 고분자 PLA를 일정 점성을 가지도록 용해시키는 제2단계;를 포함하는 것을 특징으로 한다.Another present invention for achieving this purpose is a method for producing a biodegradable polymer coating solution using biodegradable polymer PLA; A softening agent selected from the group consisting of metal silicate solutions and polyhydric alcohols; And a first step of preparing a modified biodegradable polymer compound by putting peroxide in a blender and stirring it at a temperature of 70 to 100 ° C.; A second step of dissolving the modified biodegradable polymer PLA in a polar organic solvent to have a certain viscosity.
상기 제1단계에 있어서, 제조되는 상기 개질 생분해성 고분자 PLA에 점성 개선제를 더 투입할 수 있다.In the first step, a viscosity improver may be further added to the modified biodegradable polymer PLA being produced.
상기 제1단계에서 제조되는 상기 개질 생분해성 고분자 PLA를 컴파운드 압출기를 통해 용융 및 압출하여 컴파운드 펠릿화할 수 있다.The modified biodegradable polymer PLA prepared in the first step can be melted and extruded through a compound extruder to form compound pellets.
본 발명에 따른 코팅 조성물을 이용하여 종이 또는 비닐(필름) 포장재를 코팅처리할 경우, 종이가 가지는 수분 취약을 보강할 수 있으며, 내유성, 열 접착성, 산소 차단성의 기능이 우수하므로 내용물의 유통기간 연장이 가능하며, 사용 후 폐기 시 종이는 해리 공정으로, 비닐 포장재는 용융 압출 공정을 통해 재생자원으로 회수 가능하다는 장점을 가진다.When coating paper or vinyl (film) packaging using the coating composition according to the present invention, the moisture vulnerability of paper can be strengthened, and the oil resistance, heat adhesiveness, and oxygen barrier properties are excellent, so the shelf life of the contents It can be extended and has the advantage that when discarded after use, paper can be recovered as a renewable resource through a dissociation process, and vinyl packaging can be recovered as a renewable resource through a melt extrusion process.
또한, 생분해성 고분자 필름 제조 후 종이에 합지하는 종래의 포장재 제조방법에 대비해 폴리머 사용량을 줄일 수 있어 생산성이 향상되며, 제조공정의 단순화 및 코팅층 두께 제어가 용이하여 벽지, 친환경 접착제 등 여러 산업군에 적용 가능하다는 장점을 가진다.In addition, compared to the conventional packaging material manufacturing method of manufacturing a biodegradable polymer film and then laminating it to paper, productivity is improved by reducing the amount of polymer used. The manufacturing process is simplified and the thickness of the coating layer is easy to control, making it applicable to various industries such as wallpaper and eco-friendly adhesives. It has the advantage of being possible.
도 1은 PLA에 콜로이드 실리카를 혼합 시 형성되는 개질된 PLA-실리카 분자결합 모식도.
도 2는 PLA에 PEG를 혼합 시 형성되는 개질된 PLA+PEG 분자결합 모식도.
도 3은 PLA와 PVA를 혼합 시 형성되는 PLA+PVA 분자결합 모식도.
도 4는 본 발명에 따라 개질된 PLA 코팅액과 통상의 PLA 코팅액의 유연성 거동 변화 실험 결과.Figure 1 is a schematic diagram of a modified PLA-silica molecular bond formed when mixing colloidal silica with PLA.
Figure 2 is a schematic diagram of the modified PLA+PEG molecular bond formed when mixing PEG with PLA.
Figure 3 is a schematic diagram of the PLA+PVA molecular bond formed when mixing PLA and PVA.
Figure 4 shows the results of an experiment on the change in flexibility behavior of a PLA coating solution modified according to the present invention and a conventional PLA coating solution.
이하에서는 첨부한 도면을 참조하여 본 발명을 설명하기로 한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 따라서 여기에서 설명하는 실시예로 한정되는 것은 아니다. Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention may be implemented in various different forms and, therefore, is not limited to the embodiments described herein.
먼저, 본 발명에 따른 생분해성 고분자 코팅 조성물에 대하여 설명한다.First, the biodegradable polymer coating composition according to the present invention will be described.
본 발명은 생분해성 고분자인 PLA(Poly Lactic Acid)를 코팅 베이스 바인드로 사용함에도 PLA가 가지는 표면 경도 및 분자량을 낮춤으로써 연질성 및 용해도가 우수한 바, 이를 위해 과산화물로 개질한 생분해성 고분자 PLA에 규산염 용액 및 다가 알코올로 이루어진 군으로부터 하나 이상 선택되는 연질부여제를 반응시켜 코팅 조성물을 제조한다.The present invention uses PLA (Poly Lactic Acid), a biodegradable polymer, as a coating base bind, but has excellent softness and solubility by lowering the surface hardness and molecular weight of PLA. To this end, silicate is added to the biodegradable polymer PLA modified with peroxide. A coating composition is prepared by reacting one or more softening agents selected from the group consisting of a solution and a polyhydric alcohol.
상기 생분해성 고분자 PLA는 aliphatic polyester계 생분해성 고분자로서 반복 단위에는 ester 결합과 말단기에는 hydroxyl과 carboxyl group을 가지고 있으며, 이러한 구조로 인해 가수분해 및 미생물에 의한 분해가 가능하다. 상기 PLA는 경도가 높고 탄성이 낮은 관계로, PLA를 용해한 코팅제를 종이 또는 비닐 포장재 표면에 코팅할 경우 경도가 높아 구김이나 열 실링의 가장자리가 깨지는 현상이 발생하게 된다. 따라서, 종래에는 상기 문제해결을 위하여 상용성을 가지는 PLC[poly(ε-caprolactone)] 또는 PBAT(Poly-Butylene Adipate Terephthalate)를 일부 첨가하여 개질 소재로 사용하였다. 그러나 본 발명은 기존 개질에 사용한 PCL 또는 PBAT를 사용하지 않고 과산화물을 이용해 PLA의 저분자량 제어가 가능하며, 동시에 연성을 증가시킬 수 있도록, 콜로이드 실리카계열의 규산염 용액, 다가 알코올 또는 이들과 PVA를 반응시킨 연질부여제를 이용하여 연질성 및 접착성, 고용해도를 확보하였다.The biodegradable polymer PLA is an aliphatic polyester-based biodegradable polymer that has an ester bond in the repeating unit and hydroxyl and carboxyl groups in the terminal group. This structure allows hydrolysis and decomposition by microorganisms. Since the PLA has high hardness and low elasticity, when a coating agent containing PLA is coated on the surface of paper or vinyl packaging material, the hardness is high, causing wrinkles or cracking of the edges of the heat seal. Therefore, in the past, in order to solve the above problem, a portion of compatible PLC [poly(ε-caprolactone)] or PBAT (Poly-Butylene Adipate Terephthalate) was added and used as a modified material. However, in the present invention, it is possible to control the low molecular weight of PLA using peroxide without using PCL or PBAT used in existing modifications, and at the same time, to increase ductility, a colloidal silica-based silicate solution, polyhydric alcohol, or reaction of these with PVA is used. Softness, adhesiveness, and solubility were secured using the softness imparting agent.
1. 연질부여제1. Softener
본 발명에 따른 연질부여제는 규산염 용액 및 다가 알코올로 이루어진 군으로부터 하나 이상 선택되며, 보다 바람직하게는 상기 규산염 용액 또는 다가 알코올에 수용성 폴리머인 폴리비닐알코올(PVA)과 반응시켜 형성된 젤 타입일 수 있다. 참고로, 폴리비닐알코올(polyvinyl alcohol)은 필름 성형 시 유리하며 에멀젼 상태의 수용성 코팅의 베이스 소재로서 접착성 향상을 위해 사용된다. 상기 연질부여제는 PLA 수지 대비 0.5 내지 6 중량% 첨가하는 것이 바람직하다.The softening agent according to the present invention is selected from the group consisting of silicate solution and polyhydric alcohol, and more preferably may be a gel type formed by reacting the silicate solution or polyhydric alcohol with polyvinyl alcohol (PVA), a water-soluble polymer. there is. For reference, polyvinyl alcohol is advantageous in film molding and is used as a base material for water-soluble coatings in an emulsion state to improve adhesion. The softening agent is preferably added in an amount of 0.5 to 6% by weight compared to the PLA resin.
상기 규산염은 규산나트륨, 규산칼륨을 포함하는 규산금속착화합물이며, 바람직하게는 콜로이드 실리카 형태일 수 있다.The silicate is a silicate metal complex containing sodium silicate and potassium silicate, and may preferably be in the form of colloidal silica.
상기 콜로이드 실리카는 하기 반응식 1, 2의 반응을 거쳐 젤라틴 형태로 존재하게 된다.The colloidal silica exists in the form of gelatin through the reactions of Schemes 1 and 2 below.
[반응식 1][Scheme 1]
SiO2(OH)2 / SiO3(OH) + C4H6O2)n → Si-OH-(O-CH2)n SiO 2 (OH) 2 / SiO 3 (OH) + C 4 H 6 O 2 ) n → Si-OH-(O-CH 2 ) n
[반응식 2][Scheme 2]
Na2Si(OH)2 + C4H6O2)n → Na2Si(OH)2 - (O-CH2)n Na 2 Si(OH) 2 + C 4 H 6 O 2 ) n → Na 2 Si(OH) 2 - (O-CH 2 ) n
상기 콜로이드 실리카 입자 구조는 구형이며 수용성(H2O) 용제로 사용에서 콜로이드 상태로 분산되어 있고 표면에 Si-OH와 OH-이온들이 존재하여 음전하를 형성한다. 알칼리 이온인 Na+ 이온에 의해 전기적 이중 층이 형성되어, 입자 간의 반발에의해 안정화 되어있으나 전하 밸런스가 무너지는 경우 분자끼리 서로 결합하여 응고, 겔화, 응집 현상이 발생할 수 있다. The colloidal silica particle structure is spherical and is dispersed in a colloidal state when used as a water-soluble (H 2 O) solvent, and Si-OH and OH- ions exist on the surface to form a negative charge. An electrical double layer is formed by Na+ ions, which are alkaline ions, and is stabilized by repulsion between particles. However, if the charge balance is lost, the molecules can bond to each other, causing coagulation, gelation, and aggregation.
상기 반응식 1에서, PVA를 투입하고 교반온도를 60내지 70℃에서 진행하면 도 1과 같은 젤라틴 상의 점액질이 생성된다. 일예로 나트륨 이온을 포함하는 콜로이드 실리카의 경우 미량의 나트륨 이온으로 인해 Na2SiO(OH)의 구조로도 존재할 수 있다. 이때 나트륨 이온의 과다에 따라 PLA 개질 컴파운드 용융 압출 후 소재(팰릿)의 칼라를 투명한 오렌지색을 띄게 한다.In Scheme 1, when PVA is added and the stirring temperature is performed at 60 to 70° C., gelatin-like mucilage as shown in FIG. 1 is produced. For example, in the case of colloidal silica containing sodium ions, it may exist in the structure of Na 2 SiO(OH) due to a trace amount of sodium ions. At this time, depending on the excess of sodium ions, the color of the material (pallet) turns transparent orange after melting and extruding the PLA modified compound.
이렇게 생성된 점액질은 과산화물에 의해 저분자량으로 개질된 PLA의 말단 -OH기에 수소 결합하여 최종 코팅액 고형분으로 도포된 PLA 코팅막에 탄성 및 종이 계면 접착성을 향상시킨다.The slime produced in this way hydrogen bonds to the terminal -OH group of PLA modified to a low molecular weight by peroxide, improving the elasticity and paper interfacial adhesion of the PLA coating film applied with the solid content of the final coating solution.
또한, 본 발명은 다가알코올을 연질부여제로 사용할 수 있으며, 상기 다가알코올은 2가 알코올류인 글리콜류 MEG, DEG, PEG, 3가 알코올류인 글리세린, 글리세롤 등이 될 수 있다. 상기 다가알코올을 통해 PLA 표면 분산성 증대 및 필름 압출 시 슬립성 증가 효과를 얻을 수 있다. 도 2는 PLA에 PEG를 혼합 시 형성되는 개질된 PLA+PEG 분자결합 모식도를 나타낸다.In addition, the present invention can use polyhydric alcohol as a softening agent, and the polyhydric alcohol can be dihydric alcohols such as glycols MEG, DEG, and PEG, and trihydric alcohols such as glycerin and glycerol. The polyhydric alcohol can be used to increase PLA surface dispersibility and increase slip properties during film extrusion. Figure 2 shows a schematic diagram of the modified PLA+PEG molecular bond formed when mixing PEG with PLA.
2. 과산화물을 이용한 PLA 분자량 개질2. PLA molecular weight modification using peroxide
본 발명은 과산화물을 이용하여 PLA를 저분자량으로 개질함으로써, 열접착성 및 내수성, 발수성을 높일 수 있다. 바람직하게는 상기 과산화물은 PLA 수지 대비 0.1 내지 4 중량% 투입하여 PLA를 저분자량으로 개질하는 할 수 있다.The present invention can improve heat adhesiveness, water resistance, and water repellency by modifying PLA to a low molecular weight using peroxide. Preferably, the peroxide can be added in an amount of 0.1 to 4% by weight relative to the PLA resin to modify PLA to a low molecular weight.
본 발명에 따른 PLA 개질을 위한 과산화물은 구연산(CITRIC ACID MONOHYDRATE), 과산화 수소(HYDROGEN PEROXIDE), 개미산(FORMIC ACID), 라디칼 생성 반응형 개질제로는 Peroxide계인 lauroyl peroxide, 2,5-Dimethyl-2,5-Bis(t-butyl peroxy) hexane, dicumyl peroxide 등이 있으며, 그라프트 반응형 개질제는 maleic anhydride (MAH), Glycidylmeth- acrylate 등으로 이루어진 군 중에서 선택되는 적어도 하나 이상일 수 있다. Peroxides for PLA modification according to the present invention include citric acid (CITRIC ACID MONOHYDRATE), HYDROGEN PEROXIDE, and FORMIC ACID, and radical generating reactive modifiers include peroxide-based lauroyl peroxide, 2,5-Dimethyl-2, Examples include 5-Bis(t-butyl peroxy) hexane, dicumyl peroxide, etc., and the graft reactive modifier may be at least one selected from the group consisting of maleic anhydride (MAH), Glycidylmeth-acrylate, etc.
참고로, 상기 구연산은 이중결합 (=O) 3개가 기존 PLA 또는 1단계 완충 복합체 말단의 수소에 단일결합 형태 및 탈 수소화 반응 후 단일결합 구조(-O -)로 변경하여 분자 간의 완충 역할 뿐 아니라 기존 PLA 공유결합 전자를 빼앗아 평균분자량을 감소시킨다. For reference, the citric acid has three double bonds (=O) in the form of a single bond to the hydrogen at the end of the existing PLA or first-stage buffer complex, and is changed to a single bond structure (-O -) after dehydrogenation, so it not only acts as a buffer between molecules, but also acts as a buffer between molecules. It takes away the existing PLA covalent bond electrons and reduces the average molecular weight.
아울러, 상기 구연산 외에도 과산화 수소(HYDROGEN PEROXIDE), 개미산(FORMIC ACID), 라디칼 생성 반응형 개질제로는 peroxide계인 lauroyl peroxide, 2,5-Dimethyl-2,5-Bis(t-butyl peroxy) hexane, dicumyl peroxide 등이 있으며, 그라프트 반응형 개질제는 maleic anhydride (MAH), Glycidylmeth- acrylate 등으로 이루어진 군 중에서 선택되는 적어도 하나 이상일 수 있다.In addition, in addition to the citric acid, hydrogen peroxide, formic acid, and radical generating reactive modifiers include peroxide-based lauroyl peroxide, 2,5-Dimethyl-2,5-Bis(t-butyl peroxy) hexane, and dicumyl. peroxide, etc., and the graft reactive modifier may be at least one selected from the group consisting of maleic anhydride (MAH), Glycidylmethacrylate, etc.
과산화물 구연산 또는 2,5-Dimethyl-2,5-Bis(t-butylperoxy) hexane은 비결정 폴리머 또는 선형구조 폴리머 LLDPE, LDPE, TPU, TPE, PU, PBAT, PCL 등 폴리머에 첨가하여 가압·가열하면 체인을 끊은 후 가교 반응을 수반하여 경화제 또는 가교 첨가제로 사용되고, 결정성 폴리머 PP(폴리프로필렌), PC(폴리카보네이트), PLA 등에 첨가하여 공유결합 체인을 끊어 분자량을 감소시키는 분자량 개질 첨가제로 사용한다.Peroxide citric acid or 2,5-Dimethyl-2,5-Bis(t-butylperoxy) hexane is added to amorphous polymers or linear polymers such as LLDPE, LDPE, TPU, TPE, PU, PBAT, PCL, etc. and pressurized and heated to form chains. After breaking the crosslinking reaction, it is used as a curing agent or crosslinking additive, and is used as a molecular weight modification additive to reduce the molecular weight by breaking the covalent chain by adding it to crystalline polymers such as PP (polypropylene), PC (polycarbonate), and PLA.
추가로, 개질된 PLA의 표면 점성을 낮추기 위해 점성 개선제를 더 추가할 수 있다. 상기 점성 개선제는 무기 미세분말로서 흄드 실리카, 탄산칼슘(CaCO3), 탈크, 생석회(CaO), 제올라이트계 무기 분말, 일라이트, 벤토나이트 및 이오나이트로 이루어진 군 중에서 적어도 하나 이상 선택될 수 있다. 다만, 상기 무기 미세분말에 포함된 금속이온(Ca2+, Mg2+ ,Na+, K+ 등)이 과산화물로 PLA 개질 시 생성된 라디칼에 결합되어 최종 코팅층의 점탄성 및 표면 접착력에 영향을 미칠 수 있으므로, 사용량을 최소화하는 것이 바람직하다.Additionally, a viscosity improving agent may be added to lower the surface viscosity of the modified PLA. The viscosity improver is an inorganic fine powder and may be at least one selected from the group consisting of fumed silica, calcium carbonate (CaCO 3 ), talc, quicklime (CaO), zeolite-based inorganic powder, illite, bentonite, and ionite. However, metal ions (Ca2+, Mg2+, Na+, K+, etc.) contained in the inorganic fine powder may bind to radicals generated during PLA modification with peroxide and affect the viscoelasticity and surface adhesion of the final coating layer, so minimize the amount used. It is desirable to do so.
3. 코팅액 제조3. Preparation of coating solution
상기 제조한 PLA 개질 컴파운드는 유기용매를 이용해 일정 온도(40~65℃)로 가온한 상태에서 교반 용해하여 본 발명에 따른 코팅용액을 제조한다. 상기 코팅용액의 점도는 2000 내지 3500CP인 것이 바람직하며, 상기 코팅용액의 점도를 조절하기 위하여 점도 개선제를 투입할 수 있다. The prepared PLA modified compound is stirred and dissolved while heated to a certain temperature (40-65°C) using an organic solvent to prepare a coating solution according to the present invention. The viscosity of the coating solution is preferably 2000 to 3500 CP, and a viscosity improver can be added to adjust the viscosity of the coating solution.
상기 유기용매로는 극성용매인 DMC(Dimethyl Carbonate)일 수 있으며, 이는 상기 DMC가 PLA 생분해 수지 용해성이 우수하여 벤젠, 자일렌, 톨루엔 등 인체 및 환경 유해성이 있는 유기용매를 대체할 수 있는 친환경 화학물질이기 때문이다.The organic solvent may be DMC (Dimethyl Carbonate), a polar solvent, which is an eco-friendly chemical that can replace organic solvents that are harmful to the human body and the environment, such as benzene, xylene, and toluene, due to DMC's excellent solubility in PLA biodegradable resin. Because it is a substance.
본 발명에 따른 코팅액 제조방법은 종래의 PLA 코팅액 제조방법에서 크게 벗어나지 않지만, 종래에 PLA 코팅액 제조에 탄성률 증가 및 경도 저하를 위하여 첨가 사용한 PCL, PBAT 등의 고분자를 사용하지 않고, 규산염계(콜로이드 실리카, 규산나트륨, 규산칼륨, 등)용액이나 다가 알코올, 또는 이들에 PVA를 교반시킨 복합체를 이용하여 점탄성 및 경도 개선을 통한 코팅 후 깨짐을 방지하였고 과산화물을 이용해 PLA 고유 분자량을 저분자화 개질하여 용해 농도를 기존대비 5~15 질량% 용해 속도를 기존대비(20L 코팅용액 제조, 50분/50~60℃) 3~6배(8~16분/50~60℃) 개선함으로써, 코팅용액 생산의 경제성 및 작업 용이성을 해결하여 환경친화적인 생분해 코팅 포장재의 코팅(도포)량 및 요구되는 기능성(내수, 내유, 기체차단, 열접착)을 극대화할 수 있다. The coating solution manufacturing method according to the present invention does not significantly deviate from the conventional PLA coating solution manufacturing method, but does not use polymers such as PCL and PBAT, which were previously added to the PLA coating solution to increase elastic modulus and reduce hardness, and uses silicate-based (colloidal silica). , sodium silicate, potassium silicate, etc.) solution, polyhydric alcohol, or a composite of these mixed with PVA was used to prevent cracking after coating by improving viscoelasticity and hardness, and peroxide was used to modify the intrinsic molecular weight of PLA to a lower molecular weight to increase the dissolution concentration. Economic feasibility of coating solution production by improving the dissolution rate by 5~15% by mass compared to the existing one (20L coating solution production, 50 minutes/50~60℃) 3~6 times (8~16 minutes/50~60℃) compared to the existing one. and ease of operation can be solved to maximize the coating (application) amount and required functionality (water resistance, oil resistance, gas barrier, heat bonding) of environmentally friendly biodegradable coating packaging materials.
[실험예 1] [Experimental Example 1]
생분해성 고분자 PLA와 과산화제 첨가에 따른 MI 및 작업성 평가Evaluation of MI and workability according to biodegradable polymer PLA and peroxidant addition
배합기 온도 70℃ 조건에서 분산 배합속도 150 RPM의 조건으로 하기 표 1에 따른 성분을 투입하여 진행하였다. 상기 PLA는 네이쳐웍스사 그레이드 2003D 필름용 그레이드를 사용하였고, 구연산은 무수물 granules type의 분말을 전체 중량 대비 각각 1 중량%, 2 중량% 첨가 후 증류수를 0.5 중량% 첨가하여 PLA 수지 표면에 고루게 분산하였으며, 2,5-Dimethyl-2,5-Bis(t-butylperoxy) hexane은 액상의 성상이므로 각각 전체 중량 대비 각각 0.5 중량%, 1 중량% 첨가하여 PLA 표면에 분산 혼련 배합 후 상기 작업조건으로 컴파운드 압출하였다.The ingredients according to Table 1 below were added under the condition of a mixer temperature of 70°C and a dispersion mixing speed of 150 RPM. The PLA used was Nature Works Grade 2003D film grade, and citric acid was evenly dispersed on the surface of the PLA resin by adding 1% and 2% by weight of anhydrous granules type powder, respectively, based on the total weight, and then adding 0.5% by weight of distilled water. Since 2,5-Dimethyl-2,5-Bis(t-butylperoxy) hexane is in a liquid state, 0.5% by weight and 1% by weight of the total weight were added respectively, mixed and dispersed on the PLA surface, and then compounded under the above working conditions. Extruded.
컴파운드 압출기는 20mm 트윈스크류 컴파운드 압출기를 L/D 40:1, 압출 방법은 다이 스트렌드, 냉각은 수냉 수조, 사용하였으며 배합기는 3L 수퍼믹스 배합속도 150~350 RPM을 사용하였다, 압출 온도조건은 실린드 145~165℃ 다이스 170℃로 진행하였다.The compound extruder used a 20mm twin-screw compound extruder with L/D 40:1, the extrusion method was die strand, and the cooling was in a water-cooled water bath. The mixer used a 3L Supermix mixing speed of 150 to 350 RPM. The extrusion temperature conditions were Silin. The process was carried out at 145~165℃ and die at 170℃.
(t-butylperoxy) hexane2,5-Dimethyl-2,5-Bis
(t-butylperoxy)hexane
상기 작업 후 MI를 측정하였으며, 표 2와 같이 과산화물이 PLA 분자량을 감소시키는 것을 확인하였다. After the above operation, MI was measured, and it was confirmed that peroxide reduced the PLA molecular weight, as shown in Table 2.
(t-butylperoxy) hexane 첨가량2,5-Dimethyl-2,5-Bis
(t-butylperoxy)hexane addition amount
* MI 측정조건 : 170℃, 180℃, 190℃ 2.16 Kg/10min* MI measurement conditions: 170℃, 180℃, 190℃ 2.16 Kg/10min
상기 결과와 같이, 과산화물의 종류에 따라 고분자 PLA의 분자 체인을 끊는 산화력이 상이하다는 것을 확인할 수 있으며, 구연산 대비 2,5-Dimethyl-2,5-Bis(t-butylperoxy) hexane는 산화력이 높고 소량의 첨가량에 따른 분자량 변화가 심함을 알 수 있었다.As shown in the results above, it can be seen that the oxidizing power to break the molecular chain of polymer PLA is different depending on the type of peroxide. Compared to citric acid, 2,5-Dimethyl-2,5-Bis(t-butylperoxy) hexane has a high oxidizing power and a small amount. It was found that the molecular weight changed significantly depending on the amount added.
[실시 예 1][Example 1]
과산화물 구연산 및 콜로이드 실리카졸을 이용한 PLA 분자량 개질 및 연성 보강 컴파운드 제조Manufacture of PLA molecular weight modification and ductile reinforcement compound using peroxide citric acid and colloidal silica sol
고속 배합기에 하기 표3과 같이 PLA 3.2kg과 콜로이드 실리카 졸 0.08kg을 첨가 후 온도 80℃, 속도 150RPM 시간은 10분 교반 후 구연산 0.04kg을 첨가하고, 3분 250RPM 속도로 고속 교반 후 실린더 온도 145~165℃ 조건으로 메인 피드-용융 실린더- 다이스 - 수냉 - 커팅의 일반 압출 공정으로 컴파운드 용융·압출하여 소재를 제조하였다.After adding 3.2 kg of PLA and 0.08 kg of colloidal silica sol to the high-speed mixer as shown in Table 3 below, stirred for 10 minutes at a temperature of 80°C and a speed of 150 RPM, then added 0.04 kg of citric acid, and after stirring at a high speed of 250 RPM for 3 minutes, the cylinder temperature was 145 The material was manufactured by melting and extruding the compound using the general extrusion process of main feed - melting cylinder - die - water cooling - cutting under conditions of ~165℃.
PLA 생분해성 고분자는 말단에 -OH기를 다수 포함하고 있고 고분자 체인 중간에 산소 이중결합이 다수 포함하고 있어 구연산의 수산기와 산소 이중결합이 고온고압의 트윈 압출기 실린더 내부에서 활성화되어 콜로이드 실리카 졸의 Si 4가 이온과 수소결합을 유도함과 동시에 탄성 구조체를 형성하고 PLA 사슬 체인 일부의 공유결합 끊어 분자량을 감소시킨다.PLA biodegradable polymer contains many -OH groups at the ends and many oxygen double bonds in the middle of the polymer chain, so the hydroxyl group and oxygen double bonds of citric acid are activated inside the high-temperature and high-pressure twin extruder cylinder to form Si 4 of colloidal silica sol. It induces hydrogen bonds with ions and at the same time forms an elastic structure and breaks the covalent bonds of part of the PLA chain, thereby reducing the molecular weight.
[실시 예 2][Example 2]
과산화물 구연산 및 PEG 400을 이용한 PLA 분자량 개질 및 연성 보강 컴파운드 제조Preparation of PLA molecular weight modification and ductility reinforcement compound using peroxide citric acid and PEG 400
고속 배합기에 하기 표4와 같이 PLA 3.2kg에 PEG 400을 0.08kg 첨가 후 온도 80℃, 속도 150RPM 시간은 10분 교반 후 구연산 0.04kg 첨가해 3분 250RPM 속도로 고속 교반 후 실린더 온도 145~165℃ 조건으로 메인 피드 - 용융·실린더 - 다이스 - 수냉 - 커팅의 일반 압출 공정으로 컴파운드 용융·압출하여 소제를 제조하였다. As shown in Table 4 below, 0.08 kg of PEG 400 was added to 3.2 kg of PLA in the high-speed mixer, then stirred for 10 minutes at a temperature of 80°C and a speed of 150 RPM. Then, 0.04 kg of citric acid was added and stirred at a high speed of 250 RPM for 3 minutes, and the cylinder temperature was 145-165°C. Under the conditions, the compound was melted and extruded using a general extrusion process of main feed - melting/cylinder - die - water cooling - cutting to produce the cleaning agent.
고온·고압의 트윈 압출기 실린더 내부에서 활성화되어 PEG의 말단 -OH기와 수소결합을 유도함과 동시에 탄성 구조체를 형성하고 PLA 사슬 체인 일부의 공유결합 사이로 블록체을 형성하여 탄성력 및 코팅 시 기재에 접착 상용성을 증가시킨다. 에틸렌글리콜과 시트르산의 중축합은 100℃ 이상에서 시작되어, 고분자 시트르산 젤이 생성되어 PLA 수지 물성을 연성화시킨다. 참고로 도2는 PLA와 PEG 분자결합 모식도를 나타낸다.It is activated inside the high-temperature and high-pressure twin extruder cylinder to induce hydrogen bonding with the terminal -OH group of PEG and at the same time form an elastic structure and form a block body between the covalent bonds of part of the PLA chain to increase elasticity and adhesion compatibility to the substrate during coating. increase Polycondensation of ethylene glycol and citric acid begins above 100°C, creating a polymer citric acid gel, which softens the physical properties of PLA resin. For reference, Figure 2 shows a schematic diagram of the molecular bond between PLA and PEG.
[실시 예 3][Example 3]
과산화물 구연산 및 (Si 졸+PVA Solv) 교반 합성을 이용한 PLA 분자량 개질 및 연성 보강 컴파운드 제조Manufacture of PLA molecular weight modification and ductility reinforcement compound using peroxide citric acid and (Si sol + PVA Solv) stirred synthesis
하기 표 5와 같이, 콜로이드 실리카 졸 112.5g에 PVA 무수물 고형체 12.5g를 온도 60℃ 조건에서 100RPM 속도로 중탕 교반하여 액상 배합물 Si-PVA를 제조하였다. As shown in Table 5 below, a liquid blend Si-PVA was prepared by mixing 12.5 g of PVA anhydride solid in 112.5 g of colloidal silica sol at a speed of 100 RPM at a temperature of 60°C.
다음으로, 하기 표6과 같이 수퍼믹스 배합기에, PLA 고분자 3.2kg 투입 후 상기 제조한 Si-PVA 액상 배합물 0.12kg을 첨가 후 온도 80℃, 속도 150RPM으로 10분 교반 후 구연산 0.04kg를 첨가하고, 3분 250RPM 속도로 고속 교반 후 실린더 온도 145~165℃ 조건으로 메인 피드 - 용융·실린더 - 다이스 - 수냉 - 커팅의 일반 압출 공정으로 컴파운드 용융·압출하여 소재를 제조하였다. 참고로 도 3은 PLA+PVA 분자결합 모식도를 나타낸다.Next, as shown in Table 6 below, 3.2 kg of PLA polymer was added to the supermixer, then 0.12 kg of the Si-PVA liquid mixture prepared above was added, and then stirred for 10 minutes at a temperature of 80°C and a speed of 150 RPM, and then 0.04 kg of citric acid was added, After high-speed stirring at 250 RPM for 3 minutes, the material was manufactured by melting and extruding the compound using the general extrusion process of main feed - melting/cylinder - die - water cooling - cutting under the cylinder temperature of 145~165℃. For reference, Figure 3 shows a schematic diagram of PLA+PVA molecular bonding.
[실시 예 4][Example 4]
과산화물 구연산 및 (PEG400+PVA Solv) 교반 합성을 이용한 PLA 분자량 개질 및 연성 보강 컴파운드 제조Manufacture of PLA molecular weight modification and ductility reinforcement compound using peroxide citric acid and (PEG400+PVA Solv) stirred synthesis
상기 표 5와 같이, 콜로이드 실리카와 동일한 첨가량을 대체 소재로 에틸렌 글리콜 PEG 400을 112.5g 첨가해 PVA 무수물 고형체를 상기 실시 예 3과 동일 온도조건 60℃에서 중탕 교반법, 100RPM의 속도로 PVA Solv 액상 배합물 PEG-PVA 복합소재를 제조하였다.As shown in Table 5, 112.5 g of ethylene glycol PEG 400 was added as a replacement material in the same amount as colloidal silica, and PVA anhydride solid was prepared by PVA Solv using a double boiler stirring method at 60°C under the same temperature conditions as in Example 3, at a speed of 100 RPM. A liquid blend PEG-PVA composite material was prepared.
다음으로, 하기 표 7과 같이 수퍼믹스 배합기에 PLA 고분자 3.2kg 투입 후 상기 제조한 PEG-PVA 액상 배합물 0.12kg을 첨가 후 온도 80℃, 속도 150RPM으로 10분 교반 후 구연산 0.04kg를 첨가해 3분 250RPM 속도로 고속 교반 후 실린더 온도 145~165℃ 조건으로 메인 피드 - 용융·실린더 - 다이스 - 수냉 - 커팅의 일반 압출 공정으로 컴파운드 용융·압출하여 소재를 제조하였다. Next, as shown in Table 7 below, 3.2 kg of PLA polymer was added to the supermix mixer, then 0.12 kg of the PEG-PVA liquid mixture prepared above was added, stirred for 10 minutes at a temperature of 80°C and a speed of 150 RPM, and then 0.04 kg of citric acid was added and stirred for 3 minutes. After high-speed stirring at a speed of 250 RPM, the material was manufactured by melting and extruding the compound through the general extrusion process of main feed - melting/cylinder - die - water cooling - cutting under the cylinder temperature of 145~165℃.
[실시 예 5][Example 5]
과산화물 구연산, (Si 졸+PVA Solv) 및 점성 개선제 교반 합성을 이용한 PLA 분자량 개질 및 연성 보강 컴파운드 제조Manufacture of PLA molecular weight modification and ductility reinforcement compound using peroxide citric acid, (Si sol+PVA Solv) and viscosity improver stirring synthesis
상기 실시 예 1 내지 4의 배합물은 메인피더 투입 시 PLA 표면이 끈적이고 뭉침 현상이 발생 하였는 바, 수퍼믹스 배합 후 점성 개선제인 미세 나노 분말 흄드 실리카(fumed silica)를 첨가하였다.When the mixtures of Examples 1 to 4 were added to the main feeder, the PLA surface was sticky and agglomeration occurred, so fine nano-powder fumed silica, a viscosity improver, was added after supermix mixing.
상기 표 8과 같이, 수퍼믹스 배합기에 PLA 고분자 3kg 투입 후 콜로이드 실리카 졸 0.1kg과 PVA 400을 0.05kg 첨가 후 온도 80℃, 속도 150RPM으로 10분 교반 후 구연산 0.05kg를 첨가해 3분 250RPM 속도로 고속 교반 연속 작업중 수퍼믹스 뚜껑 밴트를 이용해 흄드 실리카 0.06kg를 첨가하여 2~3분 교반 속도를 300RPM 고속배합 후 실린더 온도 145~165℃ 조건으로 메인 피드 - 용융·실린더 - 다이스 - 수냉 - 커팅의 일반 압출 공정으로 컴파운드 용융·압출하여 소재를 제조하였다. As shown in Table 8, 3 kg of PLA polymer was added to the supermix mixer, then 0.1 kg of colloidal silica sol and 0.05 kg of PVA 400 were added, stirred for 10 minutes at a temperature of 80°C and a speed of 150 RPM, and then 0.05 kg of citric acid was added and stirred at a speed of 250 RPM for 3 minutes. During continuous high-speed stirring operation, add 0.06 kg of fumed silica using the Supermix lid vent and mix at 300 RPM for 2 to 3 minutes. After high-speed mixing, main feed - melt·cylinder - die - water cooling - general cutting. The material was manufactured by melting and extruding the compound through an extrusion process.
[실시 예 6][Example 6]
용해 분산성 극대화 및 양산 최적화 하이브리드 코팅 액 고형분 소재 컴파운드 제조Manufacture of hybrid coating liquid solid material compound to maximize dissolution and dispersibility and optimize mass production
하기 표 9와 같이, 수퍼믹스 배합기를 이용 PLA 고분자 3kg 투입 후 콜로이드 실리카 졸 0.06kg과 PVA 400을 0.03kg(0.5~2중량%), PEG 400 0.04kg을 첨가 후 온도 80℃, 속도 150RPM 시간은 10분 교반 후 구연산 0.05kg를 첨가해 3분 250RPM 속도로 고속 교반 연속 작업중 수퍼믹스 뚜껑 벤트를 이용해 흄드 실리카 0.08kg를 첨가하여 2~3분 교반 속도를 300RPM 고속배합 후 실린더 온도 145~165℃ 조건으로 메인 피드 - 용융·실린더 - 다이스 - 수냉 - 커팅의 일반 압출 공정으로 컴파운드 용융·압출하여 소재를 제조하였다.As shown in Table 9 below, after adding 3 kg of PLA polymer using a supermix mixer, 0.06 kg of colloidal silica sol, 0.03 kg (0.5 to 2% by weight) of PVA 400, and 0.04 kg of PEG 400 were added, and the temperature was 80°C and the speed was 150 RPM. After stirring for 10 minutes, add 0.05 kg of citric acid and stir at high speed at 250 RPM for 3 minutes. During continuous operation, add 0.08 kg of fumed silica using the Supermix lid vent and stir for 2 to 3 minutes at high speed at 300 RPM. After mixing, cylinder temperature is 145 to 165°C. The material was manufactured by melting and extruding the compound through a general extrusion process of main feed - melting/cylinder - die - water cooling - cutting.
[실험결과][Experiment result]
1. MI(melting index) 측정1. MI (melting index) measurement
분자량 상기 실시 예 1 내지 6의 개질 PLA 및 기존 PLA의 분자량 감소 정도는 170℃, 180℃, 190℃에서 2.16kg, 10min 조건으로 용융지수 MI(melting index)를 측정하였고, 이를 하기 표 10에 정리하였다.Molecular Weight The degree of molecular weight reduction of the modified PLA and conventional PLA of Examples 1 to 6 was measured by measuring the melting index (MI) under the conditions of 2.16 kg and 10 min at 170°C, 180°C, and 190°C, and the results are summarized in Table 10 below. did.
상기 분석결과 실시 예1 및 실시 예2의 MI(melting index) 결과가 실험군 중 가장 높게 평가되었으며, 실시예 4의 경우 기존 대조구 PLA 2003D의 MI보다 낮으나 분자량이 높은것으로 판단이 되지만 실제는 PEG400+PVA Solv의 연질성분의 화학적 결합으로 점탄성율이 높아 표면 점착력의 증가로 용융되어 흐른 수지량이 적은 것은 표 11의 동점도 분석결과로 확인하였다. 바인더 폴리머인 PLA 고분자에 화학적 결합방법을 이용하여 일부분 비정질(연질성)로 개질한 PLA는 동점도에 따라 MI(melting index 용융 흐름 지수) 측정 시 분자량의 높고 낮음에 무관하게 MI가 상반되게 측정될 수 있다. As a result of the above analysis, the MI (melting index) results of Examples 1 and 2 were evaluated as the highest among the experimental groups, and in the case of Example 4, the MI was lower than that of the existing control PLA 2003D, but it was judged to have a high molecular weight, but in reality, PEG400+PVA It was confirmed by the kinematic viscosity analysis results in Table 11 that the amount of resin that melted and flowed was small due to the increase in surface adhesion due to the high viscoelasticity due to the chemical bonding of the soft components of Solv. PLA, which is a binder polymer, has been partially modified to be amorphous (soft) using a chemical bonding method. Depending on the kinematic viscosity, the MI may be measured differently regardless of the high or low molecular weight when measuring MI (melt flow index). there is.
과산화물의 첨가량에 따른 분자량조절은 위 제어 가능함을 확인하였고 점탄성 부여기능은 PLA가 과산화물에 의해 분해 시 말단체인 -OH, -COOH에 상용성을 가지는 PVA, PEG, 다가 알콜 글리세린 등의 첨가량으로 탄성률을 조절 가능함을 알 수 있다. It was confirmed that the molecular weight can be controlled according to the amount of peroxide added, and the viscoelasticity imparting function is determined by adding PVA, PEG, and polyhydric alcohol glycerin, which are compatible with the terminal chains -OH and -COOH when PLA is decomposed by peroxide. It can be seen that can be adjusted.
2. 용해 시간 및 점도 측정2. Dissolution time and viscosity measurements
표 11과 같이, 상기 실시 예 1 내지 6의 개질 PLA 수지 및 종래의 PLA 수지를 DMC 유기용제를 이용해 중탕 온도 50~60℃에서 용해 시간 비교분석 및 제조 코팅제를 24시간 냉각 후 온도 20℃에서 동점도를 분석한 최종 코팅제 용해도 및 코팅 상용 가능성을 평가하였다.As shown in Table 11, comparative analysis of the dissolution time of the modified PLA resin of Examples 1 to 6 and the conventional PLA resin at a water bath temperature of 50 to 60°C using a DMC organic solvent, and the kinematic viscosity at a temperature of 20°C after cooling the manufactured coating agent for 24 hours. The final coating solubility and coating compatibility were analyzed.
시간hour
시간hour
시간hour
참고로, 동점도는 작업 시 온도조건에 따라 달라지므로 작업 중탕기 온도를 40~55℃ 범위에서 하는 것이 바람직하다. 작업온도를 40℃보다 낮은 온도는 점도가 상승하여 동판에서 기재로 전이되는 고형분량이 적고, 코팅액의 고점도화 (2500~3500 CP이상)는 그라비어 코팅 작업 진행 시 코팅제를 올리는 베셀 내부의 동판 회전력으로 인해 베셀의 후미로 밀려 코팅액이 외부로 넘칠 수 있으며 베셀내부의 코팅액이 동판 회전시 망점 내부로 전이되는 함량이 적다.(동판의 스크린 수에 따라 달라짐) 작업온도를 55℃ 이상이면 희석용제로 사용된 DMC, BC 등의 용제가 표면 휘발(증발)로 고분자 코팅시 PLA의 표면경화로 얇은 막으로 석출되어 동판의 돗트 나이프 및 동판막(스크린)에 내부경화되어 도포량 제어가 불가능할 수 있다.For reference, kinematic viscosity varies depending on temperature conditions during work, so it is desirable to keep the double boiler temperature in the range of 40 to 55°C. If the working temperature is lower than 40℃, the viscosity increases and the amount of solids transferred from the copper plate to the substrate is small, and the high viscosity of the coating solution (above 2500~3500 CP) is due to the rotational force of the copper plate inside the vessel that raises the coating agent during the gravure coating process. The coating liquid may overflow to the outside as it is pushed to the rear of the vessel, and the amount of coating liquid inside the vessel transferred to the inside of the halftone dots when the copper plate is rotated is small. (Depends on the number of screens on the copper plate) If the working temperature is above 55℃, the diluted solvent is used. Solvents such as DMC and BC precipitate into a thin film due to surface hardening of PLA during polymer coating due to surface volatilization (evaporation) and internal hardening on the dot knife and copper plate (screen) of the copper plate, making it impossible to control the application amount.
상기 표 11에서 종래의 PLA 2003D를 이용하여 제조한 코팅액은 최종고형분 함량 20%를 사용하였고 동점도 20℃, 3500CP로 더 이상 고농축 하지 못하였다. 반면 본 발명에 따른 실시 예 1 내지 6의 경우, 고형분 함량을 최적화하면서 동점도를 낮추어 코팅층 도포량 극대화가 가능하였다. In Table 11 above, the coating solution prepared using conventional PLA 2003D used a final solid content of 20% and was no longer highly concentrated at a kinematic viscosity of 20°C and 3500CP. On the other hand, in Examples 1 to 6 according to the present invention, it was possible to maximize the amount of coating layer applied by lowering the kinematic viscosity while optimizing the solid content.
3. 내수성, 내유성, 열 접착성 및 산소 차단성 평가3. Evaluation of water resistance, oil resistance, heat adhesion and oxygen barrier properties
하기 표 12와 같이, 실시 예6의 코팅액을 이용해 그라비어 롤코터 설비로 평량 70g/m2의 그라싱지(유산지)에 코팅 작업 40m/min의 속도로 1회, 2회 코팅 처리 후 도포량(고형분 코팅량 기준)에 따른 내수성, 내유성, 열 접착성 및 산소 차단성을 평가하였다.As shown in Table 12 below, the coating solution of Example 6 was coated on grassing paper (pasteurized paper) with a basis weight of 70 g/m 2 using a gravure roll coater equipment, once and twice at a speed of 40 m/min, and then the application amount (solid content) Water resistance, oil resistance, heat adhesion, and oxygen barrier properties were evaluated (based on coating amount).
상기 결과에서 알 수 있듯이 동판의 스크린에 따른 코팅량이 달라지는 것을 확인할 수 있으며 본 기술개발에 사용된 코팅액은 기존 사용되는 수용성 또는 유성 용제로 사용되는 코팅액에 대비하여 동점도가 상대적으로 높아(끈끈함) 동판의 스크린 수가 낮을수록 도포량을 높일 수 있음을 확인하였다. As can be seen from the above results, it can be seen that the coating amount varies depending on the screen of the copper plate, and the coating liquid used in the development of this technology has a relatively high kinematic viscosity (stickiness) compared to the coating liquid used in existing water-soluble or oil-based solvents. It was confirmed that the lower the number of screens, the higher the application amount.
상기 코팅 작업 된 실험군 6종과 대조구로 코팅 처리하지 않은 원지를 이용해 각각 생수 및 대두유를 표면에 투입 후 흡습/흡유의 경과 시간을 유관관찰하였으며, 이를 하기 표 13에 정리하였다.The elapsed time of moisture absorption/oil absorption was observed after adding bottled water and soybean oil to the surface using the six types of coated experimental group and the uncoated base paper as the control group, respectively, and these are summarized in Table 13 below.
[표 13] [ Table 13 ]
<평량 70g/m2의 그라싱지(유산지)코팅 내수성, 내유성 실험 결과><Water resistance and oil resistance test results of glassing paper (pasteurized paper) coating with a basis weight of 70g/m 2 >
* 내수도 측정 방법 : 코팅면에 물, 에센스 오일 각각 2CC씩을 투입한 후 2, 6, 24시간 단위로 유관관찰을 하였다.* Method of measuring water resistance: 2 CC each of water and essence oil were added to the coated surface and observed in 2, 6, and 24 hours.
유관관찰 결과 1회 코팅한 표 13의 시료 1 내지 시료 3의 경우, 동판 스크린 수가 낮으면 도포량은 많아지지만 6시간 경과 후 모든 시료에서 수분이 종이에 침투되는 것을 확인할 수 있었다. 그라비어 동판을 이용해 코팅하는 방식은 베셀의 코팅액을 동판 스크린에 담지 한 후 돗트 나이프로 동판 표면을 직각으로 긁어 돗트(점)상으로 종이에 전사하는 방식으로 코팅을 진행하므로 용제 건조 후 돗트와 돗트사이에 공간이 생겨 물이 종이로 흡수되었다. 상기 설명의 현상으로 1회 코팅한 코팅지는 물과 대두유를 이용한 흡수(내수성), 흡유(내유성)의 결과는 6시간 경과 후 모두 종이에 침투되는 것을 확인하였다.As a result of related observations, in the case of Samples 1 to 3 in Table 13, which were coated once, if the number of copper screens was low, the amount of application increased, but it was confirmed that moisture penetrated into the paper in all samples after 6 hours. The method of coating using a gravure copper plate is to place the vessel's coating liquid on a copper plate screen, then scratch the surface of the copper plate at a right angle with a dot knife and transfer it to paper in the form of dots, so after drying the solvent, there is a gap between the dots. A space was created and water was absorbed into the paper. It was confirmed that the coated paper coated once due to the phenomenon described above was penetrated into the paper after 6 hours in terms of water absorption (water resistance) and oil absorption (oil resistance) using water and soybean oil.
2회 코팅한 시료 4~6은 동판 스크린 #100으로 진행한 도포량 9g/m2, 6시간 경과 후 흡수나 흡유 거동은 없었고 10시간 이후 종이로 침투되었다. 상기 실험결과 시료 4와 시료 5는 24시간 경과 물과 대두유가 종이로 침투되지 않는 것을 확인하였다. Samples 4 to 6, which were coated twice, were applied with a copper plate screen #100 at an application rate of 9 g/m 2 , and there was no absorption or oil absorption behavior after 6 hours, and penetrated into paper after 10 hours. As a result of the above experiment, it was confirmed that water and soybean oil did not penetrate into the paper for Samples 4 and 5 after 24 hours.
상기 결과로 그라비어 방식의 코팅 시 코팅액 점도와 스크린 수를 고려하여 2회 이상 코팅하여 그라비어 전사로 발생 되는 돗트 사이의 간극을 다회 코팅방식으로 최소 14g/m2 이상 도포하는 것이 바람직하다.As a result of the above results, when coating using the gravure method, it is desirable to apply at least 14g/m 2 of the coating at least twice to fill the gap between the dots created by gravure transfer by taking into account the viscosity of the coating solution and the number of screens.
유연성 거동 변화 실험은 개질하지 않은 PLA 코팅액과 16g/m2 코팅한 시료 4의 코팅지를 1회 접어 접지 표면에 물을 2cc 떨어트려 접지 부분의 흡습 흡유를 관찰한 결과, 도 4와 같이 분자량 개질 및 유연화 처리를 진행한 시료 4의 코팅지는 12시간 경과 하여도 접지 부분의 크랙에 따른 흡습 거동을 보이지 않았으나, 기존 PLA 코팅액을 사용한 코팅지는 15분내에 접지부에 형성된 크랙에 의해 침투되는 것을 확인하였다.In the experiment on the change in flexibility behavior, the coated paper of sample 4 coated with unmodified PLA coating solution and 16 g/m 2 was folded once and 2 cc of water was dropped on the ground surface to observe the moisture absorption of the ground portion. As a result, as shown in Figure 4, molecular weight modification and The coated paper of sample 4 that underwent softening treatment did not show moisture absorption behavior due to cracks in the grounding area even after 12 hours, but it was confirmed that the coated paper using the existing PLA coating solution was penetrated by cracks formed in the grounding area within 15 minutes.
4. 열 접착성 실험4. Thermal adhesion experiment
평량 70g/m2의 그라싱지(유산지) 코팅지에 상기 표 13의 시료 7종을 열접합 경사기를 이용해 접착 강도를 측정하였다. 강도측정 장치는 Heat seal 시험기(HS-210)이고, 실링 온도 및 시간 조건은 190~205℃ 온도로 2초간 가압 접착 후 강도를 측정하였고 표 14와 같이 종이 표면의 최종 코팅 도포량이 많은 시료 4가 접합강도가 높은 것을 확인할 수 있었다. 이는 종이 표면이 고루지 않아 평활도를 유지할 수 있는 일정량보다 작으면 실링 시 실링 용융열로 인하여 종이 내부로 함침되므로 잔류 코팅(고분자)량이 적어 고분자간 계면 용융 융착력이 떨어지는 결과를 초래함을 인지할 수 있으며 기존(개질전)에 PLA단독 코팅액은 도포량(코팅량)을 많이 하면 계면 접착력은 강하지만 실링면 가장자리의 폴리머 경화로 깨지는 현상을 초래하여 내수, 내유, 산소차단 기능을 할 수 없었다. The adhesive strength of the seven samples shown in Table 13 above was measured on coated grassing paper (pasteurized paper) with a basis weight of 70 g/m 2 using a heat bonding tilter. The strength measurement device was a heat seal tester (HS-210), and the sealing temperature and time conditions were 190 to 205°C for 2 seconds to measure the strength. As shown in Table 14, sample 4 had a large amount of final coating applied to the paper surface. It was confirmed that the bonding strength was high. This means that if the surface of the paper is uneven and is less than a certain amount that can maintain smoothness, the interior of the paper is impregnated due to the heat of sealing fusion during sealing, resulting in a small amount of residual coating (polymer), resulting in a decrease in the melting and adhesion power of the interface between polymers. In the past (before modification), the PLA single coating solution had strong interfacial adhesion if the application amount (coating amount) was large, but the polymer hardening at the edge of the sealing surface caused breakage, making it unable to perform water-resistance, oil-resistance, and oxygen-blocking functions.
수screen
number
5. 산소 투기도 및 수분 투과율 실험5. Oxygen permeability and moisture permeability experiment
상기 시료 1~6을 대상으로 산소 투기도 실험 (Oxygen Transmission Rate Tester) 및 수분 투과율(WVTR : Water. Vapor Transmission Rate)을 측정하여 고형분 코팅액 코팅 평량에 따른 투기, 투습의 경향을 확인하여 본 개발의 신뢰성을 확인하였다. 테스트 방법은 산소투과는 ASTM D3985 방법으로, 수분 투과도는 ASTM F1249 방법으로 24시간 분석하였다.Oxygen transmission rate tester (Oxygen Transmission Rate Tester) and water vapor transmission rate (WVTR) were measured for the samples 1 to 6 above to confirm the trend of air permeability and moisture permeability according to the solid coating liquid coating basis weight. Reliability was confirmed. The test method was to analyze oxygen permeability using the ASTM D3985 method and moisture permeability using the ASTM F1249 method for 24 hours.
상기 결과는 산소투과도, 수분투과도 실험에서 도포량이 많은 시료 4보다 도포량이 적은 시료 5가 좋은 것을 확인할 수 있으며 내수, 내유실험의 결과와 같이 동판 스크린 수를 달리하여 1회 코팅한 코팅지는 전사방식의 그라비어 코팅 도포 돗트 사이의 간극으로 투기, 투습이 되어 시료 1 내지 3은 기존 원지 대비는 좋은 경향을 보이지만 2회 코팅한 것에 비하여 정량적으로 큰 차이가 나는 것을 확인할 수 있다. 시료 4는 시료 5에 비교하여 도포량이 많으나 동판 스크린 수가 낮아 2회 도포 하더라도 투기 및 투습이 높은 결과를 보였다.The above results confirm that in the oxygen permeability and moisture permeability tests, sample 5 with a small application amount is better than sample 4 with a large application amount, and as shown in the results of the water resistance and oil resistance tests, the coated paper coated once with different numbers of copper plate screens is good for the transfer method. Samples 1 to 3 show a good tendency compared to the existing base paper due to air and moisture permeability through the gap between the gravure coating application dots, but it can be seen that there is a quantitative difference compared to the two-coat coating. Sample 4 had a higher application amount compared to Sample 5, but the number of copper screens was low, so even when applied twice, air permeability and moisture permeability were high.
이를 통해 본 발명에 따라 생분해성 폴리머 PLA를 표면 개질하여 제조한 코팅제의 점도에 따른 동판 스크린 수의 선정은 본 발명이 이루고자 하는 산소차단, 내수, 내유, 열접착성 등을 결정하는 주요 생산공정 기술임을 확인하였다.Through this, the selection of the number of copper plate screens according to the viscosity of the coating agent manufactured by surface modification of the biodegradable polymer PLA according to the present invention is a major production process technology that determines the oxygen blocking, water resistance, oil resistance, heat adhesiveness, etc. that the present invention aims to achieve. It was confirmed that it was.
본 발명을 첨부된 도면과 함께 설명하였으나, 이는 본 발명의 요지를 포함하는 다양한 실시 형태 중의 하나의 실시 예에 불과하며, 당 업계에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 하는 데에 그 목적이 있는 것으로, 본 발명은 상기 설명된 실시 예에만 국한되는 것이 아님은 명확하다. 따라서, 본 발명의 보호 범위는 하기의 청구범위에 의해 해석되어야 하며, 본 발명의 요지를 벗어나지 않는 범위 내에서의 변경, 치환, 대체 등에 의해 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리 범위에 포함될 것이다. 또한, 도면의 일부 구성은 구성을 보다 명확하게 설명하기 위한 것으로 실제보다 과장되거나 축소되어 제공된 것임을 명확히 한다. 또한, 청구항 부호는 이해를 돕기 위한 것일 뿐 본 발명의 형상과 구조를 첨부된 도면에 한정한다는 뜻이 아니다.Although the present invention has been described with the accompanying drawings, this is only one example among various embodiments including the gist of the present invention, and is intended to enable those skilled in the art to easily implement the present invention. For this purpose, it is clear that the present invention is not limited to the embodiments described above. Therefore, the scope of protection of the present invention should be interpreted in accordance with the following claims, and all technical ideas within the equivalent scope by change, substitution, substitution, etc. without departing from the gist of the present invention are the rights of the present invention. will be included in the scope. In addition, it should be clarified that some of the configurations in the drawings are provided in an exaggerated or reduced form than the actual figure for the purpose of explaining the configuration more clearly. In addition, the claim symbols are only for aiding understanding and do not mean that the shape and structure of the present invention is limited to the attached drawings.
Claims (10)
A biodegradable polymer coating composition prepared by reacting PLA (Poly Lactic Acid), a biodegradable polymer modified with peroxide, with one or more softness imparting agents selected from the group consisting of silicate solutions and polyhydric alcohols.
상기 규산염은 규산나트륨, 규산칼륨을 포함하는 규산금속착화합물인, 생분해성 고분자 코팅 조성물.
According to paragraph 1,
A biodegradable polymer coating composition wherein the silicate is a silicate metal complex containing sodium silicate and potassium silicate.
상기 연질부여제는 규산염 용액 또는 다가 알코올을 폴리비닐알코올(PVA)과 반응시킨 것을 포함하는, 생분해성 고분자 코팅 조성물.
According to paragraph 1,
The softening agent is a biodegradable polymer coating composition comprising a silicate solution or a polyhydric alcohol reacted with polyvinyl alcohol (PVA).
상기 과산화물은 구연산, 과산화 수소, 개미산, 라디칼 생성 반응형 개질제, 그라프트 반응형 개질제로 이루어진 군으로부터 하나 이상 선택되는, 생분해성 고분자 코팅 조성물.
According to paragraph 1,
A biodegradable polymer coating composition, wherein the peroxide is selected from the group consisting of citric acid, hydrogen peroxide, formic acid, radical generation reactive modifier, and graft reactive modifier.
A packaging material coated with the coating composition according to any one of claims 1 to 4.
상기 포장재는 종이류 또는 필름류인 것을 특징으로 하는, 포장재.
According to clause 5,
A packaging material, characterized in that the packaging material is paper or film.
극성 유기용매에 상기 개질 생분해성 고분자를 일정 점성을 가지도록 용해시키는 제2단계;를 포함하는 생분해성 고분자 코팅액 제조방법.
PLA (Poly Lactic Acid), a biodegradable polymer; A softening agent selected from the group consisting of metal silicate solutions and polyhydric alcohols; and a first step of preparing a modified biodegradable polymer compound by putting peroxide in a blender and stirring it at a temperature of 60 to 100°C;
A method for producing a biodegradable polymer coating solution comprising a second step of dissolving the modified biodegradable polymer in a polar organic solvent to have a certain viscosity.
상기 연질 부여제는 폴리비닐알코올(PVA)과 반응시킨 것을 더 포함하는, 생분해성 고분자 코팅액 제조방법.
In clause 7,
A method for producing a biodegradable polymer coating liquid, further comprising the softness imparting agent reacted with polyvinyl alcohol (PVA).
상기 제1단계는 제조되는 상기 개질 생분해성 고분자에 점성 개선제를 더 투입하는 것을 특징으로 하는, 생분해성 고분자 코팅액 제조방법.
According to clause 7 or 8,
The first step is a method for producing a biodegradable polymer coating solution, characterized in that a viscosity improver is further added to the modified biodegradable polymer being produced.
상기 제1단계에서 제조되는 상기 개질 생분해성 고분자를 컴파운드 압출기를 통해 용융 및 압출하는 것을 특징으로 하는, 생분해성 고분자 코팅액 제조방법.According to paragraph 7 or 8,
A method for producing a biodegradable polymer coating liquid, characterized in that the modified biodegradable polymer prepared in the first step is melted and extruded through a compound extruder.
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| KR102023160B1 (en) | 2019-02-22 | 2019-09-20 | (주)하늘이노베이션 | Method of preparing eco-friendly coating paper for paper cup and coating paper therefrom |
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| KR102023160B1 (en) | 2019-02-22 | 2019-09-20 | (주)하늘이노베이션 | Method of preparing eco-friendly coating paper for paper cup and coating paper therefrom |
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