KR102247843B1 - Method of eco-friendly food flexible packaging coating materials containing biodegradable catalyst - Google Patents
Method of eco-friendly food flexible packaging coating materials containing biodegradable catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/6755—Unsaturated carboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
Description
본 발명은 생분해 촉매제를 포함하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법에 관한 것으로, 더욱 자세하게는 내층 조성물 및 외층 조성물을 제조하는 단계; 상기 제조된 내층 조성물 및 외층 조성물을 공압출하는 단계를 포함하고, 상기 내층 조성물을 제조하는 단계는 폴리올, 디메틸올프로피온 산(dimethylol propionic acid: DMPA), N-메틸피놀리돈(NMP)용액 및 이소시아네이트를 혼합하여 프리폴리머를 제조하는 단계; N-메틸피놀리돈(NMP)용액에 희석시킨 중화제로 상기 프리폴리머를 중화시키고 상기 중화된 프리폴리머에 증류수를 투입하여 수분산 시킨 후, 사슬 연장제를 첨가하여 수분산 폴리 우레탄을 제조하는 단계; 상기 수분산 폴리 우레탄에 아크릴 모노머, 생분해 촉매제 및 개시제를 첨가한 후 교반하여 수용성 아크릴 폴리우레탄을 제조하는 단계; 및 상기 수용성 아크릴 폴리우레탄에 칼슘계 화합물, 과붕산소다 및 아세트산을 첨가하는 단계를 포함하고, 상기 외층 조성물을 제조하는 단계는 폴리올레핀, 에틸렌다이아민테트라아세트산(EDTA), 칼슘락테이트, 금속스테아린산 및 드로메트리졸을 혼합하는 단계를 포함하는 것을 특징으로 하는 친환경 식품용 연포장재 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a flexible packaging material for eco-friendly foods for replacing plastics comprising a biodegradation catalyst, and in more detail, the steps of preparing an inner layer composition and an outer layer composition; Coextrusion of the prepared inner layer composition and outer layer composition, and the step of preparing the inner layer composition includes polyol, dimethylol propionic acid (DMPA), N-methylpinolidone (NMP) solution, and Mixing isocyanate to prepare a prepolymer; Neutralizing the prepolymer with a neutralizing agent diluted in N-methylpinolidone (NMP) solution, adding distilled water to the neutralized prepolymer to disperse it, and then adding a chain extender to prepare a water-dispersible polyurethane; Adding an acrylic monomer, a biodegradation catalyst, and an initiator to the water-dispersible polyurethane, followed by stirring to prepare a water-soluble acrylic polyurethane; And adding a calcium-based compound, sodium perborate, and acetic acid to the water-soluble acrylic polyurethane, and preparing the outer layer composition includes polyolefin, ethylenediaminetetraacetic acid (EDTA), calcium lactate, metal stearic acid, and It relates to a method for manufacturing a flexible packaging material for eco-friendly food, characterized in that it comprises the step of mixing drometrisol.
연포장(Flexible packaging)은 플라스틱 필름, 종이, 알루미늄 포일 및 섬유 등 유연성을 가진 재료를 단일층 또는 복합 다층의 형태로 만들어 내용물의 특성에 맞게 봉투나 필름형태로 제작한 포장재와 이를 이용한 포장 방법을 의미한다.Flexible packaging is a packaging material made in the form of a bag or film according to the characteristics of the contents by making flexible materials such as plastic film, paper, aluminum foil and fiber in the form of a single layer or a multi-layered layer, and a packaging method using the same. it means.
연포장은 식품, 주류, 약품, 일반 소모품 및 유통기한 확장이 필요한 다른 제품을 저장하고 유통하기 위한 가장 경제적인 패키지 수단이다. 최종 소비 유형에 맞춰 패키징되는 제품에 적합하도록 만들어진 차단재와 함께 고안될 수 있다. 반면에 다른 베리어 패키징 포맷은 일반적으로 모든 크기에 적합하도록 제공된다. 현재의 연포장은 광범위하고 혁신적인 형태, 크기 및 모양으로 제작될 수 있으며, 열고 닫을 수 있는 지퍼와 주입구와 같은 특성을 포함할 수 있다.Flexible packaging is the most economical means of packaging for storing and distributing food, alcohol, pharmaceuticals, general consumables and other products that require extended shelf life. It can be designed with barriers made to fit the product being packaged for the type of final consumption. On the other hand, other barrier packaging formats are generally provided to fit all sizes. Current flexible packaging can be manufactured in a wide variety of innovative shapes, sizes and shapes, and can include features such as open and close zippers and spouts.
연포장은 다른 형태의 패키징보다 자원과 에너지의 소비량이 작다. 정형화된 고형 패키징의 장점을 갖고 있을 뿐만 아니라 패키징 비용, 재료 사용량, 수송비용의 측면에서도 커다란 절감 효과를 제공한다. 연포장을 활용하는 것은 패키지 가공업체에서 내용물 공급업체, 소매업체 및 최종 소비자에 이르기까지 패키지 수송비용을 최소화할 수 있다. 특히 내용물을 채우지 않았을 경우에는 고형 패키징에 비해 공간을 최소화할 수 있을 뿐만 아니라 내용물 충전 장소에서도 롤 재료를 통해 부분적인 작업을 할 수 있다. 이러한 이유 때문에 내용물이 없는 사전 제작 패키징의 수송비용은 최소화된다.Flexible packaging consumes less resources and energy than other types of packaging. Not only does it have the advantage of standardized solid packaging, but it also provides great savings in terms of packaging cost, material usage, and transportation cost. Using flexible packaging can minimize package transport costs from package processors to content suppliers, retailers and end consumers. In particular, when the contents are not filled, the space can be minimized compared to solid packaging, as well as partial work can be performed through the roll material at the contents filling place. For this reason, transportation costs for pre-production packaging without contents are minimized.
연포장에 있어 가장 중요한 점은 내용물의 보존을 위해 내용물의 특성과 운용 방법에 가장 적합한 포장재료를 선정하여 사용하는 것이다. 수분에 의해 변질이 가능한 물질이나 건조를 하여야 하는 제품, 부패를 방지하기 위하여 진공상태를 유지해야 하는 제품, 위생성이 많이 요구되는 식품과 전자레인지를 사용하여 가공할 식품, 다양한 내용물에 따라서 포장재의 구성과 물리적, 화학적, 기능적인 특성을 적절하게 선택하여 사용한다. 단일 소재로서 내용물의 보호와 품질유지 및 운용 방법, 제조 공정에 따른 제반 사항 등을 만족시키는 소재는 거의 희박한데 연포장의 경우 다양한 소재를 복합적으로 사용해 필요사항을 최대한 만족시키고 있다.The most important point in flexible packaging is to select and use the most suitable packaging material for the characteristics of the contents and the method of operation for the preservation of the contents. Materials that can be deteriorated by moisture, products that need to be dried, products that need to be kept in a vacuum to prevent spoilage, foods that require a lot of hygiene, foods to be processed using a microwave oven, and packaging according to various contents And physical, chemical, and functional properties are appropriately selected and used. As a single material, there are very few materials that satisfy the protection, quality maintenance and operation method of the contents, and all matters according to the manufacturing process, but in the case of flexible packaging, various materials are used in combination to satisfy the needs as much as possible.
연포장 소재 중 친환경(생분해성)필름 및 PVA(폴리비닐 알코올) 필름과 이축 연신 폴리프로필렌(Biaxially oriented polypropylene, BOPP) 필름, 알루미늄 포일을 이용한 소재와 종이 연포장은 그 수요가 지속적으로 확대되고 있지만 LDPE(저밀도 폴리에틸렌)의 수요는 이미 시장이 성숙되어 포화점에 이르고 있다.Among the flexible packaging materials, the demand for eco-friendly (biodegradable) films, PVA (polyvinyl alcohol) films, biaxially oriented polypropylene (BOPP) films, and materials using aluminum foil and paper flexible packaging continues to expand. The demand for LDPE (low density polyethylene) has already reached its saturation point as the market has matured.
기존 종이 포장재(다층 합지 포장재 포함) 및 용기(플라스틱 제품 포함)의 단점을 보완하여 인체에 무해하며, 자원 절약화(감량화, 재이용성, 재활용성, 재자원화 이용성, 폐기처리 용이성)와 소각시 친환경성, 매립시 분해 용이성이 뛰어나 환경을 보호할 수 있는 알칼리 해리성을 부여한 친환경적이며 재생 가능한 식품 연포장재 제조방법을 제공하는 것을 목적으로 한다.It is harmless to the human body by complementing the shortcomings of existing paper packaging materials (including multi-layered laminated packaging materials) and containers (including plastic products), saving resources (reduction, reusability, recyclability, recyclability, ease of disposal) and eco-friendly incineration Its purpose is to provide an eco-friendly and renewable food flexible packaging material manufacturing method that has excellent ease of decomposition during embedding and gives alkali dissociation properties that can protect the environment.
본 발명은 상기와 같은 문제점을 해결하기 위해 안출된 것으로, 내층 조성물 및 외층 조성물을 제조하는 단계; 상기 제조된 내층 조성물 및 외층 조성물을 공압출하는 단계를 포함하고, 상기 내층 조성물을 제조하는 단계는 폴리올, 디메틸올프로피온 산(dimethylol propionic acid: DMPA), N-메틸피놀리돈(NMP)용액 및 이소시아네이트를 혼합하여 프리폴리머를 제조하는 단계; N-메틸피놀리돈(NMP)용액에 희석시킨 중화제로 상기 프리폴리머를 중화시키고 상기 중화된 프리폴리머에 증류수를 투입하여 수분산 시킨 후, 사슬 연장제를 첨가하여 수분산 폴리 우레탄을 제조하는 단계; 상기 수분산 폴리 우레탄에 아크릴 모노머, 생분해 촉매제 및 개시제를 첨가한 후 교반하여 수용성 아크릴 폴리우레탄을 제조하는 단계; 상기 수용성 아크릴 폴리우레탄에 칼슘계 화합물, 과붕산소다 및 아세트산을 첨가하는 단계를 포함하고, 상기 외층 조성물을 제조하는 단계는 폴리올레핀, 에틸렌다이아민테트라아세트산(EDTA), 칼슘락테이트, 금속스테아린산 및 드로메트리졸을 혼합하는 단계를 포함하는 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법을 제공한다.The present invention has been devised to solve the above problems, the steps of preparing an inner layer composition and an outer layer composition; Coextrusion of the prepared inner layer composition and outer layer composition, and the step of preparing the inner layer composition includes polyol, dimethylol propionic acid (DMPA), N-methylpinolidone (NMP) solution, and Mixing isocyanate to prepare a prepolymer; Neutralizing the prepolymer with a neutralizing agent diluted in N-methylpinolidone (NMP) solution, adding distilled water to the neutralized prepolymer to disperse it, and then adding a chain extender to prepare a water-dispersible polyurethane; Adding an acrylic monomer, a biodegradation catalyst, and an initiator to the water-dispersible polyurethane, followed by stirring to prepare a water-soluble acrylic polyurethane; Including the step of adding a calcium-based compound, sodium perborate and acetic acid to the water-soluble acrylic polyurethane, the step of preparing the outer layer composition is polyolefin, ethylenediaminetetraacetic acid (EDTA), calcium lactate, metal stearic acid and draw It provides a method for manufacturing a flexible packaging material for eco-friendly food for plastic replacement, characterized in that it comprises the step of mixing mettrisol.
본 발명에 의하여 내유성, 내수성 및 열접착 강도가 뛰어나고, 사용 후 폐기시 자연에서 생분해되고, 알칼리 해리성을 가져 재생(재활용)이 용이하며, 세균증식을 방지하고 가스발생을 억제하여 식품의 장기 보관을 용이하게 하는 식품 연포장재를 제조할 수 있다. According to the present invention, it has excellent oil resistance, water resistance, and thermal bonding strength, biodegrades in nature when discarded after use, and is easy to regenerate (recycle) with alkali dissociation properties, prevents bacterial growth and suppresses gas generation for long-term storage of food. It is possible to manufacture a food flexible packaging material that facilitates.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 제조방법에 의하여 제조되는 식품 연포장재는 내층 및 외층으로 구성되며, 상기 내층은 식품이나 식재료 포장을 위한 베이스 필름으로 기능하는 것으로서 수분이나 기체의 차단성이 우수한 특징을 가지며, 상기 외층은 상기 내층 일면에 합지되는 것으로서 자외선 차단 효과를 가지는 것을 특징으로 한다. The food flexible packaging material manufactured by the manufacturing method of the present invention is composed of an inner layer and an outer layer, and the inner layer functions as a base film for packaging food or food materials, and has excellent barrier properties of moisture or gas, and the outer layer is It is laminated on one surface of the inner layer and has an ultraviolet ray blocking effect.
본 발명의 실시 예에 따른 플라스틱 대체용 친환경 식품용 연포장재 제조방법은,A method for manufacturing a flexible packaging material for eco-friendly food for plastic replacement according to an embodiment of the present invention,
내층 조성물 및 외층 조성물을 제조하는 단계; 및 상기 제조된 내층 조성물 및 외층 조성물을 공압출하는 단계를 포함하고, Preparing an inner layer composition and an outer layer composition; And coextruding the prepared inner layer composition and outer layer composition,
상기 내층 조성물을 제조하는 단계는 폴리올, 디메틸올프로피온 산(dimethylol propionic acid: DMPA), N-메틸피놀리돈(NMP)용액 및 이소시아네이트를 혼합하여 프리폴리머를 제조하는 단계; N-메틸피놀리돈(NMP)용액에 희석시킨 중화제로 상기 프리폴리머를 중화시키고 상기 중화된 프리폴리머에 증류수를 투입하여 수분산 시킨 후, 사슬 연장제를 첨가하여 수분산 폴리 우레탄을 제조하는 단계; 상기 수분산 폴리 우레탄에 아크릴 모노머, 생분해 촉매제 및 개시제를 첨가한 후 교반하여 수용성 아크릴 폴리우레탄을 제조하는 단계; 및 상기 수용성 아크릴 폴리우레탄에 칼슘계 화합물, 과붕산소다 및 아세트산을 첨가하는 단계를 포함하고,The step of preparing the inner layer composition may include preparing a prepolymer by mixing polyol, dimethylol propionic acid (DMPA), N-methylpinolidone (NMP) solution, and isocyanate; Neutralizing the prepolymer with a neutralizing agent diluted in N-methylpinolidone (NMP) solution, adding distilled water to the neutralized prepolymer to disperse it, and then adding a chain extender to prepare a water-dispersible polyurethane; Adding an acrylic monomer, a biodegradation catalyst, and an initiator to the water-dispersible polyurethane, followed by stirring to prepare a water-soluble acrylic polyurethane; And adding a calcium-based compound, sodium perborate and acetic acid to the water-soluble acrylic polyurethane,
상기 외층 조성물을 제조하는 단계는 폴리올레핀, 에틸렌다이아민테트라아세트산(EDTA), 칼슘락테이트, 금속스테아린산 및 드로메트리졸을 혼합하는 단계를 포함하여 이루어진다.The step of preparing the outer layer composition includes mixing polyolefin, ethylenediaminetetraacetic acid (EDTA), calcium lactate, metal stearic acid, and drometrisol.
상기 프리폴리머를 제조하는 단계에서 폴리올은 폴리에테르 폴리올(polyether polyol)로 바람직하게는 폴리테트라메틸렌글리콜(polytetramehtyleneglycol, PTMG)이고, 프리폴리머 100 중량부에 대하여 15 ~ 25 중량부를 사용할 수 있으며, 사용량이 15 중량부 미만일 경우 응집력이 저하될 우려가 있고, 25 중량부를 초과할 경우 내가수분해성이 저하될 우려가 있다.In the step of preparing the prepolymer, the polyol is a polyether polyol, preferably polytetramehtyleneglycol (PTMG), and 15 to 25 parts by weight may be used based on 100 parts by weight of the prepolymer, and the amount used is 15 parts by weight. If it is less than parts, there is a concern that the cohesive strength may decrease, and if it exceeds 25 parts by weight, there is a concern that the hydrolysis resistance is lowered.
상기 디메틸올 프로피온산(dimethylol propionic acid, DMPA)은 프리폴리머 100 중량부에 대하여 15 ~ 25 중량부를 사용할 수 있으며, 사용량이 15 중량부 미만일 경우 수분산 안정성이 저하될 우려가 있고, 25 중량부를 초과할 경우 내가수분해성이 저하될 우려가 있다.The dimethylol propionic acid (DMPA) may be used in 15 to 25 parts by weight based on 100 parts by weight of the prepolymer, and if the amount is less than 15 parts by weight, water dispersion stability may be deteriorated, and if it exceeds 25 parts by weight There is a fear that the hydrolysis resistance may decrease.
이소시아네이트는 지방족 디이소시아네이트로써 4,4-디시클로헥산메탄디이소시아네이트(4,4'-dicyclohexylmethane diisocyanate, H12MDI), 이소포론디이소시아네이트(isophorone diisocyanate, IPDI), 1,4-시클로헥산디이소시아네이트(1,4-cyclohexylmethane diisocyanate, CHDI) 또는 방향족 디이소시아네이트로써 4,4'-디페닐메탄 디이소시아네이트(4,4'-diphenylmethane diisocyanate, MDI), 2,4- 또는 2,6-톨루엔 디이소시아네이트(2,4- or 2,6-toluene diisocyanate, TDI)중에서 선택하여 사용할 수 있으며, 바람직하게는 이소포론 디이소시아네이트(isophorone diisocyanate, IPDI)를 사용한다. IPDI는 프리폴리머 100 중량부에 대하여 50 ~ 65 중량부를 사용할 수 있으며 상기 범위를 벗어날 경우 폴리우레탄이 충분히 합성되지 못하거나 또는 수분산 안정성이 저하될 우려가 있다.Isocyanate is an aliphatic diisocyanate, 4,4-dicyclohexanemethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate, H12MDI), isophorone diisocyanate (IPDI), 1,4-cyclohexanediisocyanate (1, 4-cyclohexylmethane diisocyanate, CHDI) or 4,4'-diphenylmethane diisocyanate (MDI) as an aromatic diisocyanate, 2,4- or 2,6-toluene diisocyanate (2,4 -or 2,6-toluene diisocyanate, TDI) can be selected and used, preferably isophorone diisocyanate (IPDI). IPDI may be used in an amount of 50 to 65 parts by weight based on 100 parts by weight of the prepolymer, and if it is out of the above range, polyurethane may not be sufficiently synthesized or water dispersion stability may be deteriorated.
상기 수분산 폴리 우레탄을 제조하는 단계는 수분산 폴리우레탄 100 중량부에 대하여 상기 제조된 프리폴리머 25 ~ 45 중량부, N-메틸피놀리돈(NMP)용액 1 ~ 3 중량부에 중화제 2 ~ 6 중량부를 혼합하여 상기 제조된 프리폴리머를 중화시키는 단계; 수분산 폴리우레탄 100 중량부에 대하여 증류수 40 ~ 60 중량부를 적하시켜주며 교반하는 단계;및 수분산 폴리우레탄 100 중량부에 대하여 사슬 연장제 5 ~ 15 중량부를 넣고 교반하는 단계를 포함하는 것을 특징으로 한다.The step of preparing the water-dispersible polyurethane includes 25 to 45 parts by weight of the prepared prepolymer and 1 to 3 parts by weight of the N-methylpinolidone (NMP) solution based on 100 parts by weight of the water-dispersion polyurethane. Neutralizing the prepared prepolymer by mixing parts; A step of stirring while dropping 40 to 60 parts by weight of distilled water based on 100 parts by weight of the water-dispersible polyurethane; And adding 5 to 15 parts by weight of a chain extender based on 100 parts by weight of the water-dispersed polyurethane and stirring. do.
상기 중화제는 트리에틸아민(triethylamine, TEA), 트리메틸아민(trimethylamine, TMA) 또는 수산화나트륨(sodium hydroxide, NaOH) 중에서 선택하여 사용할 수 있으며, 바람직하게는 트리에틸아민(triethylamine, TEA)을 사용하고, 사용량이 2 중량부 미만일 경우 수분산 안정성이 저하될 우려가 있고, 6 중량부를 초과할 경우 저장 안정성이 저하될 우려가 있고, 부가반응을 일으켜 물성이 저하될 우려가 있다.The neutralizing agent may be used by selecting from triethylamine (TEA), trimethylamine (TMA) or sodium hydroxide (NaOH), preferably triethylamine (TEA), If the amount is less than 2 parts by weight, the water dispersion stability may be deteriorated, and if it exceeds 6 parts by weight, the storage stability may be deteriorated, and there is a fear that physical properties may deteriorate due to an addition reaction.
상기 사슬연장제로는 에틸렌디아민(ethylene diamine, EDA)을 사용하며, 사용량이 5 중량부 미만일 경우 사슬연장 효과가 미비해질 우려가 있고, 15 중량부를 초과할 경우 저장 안정성이 저하될 우려가 있다.Ethylene diamine (EDA) is used as the chain extender, and if the amount is less than 5 parts by weight, the chain extension effect may be insufficient, and if it exceeds 15 parts by weight, storage stability may be deteriorated.
상기 수용성 아크릴 폴리우레탄을 제조하는 단계는 수용성 아크릴 폴리우레탄 100 중량부에 대하여 상기 수분산 폴리 우레탄 70 ~ 85 중량부, 아크릴 모노머 10 ~ 25 중량부, 생분해촉매제 1 ~ 3 중량부 및 개시제 1 ~ 3 중량부를 첨가하여 교반하는 것을 특징으로 한다.The step of preparing the water-soluble acrylic polyurethane includes 70 to 85 parts by weight of the water-dispersible polyurethane, 10 to 25 parts by weight of an acrylic monomer, 1 to 3 parts by weight of a biodegradation catalyst, and 1 to 3 parts by weight of an initiator based on 100 parts by weight of the water-soluble acrylic polyurethane. It is characterized by stirring by adding parts by weight.
상기 아크릴 모노머는 메틸메타크릴레이트, 메타아크릴레이트, 아크릴로니트릴, 에틸아크릴레이트, 에틸메타크릴레이트, 부틸메타크릴레이트, 시클로헥실 메타크릴레이트, 메타크릴로니트릴, 비닐아세테이트 중에서 선택하여 사용할 수 있으며, 바람직하게는 메틸메타크릴레이트(methylmetaacrylate, MMA)를 사용하고, 사용량이 10 중량부 미만일 경우 내구성과 내수성 향상효과가 미비해질 우려가 있으며, 25 중량부를 초과할 경우 저장 안정성이 저하될 우려가 있다.The acrylic monomer may be used by selecting from methyl methacrylate, methacrylate, acrylonitrile, ethyl acrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, methacrylonitrile, and vinyl acetate. , Preferably, methyl methacrylate (MMA) is used, and if the amount is less than 10 parts by weight, the durability and water resistance improvement effect may be insufficient, and if it exceeds 25 parts by weight, storage stability may be deteriorated. .
상기 생분해 촉매제는 아크릴 폴리우레탄을 광산화 반응으로 저분자화 및 생분해 시키는 기능을 수행하는데, 아세틸카바메이트금속염인으로 페릭아세틸카바메이트, 알미늄아세틸카바메이트, 망간아세틸카바메이트 또는 그 혼합물이 사용될 수 있는데 바람직하게는 1 ~ 3 중량부 이상을 사용하는 것이 바람직하다. 1 중량부 미만으로 사용하는 경우 최종 생분해 기간이 길어지는 단점이 있다. 또한 3 중량부를 초과할 경우 효과는 우수하지만 가격이 상승하는 단점이 있다The biodegradation catalyst performs a function of reducing the molecular weight and biodegradation of acrylic polyurethane through photooxidation reaction, and ferric acetyl carbamate, aluminum acetyl carbamate, manganese acetyl carbamate, or a mixture thereof may be used as the acetyl carbamate metal salt. It is preferable to use 1 to 3 parts by weight or more. When used in less than 1 part by weight, there is a disadvantage that the final biodegradation period is prolonged. In addition, if it exceeds 3 parts by weight, the effect is excellent, but there is a disadvantage of increasing the price.
중합을 위한 개시제가 1 ~ 3 중량부 사용되며, 개시제로는 는 AIBN(2,2'-azo-bis(isobutyronitrile)) 또는 ABN(2,2'-azo-bis(2-methylbutyronitrile)) 등이 사용되며, 바람직하게는 AIBM을 사용한다. 한편, 상기 개시제의 함량이 1 중량부 미만일 경우 개시제의 효율이 저하하여 반응이 쉽게 진행되지 못하고, 3 중량부를 초과 사용하면 순간적인 발열반응에 의하여 겔이 생성되는 문제점이 있다.1 to 3 parts by weight of an initiator for polymerization is used, and the initiator is AIBN (2,2'-azo-bis (isobutyronitrile)) or ABN (2,2'-azo-bis (2-methylbutyronitrile)). Used, preferably AIBM. On the other hand, when the content of the initiator is less than 1 part by weight, the efficiency of the initiator decreases and the reaction does not proceed easily, and when the amount of the initiator exceeds 3 parts by weight, there is a problem in that a gel is generated due to an instantaneous exothermic reaction.
상기 수용성 아크릴 폴리우레탄에 칼슘계 화합물, 과붕산소다 및 아세트산을 첨가하는 단계에서 상기 칼슘계 화합물은 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘을 포함하며, 상기 단계는 상기 수용성 아크릴 폴리우레탄 92 ~ 96 중량부에 상기 칼슘계 혼합 화합물 2 ~ 6 중량부, 과붕산소다 1 ~ 2 중량부 및 아세트산은 1 ~ 2 중량부를 첨가하는 것을 특징으로 한다.In the step of adding a calcium-based compound, sodium perborate, and acetic acid to the water-soluble acrylic polyurethane, the calcium-based compound includes calcium ferrocyanide, calcium sorbate and calcium casein, and the step includes 92 to 96 weight of the water-soluble acrylic polyurethane It is characterized in that 2 to 6 parts by weight of the calcium-based mixed compound, 1 to 2 parts by weight of sodium perborate, and 1 to 2 parts by weight of acetic acid are added to the part.
일반적으로 포장재 제조방법에서 무기 안료는 제제화 비용을 감소시킬 뿐만 아니라 포장재의 제조 또는 저장 중에, 또는 포장재에 대한 코팅 제제의 도포 중에 또는 후에 코팅 제제의 일정한 특성을 더욱 더 개선시키는 데 널리 사용되고 있으며, 상기 무기 안료 중 가장 많이 사용되는 것이 클레이와 탄산칼슘이다. 클레이는 판산형 구조로서 높은 백지광택 및 인쇄광택을 얻을 수 있다는 장점을 가지는 반면 유동성이 떨어지고 바인더 요구량이 많아진다는 단점을 가지고 있고, 탄산칼슘의 경우, 유동성, 접착력, 잉크수리성, 종이밝기, 불투명성 등에 유리한 반면 칼슘 양이온에 대한 포장재 조성물의 화학적 안정성이 더욱 크게 요구된다는 문제점이 있다.In general, in the packaging material manufacturing method, inorganic pigments are widely used not only to reduce the cost of formulation, but also to further improve certain properties of the coating formulation during manufacture or storage of the packaging material, or during or after application of the coating agent to the packaging material. Clay and calcium carbonate are the most commonly used inorganic pigments. Clay has the advantage of obtaining high white paper gloss and printing gloss as a plate-mounted structure, but has the disadvantage of low fluidity and increased binder demand.In the case of calcium carbonate, fluidity, adhesion, ink repair, paper brightness, and opacity On the other hand, there is a problem in that the chemical stability of the packaging material composition against calcium cations is further required.
따라서 본 발명자는 다양한 칼슘 화합물 중에서 안전하고 연포장재의 물리적 화학적 성질을 향상시킬 수 있는 칼슘계 화합물을 찾고자 하였으며, 비교실험을 통하여 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘이 탄산칼슘에 비하여 연포장재의 내유도, 내수도, 투기도, 투습도 및 열실링성이 향상되는 것을 발견하였고, 나아가 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘을 동일비율로 혼합하여 첨가한 연포장재의 경우 각각의 칼슘계 화합물을 첨가한 연포장재에 비하여 우수한 물리적 특성을 갖는 것을 확인하였다. Therefore, the present inventors have tried to find a calcium compound that is safe among various calcium compounds and can improve the physical and chemical properties of the flexible packaging material, and through a comparative experiment, calcium ferrocyanide, calcium sorbate, and calcium casein are contained in the soft packaging material compared to calcium carbonate. It was found that induction, water resistance, air permeability, moisture permeability, and heat-sealing properties were improved, and in the case of the flexible packaging material added by mixing calcium ferrocyanide, calcium sorbate and calcium casein at the same ratio, each calcium-based compound was added. It was confirmed that it has superior physical properties compared to the flexible packaging material.
상기 칼슘 화합물은 2 ~ 6 중량부 포함되는 것이 바람직하고, 2 중량부 미만으로 사용되는 경우 첨가 효과가 미약하며, 6 중량부를 초과할 경우 연포장재의 물성이 저하되는 단점이 있다. The calcium compound is preferably contained in 2 to 6 parts by weight, and when used in an amount of less than 2 parts by weight, the addition effect is weak, and when it exceeds 6 parts by weight, the physical properties of the flexible packaging material are deteriorated.
상기 과붕산소다(Sodium perborate, NaBO3)는 1 ~ 2 중량부 포함되는 것이 바람직하다. 과붕산소다의 함량이 1 중량부 미만이면 최종 연포장재의 내유성 및 방수성 증대, 점성 상승효과가 소망하는 수준에 이르지 못할 수 있으며, 2 중량부를 초과하면 다른 성분들의 상대적 함량 감소에 따른 불이익이 발생할 수 있고 연포장재 내층 조성물의 점도가 지나치게 상승되어 작업성이 저하될 수 있다.The sodium perborate (Sodium perborate, NaBO 3 ) is preferably contained in 1 to 2 parts by weight. If the content of sodium perborate is less than 1 part by weight, the oil resistance and waterproofing properties of the final flexible packaging material may not be increased, and the viscosity synergistic effect may not reach the desired level.If it exceeds 2 parts by weight, disadvantages may occur due to the decrease in the relative content of other ingredients. In addition, the viscosity of the inner layer composition of the flexible packaging material may be excessively increased, and thus workability may decrease.
또한 본 발명자는 상기 칼슘 양이온에 의하여 연포장재의 물성이 저하되는 것을 방지하기 위하여 상기 칼슘계 혼합 화합물 및 과붕산소다와 함께 아세트산을 더 첨가할 수 있고, 상기 아세트산은 1 ~ 2 중량부를 첨가하는 것을 특징으로 한다. In addition, the present inventors may further add acetic acid together with the calcium-based mixed compound and sodium perborate in order to prevent the physical properties of the flexible packaging material from deteriorating by the calcium cation, and adding 1 to 2 parts by weight of the acetic acid. It is characterized.
상기 첨가된 아세트산은 해리된 칼슘 양이온과 이온 결합을 통하여 아세트산칼슘을 형성할 수 있으며, 본 발명자는 아세트산을 첨가하는 경우 연포장재의 내수성, 내유성 및 열실링성이 조금 더 향상되는 것을 확인하였다.The added acetic acid can form calcium acetate through ionic bonding with the dissociated calcium cations, and the present inventors have confirmed that the water resistance, oil resistance, and heat sealing properties of the flexible packaging material are slightly improved when acetic acid is added.
상기 외층 조성물은 폴리올레핀, 에틸렌다이아민테트라아세트산(EDTA), 칼슘락테이트, 금속스테아린산 및 드로메트리졸을 혼합하여 제조될 수 있다. The outer layer composition may be prepared by mixing polyolefin, ethylenediaminetetraacetic acid (EDTA), calcium lactate, metal stearic acid, and drometrisol.
상기 외층을 제조하기 위한 조성물은 폴리올레핀 수지 75 ~ 95 중량부, 에틸렌다이아민테트라아세트산(EDTA) 1 ~ 10 중량부, 칼슘락테이트 1 ~ 10 중량부, 금속스테아린산 1 ~ 10 중량부 및 드로메트리졸 0.1 ~ 1 중량부를 포함할 수 있으며, 바람직하게는 폴리올레핀 수지 93 중량부, 에틸렌다이아민테트라아세트산(EDTA) 2 중량부, 칼슘락테이트 2 중량부, 금속스테아린산 2 중량부, 드로메트리졸 1 중량부를 포함할 수 있다.The composition for preparing the outer layer is 75 to 95 parts by weight of polyolefin resin, 1 to 10 parts by weight of ethylenediaminetetraacetic acid (EDTA), 1 to 10 parts by weight of calcium lactate, 1 to 10 parts by weight of metal stearic acid, and drometrisol 0.1 to 1 parts by weight, preferably 93 parts by weight of polyolefin resin, 2 parts by weight of ethylenediaminetetraacetic acid (EDTA), 2 parts by weight of calcium lactate, 2 parts by weight of metal stearic acid, 1 part by weight of drometrisol Can include.
상기 에틸렌다이아민테트라아세트산(EDTA)는 변색 방지제로 사용되는데, 금속이온의 결합을 방지하여 이로 인한 산 패, 변질, 변색을 방지하고, 침전물이 생기는 것을 방지하며, 상기 에틸렌다이아민테트라아세트산은 1 ~ 10 중량부 포함될 수 있다. The ethylenediaminetetraacetic acid (EDTA) is used as a discoloration inhibitor, and prevents the binding of metal ions, thereby preventing acid damage, deterioration, and discoloration, and preventing the formation of precipitates, and the ethylenediaminetetraacetic acid is 1 It may contain ~ 10 parts by weight.
상기 칼슘락테이트(calcium lactate)는 칼슘젖산염으로 불리우며, 세균증식을 방지하고 가스발생을 억제하여 식품의 장기 보관을 용이하게 하고, 포장 제품의 산도를 조절할 수 있는 기능을 하며, 상기 칼슘락테이트는 1 ~ 10 중량부 포함될 수 있다.The calcium lactate is called calcium lactate, and functions to facilitate long-term storage of food by preventing bacterial growth and suppressing gas generation, and to control the acidity of packaging products, and the calcium lactate is 1 to 10 parts by weight may be included.
상기 금속스테아린산은 스테아린산철(iron(Ⅲ) stearate), 하이드록시스테아린산철(ferric hydroxystearate) 또는 스테아린산구리(copper(Ⅱ) stearate) 중 하나 이상을 포함할 수 있고, 바람직하게는 스테아린산철(iron(Ⅲ) stearate)이며, 상기 금속스테아린산은 1 ~ 10 중량부 포함될 수 있다.The metal stearic acid may include at least one of iron (III) stearate, ferric hydroxystearate, or copper stearate (copper (II) stearate), preferably iron (III) stearate. ) stearate), and the metal stearic acid may be included in 1 to 10 parts by weight.
상기 금속스테아린산은 암모니아 및 아민류뿐만 아니라 황산 수소염, 메르캅탄 등의 악취에 대해 우수한 탈취 효과를 나타낸다. 스테아린산은 열적 안정성이 우수하여 고온의 열처리 공정이 수반되는 플라스틱, 우레탄, 고무 등의 제조공정에서도 탈취 효과를 지속적으로 유지할 수 있는 장점이 있다. The metal stearic acid exhibits excellent deodorizing effect against odors such as hydrogen sulfate and mercaptan, as well as ammonia and amines. Stearic acid is excellent in thermal stability and has the advantage of being able to continuously maintain the deodorizing effect even in the manufacturing process of plastic, urethane, rubber, etc., which is accompanied by a high-temperature heat treatment process.
금속스테아린산에 포함된 금속이온은 악취원인 물질과 이온 결합하여 착이온을 형성하는 것이면 어느 것이라도 좋으나, 본 발명에서는 이온화경향이 큰 금속 이온 중에서 Fe2+ 또는 Cu2+가 바람직하며, 상기 금속 이온은 악취의 대표적인 원인물질이 되는 트리메틸아민(TMA), NH3, H2S, 메틸메르캡탄 등과 착이온을 형성하여 공기 중의 악취를 제거하는 역할을 한다.Metal ions contained in metal stearic acid may be any one that forms complex ions by ionic bonding with a substance that is a source of odor, but in the present invention, Fe 2+ or Cu 2+ is preferable among metal ions having a large ionization tendency, and the metal ions Silver plays a role of removing odors from the air by forming complex ions such as trimethylamine (TMA), NH 3 , H 2 S, and methyl mercaptan, which are representative sources of odor.
드로메트리졸은 2-(벤조트리아졸-2-일)-4-메틸페놀로 하기의 [화학식 1]로 표시되며, 상기 드로메트리졸은 자외선을 차단하는 효과를 가지며 바람직하게는 0.1 ~ 1 중량부가 포함될 수 있다. Drometrisol is represented by the following [Chemical Formula 1] as 2-(benzotriazol-2-yl)-4-methylphenol, and the dromethrizol has an effect of blocking ultraviolet rays and is preferably 0.1 to 1 weight Additional may be included.
[화학식 1][Formula 1]
이하, 실시 예 및 실험 예를 통해 본 발명을 보다 구체적으로 설명한다. 그러나 이들 예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 이들 예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples and experimental examples. However, these examples are only for helping the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
<시약의 준비><Preparation of reagents>
수용성 폴리우레탄 수분산체의 제조시 사용된 polyol은 ether형의 폴리테트라메틸렌글리콜(polytetramehtyleneglycol, PTMG)(Mw=1,800 g/mole)로 1mmHg, 60℃에서 약 10시간 이상 진공건조를 하여 수분을 제거하여 사용하였다. 우레탄 내 친수성 관능기를 도입하기 위하여 디메틸올프로피온 산(dimethylol propionic acid: DMPA)을 추가 정체 없이 그대로 사용하였다. 중화제로는 트리에틸아민(triethylamine, TEA)을 사용하였으며, 사슬연장제로는 에틸렌디아민(ethylenediamine, EDA)을 사용하였다.The polyol used in the preparation of the water-soluble polyurethane aqueous dispersion is 1mmHg with polytetramehtyleneglycol (PTMG) (Mw=1,800 g/mole) of ether type and vacuum drying at 60℃ for about 10 hours or more to remove moisture. Was used. In order to introduce a hydrophilic functional group in the urethane, dimethylol propionic acid (DMPA) was used as it was without further stasis. Triethylamine (TEA) was used as the neutralizing agent, and ethylenediamine (EDA) was used as the chain extender.
아크릴-폴리우레탄 하이브리드 제조시 사용된 아크릴 단량체는 메틸메타크릴레이트(methyl metaacrylate, MMA)를 사용하였으며, 생분해 촉매체로는 페릭아세틸카바메이트를 사용하였고, 개시제로는 아조비스이소부티로니트릴(2,2'-azobis isobutyronitrile, AIBN)을 사용하였다. 기타 용매로는 n-메틸-2-피롤리돈(n-methyl-2-pyrrolidinone, NMP)를 사용하였다The acrylic monomer used in the manufacture of the acrylic-polyurethane hybrid was methyl methacrylate (MMA), ferric acetyl carbamate was used as the biodegradation catalyst, and azobisisobutyronitrile (2, 2'-azobis isobutyronitrile, AIBN) was used. As other solvent, n-methyl-2-pyrrolidinone (NMP) was used.
<실시예 1> <Example 1>
(1) 내층 조성물의 제조(1) Preparation of inner layer composition
먼저, 수용성 폴리우레탄 수분산체(Waterborne Polyurethane Dispersions; WPUDs)를 합성하였다. 이는 prepolymer를 mixing process에서 PTMG와 DMPA를 먼저, 반응시키고 이후 isocyanate를 첨가하는 'two shot process'방식으로 생산한다. 교반기의 두 개의 입구를 질소로 퍼지(purge)시키고 다른 한쪽 입구를 막고 진행하다 증류수를 적하시킨다.First, Waterborne Polyurethane Dispersions (WPUDs) were synthesized. This is produced by a'two shot process' method of reacting prepolymer with PTMG and DMPA first in the mixing process and then adding isocyanate. The two inlets of the stirrer are purged with nitrogen, and the other inlet is blocked and distilled water is added dropwise while proceeding.
1) 이소시아네이트기(NCO)를 갖는 프리폴리머(NCO-prepolymer)의 제조1) Preparation of NCO-prepolymer having an isocyanate group (NCO)
먼저, 교반기에 PTMG를 넣고 진공 오븐(100℃)에서 그대로 녹인 후 이를 oil bath에 설치한다. 교반기의 임펠라 속도를 100 rpm으로 고정하고 30분간 교반기 내부의 공기를 질소로 치환하여 반응을 시작한다. 그런 다음 미리 진공으로 건조한 DMPA를 반응 조건의 변화를 주지 않고 교반기에 넣어 PTMG에 녹인다.First, put PTMG in a stirrer, melt it in a vacuum oven (100°C), and install it in an oil bath. The impeller speed of the stirrer is fixed at 100 rpm and the air inside the stirrer is replaced with nitrogen for 30 minutes to start the reaction. Then, DMPA dried in a vacuum in advance is put into a stirrer without changing the reaction conditions and dissolved in PTMG.
이후 1시간 정도를 교반한 후 NMP와 IPDI를 넣는다. 그대로 1시간 정도를 더 교반한 후 온도를 50℃로 낮추고, 이후 1시간 더 교반하여 이소시아네이트기(NCO)를 갖는 프리폴리머(NCO-prepolymer)를 얻는다.After stirring for about 1 hour, NMP and IPDI are added. After stirring for an additional hour as it is, the temperature is lowered to 50° C., and then stirred for an additional hour to obtain a NCO-prepolymer having an isocyanate group (NCO).
2) 수분산 폴리우레탄 분산체 제조2) Preparation of water-dispersible polyurethane dispersion
상기 제조된 NCO-prepolymer에 NMP 용액으로 희석시킨 중화제 TEA를 넣고 중화시킨 후 일정량의 증류수를 일정한 속도로 적하시켜주며 교반속도를 300rpm으로 상승시킨다. 이후 EDA를 교반기 넣고 그 상태로 총 3시간 정도 교반을 진행하여 수분산 폴리우레탄 분산체를 얻는다.A neutralizing agent TEA diluted with an NMP solution is added to the prepared NCO-prepolymer and neutralized. Then, a certain amount of distilled water is added dropwise at a constant speed, and the stirring speed is increased to 300 rpm. Thereafter, EDA is put in a stirrer and stirring is performed for a total of 3 hours in that state to obtain a water-dispersible polyurethane dispersion.
3) 아크릴-우레탄 하이브리드 분산체 제조3) Preparation of acrylic-urethane hybrid dispersion
위의 방식으로 제조된 수용성 폴리우레탄 분산체를 준비한다. MMA와 상기 수용성 폴리우레탄 분산체를 교반기의 임펠라 속도를 1500 rpm의 고속으로 30분 정도 안정화를 시킨 후 oil bath에 설치하여 30분간 질소로 치환한다. 교반기 내부가 질소 하의 조건이 되었을 때 MMA에 AIBN 및 페릭아세틸카바메이트를 녹인 용액을 첨가하고 300 rpm으로 1시간 정도 교반하여 액상의 수용성 아크릴-우레탄 하이브리드 분산체(Waterborne Acrylic-Urethane hybrid Dispersions; WAUDs)를 제조한다.A water-soluble polyurethane dispersion prepared in the above manner is prepared. After stabilizing the MMA and the water-soluble polyurethane dispersion at a high speed of 1500 rpm for about 30 minutes, the impeller speed of the stirrer was installed in an oil bath and replaced with nitrogen for 30 minutes. When the inside of the stirrer is under nitrogen, a solution in which AIBN and ferric acetyl carbamate are dissolved in MMA is added and stirred at 300 rpm for about 1 hour to form a liquid water-soluble acrylic-urethane hybrid dispersion (WAUDs). To manufacture.
4) 칼슘계 화합물, 과붕산소다 및 아세트산 첨가4) Addition of calcium compound, sodium perborate and acetic acid
상기 제조한 액상의 수용성 아크릴-우레탄 하이브리드 분산체 용액 94 wt%에 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘을 각각 1 wt%, 과붕산소다 1.5 wt%, 아세트산 1.5 wt%를 혼합하여 내층 조성물을 제조하였다. An inner layer composition was prepared by mixing 1 wt% of calcium ferrocyanide, calcium sorbate, and calcium casein, respectively, 1.5 wt% of sodium perborate, and 1.5 wt% of acetic acid to 94 wt% of the prepared liquid aqueous acrylic-urethane hybrid dispersion solution. I did.
(2) 외층 조성물의 제조 및 연포장재 제조(2) Preparation of outer layer composition and manufacture of flexible packaging material
폴리올레핀 수지 93 wt%, 에틸렌다이아민테트라아세트산(EDTA) 2 wt%, 칼슘락테이트 2 wt%, 스테아린산철(iron(Ⅲ) stearate) 2 wt%, 드로메트리졸 1 wt%를 혼합하여 외층 조성물을 제조하였다. 93 wt% of polyolefin resin, 2 wt% of ethylenediaminetetraacetic acid (EDTA), 2 wt% of calcium lactate, 2 wt% of iron (III) stearate, and 1 wt% of drometrisol were mixed to prepare an outer layer composition. Was prepared.
이후 상기 내층 및 외층 조성물을 하나의 공압출용 다이를 통해 2층 구조의 공압출 다층필름 형태로 공압출한 다음, 상기 공압출된 다층필름을 물로 냉각시킨 후 압착롤러로 압착하여 식품 연포장재를 제조하였다. Thereafter, the inner layer and outer layer compositions are coextruded in the form of a two-layered coextrusion multilayer film through one coextrusion die, and then the coextruded multilayer film is cooled with water and then compressed with a pressing roller to form a food flexible packaging material. Was prepared.
<비교예 1><Comparative Example 1>
실시예 1에서 상기 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘 대신에 상기 제조한 액상의 수용성 아크릴-우레탄 하이브리드 분산체 용액 3 wt%를 첨가하여, 실시예 1과 동일한 방법으로 식품 연포장재를 제조하였다.In Example 1, in place of the calcium ferrocyanide, calcium sorbate, and calcium casein, 3 wt% of the prepared liquid water-soluble acrylic-urethane hybrid dispersion solution was added to prepare a food flexible packaging material in the same manner as in Example 1.
<비교예 2><Comparative Example 2>
실시예 1에서 상기 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘 대신에 탄산칼슘 3 wt%를 첨가하여, 실시예 1과 동일한 방법으로 식품 연포장재를 제조하였다.In Example 1, 3 wt% of calcium carbonate was added instead of calcium ferrocyanide, calcium sorbate, and calcium casein to prepare a food flexible packaging material in the same manner as in Example 1.
<비교예 3><Comparative Example 3>
실시예 1에서 과붕산소다 및 아세트산 대신에 액상의 수용성 아크릴-우레탄 하이브리드 분산체 용액 3 wt%를 첨가하여, 실시예 1과 동일한 방법으로 식품 연포장재를 제조하였다.In Example 1, 3 wt% of a liquid water-soluble acrylic-urethane hybrid dispersion solution was added instead of sodium perborate and acetic acid to prepare a food flexible packaging material in the same manner as in Example 1.
<비교예 4><Comparative Example 4>
실시예 1에서 드로메트리졸 1 wt% 대신에 폴리올레핀 1wt%를 첨가하여 실시예 1과 동일한 방법으로 식품 연포장재를 제조하였다. In Example 1, instead of 1 wt% drometrisol, 1 wt% of polyolefin was added to prepare a food flexible packaging material in the same manner as in Example 1.
<비교예 5><Comparative Example 5>
실시예 1에서 드로메트리졸 1 wt% 대신에 호모살레이트 1wt%를 첨가하여 실시예 1과 동일한 방법으로 식품 연포장재를 제조하였다. 상기 호모살레이트는 자외선 흡수제로 알려져 있는 물질이다. In Example 1, 1 wt% of homosalate was added instead of 1 wt% of drometrisol to prepare a food flexible packaging material in the same manner as in Example 1. The homosalate is a material known as an ultraviolet absorber.
<실험예 1><Experimental Example 1>
상기 제조된 식품 연포장재를 동일한 조건하에서 물성을 시험하여, 그 결과를 표 4로 정리하였다.The prepared food flexible packaging material was tested for physical properties under the same conditions, and the results are summarized in Table 4.
투습도: ◎< 30mg/m2, ○30~50 mg/m2, △50~200mg/m2, ×> 200mg/m2
투기도: ◎< 5cc/m2, ○5~30cc/m2, △30~60cc/m2, ×> 60cc/m2
열접착강도: ◎> 1,200 g/37mm, ○900~1,200 g/37mm, △800~900 g/37mm, ×< 800 g/37mmLegend) ◎Excellent, ○Excellent, △Medium, ×Insufficient
Water vapor transmission rate: ◎< 30mg/m 2 , ○30~50 mg/m 2 , △50~200mg/m 2 , ×> 200mg/m 2
Air permeability: ◎< 5cc/m 2 , ○5~30cc/m 2 , △30~60cc/m 2 , ×> 60cc/m 2
Thermal bonding strength: ◎> 1,200 g/37mm, ○900~1,200 g/37mm, △800~900 g/37mm, ×< 800 g/37mm
<시험방법><Test method>
내유도: KS M 7124:2008Induction resistance: KS M 7124:2008
내수도: KS M 7025:2012:12Domestic water supply: KS M 7025: 2012:12
투기도: KS M 7020:2006:11Speculative prayer: KS M 7020: 2006:11
투습도(중량법): KS M ISO 2528Water vapor transmission rate (gravity method): KS M ISO 2528
열 접착 강도: 자체시험 Thermal adhesion strength: self test
본 발명에 의해 제조된 식품 연포장재의 내유성은 KS M 7124:2008의 방법으로 시험하고, 내수성은 KS M 7025:2012:12의 방법으로 시험하고, 투기성은 KS M 7020:2006:11의 방법으로 시험하고, 투습성은 KS M ISO 2528의 방법으로 시험하고, 열접착(열실링)강도은 자체시험을 통해서 시험하였다. The oil resistance of the food flexible packaging material produced by the present invention was tested by the method of KS M 7124:2008, the water resistance was tested by the method of KS M 7025:2012:12, and the air permeability was tested by the method of KS M 7020:2006:11. It was tested, and the moisture permeability was tested by the method of KS M ISO 2528, and the thermal bonding (heat sealing) strength was tested through a self-test.
표 4를 참고하면, 페로시안화칼슘, 소르빈산칼슘, 카제인칼슘을 첨가하지 않은 비교예 1의 경우에 실시예 1에 비하여 열접착강도를 제외하고 연포장재의 물성이 저하되는 것을 확인할 수 있었으며, 특히 내수도와 투습도가 실시예 1에 비하여 현저하게 저하되는 것을 확인할 수 있었다. Referring to Table 4, in the case of Comparative Example 1 in which calcium ferrocyanide, calcium sorbate, and calcium casein were not added, it was confirmed that the physical properties of the flexible packaging material were deteriorated, except for the thermal adhesive strength, compared to Example 1, and in particular, water resistance It was confirmed that the degree and moisture permeability were significantly lowered compared to Example 1.
페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘 대신에 탄산칼슘을 첨가한 비교예 2의 경우 비교예 1의 비하여 내수도와 투습도가 약간 향상되는 것을 확인할 수 있었으나 실시예 1과 비교하였을 때는 저하된 내수도와 투습도를 나타내었다. In the case of Comparative Example 2 in which calcium carbonate was added instead of calcium ferrocyanide, calcium sorbate, and calcium caseinate, it was confirmed that the water resistance and moisture permeability were slightly improved compared to that of Comparative Example 1, but when compared to Example 1, the water resistance and moisture permeability were decreased. Indicated.
과붕산소다 및 아세트산을 제외하여 식품 연포장재를 제조한 비교예 3의 경우 실시예 1에 비하여 내수도, 투습도가 약간 저하되었으며, 또한 열접착강도가 함께 저하되는 것을 확인할 수 있었다. In the case of Comparative Example 3, in which a food flexible packaging material was prepared by excluding sodium perborate and acetic acid, it was confirmed that the water resistance and moisture permeability were slightly lowered compared to Example 1, and the thermal adhesive strength was also lowered.
실시예 1에서 드로메트리졸을 제외하고 자외선 흡수제로 알려진 호모살레이트를 첨가한 비교예 5의 경우 내유도, 내수도, 투기도 및 투습도는 실시예 1과 유사한 특징을 나타내었으나, 열접착강도가 현저하게 저하되는 것을 확인할 수 있었다. In the case of Comparative Example 5 in which homosalate known as an ultraviolet absorber was added excluding drometrisol in Example 1, the oil resistance, water resistance, air permeability and moisture permeability were similar to those of Example 1, but the thermal adhesive strength was It was confirmed that the remarkably decreased.
또한, 본 발명에 의해 제조된 식품 연포장재의 친환경성은 한국 환경부 환경표지 대상제품 및 인증기준(EL 103:2007)의 알칼리 해리성 및 분산성 시험에서 불순물이 포함되어 있지 않았으며, 점착성이 나타나지 않았다. 따라서, 재사용이 가능한 수준을 달성하였다.In addition, the eco-friendliness of the food flexible packaging material manufactured according to the present invention did not contain impurities and did not show adhesiveness in the alkali dissociation and dispersibility test of the product subject to environmental labeling and certification standards (EL 103:2007) of the Ministry of Environment of Korea. . Therefore, a level of reusability has been achieved.
아울러, 본 발명에 의해 제조된 식품 연포장재는 식품안전처 식품공전 기구 및 용기포장에 대한 기준 및 규격의 가공기재의 시험규격에 부합하여 식품 포장지로 안전하게 사용할 수 있다.In addition, the food flexible packaging material manufactured according to the present invention can be safely used as a food packaging paper in accordance with the test standards of the processing materials of the standards and standards for the food code mechanism and container packaging of the Ministry of Food Safety and Security.
<실험예 2><Experimental Example 2>
상기 실시예 1 및 비교예 1 내지 5에서 제조된 식품 연포장재의 자외선 투과율을 하기의 방법으로 측정하고, 그 결과를 하기의 표 5에 나타내었다.The ultraviolet transmittance of the food flexible packaging materials prepared in Example 1 and Comparative Examples 1 to 5 was measured by the following method, and the results are shown in Table 5 below.
* 자외선 투과율: Gretagmacbeth사의 Coloreye 7000A에 의거하여 360 nm의 파장을 갖는 자외선에 대한 투과율을 700 nm의 파장을 갖는 가시광선에 대한 투과율로 나눈 값으로 나타내었다.* Ultraviolet transmittance: According to Gretagmacbeth's Coloreye 7000A, the transmittance of ultraviolet rays having a wavelength of 360 nm is divided by the transmittance of visible rays having a wavelength of 700 nm.
투과율ultraviolet ray
Transmittance
상기 표 5를 참조하면, 드로메트리졸을 첨가하지 않은 비교예 4의 경우 자외선 투과율이 가장 낮은 것을 확인할 수 있었으며, 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘을 첨가하지 않은 비교예 1, 칼슘화합물 대신에 탄산칼슘을 첨가한 비교예 2, 과붕산소다 및 아세트산을 첨가하지 않은 비교예 3의 경우 실시예 1 보다 자외선 투과율이 낮은 것을 확인할 수 있었다. Referring to Table 5, in the case of Comparative Example 4 in which drometrisol was not added, it was confirmed that the UV transmittance was the lowest, and in Comparative Example 1 in which calcium ferrocyanide, calcium sorbate, and calcium casein were not added, instead of a calcium compound. In Comparative Example 2 to which calcium carbonate was added and Comparative Example 3 to which sodium perborate and acetic acid were not added, it was confirmed that the UV transmittance was lower than that of Example 1.
비교예 1과 비교예 2에 비하여 비교예 3의 자외선 투과율이 향상되었는데 이는 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘이 미미하게 자외선 차단 효과를 나타내는 것으로 생각된다. Compared to Comparative Example 1 and Comparative Example 2, the UV transmittance of Comparative Example 3 was improved, which is thought to show a slight UV blocking effect of calcium ferrocyanide, calcium sorbate and calcium caseinate.
또한 드로메트리졸을 대신하여 호모살레이트를 첨가한 비교예 5의 경우 실시예 1에 비하여 자외선 자단 효과가 떨어지는 것을 확인할 수 있었다. In addition, in the case of Comparative Example 5, in which homosalate was added instead of dromethrizol, it was confirmed that the ultraviolet rosewood effect was inferior compared to Example 1.
이상, 본 발명에서 설명한 것은 우수한 내유성, 내수성, 방습성 및 열접착강도를 갖는 식품 연포장재 제조방법을 위한 실시예에 불과한 것으로, 본 발명은 상기 실시예에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있으며, 단지 본 실시예는 본 발명의 개시가 완전하도록 하고, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다.As described above, what has been described in the present invention is merely an example for a method for manufacturing a food flexible packaging material having excellent oil resistance, water resistance, moisture resistance and thermal bonding strength, and the present invention is not limited to the above embodiment, but may be implemented in a variety of different forms. The present embodiment is provided only to complete the disclosure of the present invention, and to fully inform the scope of the invention to those of ordinary skill in the art to which the present invention belongs, and the present invention is the scope of the claims. Is just defined by
Claims (8)
상기 제조된 내층 조성물 및 외층 조성물을 공압출하는 단계를 포함하고,
상기 내층 조성물을 제조하는 단계는 폴리올, 디메틸올프로피온 산(dimethylol propionic acid: DMPA), N-메틸피놀리돈(NMP)용액 및 이소시아네이트를 혼합하여 프리폴리머를 제조하는 단계;
N-메틸피놀리돈(NMP)용액에 희석시킨 중화제로 상기 프리폴리머를 중화시키고 상기 중화된 프리폴리머에 증류수를 투입하여 수분산 시킨 후, 사슬 연장제를 첨가하여 수분산 폴리 우레탄을 제조하는 단계;
상기 수분산 폴리 우레탄에 아크릴 모노머, 생분해 촉매제 및 개시제를 첨가한 후 교반하여 수용성 아크릴 폴리우레탄을 제조하는 단계;
상기 수용성 아크릴 폴리우레탄에 칼슘계 화합물, 과붕산소다 및 아세트산을 첨가하는 단계를 포함하고,
상기 외층 조성물을 제조하는 단계는 폴리올레핀, 에틸렌다이아민테트라아세트산(EDTA), 칼슘락테이트, 금속스테아린산 및 드로메트리졸을 혼합하는 단계를 포함하는 것을 특징으로 하며,
상기 수용성 아크릴 폴리우레탄에 칼슘계 화합물, 과붕산소다 및 아세트산을 첨가하는 단계는
상기 수용성 아크릴 폴리우레탄 92 ~ 96 중량부에 대하여 칼슘계 화합물 2 ~ 6 중량부, 과붕산소다 1 ~ 2 중량부 및 아세트산 1 ~ 2 중량부를 첨가하는 것을 특징으로 하고,
상기 아세트산은 상기 칼슘계 화합물에서 해리된 칼슘 양이온과 이온 결합을 하여 아세트산칼슘을 형성하는 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법.
Preparing an inner layer composition and an outer layer composition;
Including the step of coextruding the prepared inner layer composition and outer layer composition,
The step of preparing the inner layer composition may include preparing a prepolymer by mixing polyol, dimethylol propionic acid (DMPA), N-methylpinolidone (NMP) solution, and isocyanate;
Neutralizing the prepolymer with a neutralizing agent diluted in an N-methylpinolidone (NMP) solution, adding distilled water to the neutralized prepolymer to disperse it, and then adding a chain extender to prepare a water-dispersible polyurethane;
Adding an acrylic monomer, a biodegradation catalyst, and an initiator to the water-dispersible polyurethane, followed by stirring to prepare a water-soluble acrylic polyurethane;
Including the step of adding a calcium-based compound, sodium perborate and acetic acid to the water-soluble acrylic polyurethane,
The step of preparing the outer layer composition is characterized in that it comprises the step of mixing polyolefin, ethylenediaminetetraacetic acid (EDTA), calcium lactate, metal stearic acid, and drometrisol,
The step of adding a calcium-based compound, sodium perborate and acetic acid to the water-soluble acrylic polyurethane
It characterized in that to add 2 to 6 parts by weight of a calcium-based compound, 1 to 2 parts by weight of sodium perborate, and 1 to 2 parts by weight of acetic acid, based on 92 to 96 parts by weight of the water-soluble acrylic polyurethane,
The acetic acid is an eco-friendly food flexible packaging material manufacturing method for plastic replacement, characterized in that by ionic bonding with the calcium cation dissociated from the calcium-based compound to form calcium acetate.
상기 칼슘계 화합물은 페로시안화칼슘, 소르빈산칼슘 및 카제인칼슘 혼합물인 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법.
The method of claim 1,
The calcium-based compound is an eco-friendly food flexible packaging method for plastic replacement, characterized in that the mixture of calcium ferrocyanide, calcium sorbate and calcium casein.
상기 금속스테아린산은 스테아린산철(iron(Ⅲ) stearate), 하이드록시스테아린산철(ferric hydroxystearate) 또는 스테아린산구리(copper(Ⅱ) stearate) 중 어느 하나 이상을 포함하는 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법.
The method of claim 1,
The metal stearic acid is an eco-friendly food lead for plastic replacement, characterized in that it contains at least one of iron (III) stearate, ferric hydroxystearate, or copper stearate (copper(II) stearate). Packaging material manufacturing method.
상기 프리폴리머를 제조하는 단계는
프리폴리머 100 중량부에 대하여 폴리올 15 ~ 25 중량부를 진공 오븐에서 60 ~ 80℃에 녹인 후, 내부 공기를 질소로 치환하여 교반하는 단계;
프리폴리머 100 중량부에 대하여 디메틸올프로피온 산 15 ~ 25 중량부를 첨가하여 교반하는 단계;및
프리폴리머 100 중량부에 대하여 N-메틸피놀리돈(NMP)용액 1 ~ 5 중량부 및 이소시아네이트 50 ~ 65 중량부를 첨가하여 교반한 후 온도를 50℃로 낮추는 단계;를 포함하는 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법.
The method of claim 1,
The step of preparing the prepolymer is
Dissolving 15 to 25 parts by weight of polyol in a vacuum oven at 60 to 80° C. based on 100 parts by weight of the prepolymer, then replacing the internal air with nitrogen and stirring;
Stirring by adding 15 to 25 parts by weight of dimethylolpropionic acid based on 100 parts by weight of the prepolymer; And
Replacing a plastic comprising: adding 1 to 5 parts by weight of an N-methylpinolidone (NMP) solution and 50 to 65 parts by weight of an isocyanate and reducing the temperature to 50° C. based on 100 parts by weight of the prepolymer. Manufacturing method of flexible packaging material for eco-friendly food.
상기 수분산 폴리 우레탄을 제조하는 단계는 상기 수분산 폴리우레탄 100 중량부에 대하여 프리폴리머 25 ~ 45 중량부, N-메틸피놀리돈(NMP)용액 1 ~ 3 중량부에 중화제 2 ~ 6 중량부를 혼합하여 프리폴리머를 중화시키는 단계;
증류수 40 ~ 60 중량부를 적하시켜주며 교반하는 단계;및
사슬 연장제 5 ~ 15 중량부를 넣고 교반하는 단계를 포함하는 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법.
The method of claim 1,
In the preparing of the water-dispersible polyurethane, 2 to 6 parts by weight of a neutralizing agent are mixed with 25 to 45 parts by weight of the prepolymer and 1 to 3 parts by weight of the N-methylpinolidone (NMP) solution based on 100 parts by weight of the water-dispersible polyurethane. To neutralize the prepolymer;
Stirring while adding 40 to 60 parts by weight of distilled water dropwise; And
5 to 15 parts by weight of a chain extender and a method of manufacturing a flexible packaging material for eco-friendly food for plastic replacement, comprising the step of stirring.
상기 수용성 아크릴 폴리우레탄을 제조하는 단계는
수용성 아크릴 폴리우레탄 100 중량부에 대하여 상기 수분산 폴리 우레탄
70 ~ 85 중량부, 아크릴 모노머 10 ~ 25 중량부, 생분해 촉매제 1 ~ 3 중량부 및 개시제 1 ~ 3 중량부를 첨가하여 교반하는 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법.
The method of claim 1,
The step of preparing the water-soluble acrylic polyurethane
The water-dispersible polyurethane based on 100 parts by weight of water-soluble acrylic polyurethane
70 to 85 parts by weight, 10 to 25 parts by weight of acrylic monomer, 1 to 3 parts by weight of biodegradation catalyst, and 1 to 3 parts by weight of initiator are added and stirred.
상기 폴리올은 폴리테트라메틸렌글리콜(polytetramehtyleneglycol, PTMG)이고, 상기 이소시아네이트는 이소포론디이소시아네이트(isophorone diisocyanate,IPDI)이고, 상기 중화제는 트리에틸아민(triethylamine, TEA)이고, 상기 사슬 연장제는 에틸렌디아민(ethylene diamine, EDA)이고, 상기 아크릴 모노머는 메틸메타크릴레이트(methylmetaacrylate, MMA)이고, 상기 생분해 촉매제는 페릭아세틸카바메이트이고, 상기 개시제는 아조비스이소부티로니트릴(2,2'-azobis isobutyronitrile, AIBN)이고, 상기 금속스테아린산은 스테아린산철(iron(Ⅲ) stearate)인 것을 특징으로 하는 플라스틱 대체용 친환경 식품용 연포장재 제조방법.
The method of claim 1,
The polyol is polytetramehtyleneglycol (PTMG), the isocyanate is isophorone diisocyanate (IPDI), the neutralizing agent is triethylamine (TEA), and the chain extender is ethylenediamine ( ethylene diamine, EDA), the acrylic monomer is methyl methacrylate (MMA), the biodegradation catalyst is ferric acetyl carbamate, the initiator is azobisisobutyronitrile (2,2'-azobis isobutyronitrile, AIBN), and the metal stearic acid is iron (III) stearate.
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