KR100744764B1 - Release Paper Formed with Polyvinyl Alcohol and Polyvinyl Pyrrolidone Films Containing Proteins and Methods of Preparation Thereof - Google Patents

Release Paper Formed with Polyvinyl Alcohol and Polyvinyl Pyrrolidone Films Containing Proteins and Methods of Preparation Thereof Download PDF

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KR100744764B1
KR100744764B1 KR1020050105457A KR20050105457A KR100744764B1 KR 100744764 B1 KR100744764 B1 KR 100744764B1 KR 1020050105457 A KR1020050105457 A KR 1020050105457A KR 20050105457 A KR20050105457 A KR 20050105457A KR 100744764 B1 KR100744764 B1 KR 100744764B1
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release paper
polyvinyl alcohol
resin
pva
polyvinyl pyrrolidone
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KR20070048405A (en
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김지현
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
    • 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
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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
    • C08F216/02—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 by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • C08J2329/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic 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
    • C08J2339/00—Characterised by the use 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

본 발명은 단백질이 첨가된 폴리비닐 알콜 필름이 형성된 이형지의 제조 방법에 관한 것으로서, 원지위에 제올라이트 코팅을 하고 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 표면 코팅한 후 건조 하여 이형지를 제조하는 단계;The present invention relates to a method for producing a release paper on which a polyvinyl alcohol film is added to a protein, comprising a step of preparing a release paper by applying a zeolite coating on a base paper and surface-coating a resin containing an acrylic resin with a spin coating machine, followed by drying. ;

상기 제조된 이형지를 냉수를 포함하고 있는 반응조에 삽입하고, 폴리비닐 알콜 수지를 반응조의 반응액의 10% 내지 20중량%가 되도록 투입하여 용해시키는 단계;Inserting the prepared release paper into a reaction tank containing cold water, and dissolving the polyvinyl alcohol resin so as to be 10% to 20% by weight of the reaction solution of the reaction tank;

용해 반응시킨 후 냉각시킨 후 단백질을 첨가하여 상기 이형지 위에 레진을 형성하는 단계; 및Dissolution reaction and cooling followed by addition of protein to form a resin on the release paper; And

형성된 레진을 소정의 형태로 압출하는 성형과정을 포함하는 것을 특징으로 하는 생분해 촉진용 폴리비닐 알콜 필름이 형성된 이형지 제조방법 및 이에 의해 생산되는 생분해 촉진용 폴리비닐 알콜 필름이 형성된 이형지에 관한 것이다.The present invention relates to a release paper manufacturing method for forming a biodegradation-promoting polyvinyl alcohol film comprising a molding process of extruding the formed resin into a predetermined form, and a release paper on which a biodegradation-promoting polyvinyl alcohol film is produced thereby.

폴리비닐 알콜, 폴리비닐 피롤리돈, 생분해 Polyvinyl alcohol, polyvinyl pyrrolidone, biodegradable

Description

단백질이 첨가된 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조 방법{ Release Paper Formed with Polyvinyl Alcohol and Polyvinyl Pyrrolidone Films Containing Proteins and Methods of Preparation Thereof}Release Paper Formed with Polyvinyl Alcohol and Polyvinyl Pyrrolidone Films Containing Proteins and Methods of Preparation Thereof}

본 발명은 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조 방법 및 이 제조방법에 의하여 생산된 이형지에 관한 것이다. The present invention relates to a method for producing a release paper on which a polyvinyl alcohol and polyvinyl pyrrolidone film for promoting biodegradation, and a release paper produced by the production method.

대표적인 수용성 고분자인 폴리비닐알콜계 중합체(이하, PVA라고 약칭하는 경우가 있다)는 수용성인 것에 추가하여, 강도 특성 및 막 제조성의 점에서 우수하며 이의 특성을 살리고, 통상적인 비닐론 섬유 또는 고강력 비닐론 섬유의 원료로서 또는 섬유가공재, 종이용 코팅재, 종이용 내부첨가제, 접착제, 유화안정제, 필름, 부티랄 수지, 화장품, 의약품 및 세라믹 결합제, 제지 접착제나 제지 표면 싸이징 (인쇄적성 향상제) 등의 용도로 광범위하게 사용되고 있다. Polyvinyl alcohol-based polymer (hereinafter sometimes referred to as PVA), which is a representative water-soluble polymer, is excellent in strength properties and film manufacturability in addition to water-soluble, and utilizes its properties. Use as raw materials of textiles, textile processing materials, coating materials for paper, internal additives for paper, adhesives, emulsion stabilizers, films, butyral resins, cosmetics, pharmaceuticals and ceramic binders, paper adhesives and paper surface sizing (printability enhancing agents) It is widely used.

PVA를 적용하고자 하는 용도에 따라서는 저온수에 대한 용해성이 낮으며 고온수에 빠르게 용해된다는 성질을 갖는 PVA가 요구되는 경우가 있다. Depending on the intended use of the PVA, there is a case where a PVA having low solubility in low temperature water and rapidly dissolving in high temperature water is required.

통상적인 PVA는 수용액 형태로 사용되지만, 종이 등의 기재 위에 고전단 속도하에 도포할 때에 도포액의 점도가 상승하여, 도포액이 선 모양으로 되거나 도포액이 비산하는 등의 문제가 생기는 점으로부터 PVA의 입자직경을 작게 하여, 수성 슬러리의 형태로 사용한다는 검토가 수행되고 있다. 그러나 시멘트와 같은 무기물을 초조(抄造)법에 의해 성형하도록 하는 경우에 PVA를 수성 슬러리의 형태로 사용하면 PVA의 일부가 수중으로 용출되어, 성형물 중에서 제품 수율이 저하되거나 배수에 PVA가 유출되는 등의 문제가 생기는 점으로부터 저온수에 대한 용해성이 낮은 PVA가 요구되고 있다. Although conventional PVA is used in the form of an aqueous solution, the viscosity of the coating liquid increases when the coating liquid is applied on a substrate such as paper at high shear speed, which causes problems such as the coating liquid becoming linear or the coating liquid scattering. Examination has been carried out to reduce the particle diameter of the resin and to use it in the form of an aqueous slurry. However, in the case of forming an inorganic material such as cement by an evaporation method, when PVA is used in the form of an aqueous slurry, a part of the PVA is eluted in water, and the yield of the product in the molded product is lowered or the PVA is leaked to the drainage. In view of the problem of PVA, low solubility in low temperature water is required.

통상적으로 PVA는 폴리비닐에스테르계 중합체(이하, PVE라고 약칭하는 경우가 있다)를 염기성 촉매의 존재하에 알콜과 에스테르 교환반응시킴으로써 제조된다. 종래부터 공지되어 있는 PVA의 제조방법을 열거하면 하기와 같다. Usually, PVA is produced by transesterifying a polyvinyl ester polymer (hereinafter sometimes referred to as PVE) with an alcohol in the presence of a basic catalyst. It is as follows when the manufacturing method of PVA conventionally known is enumerated.

미국 특허 제2,642,419호 명세서에는 농도 24 내지 40중량%의 PVE의 메탄올 용액과 수산화나트륨의 메탄올 용액과의 혼합물을 연속적으로 벨트 컨베이어 위에 공급하여, 메타노리시스 반응에 의해 수득되는 겔상물을 분쇄 및 건조하는 것에 의한 PVA 분말의 제조방법(소위 벨트식 비누화법)에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말은 저온에서도 물에 용해되므로 PVA 분말의 표면만이 용해되어 응집하여, 괴상화한다. 따라서 연속 용해장치 등을 사용하여 물에 용해시키는 데 적합하지 않다. 또한, 본 방법에 따라 수득되는 PVA 분말은 이를 제조할 때에 사용하는 메탄올 및 메타노리시스 반응에 의해 생성되는 카복실산에스테르 등의 휘발성 유기 화합물 및 아세트산나트륨 등의 불휘발성 화합물을 상당량 함유하고 있다. PVA 분말에 함유되는 휘발성 유기 화합물이 많으면 PVA 분말을 취급할 때에 작업장 환경이 저하되며, 다시 PVA 수용액의 폐수처리가 필요해진다. 또한, 아세트산나트륨 등의 불휘발성 화합물이 PVA 분말에 함유되어 있는 경우에는 PVA 분말을 전기부품, 전자부품, 세라믹 결합제 등의 용도에 사용하는 경우에 절연불량 등의 문제가 생길 염려가 있다. US Pat. No. 2,642,419 discloses a mixture of a methanol solution of PVE in a concentration of 24 to 40 wt. The manufacturing method (so-called belt saponification method) of PVA powder by doing is disclosed. Since the PVA powder obtained by this method is soluble in water even at low temperatures, only the surface of the PVA powder is dissolved, aggregated, and agglomerated. Therefore, it is not suitable for dissolving in water using a continuous dissolving device or the like. In addition, the PVA powder obtained by the present method contains a considerable amount of volatile organic compounds such as carboxylic acid esters produced by methanol and metanosis reaction and nonvolatile compounds such as sodium acetate, which are used in producing them. If there are many volatile organic compounds contained in PVA powder, the workplace environment will fall when handling PVA powder, and wastewater treatment of PVA aqueous solution is needed again. In addition, when non-volatile compounds such as sodium acetate are contained in the PVA powder, problems such as poor insulation may occur when the PVA powder is used for applications such as electric parts, electronic parts, ceramic binders, and the like.

일본 특허공보 제(소)40-3700호에는 PVE를 알콜과 에스테르 교환반응시킬 때에 이의 반응계에 PVE의 메탄올 용액을 단속적으로 공급하는 PVA 분말의 제조방법에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말은 온수 또는 열수에 용해시키려고 해도 멍울이 생겨 균일한 수용액이 수득되지 않는 점으로부터 저온의 물에 투입한 다음, 물의 온도를 서서히 승온하는 것으로 물에 용해시키는 방법이 채용되고 있으며 용해에 장시간을 요한다는 문제가 있다. 또한 이러한 PVA 분말은 미세 분말의 비율이 많은 점으로부터 개봉할 때에 미세 분말이 비산되기 쉽다는 문제가 있다. Japanese Patent Publication No. 40-3700 discloses a method for producing PVA powder in which a methanol solution of PVE is intermittently supplied to a reaction system thereof when a PVE is transesterified with an alcohol. The PVA powder obtained by this method is added to low-temperature water from the point that lumps are generated even when trying to dissolve in hot water or hot water, and a uniform aqueous solution is not obtained, and then the temperature of the water is gradually raised to dissolve it in water. There is a problem that it takes a long time to dissolve. In addition, such PVA powder has a problem that the fine powder is likely to be scattered when opened due to the high proportion of the fine powder.

일본 특허공보 제(소)45-33191호에는 PVE를 알콜과 에스테르 교환반응시킬 때에 PVE의 메탄올 용액을 반응 혼합물 중의 가용성 중합체의 농도가 1중량%를 초과하지 않도록 하는 비율로 연속적으로 공급하여, 반응 혼합물로부터 PVA 슬러리를 연속적으로 회수하는 PVA 분말의 제조방법에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말에 대해서도 특허문헌 2에 관해 말한 것과 동일한 문제점이 지적된다. In Japanese Patent Publication No. 45-33191, when a PVE is transesterified with an alcohol, a methanol solution of PVE is continuously supplied at a rate such that the concentration of the soluble polymer in the reaction mixture does not exceed 1% by weight. A method for producing a PVA powder for continuously recovering a PVA slurry from a mixture is disclosed. The same problem as said about patent document 2 is also pointed out about the PVA powder obtained by this method.

일본 특허공보 제(소)46-9826호에는 비누화도 97 내지 98.5몰%의 PVA의 메틸 아세테이트. 메탄올 혼합용매의 슬러리에 비누화도 10 내지 40몰%의 부분 비누화 PVA의 메틸 아세테이트·메탄올 혼합용매 및 비누화 촉매의 메탄올 용액을 반응 혼합물 중의 가용성 중합체의 농도가 1중량%를 초과하지 않도록 하는 비율로 연속적으로 공급하는 동시에 반응 혼합물로부터 PVA 슬러리를 연속적으로 인출하여 탈액 및 건조하는 PVA 분말의 제조방법에 관해서 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말에 대해서도 특허문헌 2에 관해서 기재된 것과 동일한 문제점이 지적된다. Japanese Patent Publication No. 46-9826 describes methyl acetate of PVA having a degree of saponification of 97 to 98.5 mol%. Methanol solution of methyl acetate-methanol mixed solvent and saponification catalyst of partially saponified PVA having a degree of saponification of 10-40 mol% in a slurry of methanol mixed solvent was continuously used at a ratio such that the concentration of soluble polymer in the reaction mixture did not exceed 1% by weight. Disclosed is a method for producing PVA powder in which the PVA slurry is continuously withdrawn from the reaction mixture while being fed into the solution to be liquefied and dried. The same problem as that described with respect to patent document 2 is also pointed out about the PVA powder obtained by this method.

물에 용해시킬 때에 생기는 괴상화 또는 멍울의 문제의 해결을 목적하는 PVA 분말의 제조방법이 제안되어 있다. A method for producing PVA powder has been proposed for the purpose of solving the problem of agglomeration or lumps produced when dissolved in water.

일본 특허공보 제(소)54-7311호에는 비누화도 93 내지 100몰%의 PVA를 메탄올, 물 등의 혼합용매 속에서 50℃ 이상의 온도로 가열하는 것에 의한 냉수에서의 용해성이 감소된 PVA 분말의 제조방법에 관해서 개시되어 있다. 그러나, 수득되는 PVA 분말은 고온수에 대한 용해성이 개선되어 있다고는 말하기 어렵다. 또한, 본 방법은 일단 제조된 PVA를 가열처리하므로 공정이 번잡해지고, 이를 위한 장치를 별도로 필요로 할 뿐만 아니라 에너지 효율도 낮다. Japanese Patent Publication No. 54-7311 discloses a PVA powder having reduced solubility in cold water by heating PVA having a saponification degree of 93 to 100 mol% to a temperature of 50 ° C or higher in a mixed solvent such as methanol and water. A manufacturing method is disclosed. However, it is difficult to say that the obtained PVA powder has improved solubility in hot water. In addition, the method heats the PVA once produced, which makes the process complicated, and requires a separate device for this, and also has low energy efficiency.

일본 공개특허공보 제2002-53616호에는 특정한 아조계 중합개시제를 저온으로 유지하면서 공급 라인을 통하여 아세트산비닐의 중합계에 도입하여, 아세트산비닐의 중합에 의해 수득되는 폴리아세트산비닐을 비누화하는 것에 의한 물에 대한 용해성이 개선된 PVA의 제조방법이 개시되어 있다. 본 방법에 따르면 결정성이 높은 PVA를 수득할 수 있지만, 저온에서 용해되기 어려우며 고온에서 빠르게 용해하는 PVA를 수득할 수 없다. 또한, 이러한 PVA는 건조에 의해 휘발성 유기 화합물의 함유량을 감소시키는 것이 곤란하며, 휘발성 유기 화합물이 잔존하면 작업환경의 악화를 초래한다. 또한, 본 방법에서는 중합촉매의 공급 라인을 저온으로 유지하기 위해 온도관리를 충분하게 실시하는 것이 필요하다. Japanese Laid-Open Patent Publication No. 2002-53616 discloses water by introducing a polyacetate obtained by polymerization of vinyl acetate by introducing a specific azo polymerization initiator into a polymerization system of vinyl acetate through a supply line while maintaining a low temperature. A method for preparing PVA with improved solubility in water is disclosed. According to this method, PVA having high crystallinity can be obtained, but PVA which is difficult to dissolve at low temperature and rapidly dissolves at high temperature cannot be obtained. In addition, it is difficult for such PVA to reduce the content of volatile organic compounds by drying, and deterioration of the working environment occurs when the volatile organic compounds remain. Moreover, in this method, it is necessary to perform sufficient temperature control in order to keep the supply line of a polymerization catalyst at low temperature.

일본 공개특허공보 제2000-265026호에는 입자직경 500 내지 1000μm의 입자를 20중량% 이상 함유하는 용해성이 우수한 PVA 분말이 개시되어 있다. 특허문헌 7에 제안되어 있는 PVA 분말은 저온수에서 용해할 때에 멍울로 되기 어렵다는 성질이 있지만, 입자직경이 크므로 용해에 장시간을 요하며, 실용성이 결핍된다. Japanese Laid-Open Patent Publication No. 2000-265026 discloses a PVA powder having excellent solubility containing 20% by weight or more of particles having a particle diameter of 500 to 1000 µm. PVA powder proposed in Patent Literature 7 has a property of hardly becoming vacant when dissolved in low temperature water. However, since the particle diameter is large, it takes a long time to dissolve and lacks practicality.

일본 공개특허공보 제(평)8-301936호에는 공지된 방법에 수득된 PVA를 140℃의 온도에서 무용매로 2시간 동안 가열하는 방법이 개시되어 있다. 본 방법에 따르면 PVA 분말의 용해특성의 온도 의존성은 커지지만, 특허문헌 5에 관해서 기재된 바와 동일하게 일단 제조한 PVA를 가열처리하므로 공정이 번잡해지며 또한, 이를 위한 장치를 별도로 필요로 할 뿐만 아니라 에너지 효율도 낮다. Japanese Laid-Open Patent Publication No. Hei 8-301936 discloses a method of heating PVA obtained in a known method for 2 hours with no solvent at a temperature of 140 ° C. According to this method, the temperature dependence of the dissolution characteristics of the PVA powder is increased, but the process is complicated by heat treatment of the PVA once prepared as described with respect to Patent Document 5, and not only requires a separate device for this. Energy efficiency is also low.

물에 대한 용해성이 개선된 PVA의 제조방법에 대해서도 제안되어 있다. A method for producing PVA with improved solubility in water has also been proposed.

일본 공개특허공보 제(평)9-316272호에는 비누화도 20 내지 60몰%의 부분 비누화 PVA와 PVE의 혼합 용액을 비누화로 처리하는 것에 의한 다공성의 PVA 분말의 제조방법이 개시되어 있다. 본 방법에 따라 수득되는 PVA 분말은 저온수에 대한 용해성이 억제되어 있다는 점에서는 개선되어 있지만, 물의 온도를 상승시킬 때에 용해성의 점에서 또한 개선의 여지가 있다. 또한, 본 방법에서는 부분 비누화 PVA를 사용하므로 PVE의 예비적인 비누화 공정이 필요해진다. Japanese Laid-Open Patent Publication No. Hei 9-316272 discloses a method for producing porous PVA powder by treating a mixed solution of partially saponified PVA and PVE having a saponification degree of 20 to 60 mol% by saponification. Although the PVA powder obtained by the present method is improved in that the solubility in low temperature water is suppressed, there is room for improvement in terms of solubility when raising the temperature of water. In addition, the present method uses partially saponified PVA, which requires a preliminary saponification process of PVE.

일본 공개특허공보 제(평)8-188619호에는 PVE를 당해 PVE, PVA 및 알콜의 어느 것에도 용해되지 않는 유동 파라핀 등의 분산매 중에 분산시켜 비누화하는 것에 의한 PVA 미립자의 제조방법이 개시되어 있다. 본 방법에 따라 수득되는 PVA 미립자는 저온수에 대한 용해성이 억제되어 있다는 점에서는 개선되어 있지만, 다공성이 아니므로 PVA 중에 포함되는 휘발성 유기 화합물을 제거하는 것이 곤란하다는 문제가 있다. 또한, 본 방법에서는 폴리비닐피롤리돈 등의 분산제를 사용하는 것이 필요하며, 이들을 PVA 중에서 제거하기 위해서는 번잡한 공정이 필요하다. Japanese Laid-Open Patent Publication No. Hei 8-188619 discloses a method for producing PVA fine particles by dispersing PVE in a dispersion medium such as liquid paraffin that is not dissolved in any of the PVE, PVA, and alcohol. Although the PVA fine particles obtained by the present method have been improved in that the solubility in low temperature water is suppressed, there is a problem that it is difficult to remove volatile organic compounds contained in PVA because they are not porous. Moreover, in this method, it is necessary to use dispersing agents, such as polyvinylpyrrolidone, and a complicated process is needed in order to remove these in PVA.

저온수에 대한 용해성이 낮은 것으로 계분(멍울)상태로 되기 어려우며 또한 고온수에 빠르게 용해한다는 특성을 갖는 PVA가 강력하게 요청되고 있다. 과거에 저온수에 대한 용해성이 억제되어 있는 PVA가 제안되어 있지만, 작은 온도변화로 물에 대한 용해특성이 충분하게 크게 변화되는 PVA는 아직 수득되고 있지 않다. 또한, 종래에는 저온수에 대한 용해성을 억제하기 위해서 여분의 공정 또는 조작을 필요로 하고 있다. There is a strong demand for PVA, which has low solubility in low temperature water, which is difficult to become powdery, and which quickly dissolves in high temperature water. In the past, PVA in which solubility in low temperature water is suppressed has been proposed, but PVA whose solubility in water is sufficiently largely changed due to a small temperature change has not been obtained. In addition, conventionally, an extra process or operation is required in order to suppress solubility in low temperature water.

폴리비닐 피롤리돈(PVP)는 N-비닐-2-피롤리돈의 중합체로서 흡습성이 있으며, 물, 알코올에 녹고 탄화수소에 녹지 않는다. 저분자량인 것은 대용혈장제로 사용되는 인체에 매우 안정적인 물질이다. 그 외에 폴리비닐 피롤리돈은 수용성 접착제, 입술 연지형 접착제, 종이의 접착제로 사용되고 있다. 기존에 사용되는 일반적인 합성수지는 일상생활에 많이 사용되고 있으나 이러한 합성수지는 이를 폐기하는 경우 자연환경에서 분해가 일어나지 않고 소각하는 경우 다이옥신 같은 유해물질이나 지구 온난화를 일으킨다고 의심되는 이산화탄소를 발생하는 등 환경오염의 문제의 주범 중의 하나로 인식되고 있다. 최근 그 수요가 급속히 증가하고 있는 1회용 포장재료는 소비가 많음에도 불구하고 회수가 어려워 그 대로 방치되는 경우가 많으며 노업용 필름의 경우 완전한 회수가 어려운 단점이 있다. 그 때문에 최근에는 자연환경에서 쉽게 분해가 일어나는 수지 또는 필름의 개발이 요구되고 있다.   Polyvinyl pyrrolidone (PVP) is a polymer of N-vinyl-2-pyrrolidone, hygroscopic, soluble in water, alcohol and insoluble in hydrocarbons. Low molecular weight is a very stable substance to the human body used as a substitute plasma. In addition, polyvinyl pyrrolidone is used as a water-soluble adhesive, a lip adhesive, and an adhesive for paper. Conventional synthetic resins used in the past are widely used in daily life. However, when these wastes are disposed of, they are not decomposed in the natural environment, and when incinerated, they generate harmful substances such as dioxin or carbon dioxide suspected of causing global warming. It is recognized as one of the main culprit of the problem. Disposable packaging materials, whose demand is rapidly increasing in recent years, are often difficult to recover even though they are consumed in many cases. Therefore, in recent years, the development of resins or films that easily decompose in the natural environment has been required.

본 발명은 상기와 같은 문제점을 해소하기 위한 것으로서 폴리비닐 알코올 및 폴리비닐 피롤리돈 필름이 형성된 이형지를 제조하는 방법에 있어서 단백질을 첨가하여 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조 방법 및 이 제조방법에 의하여 생산된 이형지를 제공하는 것이다. The present invention is to solve the above problems, the polyvinyl alcohol and polyvinyl pyrrolidone film is formed in the method for producing a release paper is added to the polyvinyl alcohol and polyvinyl pyrrolidone film for promoting biodegradation It is to provide a method for producing a release paper and a release paper produced by the production method.

본 발명은 폴리비닐 알코올 및 폴리비닐 피롤리돈 필름이 형성된 이형지를 제조하는 방법에 있어서 단백질을 첨가하여 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조 방법 및 이 제조방법에 의하여 생산된 이형지에 관한 것이다. The present invention provides a method for producing a release paper on which a polyvinyl alcohol and a polyvinyl pyrrolidone film are formed, and a method for producing a release paper on which a polyvinyl alcohol and polyvinyl pyrrolidone film for promoting biodegradation is formed by adding a protein. It relates to a release paper produced by.

상기와 같은 목적을 달성하기 위하여 본 발명은 단백질을 함유하여 생분해 촉진되는 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조 방법 및 이에 생산된 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지를 제공한다.  In order to achieve the above object, the present invention provides a method for preparing a release paper in which a polyvinyl alcohol and polyvinyl pyrrolidone film containing a protein is biodegradable, and a polyvinyl alcohol and polyvinyl pyrrolidone film produced therein is formed. Provide release paper.

원지위에 제올라이트 코팅을 하고 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 표면 코팅한 후 건조 하여 이형지를 제조하는 단계;Preparing a release paper by zeolite coating on a base material and surface-coating a resin containing an acrylic resin with a spin coating machine, followed by drying;

상기 제조된 이형지를 냉수를 포함하고 있는 반응조에 삽입하고, 폴리비닐 알콜 및 수용성 폴리비닐 피롤리돈 수지가 반응조의 반응액의 10% 내지 20 중량%가 되도록 투입하여 용해시키는 단계;Inserting the prepared release paper into a reaction tank containing cold water, and dissolving the polyvinyl alcohol and the water-soluble polyvinyl pyrrolidone resin so as to be 10% to 20% by weight of the reaction solution of the reaction tank;

용해 반응시킨 후 냉각시킨 후 단백질을 첨가하여 상기 이형지 위에 레진을 형성하는 단계; 및Dissolution reaction and cooling followed by addition of protein to form a resin on the release paper; And

형성된 레진을 소정의 형태로 압출하는 성형과정을 포함하는 것을 특징으로 하는 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지를 제공한다.It provides a release paper formed with a polyvinyl alcohol and polyvinyl pyrrolidone film for promoting biodegradation, characterized in that it comprises a molding process of extruding the formed resin into a predetermined form.

보다 상세히 설명하면, 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 35-45미크론으로 표면 코팅한 후 약 5m 내지 30 m의 건조로에서 95°C 내지 105°C로 바람직하게는 99°C 내지 101°C로 보다 바람직하게는 100°C로 건조 통과시켜서 이형지를 제조한다. 이 때 바람직하게는 고투명 아크릴계 레진 23% 내지 27%를 함유한 수지를 사용하며 보다 바람직하게는 고투명 아크릴계 레진 25%를 함유한 수지를 사용한다. In more detail, after the surface coating of the resin containing the acrylic resin to 35-45 microns with a spin coating machine, 95 ° C to 105 ° C in a drying furnace of about 5 m to 30 m, preferably 99 ° C to 101 ° More preferably with C to dry through 100 ° C. to produce a release paper. In this case, preferably, a resin containing 23% to 27% of high transparency acrylic resin is used, and more preferably a resin containing 25% of high transparency acrylic resin is used.

아크릴계 레진이 코팅되어진 평량 80-150g 의 이형지 표면위에 폴리비닐 피롤리돈 레진, 바람직하게는 폴리비닐 피롤리돈 k-30 또는k-90 레진과 고형분의 10% 내지 20% 중량비의 폴리비닐을 반응조에 투입하여 용해시킨다. 이때 반응조의 온도는 105°C 내지 115°C로 바람직하게는 108°C 내지 112°C로 보다 바람직하게는 110°C를 유지한다. 그런 다음 반응조를 55°C 내지 65°C로 바람직하게는 58°C 내지 62°C로 보다 바람직하게는 60°C로 냉각 시킨 후 단백질을 투입하여 반응을 종결시킨다. 단백질은 모든 종류의 단백질을 사용할 수 있으며 천연단백질인 카제인(우유로부터 추출) 또는 두유의 사용이 가능하고 그 중량비는 3% 내지 7%로 바람직하게는 4% 내지 6%로 보다 바람직하게는 5% 중량비로 투여한다. A polyvinyl pyrrolidone resin, preferably polyvinyl pyrrolidone k-30 or k-90 resin and polyvinyl in a proportion of 10% to 20% by weight of solids on a surface of 80-150 g of a release paper coated with acrylic resin To dissolve. At this time, the temperature of the reaction vessel is maintained at 105 ° C to 115 ° C, preferably 108 ° C to 112 ° C more preferably 110 ° C. Then, the reaction tank is cooled to 55 ° C to 65 ° C, preferably 58 ° C to 62 ° C, more preferably to 60 ° C, and then the protein is added to terminate the reaction. Proteins can be used in all kinds of proteins, and can be used as a natural protein casein (extracted from milk) or soy milk, the weight ratio of 3% to 7%, preferably 4% to 6%, more preferably 5% Administration by weight ratio.

코팅 방법은 스핀코타 방식으로 시행되어야 하며 건조로는 수평으로 유지된 상태에서 약 15-150 미크론 의 두께의 필름을 제조 생산 한다.The coating method should be spin-coated and the drying furnace will produce a film about 15-150 microns thick while being kept horizontal.

이 하 본 발명에 따른 바람직한 실시예를 상세히 설명한다. Hereinafter, a preferred embodiment according to the present invention will be described in detail.

[실시예 1] 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름 제조Example 1 Preparation of Polyvinyl Alcohol and Polyvinyl Pyrrolidone Film

평량 145g/m2 이상 원지위에 제올라이트 코팅을 10 미크론 코팅하고 고투명 아크릴 수지 250g: 메틸 에틸 케톤(Methyl ethyl Ketone; mEK) 400g: 키실렌 200g : 톨루엔 150g의 조성비를 가지는 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 25 미크론으로 표면 코팅한 후 약 5m 내지 30 m의 건조로에서 100°C로 건조 통과시켜서 이형지를 제조한다. 상기 제조된 이형지를 10℃의 냉수를 포함하고 있는 반응조에 삽입하고, 폴리비닐알콜과 폴리비닐 피롤리돈이 반응조의 반응액의 15 -25중량%가 되도록 투입한다. 빙초산 또는 황산을 반응조 반응액의 1 내지 25 중량%가 되도록 투입시킨 후 반응조의 온도를 서서히 올려서 반응조의 온도가 110°C를 유지한다. 그런 다음 반응조를 60°C로 냉각 시킨 후 단백질을 투입하여 반응을 종결시킨다. 단백질은 천연단백질인 카제인(우유로부터 추출) 또는 두유의 사용이 가능하고 그 중량비는 5% 중량비로 투여한다. 상기 이형지 위에 형성된 레진을 소정의 형태로 압출 성형하여 생분해 촉진되는 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지를 제조한다. 10 microns of zeolite coating on a basis weight of 145g / m 2 or more, high transparency acrylic resin 250g: methyl ethyl ketone (mEK) 400g: xylene 200g: acrylic resin containing acrylic resin having a composition ratio of 150g toluene Release paper is prepared by surface coating 25 microns with a spin coating machine and then passing through dry at 100 ° C. in a drying furnace of about 5 m to 30 m. The release paper prepared above was inserted into a reaction tank containing cold water at 10 ° C., and polyvinyl alcohol and polyvinyl pyrrolidone were added so as to be 15-25 wt% of the reaction solution of the reaction tank. Glacial acetic acid or sulfuric acid is added to 1 to 25% by weight of the reaction tank reaction solution and then gradually raise the temperature of the reaction tank to maintain the temperature of the reactor 110 ° C. Then, the reactor is cooled to 60 ° C. and the protein is added to terminate the reaction. Protein can be used as a natural protein casein (extracted from milk) or soy milk and the weight ratio is administered in 5% by weight. The resin formed on the release paper is extruded into a predetermined form to prepare a release paper having a polyvinyl alcohol and a polyvinyl pyrrolidone film which is biodegradable.

본 발명의폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지 제조를 위한 구체적 성분비는 표 1에 나타내었다. Table 1 shows the specific component ratios for preparing the release paper on which the polyvinyl alcohol and polyvinyl pyrrolidone films of the present invention are formed.

[표1] 본 발명의 필름코팅제 조성비[Table 1] Composition ratio of film coating agent of the present invention

필름코팅제 조성비Film Coating Composition 폴리비닐 알코올(PVA)Polyvinyl Alcohol (PVA) 90g90 g 물 (증류수)Water (distilled water) 850g850 g 폴리비닐 피롤리돈Polyvinyl pyrrolidone 50g50 g 단백질protein 10g10 g

본 발명에 있어서 폴리비닐 알코올 및 폴리비닐 피롤리돈을 이용한 필름을 제조하는 방법에 있어서 단백질을 첨가하여 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조 방법 및 이 제조방법에 의하여 생산된 이형지을 제공할 수 있다. In the present invention, a method for producing a film using polyvinyl alcohol and polyvinyl pyrrolidone, and a method for producing a release paper on which a polyvinyl alcohol and polyvinyl pyrrolidone film for promoting biodegradation is formed by adding a protein. Release paper produced by the present invention can be provided.

본 발명에 의하여 단백질을 첨가한 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름의 특성은 다음과 같다.  The properties of the polyvinyl alcohol and polyvinyl pyrrolidone films added with protein according to the present invention are as follows.

① 장기 보존 및 영구적인 보존성을 지닌 특징을 갖는다.① It has the characteristics of long-term preservation and permanent preservation.

② 토양 중에 매립하였을 때 토양이 수분 27% 함유할 경우 1일에서 4개월 안에 상기 필름의 분자가 모두 분산되어지며 어떠한 유기용제의 폐해가 발생 되지 않는다. ② When landfilled in soil, if the soil contains 27% water, all molecules of the film are dispersed within 1 to 4 months, and no organic solvent is caused.

③ 단백질을 함유함으로 인하여 미생물의 영양분이 되며 단순한 분산이 아닌 실질적인 생분해 순환고리를 형성하고 활성화 시켜 환경오염을 근본적으로 발생시키지 않는다. ③ By containing protein, it becomes the nutrient of microorganism and does not fundamentally cause environmental pollution by forming and activating the actual biodegradable ring, not just dispersion.

본 발명의 제조방법 및 제품에 의하여 자연환경에서 분해가 어려운 기존의 폴리 에틸렌(PE), 폴리 에틸렌 테레프탈레이트(PET), 실리콘 및 폴리염화비닐(PVC) 필름이 형성된 이형지 등을 대체 할 수 있는 효과를 가져올 수 있다. Effect of replacing the release paper formed with the existing polyethylene (PE), polyethylene terephthalate (PET), silicone and polyvinyl chloride (PVC) film difficult to decompose in the natural environment by the manufacturing method and the product of the present invention Can be imported.

Claims (3)

원지위에 제올라이트 코팅을 하고 아크릴계 레진을 함유한 수지를 스핀 코팅 머신으로 표면 코팅한 후 건조 하여 이형지를 제조하는 단계;Preparing a release paper by zeolite coating on a base material and surface-coating a resin containing an acrylic resin with a spin coating machine, followed by drying; 상기 제조된 이형지를 냉수를 포함하고 있는 반응조에 삽입하고, 폴리비닐 알콜 및 수용성 폴리비닐 피롤리돈 수지가 반응조의 반응액의 10% 내지 20중량%가 되도록 투입하여 용해시키는 단계;Inserting the prepared release paper into a reaction tank containing cold water, and dissolving the polyvinyl alcohol and the water-soluble polyvinyl pyrrolidone resin so as to be 10% to 20% by weight of the reaction solution of the reaction tank; 용해 반응시킨 후 냉각시킨 후 단백질을 첨가하여 상기 이형지 위에 레진을 형성하는 단계; 및Dissolution reaction and cooling followed by addition of protein to form a resin on the release paper; And 상기 형성된 레진을 소정의 형태로 압출하는 성형과정을 포함하는 것을 특징으로 하는 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조방법.Method of producing a release paper formed with a polyvinyl alcohol and polyvinyl pyrrolidone film for promoting biodegradation, characterized in that it comprises a molding process of extruding the formed resin into a predetermined form. 제 1항에 있어서, 단백질은 4% 내지 6%의 중량비로 첨가하는 것을 특징으로 하는 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지의 제조방법.The method of claim 1, wherein the protein is added to the weight ratio of 4% to 6% biodegradation promoting polyvinyl alcohol and polyvinyl pyrrolidone film is a method for producing a release paper formed. 제1항 또는 제2항의 제조 방법에 의하여 생산된 생분해 촉진용 폴리비닐 알콜 및 폴리비닐 피롤리돈 필름이 형성된 이형지.A release paper on which a biodegradation-promoting polyvinyl alcohol and polyvinyl pyrrolidone film produced by the method of claim 1 or 2 is formed.
KR1020050105457A 2005-11-04 2005-11-04 Release Paper Formed with Polyvinyl Alcohol and Polyvinyl Pyrrolidone Films Containing Proteins and Methods of Preparation Thereof KR100744764B1 (en)

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JPH03247645A (en) * 1990-02-27 1991-11-05 Three S Technol Bv Photodegradable or microbially degradable thermoplastic polymer composition or film
JPH0523557A (en) * 1991-07-24 1993-02-02 Asahi Chem Ind Co Ltd Hydrophilic heat-resistant film and its manufacture
JPH11217457A (en) 1998-02-04 1999-08-10 Nippon Synthetic Chem Ind Co Ltd:The Film for embroidering substrate
JP2000238194A (en) 1999-02-22 2000-09-05 Daicel Chem Ind Ltd Biodegradable laminate film and agricultural biodegradable film
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JPH03247645A (en) * 1990-02-27 1991-11-05 Three S Technol Bv Photodegradable or microbially degradable thermoplastic polymer composition or film
JPH0523557A (en) * 1991-07-24 1993-02-02 Asahi Chem Ind Co Ltd Hydrophilic heat-resistant film and its manufacture
JPH11217457A (en) 1998-02-04 1999-08-10 Nippon Synthetic Chem Ind Co Ltd:The Film for embroidering substrate
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JP2000238194A (en) 1999-02-22 2000-09-05 Daicel Chem Ind Ltd Biodegradable laminate film and agricultural biodegradable film

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