KR19990042596A - Method of producing polyamide film - Google Patents

Method of producing polyamide film Download PDF

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KR19990042596A
KR19990042596A KR1019970063459A KR19970063459A KR19990042596A KR 19990042596 A KR19990042596 A KR 19990042596A KR 1019970063459 A KR1019970063459 A KR 1019970063459A KR 19970063459 A KR19970063459 A KR 19970063459A KR 19990042596 A KR19990042596 A KR 19990042596A
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film
acid
magnesium
polyamide
organic
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KR1019970063459A
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KR100293355B1 (en
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이귤섭
최수명
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전원중
주식회사 효성
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Priority to JP31698098A priority patent/JP3202701B2/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04Preparatory processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyamides (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

본 발명은 폴리아미드 수지의 중합시에 무기입자와 말단조절제로서 유기 모노아민 및 유기 모노카르복실산을 폴리아미드 수지 100에 대하여 0.1 내지 5.0중량% 첨가하고 촉매로서 마그네슘 화합물 10 내지 1000ppm을 첨가하여 중합한 후 티다이법 또는 인플레이션법으로 압출하는 것을 특징으로 하는 폴리아미드 필름의 제조방법을 제공하는 것으로, 다이라인 및 피시아이가 감소되어 인쇄성이 우수하고, 투명성 및 슬립성이 우수한 폴리아미드 필름을 얻을 수 있게된다.The present invention is polymerized by adding 0.1 to 5.0% by weight of organic monoamine and organic monocarboxylic acid as inorganic particles and end-controlling agent with respect to polyamide resin 100 and adding 10 to 1000 ppm of magnesium compound as catalyst during the polymerization of polyamide resin. The present invention provides a method for producing a polyamide film, which is then extruded by a Ti-die method or an inflation method. A die-line and fisheye is reduced, so that a polyamide film having excellent printability and excellent transparency and slipperiness can be obtained. You will get

Description

폴리아미드 필름의 제조방법Method of producing polyamide film

본 발명은 용융안정성이 우수하고, 외관이 양호하며 투명성과 슬립성이 향상된 폴리아미드 필름의 제조방법에 관한 것으로, 보다 상세하게는 락탐류에 유기 모노아민 및 유기 모노카르복실산을 중합물 말단조절제로 투입하고 마그네슘 화합물 촉매하에서 중합한 후 이를 티다이법 혹은 인플레이션법으로 제조하는 것을 특징으로 하는 외관이 우수하고 투명성 및 슬립성이 향상된 폴리아미드 필름의 제조방법에 관한 것이다.The present invention relates to a method for producing a polyamide film having excellent melt stability, good appearance, and improved transparency and slip properties. More specifically, organic monoamine and organic monocarboxylic acid may be used as a polymer end-controlling agent in lactams. The present invention relates to a method for producing a polyamide film having excellent appearance, improved transparency and slippery properties, characterized in that it is added and polymerized under a magnesium compound catalyst, and then produced by a Ti-die method or an inflation method.

폴리아미드 필름은 가스차단성과 기계적 성질 및 열적특성이 타재료에 비하여 우수하여 식품포장용으로 주로 사용되고 있을 뿐만 아니라 인쇄공정을 거쳐 단층필름으로 사용되거나 타 수지필름과 적층필름 또는 타재료의 라미네이트 필름으로 사용되고 있다.Polyamide film has excellent gas barrier properties, mechanical properties, and thermal properties compared to other materials, so it is not only used for food packaging but also as a single layer film through printing process or as a laminate film of other resin film, laminated film or other materials. have.

일반적으로 폴리아미드 필름은 통상 폴리아미드 중합물을 적절한 조건하에서 압출하여 제조되는데, 폴리아미드 수지를 지속적으로 압출하는 경우 모노머 및 올리고머와 같은 휘발성 물질이 생겨 다이표면에 붙고, 부착된 물질은 고온의 공기 중에서 산화하여 탄화물로 변성되는 문제점이 발생한다. 또한, 다이표면에 축적된 탄화물은 용융된 폴리아미드의 흐름을 방해하고, 폴리아미드 용융물에 혼합되어 다이라인(die-line)을 발생시키고 피시아이(fish eye)를 증가시켜 필름외관이 불량해지고 필름의 투명성과 슬립성을 악화시킨다.In general, polyamide films are usually produced by extruding a polyamide polymer under appropriate conditions. When the polyamide resin is continuously extruded, volatile substances such as monomers and oligomers are formed and adhered to the die surface, and the attached material is exposed to high temperature air. The problem of oxidation and degeneration of carbides occurs. In addition, carbides that accumulate on the die surface disrupt the flow of molten polyamide and are mixed into the polyamide melt to produce die-lines and increase fish eyes, resulting in poor film appearance and film Worsens the transparency and slipperiness.

폴리아미드 필름에 있어서, 투명성이 불량한 경우에는 필름에 균일하게 인쇄하는 것이 어렵고, 슬립성이 나쁜 경우에는 인쇄공정시 필름끼리의 부착현상 즉, 블록킹이 일어나 작업을 저하시키고 다색인쇄시 인쇄변형이 발생하게 된다. 따라서, 폴리아미드 필름의 투명성과 슬립성은 필름의 생산성은 물론 품질과 상품가치의 관점에서 중요한 특성이 된다.In the polyamide film, it is difficult to print uniformly on the film when the transparency is poor, and when the slip property is poor, adhesion between the films occurs during the printing process, that is, blocking occurs, which lowers work and print deformation occurs when printing in multicolor printing. Done. Therefore, the transparency and slipperiness of the polyamide film becomes an important characteristic in terms of the productivity of the film as well as the quality and product value.

폴리아미드 필름의 슬립성을 향상시키기 위한 방법으로, 일본특허 53-45226에는 폴리에틸렌을 배합하는 방법이 제안되어 있으며, 일본 특허 54-4741에는 표면활성이 높은 무기입자를 조합하는 방법이 제안되어 있다. 그러나, 폴리에틸렌을 배합하는 방법은 종래의 문제점인 필름의 투명성을 저하시키는 단점이 있고, 무기입자를 조합하는 방법은 폴리아미드 수지의 용융안정성을 악화시켜 피시아이라는 입자형태의 결함과 다이라인으로 인하여 외관이 양호한 필름을 연속적으로 생산하기 곤란한 단점이 있다. 또한, 무기입자의 조합시에 무기입자로서 실리카만을 배합하는 경우, 투명성과 슬립성은 비교적 양호한 필름을 얻을 수 있지만, 다이라인 및 피시아이가 발생하기 쉬운 단점이 있다.As a method for improving the slip property of a polyamide film, Japanese Patent 53-45226 proposes a method of blending polyethylene, and Japanese Patent 54-4741 proposes a method of combining inorganic particles having high surface activity. However, the method of blending polyethylene has the disadvantage of lowering the transparency of the film, which is a conventional problem, and the method of combining inorganic particles deteriorates the melt stability of the polyamide resin, resulting in defects in the form of particles called diessia and die line. There is a disadvantage in that it is difficult to continuously produce a film having a good appearance. In addition, when only silica is mixed as an inorganic particle in the combination of the inorganic particles, a film having a relatively good transparency and slipperiness can be obtained, but there is a disadvantage in that die lines and fisheye are easily generated.

본 발명의 목적은 상기와 같은 종래의 문제점을 극복하기 위한 것으로, 압출시에 다이라인이 발생하지 않고, 피시아이가 감소된 투명성 및 슬립성이 우수한 폴리아미드 필름의 제조방법을 제공하는 것이다.An object of the present invention is to overcome the conventional problems as described above, to provide a method for producing a polyamide film excellent in transparency and slip properties without die line generated during extrusion, reduced fisheye.

즉, 본 발명은 폴리아미드 수지의 중합시에 무기입자와 말단조절제로서 유기 모노아민 및 유기 모노카르복실산을 폴리아미드 수지 100에 대하여 0.1 내지 5.0중량% 첨가하고 촉매로서 마그네슘 화합물 10 내지 1000ppm을 첨가하여 중합한 후 압출하는 것을 특징으로 하는 폴리아미드 필름의 제조방법을 제공하는 것이다.That is, the present invention adds 0.1 to 5.0% by weight of organic monoamine and organic monocarboxylic acid as inorganic particles and terminal control agent to the polyamide resin 100, and 10 to 1000 ppm of magnesium compound as a catalyst during polymerization of the polyamide resin. It is to provide a method for producing a polyamide film, characterized in that the polymerization by extrusion.

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

본 발명의 폴리아미드 수지의 중합시에 사용되는 모노머는 락탐류 또는 ω-아미노산류가 바람직한데, 락탐류로서는 ε-카프로락탐, 카프릴락탐, 라우릴락탐,α-피롤리돈, α-피페리돈등이 바람직하며, ω-아미노산류로서는 6-아미노카프로익산, 7-아미노헵타노익산, 9-아미노노나노익산, 11-아미노운데카노익산 등이 바람직하다.The monomers used in the polymerization of the polyamide resin of the present invention are preferably lactams or ω-amino acids. As the lactams, ε-caprolactam, capryllactam, lauryllactam, α-pyrrolidone and α-py Ferridone and the like are preferable, and as the? -Amino acids, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and the like are preferable.

본 발명의 슬립성 향상을 위하여 첨가되는 무기입자로서는 습식실리카 또는 건식실리카 어느것이라도 가능하며 BET법에 따라 비표면적이 50㎡/g 이상이고, JIS K 5101 규정에 따라 측정된 흡유량이 50㎖/g 이상인 것이 바람직하며, 폴리아미드 수지 100중량부에 대하여 0.1 내지 0.2중량부를 마그네슘 화합물과 유기 모노아민 또는 마그네슘 화합물과 유기 모노카르복실산과 함께 사용한다.Inorganic particles added to improve the slip properties of the present invention may be either wet silica or dry silica, having a specific surface area of 50 m 2 / g or more according to the BET method, and an oil absorption amount measured according to JIS K 5101. It is preferable that it is more than the above, 0.1-0.2 weight part is used with a magnesium compound, an organic monoamine, or a magnesium compound, and an organic monocarboxylic acid with respect to 100 weight part of polyamide resins.

또한, 본 발명에서 슬립성 향상 및 열안정성을 강화시키기 위하여 촉매제로 사용되는 마그네슘 화합물로는 마그네슘아세테이트, 마그네슘옥사이드, 마그네슘아이오다이드, 마그네슘스테아레이트,마그네슘클로라이드로 이루어진 군으로 부터 1종 이상 선택되고, 폴리아미드에 대하여 10 내지 1000ppm사용한다. 마그네슘 화합물의 첨가량이 10ppm 미만이면 다이라인 억제효과가 미흡하고, 1000ppm을 초과하는 경우에는 다이라인은 발생하지 않지만 필름의 물성 저하를 초래하게 된다.In addition, the magnesium compound used as a catalyst in order to improve the slip properties and thermal stability in the present invention is selected from the group consisting of magnesium acetate, magnesium oxide, magnesium iodide, magnesium stearate, magnesium chloride 10-1000 ppm is used with respect to polyamide. If the added amount of the magnesium compound is less than 10ppm, the die line suppression effect is inadequate, and if it exceeds 1000ppm, the die line does not occur, but the physical properties of the film is reduced.

본 발명에서 사용되는 모노아민 및 모노 카르복실산은 촉매로 마그네슘 화합물을 단독으로 사용하는 경우 발생할 수 있는 중합점도의 저하 및 불균일 발생을 방지하기 위하여 폴리아미드 사슬 구조의 양말단 안정제로서 첨가되는 것으로,유기 모노 아민은 부틸아민, 이소프로필아민, 헥실아민, 옥틸아민, 도데실아민, 벤질아민, 시클로헥실아민 등이 바람직하고, 모노 카르복실산으로는 초산, 프로피온산, 부티릭산, 카프로익산, 카프릭산, 벤조익산 등이 바람직하다.Monoamines and monocarboxylic acids used in the present invention are added as a sock end stabilizer of a polyamide chain structure in order to prevent a decrease in polymerization viscosity and occurrence of nonuniformity, which may occur when a magnesium compound is used alone as a catalyst. Monoamine is preferably butylamine, isopropylamine, hexylamine, octylamine, dodecylamine, benzylamine, cyclohexylamine and the like, and monocarboxylic acids include acetic acid, propionic acid, butyric acid, caproic acid and capric acid. , Benzoic acid and the like are preferable.

또한, 상기에서 언급한 모노아민 및 모노카르복실산의 첨가방법은 실리카 및 마그네슘 화합물중에서 선택된 1종과 상기에서 언급한 모노아민 중에서 선택된 1종을 폴리아미드 대비 0.1 내지 5.0중량%의 비율로 중합단계에서 함께 첨가하거나 모노아민 대신 모노카르복실산을 실리카 및 마그네슘 화합물과 함께 중합하거나 실리카, 마그네슘 화합물, 모노아민 및 모노카르복실산을 함께 첨가하여 중합하는 것이 바람직하다.In addition, the method of adding the monoamine and monocarboxylic acid mentioned above is a polymerization step of one selected from silica and magnesium compounds and one selected from the above-mentioned monoamine in a ratio of 0.1 to 5.0% by weight relative to the polyamide It is preferred to polymerize together by adding together or polymerizing monocarboxylic acids together with silica and magnesium compounds instead of monoamines or by adding together silica, magnesium compounds, monoamines and monocarboxylic acids.

모노아민 및 모노카르복실산의 첨가량이 0.1 중량% 미만이면 중합점도 불균일 현상이 개선되지 않으며, 5.0중량%를 초과하는 경우에는 다이라인 현상과 중합점도 저하로 인한 필름물성의 악화를 초래하게된다.If the amount of the monoamine and the monocarboxylic acid is less than 0.1% by weight, the polymerization viscosity nonuniformity is not improved. When the amount of the monoamine and the monocarboxylic acid is more than 5.0% by weight, the film properties are deteriorated due to the die line phenomenon and the polymerization viscosity.

또한, 유기 모노아민 및 유기 모노카르복실산을 중합공정에 첨가한 결과 적정량의 모노산 혹은 모노아민을 마그네슘 화합물 존재하에서 중합함으로써 폴리머칩과 제막필름의 폴리머 점도변화값(Δηrel)이 0.5 이하로 용이하게 억제되고 폴리머의 반응속도를 증가시킬 뿐만 아니라 제막공정중에 실질적인 반응평형에 도달하여 균일하고 양호한 물성을 얻을 수 있게된다.In addition, as a result of adding the organic monoamine and the organic monocarboxylic acid to the polymerization step, by polymerizing an appropriate amount of monoacid or monoamine in the presence of a magnesium compound, the polymer viscosity change value (Δη rel ) of the polymer chip and the film forming film is 0.5 or less. Not only is it easily suppressed and increases the reaction rate of the polymer, but also achieves a substantial reaction equilibrium during the film forming process to obtain uniform and good physical properties.

여기서 폴리머의 점도변화값(Δηrel)과 슬립성 및 투명성의 관계에 대하여 살펴보면, 용융 압출을 위한 충분한 변성효과를 얻기 위해서는 하기식에 의하여 나타낼 수 있는 압출후의 폴리머 점도변화값(Δηrel)이Here, the relationship between the viscosity change value (Δη rel ) of the polymer and the slip property and transparency is described. In order to obtain a sufficient modification effect for melt extrusion, the polymer viscosity change value (Δη rel ) after extrusion can be expressed by the following equation.

Δηrel= (폴리머칩과 98%황산으로 제조한 1%용액 - 황산의 상대점도) - (필름과 98%황산으로 제조한 1% 용액 - 황산의 상대점도)Δη rel = (1% solution made of polymer chip and 98% sulfuric acid-relative viscosity of sulfuric acid)-(1% solution made of film and 98% sulfuric acid-relative viscosity of sulfuric acid)

약 0.5 이하일 것이 요구되는데, 고점도의 폴리머를 사용하거나 상기 조건을 만족하지 않는 경우에는 압출기에서 체류시간 중에 실질적으로 평형에 도달하지 않아 압출시 모노머, 올리고머의 다량발생과 아울러 야기되는 다이라인 현상과 변성으로 인한 필름의 피시아이가 다량 발생하게 되어 필름의 외관이 불량해지고, 슬립성 저하로 인쇄성이 우수한 필름의 제조가 어렵게된다.It is required to be about 0.5 or less. If a high viscosity polymer is used or the above conditions are not satisfied, the extruder does not substantially reach equilibrium during the residence time, and thus die-line phenomenon and denaturation caused by a large amount of monomers and oligomers are caused during extrusion. Due to the large amount of fisheye generated in the film, the appearance of the film is deteriorated, and it is difficult to manufacture a film having excellent printability due to a decrease in slip property.

본 발명에서는 상기와 같은 성분외에 필름의 윤활성을 더욱 양호하게 하기 위하여 중합에서 얻어진 폴리아미드 수지에 에틸렌비스스테라마이드(Ethylenebissteramide : EBS)를 첨가하여 필름을 제조할 수 있다.In the present invention, in order to further improve the lubricity of the film in addition to the above components, the film can be prepared by adding ethylene bissteramide (EBS) to the polyamide resin obtained in the polymerization.

폴리아미드 필름중에 마그네슘 화합물과 모노아민 및 모노카르복실산을 균일하게 분산시키기 위하여 폴리머 칩과 각 첨가제를 별도의 믹서나 블렌더로 미리 혼합 투입하거나 중합시 투입 또는 압출기에 직접 투입하는 방법이 바람직한데, 중합시 투입하는 방법이 분산의 균일성을 위하여 가장 바람직하다.In order to uniformly disperse the magnesium compound, monoamine and monocarboxylic acid in the polyamide film, a method of pre-mixing the polymer chip and each additive with a separate mixer or blender, or during polymerization or directly in the extruder is preferable. The method of adding during polymerization is most preferred for uniformity of dispersion.

또한, 본 발명에 의하여 제조된 폴리아미드 중합물은 티다이법 혹은 인플레이션법을 통하여 필름으로 제조하게 된다.In addition, the polyamide polymer prepared according to the present invention is to be produced into a film through the Ti-die method or inflation method.

이하 본 발명을 실시예를 들어 더욱 상세히 설명하고자 하나 본 발명이 하기 실시예에 의하여 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

실시예 1∼7Examples 1-7

카프로락탐 100중량부, 실리카 0.2 중량부, 물 2중량부 및 표 1에 나타낸 바와 같이 유기 모노아민, 유기 모노카르복실산 및 마그네슘 화합물의 조성을 변화시켜 중합반응기에 넣고 260℃에서 6시간 중합시키고, 이후 내압을 제거하고 220토르(torr)의 감압으로 4시간 동안 반응시켜 일정한 상대점도를 갖는 폴리아미드를 제조하였으며, 각각의 상대점도는 표 1에 나타내었다. 얻어진 폴리아미드 칩을 추출, 건조한 뒤 EBS를 각각의 폴리아미드 수지에 대하여 0.1 중량%로 배합한 수지 N1∼N7을 직경 40mmø의 압출기를 이용하여 수지온도 270℃, 냉각출구온도 40℃로 두께 25㎛의 필름을 제막하였다. 그리고 제막개시 4시간 후의 필름을 사용하여 다이라인의 유무, 피시아이의 수를 육안으로 관찰하고, 또한 제막개시 1시간이 경과한 필름을 사용하여 투명도 및 슬립성을 평가하기 위하여 각각의 헤이즈 값과 정지 마찰계수를 측정하여 표 2에 나타내었다.100 parts by weight of caprolactam, 0.2 parts by weight of silica, 2 parts by weight of water and the composition of the organic monoamine, the organic monocarboxylic acid and the magnesium compound were changed as shown in Table 1, put into a polymerization reactor and polymerized at 260 ° C. for 6 hours, After removing the internal pressure and reacted for 4 hours at a reduced pressure of 220 torr (torr) to prepare a polyamide having a constant relative viscosity, each relative viscosity is shown in Table 1. After extracting and drying the obtained polyamide chip, resins N1 to N7 containing EBS in an amount of 0.1% by weight with respect to each polyamide resin were 25 mm thick at a resin temperature of 270 ° C. and a cooling exit temperature of 40 ° C. using an extruder having a diameter of 40 mm. Film was formed into a film. In order to visually observe the presence or absence of die lines and the number of fisheyes using the film 4 hours after the start of film formation, and to evaluate the transparency and slip properties using the film having passed 1 hour after the start of film formation, The static friction coefficient was measured and shown in Table 2.

비교예 1∼3Comparative Examples 1 to 3

카프로락탐 100중량부, 실리카 0.2중량부, 물 2중량부 및 표 1에서 나타낸 바와 같이 모노아민 혹은 모노카르복실산 화합물을 각각 중합반응기에 넣고 260℃에서 6시간 중합시키고, 이후 내압을 제거한 후 220토르의 감압으로 4시간 동안 반응시켜 일정한 상대점도를 갖는 폴리아미드를 제조하였으며 각각의 상대점도는 표 1에 나타내었다. 이후 EBS를 배합한 수지 N8∼N10을 실시예와 같은 방법으로 필름을 제조한 후 물성을 평가하여 표 2에 나타내었다.100 parts by weight of caprolactam, 0.2 parts by weight of silica, 2 parts by weight of water and the monoamine or monocarboxylic acid compound as shown in Table 1 were each added to a polymerization reactor and polymerized at 260 ° C. for 6 hours. The reaction was carried out under reduced pressure of Thor for 4 hours to prepare a polyamide having a constant relative viscosity, each of which is shown in Table 1. Thereafter, the resins N8 to N10 blended with EBS were prepared in the same manner as in Example, and the physical properties thereof were shown in Table 2 below.

마그네슘 첨가량(ppm)Magnesium addition amount (ppm) 모노카르복실산a)첨가량(중량%)Monocarboxylic acid a) addition amount (weight%) 모노아민b)첨가량(중량%)Monoamine b) Amount added 중합점도(RV)Polymerization Viscosity (RV) 칩과필름의 점도차이Viscosity Difference between Chip and Film 실시예 1Example 1 50c) 50 c) 0.50.5 0.50.5 2.702.70 0.10.1 실시예 2Example 2 100c) 100 c) 1.51.5 -- 2.652.65 0.20.2 실시예 3Example 3 250c) 250 c) -- 2.02.0 2.632.63 0.30.3 실시예 4Example 4 100c) 100 c) 2.02.0 2.02.0 2.652.65 0.20.2 실시예 5Example 5 200d) 200 d) 1.01.0 2.02.0 2.672.67 0.20.2 실시예 6Example 6 500d) 500 d) 2.02.0 1.01.0 2.622.62 0.50.5 실시예 7Example 7 100f) 100 f) 0.50.5 0.50.5 2.652.65 0.40.4 비교예 1Comparative Example 1 -- -- -- 2.722.72 0.60.6 비교예 2Comparative Example 2 -- 5.05.0 -- 2.682.68 0.50.5 비교예 3Comparative Example 3 -- -- 5.05.0 2.662.66 0.60.6

a)초산 b)벤질아민 c)마그네슘아세테이트 d)마그네슘클로라이드a) acetic acid b) benzylamine c) magnesium acetate d) magnesium chloride

f)마그네슘스테아레이트f) magnesium stearate

헤이즈(%)Haze (%) 정지마찰계수Static friction coefficient 다이라인 유무Die line presence 피시아이(개)Fishia () 실시예 1Example 1 N1N1 2.12.1 0.420.42 radish 33 실시예 2Example 2 N2N2 2.02.0 0.420.42 radish 55 실시예 3Example 3 N3N3 2.52.5 0.400.40 radish 66 실시예 4Example 4 N4N4 3.03.0 0.500.50 radish 1010 실시예 5Example 5 N5N5 2.32.3 0.440.44 radish 1010 실시예 6Example 6 N6N6 2.62.6 0.470.47 radish 1313 실시예 7Example 7 N7N7 2.82.8 0.410.41 radish 1111 비교예 1Comparative Example 1 N8N8 3.63.6 0.650.65 U 2020 비교예 2Comparative Example 2 N9N9 3.03.0 0.600.60 U 1515 비교예3Comparative Example 3 N10N10 3.03.0 0.550.55 U 1717

물성측정 방법Property measurement method

(1) 헤이즈 : 헤이즈메타(동경전색(주))를 이용하여 측정하였다.(1) Haze: It measured using haze meter (Tokyo Color Co., Ltd.).

(2) 슬립성 : 상대습도 65%, 온도 23℃의 조건하에서 평행 이동식에 따라 정지 마찰계수(㎲)를 측정하였다.(2) Slipperiness: The static friction coefficient was measured by parallel movement under the condition of 65% relative humidity and 23 ° C temperature.

(3) 다이라인 및 피시아이 : 필름을 300 ×300㎜로 절단하여 그 부분을 육안으로 관찰하고 40㎛ 이상 크기의 피시아이의 수를 측정하였다.(3) Die line and fisheye: The film was cut into 300x300 mm, the part was visually observed, and the number of fisheye of 40 micrometers or more was measured.

본 발명에 따라서 마그네슘 화합물과 모노아민 및 모노 카르복실산을 병용하여 사용함으로써 인쇄성을 저하시키는 다이라인의 방지 및 용융안정성 개선효과를 얻어 필름의 외관이 양호하고, 피시아이가 감소하여 투명성 및 슬립성 향상으로 인쇄성이 양호하고 물성이 개선된 폴리아미드 필름을 수득할 수 있게 된다.According to the present invention, by using a magnesium compound in combination with monoamine and mono carboxylic acid, it is possible to prevent dielines and improve melt stability, which reduces printability. Improving the properties makes it possible to obtain a polyamide film having good printability and improved physical properties.

Claims (3)

폴리아미드 수지의 중합시에 무기입자와 말단조절제로서 유기 모노아민 및 유기 모노카르복실산을 폴리아미드 수지 100에 대하여 0.1 내지 5.0중량% 첨가하고 촉매로서 마그네슘 화합물 10 내지 1000ppm을 첨가하여 중합한 후 압출하는 것을 특징으로 하는 폴리아미드 필름의 제조방법.At the time of polymerization of the polyamide resin, 0.1 to 5.0% by weight of an organic monoamine and an organic monocarboxylic acid as inorganic particles and an end regulator are added to the polyamide resin 100, and 10 to 1000 ppm of a magnesium compound is added as a catalyst, followed by extrusion. Method for producing a polyamide film, characterized in that. 제 1항에 있어서, 상기 유기 모노아민으로는 부틸아민, 이소프로필아민, 헥실아민, 옥틸아민, 도데실아미, 벤질아민, 시클로헥실아민로 이루어진 군으로 부터 선택되고, 상기 유기 모노 카르복실산은 초산, 프로피온산, 부티릭산, 카프로익산, 카프릭산, 벤조익산 등으로 이루어진 군으로 부터 선택되는 것을 특징으로 하는 폴리아미드 필름의 제조방법.According to claim 1, wherein the organic monoamine is selected from the group consisting of butylamine, isopropylamine, hexylamine, octylamine, dodecylami, benzylamine, cyclohexylamine, wherein the organic mono carboxylic acid is acetic acid , Propionic acid, butyric acid, caproic acid, capric acid, benzoic acid and the like. 제 1항에 있어서, 상기 마그네슘 화합물은 마그네슘아세테이트, 마그네슘옥사이드, 마그네슘아이오다이드, 마그네슘스테아레이트, 마그네슘클로라이드로 이루어진 군으로 부터 1종 이상 선택되는 것을 특징으로 하는 폴리아미드 필름의 제조방법.The method of claim 1, wherein the magnesium compound is at least one selected from the group consisting of magnesium acetate, magnesium oxide, magnesium iodide, magnesium stearate, and magnesium chloride.
KR1019970063459A 1997-11-27 1997-11-27 Method for producing polyamide film KR100293355B1 (en)

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