KR100558567B1 - Method for producing biaxially stretched polyester film - Google Patents

Method for producing biaxially stretched polyester film Download PDF

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KR100558567B1
KR100558567B1 KR1019980000244A KR19980000244A KR100558567B1 KR 100558567 B1 KR100558567 B1 KR 100558567B1 KR 1019980000244 A KR1019980000244 A KR 1019980000244A KR 19980000244 A KR19980000244 A KR 19980000244A KR 100558567 B1 KR100558567 B1 KR 100558567B1
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film
weight percent
biaxially stretched
polyester film
weight
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KR19990065121A (en
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임대우
서정태
전해상
윤상규
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도레이새한 주식회사
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

폴리에틸렌테레프탈레이트가 주성분인 폴리에스테르 중합체를 티-다이(T-DIE)로 일정온도에서 용융, 압출하여 냉각드럼에서 무정형의 시트를 제조하고 통상의 방법으로 다수의 롤을 통과시키면서 종방향으로 80℃내지 130℃에서 2내지 5배연신한 다음 0.5내지 10중량퍼센트의 음이온성 수성폴리우레탄제, 0.001내지 5.0중량퍼센트의 멜라민계 경화제 및 0.001내지 6.0중량 퍼센트의 계면활성제를 첨가, 증류수와 혼합 희석하여 농도가 0.5 내지 10.002중량퍼센트인 수분산체를 단위면적당(㎡) 1내지 20그램을 적어도 한면이상에 그라비아 코우터(GRAVURE COATER) 또는 로드 코우터 (ROD COATER)로 도포하여 1.0내지 5.0배 횡방향으로 연신, 건조 및 결정화를 행하여 제조하는 데 음이온성 폴리우레탄 수분산체는 피막형성온도가 0℃이하, 신도 300퍼센트 내지 400퍼센트, 탄성율이 150Kg/㎟ 내지 160Kg/㎟인 폴리에스테르계 폴리우레탄 조성체이며 내수성 및 접착력 향상을 위하여 경화제는 각종의 멜라민계 중에서 PH가 8.0내지 10인 메틸계멜라민 및 도포성향상을 위하여 계면활성제는 PH가 9.0내지 11인 설폰산계 조성체를 사용하여 제조한 이축연신 필름을 사용한 적층의 포장재를 98도의 끓는 물에 60분 동안 방치하더라도 도포된 필름이 떨어지지 않는 것을 특징으로 하는 즉, 금속증착재료 및 잉크와의 접착성이 부여됨과 동시에 내수성 매우 우수한 각종포장재료용 이축연신 폴리에스테르 필름 제품을 제조하는 방법을 제공하는 것이다.A polyester polymer composed mainly of polyethylene terephthalate is melted and extruded at a predetermined temperature with a T-DIE to prepare an amorphous sheet in a cooling drum, and a plurality of rolls are passed through a plurality of rolls in a conventional manner at a temperature of 80 ° C. 2 to 5 times stretching at 130 to 130 ° C., and then 0.5 to 10 weight percent of anionic aqueous polyurethane agent, 0.001 to 5.0 weight percent of melamine-based curing agent, and 0.001 to 6.0 weight percent of surfactant are mixed and diluted with distilled water. 1 to 20 grams of water dispersion (0.5 to 10.002% by weight) per unit area (m2) is applied to at least one surface with a gravure coater or rod coater and stretched 1.0 to 5.0 times in the transverse direction. Anionic polyurethane water dispersion is produced by drying, crystallization, and the film forming temperature is below 0 ℃, elongation 300% to 400%, elastic modulus The polyester-based polyurethane composition is 150Kg / mm 2 to 160Kg / mm 2, and the curing agent has a pH of 8.0 to 10 among various melamine-based melamines, and the surfactant has a pH of 9.0 to improve coating properties. The laminated film using the biaxially oriented film prepared using the sulfonic acid-based composition of 11 to 11, even if left for 60 minutes in boiling water of 98 degrees, characterized in that the applied film does not fall, that is, with the metal deposition material and ink The present invention provides a method for producing biaxially stretched polyester film products for various packaging materials which are provided with adhesion and have excellent water resistance.

Description

이축연신 폴리에스테르 필름의 제조방법Method for producing biaxially stretched polyester film

본 발명은 금속재료 및 잉크와의 접착성을 부여함과 동시에 내수성이 아주 우수한 포장재용 이축연신 폴리에스테르 필름의 제조방법에 관한 것이다.The present invention relates to a method for producing a biaxially stretched polyester film for a packaging material, which provides adhesion with a metal material and ink, and has excellent water resistance.

일반적으로 폴리에스테르는 고결정성 및 고연화점, 강신도, 굴곡강도, 내약품성, 내열성, 투명성, 가스배리어(GAS BARRIER) 등이 우수하여 포장재료, 전기절연재료, 자기기록재료, 섬유제품, 사진재료 등 광범위하게 사용되고 있는데 이러한 용도에는 접착성이 요구되는 경우가 많다.In general, polyester is excellent in high crystallinity, softening point, elongation, flexural strength, chemical resistance, heat resistance, transparency, gas barrier, etc., so it is a packaging material, electrical insulation material, magnetic recording material, textile product, photographic material, etc. It is widely used, but adhesiveness is often required for such applications.

예를 들면, 포장재료에는 인쇄잉크, 금속재료 및 라미네이션 재료와의 접착성, 사진재료에는 젤라틴 및 감광성 조성체와의 접착성, 자기기록용 재료에는 자성체 조성물과의 접착성 등이 요구되며 이축연신 폴리에스테르 필름에 접착성을 부여하는 방법으로는 특정의 폴리에스테르 조성물들을 공중합하여 공압출는 방법, 코로나 방전처리, 플라즈마 처리, 자외선 조사처리 및 특정의 유기화합물 또는 무기화합물을 이용하는 도포법 등이 알려져 있는데 이러한 방법들 중에서 용도별 요구특성 및 생산비 등을 고려하여 이상적인 방법을 선택 사용한다. 또한 도포법에는 폴리에스테르 필름과의 친화성이 높은 조성체를 사용하여 리버스 롤 코우터(REVERSE ROLL COATER), 로드 코우터(ROD COATER), 그라비아 코우터(GRAVURE COATER) 등이 공지되고 있다. 그러나 이러한 방법 중 특정의 수분산성 유기화합물 및 무기화합물을 이용하는 도포법에 있어서, 포장재료에 주로 사용되는 방법은 현재 여러 가지의 바인더 및 첨가제를 사용하는 경우가 대부분인데 종래의 방법들을 살펴보면 일본특개 소57-262369호의 경우 폴리우레탄 수분산체에 비이온계 계면활성제가 혼합된 조성물을 결정배향 완료전의 폴리에스테르 필름에 도포한 후 연신하여 접착성이 부여된 제품을 얻게되나, 이 발명은 자기도료, 세로판 잉크, 사진용 젤라틴 도료와의 접착력을 향상시킨 것으로 금속증착재료와의 접착이 불가능 하다. 또한 일본 특개소 60-248232, 특개소63-249650호 등은 폴리에스테르 변성 공중합체를 이용하여 접착력을 향상하지만 내수성이 저하되어 액체상태의 제품을 보관하는 포장재료로의 사용이 불가능하다.For example, packaging materials require printing ink, adhesion to metal materials and lamination materials, photographic materials to gelatin and photosensitive compositions, magnetic recording materials to magnetic compositions, and biaxial stretching. As a method of imparting adhesiveness to a polyester film, a method of copolymerizing specific polyester compositions and co-extrusion, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, and a coating method using a specific organic or inorganic compound are known. Among these methods, the ideal method is selected considering the required characteristics and production cost. In the coating method, a reverse roll coater, a rod coater, a gravure coater, etc. are known using a composition having a high affinity with a polyester film. However, in the coating method using a specific water-dispersible organic compound and inorganic compound among these methods, the most commonly used method for packaging materials is currently using a variety of binders and additives. In the case of 57-262369, a composition in which a non-ionic surfactant is mixed with a polyurethane water dispersion is applied to a polyester film before completion of crystal orientation, followed by stretching to obtain a product to which adhesiveness is given. Adhesion with plate ink and gelatin paint for photo is improved. In addition, Japanese Patent Application Laid-Open No. 60-248232 and Japanese Patent Laid-Open No. 63-249650 use polyester modified copolymers to improve adhesion, but the water resistance is lowered, making it impossible to use them as packaging materials for storing liquid products.

본 발명에서는 상기와 같은 문제점을 개선하기 위하여 액체상태의 제품 포장재료 또는 냉동가공식품 포장재료, 예를 들면 리키드 박스 (liquid box), 레토르트(retort)포장 등에 쓰이는 금속증착재료 및 폴리에틸렌수지 또는 필름과의 접착력이 우수하고 끓는 물에서도 접착력이 저하되지 않는 내수성을 개선시킨 이축연신 폴리에스테르 필름 제조방법을 제공하는 것이다..In the present invention, in order to improve the above-mentioned problems, metal deposition materials and polyethylene resins or films used in liquid product packaging materials or frozen processed food packaging materials, for example, liquid box, retort packaging, etc. It is to provide a biaxially stretched polyester film production method which is excellent in adhesion to and improved water resistance that does not degrade even in boiling water.

본 발명은 폴리에스테르 중합체를 용융, 압출, 성형하여 종방향으로 2내지 5배 연신한 후 0.5내지 10중량퍼센트의 음이온성 수성폴리우레탄 0.001내지 5.0중량퍼센트의 멜라민계 경화제 및 0.001내지 6.0중량 퍼센트의 계면활성제를 첨가, 증류수와 혼합 희석하여 제조한 것으로 농도가 0.5 내지 10.002중량퍼센트인 수분산체를 필름의 적어도 한 면 이상에 단위면적당(㎡) 1내지 20그램 도포하여 1 내지 5배 횡방향으로 연신, 건조 및 결정화를 행하여 최종필름으로 만든 적층의 포장재로서, 98℃의 물에 30분 동안 방치하더라도 도포된 필름이 떨어지지 않는 것을 특징으로 하는 내수성이 우수한 이축연신 폴리에스테르 필름의 제조방법에 관한 것으로,According to the present invention, the polyester polymer is melted, extruded and molded to be stretched 2 to 5 times in the longitudinal direction, and then 0.5 to 10 weight percent of anionic aqueous polyurethane 0.001 to 5.0 weight percent of melamine-based curing agent and 0.001 to 6.0 weight percent It was prepared by adding and diluting a surfactant with distilled water. The aqueous dispersion having a concentration of 0.5 to 10.002% by weight was applied to at least one side of the film by applying 1 to 20 grams (m 2) per unit area and stretching it in the transverse direction 1 to 5 times. And a method of manufacturing a biaxially stretched polyester film having excellent water resistance, characterized in that the laminated film is dried and crystallized and made into a final film, and the coated film does not fall even if left in water at 98 ° C. for 30 minutes.

상기에서 음이온성 폴리우레탄은 폴리올과 폴리이소시아네이트로 구성되는데 이때 사용되는 폴리올의 종류에는 물, 디아미노사이클로헥산디메탄, 디네틸렌디아민, 디아미노디페닐메탄, 폴리카프락탐계 폴리에스테르 폴리올류, 에틸렌디아민, 폴리옥시 프로필렌글리콜계의 폴리에테르 폴리올 형태, 폴리옥시프로필렌글리콜, 에틸렌글리콜, 네오펜틸글리콜, 디에틸렌글리콜 등이 있고, 폴리이소시아네이트의 종류에는 이소보론디이소시아네이트, 디클로로헥사메탄디이소시아네이트, 헥사메틸렌디이소시아네이트, 톨루엔디이소시아네이트, 크실렌디이소시아네이트 등의 형태가 있다. 음이온성 폴리우레탄은 폴리우레탄 형성성분의 폴리올과 폴리이소시아네이트 혼합물, 가교제는 음이온성 화합물을 주로 사용하며 폴리우레탄 활성수소기가 있는 특정의 화합물을 반응시켜 제조할 수 있다. 폴리우레탄의 형성성분 및 음이온성의 화합물 제조방법에는 예를 들면 방향족이소시아네이트 화합물을 설폰화하는 방법으로 얻을 수 있으며, 또 디카르본산염, 아미노 알콜류의 작산에스테르염을 사용할 수 있다. 폴리우레탄의 활성 수소기 및 특정의 화합물을 반응시켜 제조하는 방법으로는 디카르본산 무수물, 텍트라카르본산 무수물, 에폭시카르본산, 에폭시 수지, 설폰산 등을 사용할 수 있다. 폴리우레탄조성물 중에서 음 이온성은 -SO3, -OSO3, -COOH기 등을 사용할 수 있으나 특히 설폰산 염기가 우수하며 폴리우레탄의 음이온성의 양은 0.02~8.0중량퍼센트가 좋은 데 양에 따라 도포후의 내수성이 좌우된다.The anionic polyurethane is composed of polyols and polyisocyanates. The polyols used here include water, diaminocyclohexanedimethane, dinetilenediamine, diaminodiphenylmethane, and polycaplactam polyester polyols and ethylene. Diamine, polyoxypropylene glycol-based polyether polyol form, polyoxypropylene glycol, ethylene glycol, neopentyl glycol, diethylene glycol, and the like. Diisocyanate, toluene diisocyanate, xylene diisocyanate and the like. Anionic polyurethanes may be prepared by reacting a polyol of a polyurethane-forming component with a polyisocyanate mixture and a crosslinking agent mainly using an anionic compound and having a specific compound having a polyurethane active hydrogen group. As a forming component of an polyurethane and a manufacturing method of an anionic compound, it can be obtained, for example by the method of sulfonating an aromatic isocyanate compound, and the diacid ester salt of dicarboxylic acid and amino alcohol can be used. Dicarboxylic acid anhydride, tetracarboxylic acid anhydride, epoxycarboxylic acid, epoxy resin, sulfonic acid, etc. can be used as a method of making the polyurethane react with the active hydrogen group and a specific compound. Among the polyurethane compositions, the anionic property can be -SO 3 , -OSO 3 , -COOH group, but especially the sulfonic acid base is excellent, and the amount of anionicity of polyurethane is 0.02 ~ 8.0% by weight. This depends.

그리고 본 발명에 사용되는 경화제로 접착성 및 내수성을 보완할 수 있는 데 주로 사용되는 것은 에폭시계, 멜라민수지계 등을 주로 사용되며, 멜라민계가 수분산체의 경시안정성 측면에서는 유리한 측면이 있다. 또한, 도포균일성 향상 및 소포특성을 부여하기 위하여 기타 첨가제를 혼합하는 경우가 있는데 스테아레이트염, 라우릴설폰산염계 등의 음이온 형태, 에틸렌옥사이드와 프로필렌옥사이드의 공중합체인 비이온 형태, 염화암모늄계통의 양이온 및 양쪽성 형태의 계면활성제를 사용하거나 부틸인산염, 디부틸인산염, 트리부틸인산염 등의 알킬 인산염류 또는 실리콘계등의 소포제를 사용하기도 한다.And mainly used to complement the adhesiveness and water resistance as a curing agent used in the present invention is mainly used epoxy-based, melamine resins, etc., melamine-based has a favorable aspect in terms of time stability of the water dispersion. In addition, other additives may be mixed in order to improve coating uniformity and give anti-foaming properties. Anionic forms such as stearate salts and lauryl sulfonate salts, nonionic form copolymers of ethylene oxide and propylene oxide, and ammonium chloride salts A cation and amphoteric type of surfactant may be used, or an alkyl phosphate such as butyl phosphate, dibutyl phosphate, tributyl phosphate, or an antifoaming agent such as silicone may be used.

본 발명에 따른 내수성이 우수한 이축연신 폴리에스테르 필름의 제조방법을 구체적으로 설명하면 다음과 같다.Referring to the production method of the biaxially stretched polyester film excellent in water resistance according to the present invention in detail.

폴리에틸렌테레프탈레이트가 주성분인 폴리에스테르 중합체를 티-다이(T-DIE)로 일정온도에서 용융, 압출하여 냉각드럼에서 무정형의 시트를 제조하고 통상의 방법으로 다수의 롤을 통과시키면서 종방향으로 80℃내지 130℃에서 2내지 5배 연신한 후 0.5∼10중량%의 음이온성 수성 폴리우레탄과 0.001∼5.0중량%의 멜라민계 경화제 및 0.001∼6.0중량%의 계면활성제를 첨가하고 증류수와 혼합 희석시켜 농도가 0.5∼10.002중량%인 수분산체를 제조하고, 이 수분산체를 필름의 적어도 한면 이상에 단위면적(1㎡)당 1∼20그램을 그라비아 코우터(GRAVURE COATER)또는 로드 코우터(ROD COATER)로 도포한 후 횡방향으로 1내지 5배 연신하고 건조 및 결정화를 행하여 제조한다. A polyester polymer composed mainly of polyethylene terephthalate is melted and extruded at a predetermined temperature with a T-DIE to prepare an amorphous sheet in a cooling drum, and a plurality of rolls are passed through a plurality of rolls in a conventional manner at a temperature of 80 ° C. After stretching 2 to 5 times at 130 占 폚, 0.5-10% by weight of anionic aqueous polyurethane, 0.001-5.0% by weight of melamine-based curing agent and 0.001-6.0% by weight of surfactant were added and mixed and diluted with distilled water. A water dispersion of 0.5 to 10.002% by weight is prepared, and 1 to 20 grams per unit area (1 m 2) of at least one surface of the film is gravure coater or rod coater. After the coating, the film is stretched 1 to 5 times in the transverse direction, and dried and crystallized.

상기 음이온성 수성 폴리우레탄을 0.5중량% 미만으로 첨가하면 각종 재료와의 접착력이 저하되고, 10중량%를 초과하여 첨가할 경우 지나친 접착력에 의해 내수성 저하 및 블록킹에 의한 접착제의 전이현상이 발생하므로 바람직하기는 1.0중량% 내지 8.0중량% 첨가하는 것이 가장 유리하며, 멜라민계 경화제의 경우 0.001중량% 미만을 첨가하면 만족스러운 접착력과 내수성 확보가 어렵고 5.0중량%를 초과하여 첨가하면 도포시 도포층이 갈라지는 결점이 발생하므로 바람직하기는 0.1중량% 내지 3.5중량%를 첨가하는 것이 유리하다. 또한 계면 활성제는 0.001중량% 미만 또는 6.0중량%를 초과하여 첨가시에는 도포결점발생과 거품의 과량 발생 및 접착력 저하 등의 문제점이 있으므로 바람직하기는 0.1중량% 내지 4.0중량% 첨가하는 것이 유리하다.When the anionic aqueous polyurethane is added in an amount less than 0.5% by weight, the adhesive strength with various materials is lowered. When the anionic water-based polyurethane is added in an amount of more than 10% by weight, the water resistance decreases due to excessive adhesion and the transition phenomenon of the adhesive due to blocking is preferable. It is most advantageous to add 1.0% by weight to 8.0% by weight, and in the case of melamine-based curing agent, if it is less than 0.001% by weight, it is difficult to secure satisfactory adhesive strength and water resistance. It is advantageous to add 0.1% to 3.5% by weight since defects occur. In addition, when the surfactant is added less than 0.001% by weight or more than 6.0% by weight, there are problems such as coating defects, excessive generation of bubbles and deterioration of adhesive strength, and it is preferable to add 0.1% to 4.0% by weight.

뿐만 아니라, 수분산체는 피막형성온도가 0℃이하, 신도 300퍼센트 내지 400퍼센트, 탄성율이 150Kg/㎟ 내지 160Kg/㎟인 폴리우레탄 조성체이며, 내수성 및 접착력 향상을 위하여 경화제는 각종의 멜라민계 중에서 PH가 8.0내지 10인 메틸계멜라민을, 그리고 도포성 향상을 위하여 계면활성제는 PH가 9.0내지 11인 설폰산계 조성체를 사용하여 접착성이 부여됨과 동시에 내수성이 우수한 이축연신 필름을 제조할 수 있다.In addition, the water dispersion is a polyurethane composition having a film forming temperature of less than 0 ℃, elongation of 300% to 400%, elastic modulus of 150Kg / ㎜ ~ 160Kg / ㎜, and the curing agent in various melamine system to improve water resistance and adhesion Methyl melamine having a pH of 8.0 to 10 and a surfactant can be prepared using a sulfonic acid-based composition having a pH of 9.0 to 11 to improve adhesion, and a biaxially stretched film having excellent water resistance can be prepared. .

본 발명에서 제조한 이축연신 폴리에스테르 필름을 사용하여 만든 각종의 적층 포장재는 98℃의 물에 30분 동안 방치하더라도 도포된 필름이 떨어지지 않는 것이 특징이다.Various laminated packaging materials made using the biaxially stretched polyester film prepared in the present invention are characterized in that the applied film does not fall even if left in water at 98 ° C. for 30 minutes.

본 발명에서 특성치 평가는 다음의 측정법 및 평가기준에 의하여 평가하였다.Characteristic evaluation in the present invention was evaluated by the following measurement method and evaluation criteria.

(1) 금속증착재료의 접착성(1) Adhesiveness of metal deposition materials

이축연신 폴리에스테르 필름에 알루미늄을 증착된 제품에 썰린필름을 130도에서 2KG/㎟압력으로 1분동안 합지한 후 가로 12.5㎝ 세로 2.54㎝크기 시료를 제작한 후 90도 방향으로 박리할 때 부여되는 힘으로 평가 한다.It is given when the film sliced on a product coated with aluminum on a biaxially stretched polyester film is laminated at 130 ° C for 2 minutes at a pressure of 2KG / mm2, and then peeled in a 90 ° direction after making a 12.5cm wide 2.54cm size sample. Evaluate by force.

(2) 잉크접착성(2) ink adhesiveness

ASTMD-3359에 준하여 평가하여 그 결과를 아래와 같이 평가 하였다.The evaluation was conducted according to ASTMD-3359 and the results were evaluated as follows.

(3) 신도, 탄성율의 측정(3) Measurement of elongation and elastic modulus

도요세이키사의 제품을 사용하여 ASTM-D882 규격에 의하여 평가하였다.It evaluated by ASTM-D882 standard using the product of Toyo Seiki company.

○ : 접착력 양호한 경우○: good adhesion

△ : 부분적인 접착력이 있을 경우△: partial adhesion

× : 접착력이 전혀 나타나지 않는 경우 ×: When no adhesive force appears at all

(4) 내수성의 평가(4) evaluation of water resistance

알루미늄 금속이 증착된 이축연신 폴리에스테르 필름에 폴리에틸렌이미드 접착제를 코팅한 후 20미크론 폴리에틸렌필름을 130도에서 30초 동안 4kg/㎟ 압력으로 합지한 후 가로 5㎝ 세로 5㎝ 크기의 시료를 98℃의 물속에 30분간 방치 후 폴리에틸렌 필름과 박리되는 상태를 아래와 같이 표시한다.After coating polyethyleneimide adhesive on the biaxially stretched polyester film on which aluminum metal was deposited, the 20 micron polyethylene film was laminated at 130 ° C for 4 seconds at a pressure of 4 kg / mm2, and the sample was 5 cm wide and 5 cm long at 98 ° C. After leaving for 30 minutes in water, the state peeled from the polyethylene film is indicated as follows.

○ : 박리가 되지 않을 경우○: When peeling off

△ : 부분박리 될 경우△: partly peeled off

× : 완전 박리될 경우 ×: when completely peeled off

이하 실시예 및 비교예를 들어 본 발명을 좀 더 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

실시예 1Example 1

고유점도 0.65인 폴리에스테르 중합체를 티-다이(T-DIE)오 280℃에서 용융,압출하여 35℃의 냉각드럼에서 무정형의 시트를 제조하고 종방향으로 95℃에서 4.0배 연신한 후 음이온성 폴리우레탄(에틸렌글리콜과 헥사메틸렌디이소시아네이트가 1:1몰비로 반응된 것) 4.0중량퍼센트, PH가 9인 멜라민계 경화제를 1.0중량퍼센트,톨루엔설폰산을 0.8중량퍼센트가 함유된 수분산체를 로드 코우터(ROD COATER)를 이용하여 5 g/㎡ 도포두께로 코팅한 후 130℃에서 건조와 동시에 횡방향으로 3.0배 연신하고 210℃에서 결정화를 하여 평균두께 12미크론의 이축연신 필름을 제조하였다.A polyester polymer having an intrinsic viscosity of 0.65 was melted and extruded at 280 ° C. to prepare an amorphous sheet in a cooling drum at 35 ° C., stretched 4.0 times at 95 ° C. in a longitudinal direction, and then anionic poly A load dispersion containing 4.0% by weight of urethane (the reaction of ethylene glycol and hexamethylene diisocyanate in a 1: 1 molar ratio), 1.0% by weight of a melamine-based curing agent having a pH of 9, and 0.8% by weight of toluenesulfonic acid. After coating at 5 g / ㎡ coating thickness using a ROD COATER (A), the film was stretched 3.0 times in the transverse direction at the same time drying at 130 ℃ and crystallized at 210 ℃ to prepare a biaxially stretched film having an average thickness of 12 microns.

상기에서 제조한 이축연신 폴리에스테르 필름에 두께 500옴스트롬(Å) 알루미늄증착을 하여 그 결과를 <표 1>에 기술하였다. 그 결과 실시예 1가 가장 양호한 결과를 얻을 수 있었다.500 ohm thick aluminum deposition was carried out on the biaxially stretched polyester film prepared above, and the results are shown in <Table 1>. As a result, Example 1 was able to obtain the best result.

비교예 1Comparative Example 1

상기 실시예 1에서 음이온성 폴리우레탄 대신 시중에서 구입한 폴리우레탄(독일바이엘사 제품; 상품명 DLN)을 4.0중량퍼센트, 에폭시계 경화제를 1.0중량퍼센트, 계면활성제(일본 유지사의 상품명 NS-210제품)을 0.2중량퍼센트 혼합하여 제조하였고 그외는 실시예 1과 동일하게 실시하여 그결과를 <표 1>에 기술하였다.In Example 1, instead of the anionic polyurethane, commercially available polyurethane (manufactured by German Bayer Company; trade name DLN) was 4.0 wt%, epoxy curing agent was 1.0 wt%, and a surfactant (trade name NS-210 manufactured by Nippon Oil Industries, Ltd.) Was prepared by mixing 0.2% by weight, and else the same as in Example 1 and the results are shown in Table 1.

비교예 2Comparative Example 2

상기 실시예 1에서 음이온성 폴리우레탄 대신 시중에서 구입한 수용성 폴리에스테르(일본 합성사 제품; 상품명 WR901)을 4.5중량퍼센트 함유된 된 것을 사용하여 제조하였고 그외는 실시예 1과 동일하게 실시하여 그결과를 <표 1>에 기술하였다In Example 1, instead of the anionic polyurethane, a commercially available water-soluble polyester (manufactured by Nippon Synthetic Co., Ltd .; brand name WR901) was prepared containing 4.5 wt%, and the same procedure as in Example 1 was conducted. It is described in Table 1.

실시예 2 ~ 5 및 비교예 3 ~ 5Examples 2 to 5 and Comparative Examples 3 to 5

실시예 1에서 수분산체의 조성물중 실시예 1과 동일한 접착제, 경화제 및 계면활성제를 사용하여 각 성분의 함량만을 변경하되 수분산체의 첨가량 및 그 결과를 <표 1>에 기술하였다In Example 1, only the content of each component was changed by using the same adhesive, curing agent, and surfactant as in Example 1, but the amount of the aqueous dispersion and the results thereof are described in Table 1.

<표 1>TABLE 1

본 발명은 금속증착재료와 잉크 등에 대한 접착성이 뛰어나고 내수성을 부여함으로써 각종 포장재로 사용할 때 특히 내열, 내수에 대한 안정성을 보장할 수 있는 이축연신 폴리에스테르 필름을 얻을 수 있다.The present invention can obtain a biaxially stretched polyester film that can guarantee stability against heat and water, especially when used in various packaging materials by providing excellent adhesion to metal deposition materials and inks and water resistance.

Claims (3)

폴리에스테르 중합체를 공지의 방법으로 용융, 압출, 성형하고 종방향으로 연신한 다음 0.5내지 10중량퍼센트의 음이온성 폴리우레탄 0.001내지 5.0중량퍼센트의 멜라민계 경화제 및 0.001 내지 6.0중량퍼센트의 설폰산계 계면활성제를 첨가하고 증류수와 혼합 희석하여 농도가 0.5내지 10.002중량퍼센트가 되도록 제조한 수분산체를 필름의 적어도 한 면 이상에 단위면적당(㎡) 1내지 20그램 도포하여 1.0내지 5.0배 횡방향으로 연신 및 건조시켜 필름으로 제조함을 특징으로 하는 내수성이 우수한 이축연신 폴리에스테르 필름의 제조방법Melting, extruding, molding and stretching longitudinally the polyester polymer in a known manner, then 0.5 to 10 weight percent anionic polyurethane 0.001 to 5.0 weight percent melamine-based curing agent and 0.001 to 6.0 weight percent sulfonic acid surfactant Was added and diluted with distilled water to give a concentration of 0.5 to 10.002% by weight of the aqueous dispersion applied to at least one side of the film (m 2) 1 to 20 grams per unit area, stretched and dried 1.0 to 5.0 times in the transverse direction To produce a biaxially stretched polyester film having excellent water resistance 제1항에 있어서,The method of claim 1, 음이온성 폴리우레탄의 피막형성 온도가 0℃이하, 신도 300퍼센트 내지 400퍼센트, 탄성율이 150Kg/㎟ 내지 160Kg/㎟인 것을 특징으로 하는 이축연신 폴리에스테르 필름의 제조방법Method for producing biaxially stretched polyester film, characterized in that the film forming temperature of the anionic polyurethane is 0 ℃ or less, elongation 300% to 400%, elastic modulus 150Kg / mm2 to 160Kg / mm2 제1항에 있어서,The method of claim 1, 계면활성제는 스테아레이트염, 라우릴설폰산염, 에틸렌옥사이드와 프로필렌옥사이드공중합체, 톨루엔설폰산 등의 조성물로 된 것 중에서 한가지 이상 선택 사용함을 특징으로 하는 이축연신 폴리에스테르 필름의 제조방법Surfactant is a method for producing a biaxially stretched polyester film, characterized in that at least one selected from the composition consisting of stearate salt, lauryl sulfonate, ethylene oxide and propylene oxide copolymer, toluenesulfonic acid, etc.
KR1019980000244A 1998-01-08 1998-01-08 Method for producing biaxially stretched polyester film KR100558567B1 (en)

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KR100483655B1 (en) * 1999-11-23 2005-04-19 에스케이씨 주식회사 The processing method of polyester film
KR100718920B1 (en) * 2001-12-11 2007-05-16 주식회사 코오롱 Manufacturing method for good adhesion polyester film for melted polyethylene
KR100839111B1 (en) * 2003-02-17 2008-06-19 주식회사 코오롱 Polyester film for artificial marble molding and their preparation method
KR20050087505A (en) * 2004-02-27 2005-08-31 주식회사 코오롱 Manufacturing method for good adhesion polyester film
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KR930019401A (en) * 1992-03-31 1993-10-18 미리암 디. 메코나헤이 Polymeric release film
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