KR100596201B1 - A coating composition and laminating polyester film coated with the same - Google Patents
A coating composition and laminating polyester film coated with the same Download PDFInfo
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- KR100596201B1 KR100596201B1 KR1020000016077A KR20000016077A KR100596201B1 KR 100596201 B1 KR100596201 B1 KR 100596201B1 KR 1020000016077 A KR1020000016077 A KR 1020000016077A KR 20000016077 A KR20000016077 A KR 20000016077A KR 100596201 B1 KR100596201 B1 KR 100596201B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/36—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/36—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with nitrogen-containing compounds, e.g. by nitration
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- C08J2431/00—Characterised by the use of 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 acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2431/04—Homopolymers or copolymers of vinyl acetate
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Abstract
본 발명은 라미네이션용 폴리에스테르 필름의 적어도 일면에 도포되는 코팅 조성물에 관한 것으로서, 아민 변성 폴리올레핀 수지 0.01 내지 5중량%, 이염화규소 0.01 내지 3중량% 및 나머지량의 용매를 포함하는 것을 특징으로 하는 코팅 조성물을 제공한다. 본 발명에 따른 코팅 조성물이 도포된 폴리에스테르 필름은 폴리올레핀 수지와의 접착력이 우수하여 라미네이션 용도로 유용할 뿐만 아니라, 슬립성이 우수하여 필름사이에 블로킹이 일어나는 것을 방지할 수 있다.The present invention relates to a coating composition applied to at least one side of the polyester film for lamination, characterized in that it comprises 0.01 to 5% by weight of the amine-modified polyolefin resin, 0.01 to 3% by weight of silicon dichloride and the remaining amount of solvent It provides a coating composition. The polyester film coated with the coating composition according to the present invention is excellent in adhesiveness with a polyolefin resin and is useful for lamination, and also has excellent slip property to prevent blocking between films.
Description
본 발명은 코팅 조성물 및 이를 이용하여 도포된 라미네이션용 폴리에스테르 필름에 관한 것으로서, 보다 상세하게는 인캡슐레이션(Encapsulation)용 폴리에스테르 필름에 도포시 폴리올레핀 수지와의 접착력 및 슬립성을 향상시킬 수 있는 코팅 조성물 및 이를 이용하여 도포된 폴리에스테르 필름에 관한 것이다. The present invention relates to a coating composition and a polyester film for lamination applied using the same, and more particularly, to improve adhesion and slip property with a polyolefin resin when applied to a polyester film for encapsulation. A coating composition and a polyester film applied using the same.
폴리에틸렌테레프탈레이트로 대표되는 폴리에스테르 필름은 기계적 특성이 우수하여 포장재, 자기 테이프, 그래픽 필름 등 다양한 용도로 많이 이용되고 있다. 폴리에스테르 필름은 그 용도에 따라 다른 고분자 수지로 이루어진 필름과 접착하여 사용하기도 하는데, 이 경우 폴리에스테르 필름의 접착력이 요구된다.Polyester films represented by polyethylene terephthalate have excellent mechanical properties and are widely used in various applications such as packaging materials, magnetic tapes, and graphic films. The polyester film may be used by adhering to a film made of another polymer resin according to its use, in which case the adhesive force of the polyester film is required.
특히, 통상적으로 인캡슐레이션(Encapsulation) 또는 라미넥스(Laminex) 필름이라고 불리우는 라미네이션용 필름은 기계적 특성 및 열적 특성이 요구되는 것 외에도, 투명성이 우수해야 하므로 폴리에스테르 필름이 많이 사용되고 있는데, 일반적으로 폴리에스테르 필름상에 저밀도 폴리에틸렌을 압출 코팅한 후 다시 그 위에 에틸렌비닐아세테이트를 압출 코팅하여 3층 구조의 필름으로 제조되고 있다. 그 러나, 폴리에스테르는 불활성기를 갖는 구조로 되어 있으므로 폴리에스테르 필름과 그 위에 압출 코팅된 저밀도 폴리에틸렌 사이의 접착력이 불량하다. 따라서, 라미넥스 필름 생산업체에서는 고투명 폴리에스테르 필름 표면에 코로나 방전 처리를 하고 앵커(Anchor) 코팅을 한 후 저밀도 폴리에틸렌을 압출 코팅하므로써 폴리에스테르 필름과 폴리에틸렌 사이의 접착력을 향상시키는 방법이 이용되고 있다.In particular, a film for lamination, commonly referred to as an encapsulation or laminex film, is required to have excellent transparency in addition to mechanical and thermal properties, and polyester films are generally used. After extrusion coating low-density polyethylene on the ester film, it is again extruded and coated with ethylene vinyl acetate to produce a three-layer film. However, since the polyester has a structure having an inert group, the adhesion between the polyester film and the low density polyethylene coated thereon is poor. Accordingly, a laminating film producer is using a method of improving adhesion between the polyester film and polyethylene by performing corona discharge treatment on the surface of the high-transparent polyester film, anchor coating, and extrusion coating low density polyethylene.
그러나, 이러한 방법은 코로나 처리 장치나 그라비어 코터와 같은 고가의 장비를 필요로 한다. 특히 가장 많이 사용하고 있는 우레탄계 2액형 앵커액은 환경 오염을 일으킬 뿐만 아니라, 폴리에스테르 필름 표면에 앵커 코팅한 후 폴리에틸렌을 압출 코팅한 후에도 50 ~ 60℃의 온도에서 2, 3일 동안 숙성시켜야만 접착력이 발현되어 공정시간이 길어지는 문제점이 있다. 또한, 코팅된 앵커액으로 인한 폴리에스테르 필름간의 블로킹을 막기 위해 폴리에틸렌을 광폭으로 압출코팅해야 하므로 제품 손실이 큰 문제점이 있다. However, these methods require expensive equipment such as corona treatment devices or gravure coaters. In particular, urethane-based two-component anchor liquids, which are most used, not only cause environmental pollution, but also need to be aged for two or three days at 50 to 60 ° C even after anchor coating on the surface of polyester film and extrusion coating of polyethylene. There is a problem in that the process time is long. In addition, in order to prevent blocking between polyester films due to the coated anchor liquid, polyethylene must be extruded in a wide width, thereby causing a large product loss.
따라서, 코로나 처리나 앵커 코팅 등 부수적인 공정이 필요 없도록 하기 위하여, 고투명 폴리에스테르 필름의 연신공정 전 또는 종연신과 횡연신 사이에 폴리에스테르 필름과 압출코팅된 저밀도 폴리에틸렌과의 접착력을 향상시킬 수 있는 고분자 조성물을 폴리에스테르 필름에 코팅하는 방법에 관한 연구가 활발히 진행되고 있는데, 이러한 코팅공정을 통상적으로 인라인(In-Line)코팅이라고 부른다.Therefore, in order to eliminate the need for ancillary processes such as corona treatment or anchor coating, a polymer capable of improving the adhesion between the polyester film and the low-density polyethylene coated with the extrusion film before the stretching process of the high-transparent polyester film or between longitudinal stretching and transverse stretching. There is an active research on the method of coating the composition on the polyester film, and this coating process is commonly called an in-line coating.
이러한 인라인 코팅 방법으로, 미국 특허 제4,410,600호에는 스티렌과 말레익-안하이드라이드로 이루어진 공중합체를 이축배향된 폴리에스테르 필름에 인라인 코팅하므로써 저밀도 폴리에틸렌과 폴리에스테르 필름 사이의 접착력을 부여하고자 하였다. 그러나, 이러한 방법으로 제조된 필름은 접착력이 부족하여 폴리에스테르 필름의 코팅면에 별도의 코로나 처리가 필요할 뿐만 아니라, 기존의 폴리에틸렌 압출코팅 공정조건으로는 폴리에스테르 필름과의 접착력이 충분치 않으므로 폴리에틸렌의 용융온도를 높여야 하는 문제점이 있다. With this inline coating method, US Pat. No. 4,410,600 attempts to impart adhesion between low density polyethylene and polyester film by inline coating a copolymer of styrene and maleic-anhydride onto a biaxially oriented polyester film. However, the film produced by this method lacks the adhesive force and requires a separate corona treatment on the coated surface of the polyester film, and melts polyethylene because the existing polyethylene extrusion coating process does not have sufficient adhesive force with the polyester film. There is a problem to increase the temperature.
또한, 미국 특허 제4,571,363호에는 열경화성 아크릴 고분자를 인라인 코팅하여 아이오노머(Ionomer)와의 접착력을 향상시키는 방법이 개시되어 있고, 미국 특허 제5,022,944호에는 가수화된 아미노실란을 폴리에스테르 필름에 코팅하여 아이오노머나 폴리에틸렌과의 접착력을 부여하는 방법이 개시되어 있다. 그러나, 상기 특허들에 개시된 방법은 충분한 접착력을 부여하지 못하는 문제가 있다.In addition, U.S. Patent No. 4,571,363 discloses a method of improving the adhesion to ionomers by inline coating a thermosetting acrylic polymer, and U.S. Patent No. 5,022,944 discloses a hydrophobic aminosilane coated on a polyester film to A method of imparting adhesion to an onomer or polyethylene is disclosed. However, the method disclosed in the above patents does not provide sufficient adhesion.
따라서, 본 발명이 이루고자 하는 기술적 과제는 상기 문제점 해결하여 인캡슐레이션(Encapsulation)용 폴리에스테르 필름에 인라인 코팅시 폴리올레핀 수지와의 접착력 및 슬립성을 향상시킬 수 있는 코팅 조성물을 제공하는데 있다.Therefore, the technical problem to be achieved by the present invention is to provide a coating composition that can improve the adhesion and slip properties with a polyolefin resin when inline coating on the polyester film for encapsulation (Encapsulation) by solving the above problems.
본 발명이 이루고자 하는 다른 기술적 과제는 상기 코팅 조성물을 이용하여 도포된 라미네이션용 폴리에스테르 필름을 제공하는데 있다.Another object of the present invention is to provide a polyester film for lamination applied by using the coating composition.
상기 기술적 과제를 달성하기 위하여 본 발명은, 라미네이션용 폴리에스테르 필름의 적어도 일면에 도포되는 코팅 조성물에 있어서, 상기 코팅 조성물은 아민 변성 폴리올레핀 수지 0.01 내지 5중량%, 이염화규소 0.01 내지 3중량% 및 나머지량의 용매를 포함하는 것을 특징으로 하는 코팅 조성물을 제공한다.In order to achieve the above technical problem, the present invention, in the coating composition applied to at least one side of the polyester film for lamination, the coating composition is 0.01 to 5% by weight of amine-modified polyolefin resin, 0.01 to 3% by weight of silicon dichloride and It provides a coating composition comprising a residual amount of solvent.
본 발명에 따른 코팅 조성물에 있어서, 아민 변성 폴리올레핀 수지로는 하기 화학식 1로 표시되는 화합물, 하기 화학식 2로 표시되는 화합물, 또는 이들의 혼합물을 사용하는 것이 바람직하다.In the coating composition according to the present invention, it is preferable to use a compound represented by the following formula (1), a compound represented by the following formula (2), or a mixture thereof as the amine-modified polyolefin resin.
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본 발명에 따른 코팅 조성물에 있어서, 이염화규소의 평균입경은 0.5㎛인 것이 바람직하다.In the coating composition according to the present invention, the average particle diameter of silicon dichloride is preferably 0.5 μm.
본 발명에 따른 코팅 조성물은 폴리에스테르 필름에 대한 코팅 조성물의 젖음성을 향상시키기 위하여 플루오린계 계면활성제를 더 포함하는 것이 바람직하며, 플루오린계 계면활성제의 함량은 상기 고분자 조성액 총중량을 기준으로 0.01 내지 0.5 중량%인 것이 더욱 바람직하다.The coating composition according to the present invention preferably further comprises a fluorine-based surfactant in order to improve the wettability of the coating composition on the polyester film, the content of the fluorine-based surfactant is 0.01 to 0.5 weight based on the total weight of the polymer composition It is more preferable that it is%.
상기 다른 기술적 과제를 달성하기 위하여 본 발명은, 본 발명에 따른 코팅 조성물이 적어도 일면에 도포되어 열처리된 것을 특징으로 하는 라미네이션용 폴리에스테르 필름을 제공한다.In order to achieve the above another technical problem, the present invention provides a polyester film for lamination, characterized in that the coating composition according to the present invention is applied to at least one surface and heat-treated.
본 발명에 따른 라미네이션용 폴리에스테르 필름에 있어서, 코팅 조성물은 필름의 종방향 연신 전 또는 종방향 연신과 횡방향 연신 사이에 도포될 수 있다.In the polyester film for lamination according to the present invention, the coating composition may be applied before the longitudinal stretching of the film or between the longitudinal stretching and the transverse stretching.
본 발명에 따른 라미네이션용 폴리에스테르 필름에 있어서, 코팅 조성물이 코팅된 폴리에스테르 필름상에 폴리올레핀 수지층, 특히 저밀도 폴리에틸렌으로 이루어진 수지층이 더 코팅되는 것이 바람직하며, 폴리올레핀 수지가 코팅된 후 그 위에 에틸렌비닐아세테이트가 더 코팅될 수 있다.In the polyester film for lamination according to the present invention, it is preferable that a polyolefin resin layer, in particular a resin layer made of low density polyethylene, is further coated on the polyester film coated with the coating composition, and after the polyolefin resin is coated, Vinyl acetate may be further coated.
이하에서는 본 발명에 따른 코팅 조성물 및 이를 이용하여 제조된 폴리에스테르 필름을 보다 상세하게 설명하고자 한다.Hereinafter will be described in more detail the coating composition and the polyester film produced using the same according to the present invention.
본 발명은, 라미네이션용 폴리에스테르 필름의 적어도 일면에 도포되는 코팅 조성물에 있어서, 상기 코팅 조성물은 아민 변성 폴리올레핀 수지 0.01 내지 5중량%, 이염화규소 0.01 내지 3중량% 및 나머지량의 용매를 포함하는 것을 특징으로 하는 코팅 조성물을 제공한다.The present invention is a coating composition applied to at least one side of the polyester film for lamination, wherein the coating composition comprises 0.01 to 5% by weight of the amine-modified polyolefin resin, 0.01 to 3% by weight of silicon dichloride and the remainder of the solvent It provides a coating composition, characterized in that.
본 발명의 코팅 조성물에 있어서, 아민 변성 폴리올레핀 수지는 폴리에스테르 필름과 폴리올리핀 수지 사이에 접착력을 부여하는 기능을 한다. 본 발명의 일 실시예에 따른 아민 변성 폴리올레핀 수지의 제조방법을 예를 들어 살펴보면 다음과 같다.In the coating composition of the present invention, the amine-modified polyolefin resin functions to impart adhesive force between the polyester film and the polyolefin resin. Looking at the manufacturing method of the amine-modified polyolefin resin according to an embodiment of the present invention as an example.
하기 반응식 1을 참조하면, 1,2-디클로로에탄을 암모니아와 반응시키면 베타-클로로에틸아민(β-clloroethylamine)을 거쳐 아지리딘(Aziridine) 모노머가 생성된다. Referring to Scheme 1 below, when 1,2-dichloroethane is reacted with ammonia, an aziridine monomer is produced through beta-chloroethylamine.
이어서, 하기 반응식 2에 나타난 바와 같이 아지리딘 모노머를 산촉매하에서 개환중합시키면 최종적으로 수용성 아민 변성 폴리올레핀이 얻어진다.Subsequently, ring-opening polymerization of the aziridine monomer under an acid catalyst, as shown in Scheme 2, finally yields a water-soluble amine-modified polyolefin.
상기 반응식 2에서, x 및 y는 각각 1 이상의 양의 정수임.In Scheme 2, x and y are each a positive integer of 1 or more.
이와 같이 생성된 수용성 아민 변성 폴리올레핀 수지의 1차 아민기는 폴리에스테르 필름 표면의 수산화기 또는 카르복실기와 아미데이션(Amidation) 또는 이미데이션(Imidation) 반응하여 아미드 결합 또는 이미드 결합을 형성하므로써 수용성 변성 폴리올레핀 도막과 고투명 폴리에스테르 필름간에 화학결합을 형성한다. 폴리에스테르 필름의 연신과정에서 이러한 관능기의 활성도는 더욱 커지므로 폴리에테르 필름과의 접착력은 더욱 커지게 된다. 또한, 상기 아민 변성 폴리올레핀 수지를 포함하는 코팅 조성물을 고투명 폴리에스테르 필름 표면에 도포하여 건조시키면, 라미넥스 공정중 압출코팅되는 폴리에틸렌과의 계면접착력이 아민 변성 폴리올레핀 도막의 아미드 또는 이미드 결합에 의해 향상된다.The primary amine group of the water-soluble amine-modified polyolefin resin thus produced is formed by an amidation or imidation reaction of a hydroxyl group or a carboxyl group on the surface of the polyester film to form an amide bond or an imide bond, thereby forming an amide bond or an imide bond. Form chemical bonds between the highly transparent polyester films. In the drawing process of the polyester film, the activity of these functional groups becomes greater, and thus the adhesion with the polyether film becomes larger. In addition, when the coating composition comprising the amine-modified polyolefin resin is applied to the surface of the high-transparent polyester film and dried, the interfacial adhesion with polyethylene which is extruded and coated during the lamination process is improved by the amide or imide bond of the amine-modified polyolefin coating. do.
본 발명의 코팅 조성물에 함유되는 아민 변성 폴리올레핀 수지로는 하기 화학식 1 또는 화학식 2로 표시되는 반복단위를 갖는 수지를 사용하는 것이 바람직하다.As the amine-modified polyolefin resin contained in the coating composition of the present invention, it is preferable to use a resin having a repeating unit represented by the following formula (1) or (2).
<화학식 1><Formula 1>
<화학식 2>
<Formula 2>
본 발명에 따른 코팅 조성물에 있어서, 아민 변성 폴리올레핀 수지의 함량은 코팅 조성물 총중량을 기준으로 0.01 내지 5중량%인 것이 바람직한데, 0.01중량% 미만이면 압축코팅되는 폴리올레핀과의 접착력이 부족하게 되고, 5중량%를 초과하면 코팅 조성물이 도포된 폴리에스테르 필름간의 블로킹(Blocking) 현상이 심화되어 언와인딩(Unwinding)시 필름의 파단이 발생하는 문제점이 있다.In the coating composition according to the present invention, the content of the amine-modified polyolefin resin is preferably 0.01 to 5% by weight based on the total weight of the coating composition, if less than 0.01% by weight is insufficient adhesion to the polyolefin to be compression-coated, 5 If the weight percentage is exceeded, the blocking phenomenon between the polyester film to which the coating composition is applied is intensified, and thus there is a problem that breakage of the film occurs during unwinding.
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본 발명의 코팅 조성물에 있어서, 이염화규소는 코팅 도막의 조도를 높여 필름의 내블로킹성과 슬립성을 향상시키는 기능을 한다. 이염화규소의 함량은 코팅 조성물 종중량을 기준으로 0.01 내지 3중량%인 것이 바람직한데, 0.01중량% 미만인 경우에는 슬립성 개선 및 블로킹 방지 효과가 불량해지고, 3중량%를 초과하는 경우에는 폴리에스테르 필름의 투명성이 저하되어 라미넥스 필름 용도로 사용하기 어렵다. 상기 이염화규소의 평균입경이 0.5㎛일 때 내블로킹성 및 슬립성을 가장 향상시킬 수 있다.In the coating composition of the present invention, silicon dichloride functions to increase the roughness of the coating film and to improve the blocking resistance and slip resistance of the film. The content of silicon dichloride is preferably 0.01 to 3% by weight based on the final weight of the coating composition. If the content is less than 0.01% by weight, the improvement of the slip property and the antiblocking effect is poor, and the content of the polyester dichloride is greater than 3% by weight. Transparency of a film falls and it is difficult to use it for a lamination film use. When the average particle diameter of the silicon dichloride is 0.5 μm, blocking resistance and slip resistance may be most improved.
본 발명에 따른 코팅 조성물은 코팅 조성물이 폴리에스테르 필름에 도포될 때 젖음성을 향상시키기 위하여 플루오린계 계면활성제를 더 포함하는 것이 바람직하다. 상기 플루오린계 계면활성제의 함량은 상기 고분자 조성액 총중량을 기준으로 0.01 내지 0.5 중량%인 것이 더욱 바람직하다.The coating composition according to the invention preferably further comprises a fluorine-based surfactant to improve the wettability when the coating composition is applied to the polyester film. The content of the fluorine-based surfactant is more preferably 0.01 to 0.5% by weight based on the total weight of the polymer composition solution.
본 발명의 코팅 조성물에 있어서, 용매로는 예를 들어 물과 같은 극성용매를 사용할 수 있다. 특히, 용매로서 물을 사용할 경우, 종래 라미넥스 필름 생산업체에서 사용하고 있는 용제형 2액형 폴리우레탄계 앵커액 사용에 따른 환경오염의 문제나 화재 위험성 등을 방지할 수 있다.In the coating composition of the present invention, for example, a polar solvent such as water may be used as the solvent. In particular, when water is used as the solvent, it is possible to prevent a problem of environmental pollution or fire hazard due to the use of a solvent-type two-component polyurethane-based anchor liquid used in the conventional Lanex film manufacturer.
본 발명은 전술한 코팅 조성물들이 적어도 일면에 도포되어 열처리된 것을 특징으로 하는 라미네이션용 폴리에스테르 필름을 제공한다. 본 발명의 라미네에션용 폴리에스테르 필름은 다음과 같은 방법으로 제조될 수 있다.The present invention provides a polyester film for lamination, characterized in that the above-described coating compositions are applied to at least one surface and heat-treated. The polyester film for lamination of the present invention can be produced by the following method.
먼저, 본 발명의 라미네이션용 폴리에스테르 필름을 구성하는 폴리에스테르 수지는 다가 유기산 성분과 다가 알코올 성분을 중축합시켜 제조되는데, 상기 유기산 성분으로는 카르복실산, 특히 방향족 디카르복실산이 바람직하며, 상기 알코올 성분으로서는 글리콜, 특히 알킬렌 글리콜이 바람직하다.First, the polyester resin constituting the polyester film for lamination of the present invention is prepared by polycondensing a polyhydric organic acid component and a polyhydric alcohol component, wherein the organic acid component is preferably a carboxylic acid, particularly an aromatic dicarboxylic acid. As an alcohol component, glycol, especially alkylene glycol is preferable.
상기 방향족 디카르복실산의 구체적인 예로서는, 디메틸 테레프탈산, 테레프탈산, 이소프탈산, 나프탈렌 디카르복실산, 사이클로헥산 디카르복실산, 디페녹시에탄 디카르복실산, 디페닐 디카르복실산, 디페닐에테르 디카르복실산, 안트라센 디카르복실산 또는 α,β-비스(2-클로로페녹시)에탄-4,4'-디카르복실산 등을 들 수 있으며, 이들 중 디메틸 테레프탈산 또는 테레프탈산이 특히 바람직하다.Specific examples of the aromatic dicarboxylic acid include dimethyl terephthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl dicarboxylic acid and diphenyl ether. Dicarboxylic acid, anthracene dicarboxylic acid or α, β-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and the like, among which dimethyl terephthalic acid or terephthalic acid is particularly preferred. .
상기 알킬렌 글리콜의 구체적인 예로서는, 에틸렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 펜타메틸렌 글리콜, 헥사메틸렌 글리콜 또는 헥실렌 글리콜 등을 들 수 있으며, 이들 중 에틸렌 글리콜이 특히 바람직하다.Specific examples of the alkylene glycol include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol or hexylene glycol, and among these, ethylene glycol is particularly preferable.
이렇게 제조된 폴리에스테르 수지는 용융압출되어 비결정 쉬이트(sheet)로 제조된다. 이어서, 비결정 쉬이트를 종방향으로 바람직하게는 3 내지 5배 연신하고, 다시 횡방향으로 바람직하게는 3 내지 5배 연신하여 2축배향 폴리에스테르 필름을 제조한다. 이 때, 본 발명의 코팅 조성물은 연신공정 전후에 도포할 수 있다. 즉, 영국 특허 제1,411,564호에 개시된 바와 같이 종연신 공정 전에 도포할 수 있고, 횡연신 후 열고정 전에 도포할 수도 있으나, 미국 특허 제4,214,035호에 개시된 바와 같이 종연신과 횡연신 사이에 도포한 후 연신공정의 열처리에 의해 물과 같은 용매를 제거하는 것이 바람직하다.The polyester resin thus prepared is melt-extruded into an amorphous sheet. Next, the amorphous sheet is preferably stretched 3 to 5 times in the longitudinal direction, and preferably 3 to 5 times in the transverse direction to prepare a biaxially oriented polyester film. At this time, the coating composition of the present invention can be applied before and after the stretching step. That is, it may be applied before the longitudinal stretching process as disclosed in British Patent No. 1,411,564, or may be applied before heat setting after transverse stretching, but it may be applied after longitudinal stretching and transverse stretching as disclosed in US Pat. No. 4,214,035. It is preferable to remove a solvent such as water by the heat treatment of the process.
본 발명의 코팅 조성물을 폴리에스테르 필름에 도포하는 방법에는 그라비어 롤이나 리버그 그라비아 롤과 같은 롤을 이용하거나, 메이어 바를 이용하거나, 에어 나이프를 이용하는 통상적인 도포방법이 모두 사용될 수 있으며, 폴리에스테르 필름에 도포된 코팅 조성물은 연신공정에서 열경화 및 건조가 이루어지게 된다.In the method of applying the coating composition of the present invention to a polyester film, a roll such as a gravure roll or a rib gravure roll, a mayer bar, or a conventional coating method using an air knife may be used, and a polyester film may be used. The coating composition applied to the thermal curing and drying is done in the stretching process.
본 발명에 따른 라미네이션용 폴리에스테르 필름에 있어서, 코팅 조성물은 필름 일면 또는 양면에 도포될 수 있으며, 일면에 코팅될 경우 다른 면에는 미국 특허 제4,214,035호에 개시된 열경화성 아크릴이나 메타크릴 고분자 수지를 도포할 수도 있다.In the polyester film for lamination according to the present invention, the coating composition may be applied to one side or both sides of the film, and when coated on one side, the other side may be coated with a thermosetting acrylic or methacrylic polymer resin disclosed in US Pat. No. 4,214,035. It may be.
코팅 조성물이 도포된 본 발명의 라미네이션용 폴리에스테르 필름에는 폴리올레핀 수지, 바람직하게는 저밀도 폴리에틸렌으로 이루어진 수지층이 코팅될 수 있으며, 상기 코팅된 폴리올레핀 수지층상에 다른 수지, 특히 에틸렌비닐아세테이트 수지가 더 코팅될 수도 있다.The polyester film for lamination of the present invention to which the coating composition is applied may be coated with a resin layer made of polyolefin resin, preferably low density polyethylene, and further coated with another resin, especially ethylene vinyl acetate resin, on the coated polyolefin resin layer. May be
이하, 실시예 및 비교예를 통해 본 발명을 보다 상세히 설명하기로 한다. 다만, 본 발명의 범위가 하기 실시예로 한정되는 것이 아님은 물론이다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it is a matter of course that the scope of the present invention is not limited to the following examples.
실시예 1Example 1
하기 화학식 1로 표시되는 아민 변성 폴리올레핀 수지 2.0중량%, 평균입경이 0.5㎛인 이염화규소 0.5중량%, 플로린계 계면활성제 0.08중량% 및 나머지 량의 물을 혼합하여 코팅 조성물을 제조하였다.A coating composition was prepared by mixing 2.0 wt% of the amine-modified polyolefin resin represented by Formula 1, 0.5 wt% of silicon dichloride having an average particle diameter of 0.5 μm, 0.08 wt% of a florin-based surfactant, and the remaining amount of water.
<화학식 1><Formula 1>
용융압출한 폴리에틸렌테레프탈레이트 미연신 쉬이트를 종방향으로 80℃에서 3.5배 연신시킨 후, 폴리에틸렌테레프탈레이트 필름의 한쪽 면에 상기 제조한 코팅 조성물을 메이어 바 코팅방식을 이용하여 두께가 3.0㎛가 되도록 도포하였다. 이어서, 코팅 조성물이 도포된 폴리에틸렌테레프탈레이트 필름을 횡방향으로 230℃에서 3.5배 연신하면서 건조시켜 최종적으로 50㎛ 두께의 코팅물이 도포된 폴리에틸렌테레프탈레이트 필름을 제조하였다.After stretching the melt-extruded polyethylene terephthalate unstretched sheet 3.5 times at 80 ° C. in the longitudinal direction, the prepared coating composition on one side of the polyethylene terephthalate film was made to have a thickness of 3.0 μm by using a Meyer bar coating method. Applied. Subsequently, the polyethylene terephthalate film to which the coating composition was applied was stretched 3.5 times at 230 ° C. in the transverse direction to prepare a polyethylene terephthalate film to which a coating having a thickness of 50 μm was finally applied.
실시예 2Example 2
아민 변성 폴리올레핀 수지의 함량을 5.0중량%로 하여 제조한 코팅 조성물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.
실시예 3
아민 변성 폴리올레핀 수지로서 하기 화학식 2로 표시되는 아민 변성 폴리올레핀 수지 2.0중량%를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.
<화학식 2>
실시예 4
아민 변성 폴리올레핀 수지 함량 5.0중량% 및 이염화규소 함량 2.0중량%로 하여 제조한 코팅 조성물을 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that the coating composition prepared with the content of the amine-modified polyolefin resin was 5.0 wt%.
Example 3
A film was prepared in the same manner as in Example 1, except that 2.0 wt% of the amine-modified polyolefin resin represented by the following Formula 2 was used as the amine-modified polyolefin resin.
<Formula 2>
Example 4
A film was prepared in the same manner as in Example 3, except that the coating composition prepared with an amine-modified polyolefin resin content of 5.0 wt% and silicon dichloride content of 2.0 wt% was used.
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실시예 5Example 5
이염화규소의 함량을 2.0중량%로 하여 제조한 코팅 조성물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that the coating composition prepared with the silicon dichloride content of 2.0 wt% was used.
비교예 1Comparative Example 1
코팅 조성물을 도포하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.A film was prepared in the same manner as in Example 1 except that the coating composition was not applied.
비교예 2Comparative Example 2
이염화 규소를 포함시키지 않은 코팅 조성물을 도포한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that the coating composition containing no silicon dichloride was applied.
비교예 3Comparative Example 3
이염화규소 함량을 5.0중량%로 하여 코팅조성물을 제조한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.A film was prepared in the same manner as in Example 1, except that the coating composition was prepared with a silicon dichloride content of 5.0 wt%.
비교예 4Comparative Example 4
폴리에스테르 필름을 열고정한 후, 실시예 1과 동일한 코팅 조성물을 폴리에스테르 필름에 라인속도 60m/min, 건조온도 70℃의 조건에서 오프 라인(Off line) 코팅한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.After heat-setting the polyester film, the same coating composition as in Example 1 was applied to the polyester film in the same manner as in Example 1, except that the coating was performed off-line at a line speed of 60 m / min and a drying temperature of 70 ° C. The film was prepared by the method.
비교예 5Comparative Example 5
코팅 조성물로서 실시예 1과 동일한 코팅 조성물을 사용한 것을 제외하고는 비교예 1과 동일한 방법으로 필름을 제조하였다. A film was prepared in the same manner as in Comparative Example 1 except that the same coating composition as in Example 1 was used.
비교예 6Comparative Example 6
코팅 조성물로서 수분산성 아크릴계 수지를 포함하는 조성물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다.A film was manufactured in the same manner as in Example 1, except that a composition including a water-dispersible acrylic resin was used as the coating composition.
비교예 7Comparative Example 7
코팅 조성물로서 종래의 우레탄계 앵커제를 포함하는 조성물을 사용한 것을 제외하고는 비교예 1과 동일한 방법으로 필름을 제조하였다.A film was manufactured in the same manner as in Comparative Example 1 except that a composition including a conventional urethane anchor agent was used as the coating composition.
상기 실시예 및 비교예에 따라 제조된 필름을 이용하여 다음과 같은 방법으로 라미넥스 필름을 제조하였다. 코팅 조성물이 도포된 필름면이 티-다이를 향하도록 하고, 310℃로 유지되는 티-다이를 통해 밀도가 0.916g/㎤이고 용융지수가 5.0g/10min인 저밀도 폴리에틸렌(현대석유화학 XL500)을 용융압출하여 필름에 코팅 하였다. 이어서, 표면온도가 20℃, 직경이 400mm이고 50rpm의 속도로 회전하는 냉각롤 사이에 필름을 삽입시켜 8Kgf/㎠의 압력으로 밀착시키고 오실레이션 공정을 거쳐 75㎛ 두께의 라미넥스 필름을 제조하여 각종 물성을 다음의 방법으로 측정하여 그 결과를 표 1에 나타냈다. Using the films prepared according to the above Examples and Comparative Examples to produce a laminating film in the following manner. The film surface to which the coating composition is applied is directed toward the tee die, and a low density polyethylene (Hyundai Petrochemical XL500) having a density of 0.916 g / cm 3 and a melt index of 5.0 g / 10 min is passed through the tee die at 310 ° C. Melt extruded and coated on the film. Subsequently, a film was inserted between cooling rolls rotating at a speed of 50 rpm with a surface temperature of 20 ° C. and a diameter of 400 mm. The film was brought into close contact with a pressure of 8 kgf / cm 2, and a lamination film having a thickness of 75 μm was prepared through an oscillation process. Physical properties were measured by the following method, and the results are shown in Table 1.
(1) 접착력(1) adhesion
저밀도 폴리에틸렌 수지가 압출코팅된 실시예 및 비교예의 라미넥스 필름을 폭 25mm, 길이 300mm의 시편으로 제작한 후, 인스트롱(Instron)사의 UTM을 사용하여 200mm/min의 속도로 T형 박리를 실시하여 폴리에스테르 필름과 저밀도 폴리에틸렌 수지층간의 접착력을 측정하였다.After producing the laminate film of the Examples and Comparative Examples of the low-density polyethylene resin extrusion coating of 25mm in width, 300mm in length, T-type peeling at 200mm / min using an Instron UTM The adhesive force between the polyester film and the low density polyethylene resin layer was measured.
(2) 마찰계수(2) coefficient of friction
코팅 조성물로 도포된 필름의 정마찰 계수 및 동마찰 계수를 ASTM D1894에 따라 측정하였다.The static and dynamic friction coefficients of the film applied with the coating composition were measured according to ASTM D1894.
(3) 헤이즈(Haze)(3) Haze
DIN 4768에 따라 필름의 헤이즈를 평가하였다.The haze of the film was evaluated according to DIN 4768.
표 1을 참조하면, 본 발명에 따른 코팅 조성물이 도포되어 제조된 라미네이션용 폴리에스테르 필름은 투명도가 우수할 뿐만 아니라 폴리에틸렌과의 접착력이 양호하며 마찰계수가 낮아 필름간 블로킹도 방지됨을 알 수 있다.
Referring to Table 1, it can be seen that the polyester film for lamination prepared and coated with the coating composition according to the present invention not only has excellent transparency, but also has good adhesion with polyethylene and a low coefficient of friction to prevent blocking between films.
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이에 비하여 코팅 조성물을 도포하지 않은 필름(비교예1)은 접착력이 매우 불량함을 알 수 있다. 또한, 본 발명의 코팅 조성물에 이염화규소를 첨가하지 않은 필름(비교예 2)은 필름 표면의 마찰계수가 크므로 필름의 리와인더 또는 언와인딩시 필름이 파단되거나 라미넥스 공정중에 라미넥스 필름간 블로킹이 발생하여 생산성이 저하되는 문제점이 발생할 수 있으며, 이산화규소의 함량이 본 발명의 범위를 벗어난 코팅 조성물을 도포한 필름(비교예 3)은 마찰계수는 낮아지나 투명성이 저하되어 라미넥스 필름으로 사용하기 어렵게 됨을 알 수 있다.In contrast, it can be seen that the film (Comparative Example 1) not coated with the coating composition is very poor in adhesive strength. In addition, the film which does not add silicon dichloride to the coating composition of the present invention (Comparative Example 2) has a large coefficient of friction on the surface of the film, so that the film breaks during rewinding or unwinding of the film, or blocks between laminax films during the lamine process. This may cause a problem that the productivity is lowered, the film coated with a coating composition in which the content of silicon dioxide is out of the scope of the present invention (Comparative Example 3) is used as a laminating film because the friction coefficient is lowered but the transparency is lowered It can be seen that it is difficult to do.
한편, 비교예 4, 5 및 비교예 7과 같이 폴리에스테르 필름을 열고정한 후에 프라이머 코팅을 하는 오프라인 코팅법에 따라 제조하면 실시예에 따른 인라인 코팅법에 따라 제조한 필름보다 접착력이 저하되는 것을 알 수 있다. 또한, 본 발명의 아민 변성 폴리올레핀 수지 대신 수분산성 아크릴계 수지를 사용한 필름(비교예 6)은 폴리에틸렌 수지와 결합할 수 있는 관능기가 부족하여 결국 접착력이 저하됨을 알 수 있다.On the other hand, after the polyester film is heat-set as in Comparative Examples 4, 5 and Comparative Example 7, and prepared according to the off-line coating method to apply a primer coating it can be seen that the adhesive strength is lower than the film prepared according to the inline coating method according to the embodiment Can be. In addition, it can be seen that the film (Comparative Example 6) using a water dispersible acrylic resin instead of the amine-modified polyolefin resin of the present invention lacks a functional group capable of bonding with a polyethylene resin, resulting in a decrease in adhesive strength.
종래에 사용되고 있는 용제형 2액형 폴리우레탄계 앵커를 사용하여 제조된 필름(비교예 7)의 접착력을 살펴보면, 본 발명에 따른 코팅 조성물을 이용하여 제조된 필름과 유사한 접착력을 보이고 있다. 따라서, 본 발명에 따른 코팅 조성물을 이용하여 필름을 제조하면 전술한 바와 같은 앵커액 사용의 문제점을 발생시키지 않고도 충분한 접착력 및 내블로킹성을 갖는 라미넥스용 폴리에스테르 필름을 제조할 수 있음을 알 수 있다.Looking at the adhesive force of the film (Comparative Example 7) prepared using a solvent-type two-component polyurethane-based anchor used in the prior art, it shows a similar adhesion to the film produced using the coating composition according to the present invention. Therefore, it can be seen that when the film is prepared using the coating composition according to the present invention, a polyester film for laminex having sufficient adhesive force and blocking resistance can be produced without causing problems of the use of the anchor liquid as described above. have.
상기한 바와 같이, 본 발명에 따른 코팅 조성물을 라미네이션용 폴리에스테르 필름에 도포하면 필름의 고투명성을 유지하면서도 폴리올레핀 수지와 폴리에스테르 필름 사이의 접착력이 향상될 뿐만 아니라, 필름의 슬립성도 개선되므로 필름사이에 블로킹이 일어나는 것을 방지할 수 있다.As described above, applying the coating composition according to the present invention to the polyester film for lamination not only improves the adhesive force between the polyolefin resin and the polyester film while maintaining the high transparency of the film, but also improves the slip property of the film between the films. Blocking can be prevented from occurring.
Claims (12)
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| KR101519386B1 (en) * | 2008-12-31 | 2015-05-12 | 코오롱인더스트리 주식회사 | Coating composition and film for Write on and Wipe off |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0637603A1 (en) * | 1993-08-05 | 1995-02-08 | Ici Americas Inc. | Polymeric film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0637603A1 (en) * | 1993-08-05 | 1995-02-08 | Ici Americas Inc. | Polymeric film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101519386B1 (en) * | 2008-12-31 | 2015-05-12 | 코오롱인더스트리 주식회사 | Coating composition and film for Write on and Wipe off |
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