KR20110077864A - Biaxyally oriented polyester thermal adhesive film - Google Patents

Biaxyally oriented polyester thermal adhesive film Download PDF

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KR20110077864A
KR20110077864A KR1020090134534A KR20090134534A KR20110077864A KR 20110077864 A KR20110077864 A KR 20110077864A KR 1020090134534 A KR1020090134534 A KR 1020090134534A KR 20090134534 A KR20090134534 A KR 20090134534A KR 20110077864 A KR20110077864 A KR 20110077864A
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adhesive film
heat
polyester
thermal adhesive
amorphous
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KR1020090134534A
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KR101695921B1 (en
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최미주
김상묵
허혜영
정태형
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에스케이씨 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/06—Homopolymers or copolymers of esters of polycarboxylic acids
    • C09J131/08—Homopolymers or copolymers of esters of polycarboxylic acids of phthalic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

PURPOSE: A biaxially oriented polyester thermal adhesive film is provided to ensure excellent heat resistance and transparency compared with existing polyolefin thermal adhesive film and to improve release strength. CONSTITUTION: A biaxially oriented polyester thermal adhesive film comprises crystalline polyester and amorphous copolymerized polyester, wherein haze is 10% or less and a melting temperature is more than 200 °C. The adhesive strength of the thermal adhesive film is 1.5-5.0 kgf/15mm when the thermal adhesive film is self-adhered at 200-250 °C for 1 second after the lamination of a substrate layer. The crystalline polyester is included in the amount of 10-60 weight% based on the total weight of the thermal adhesive film.

Description

이축연신 폴리에스터 열접착 필름{BIAXYALLY ORIENTED POLYESTER THERMAL ADHESIVE FILM}Biaxially Stretched Polyester Thermal Adhesive Film {BIAXYALLY ORIENTED POLYESTER THERMAL ADHESIVE FILM}

본 발명은 내열성이 요구되는 식품 포장재(pouch)의 실란트(sealant)로서 사용될 수 있는 이축연신 폴리에스터 열접착 필름에 관한 것이다.The present invention relates to biaxially stretched polyester thermal adhesive films that can be used as sealants for food pouches that require heat resistance.

최근 편리성이 강조되면서 저장성 가공식품, 일명 레토르트(retort) 식품이 크게 발달되고 있다. 레토르트 식품 중에서도 전자레인지를 이용하는 식품의 경우에는 음식물의 온도가 포장재로 사용되는 폴리올레핀의 융점 이상으로 올라가는 경우가 많다. Recently, as convenience is emphasized, shelf-life processed foods, also known as retort foods, are greatly developed. Among retort foods, foods using a microwave oven often rise above the melting point of the polyolefin used as a packaging material.

그러나, 기존의 무연신 폴리프로필렌(CPP, cast polypropylene)의 경우 융점이 160℃ 이하이기 때문에 전자레인지로 조리되는 식품에 사용할 경우 내열성이 충분하지 않았다. 특히, 내용물의 지방함량이 많거나 점도가 높거나 건더기가 크거나 또는 매운맛이 강한 경우에는 음식물과 포장재가 맞닿는 계면에서의 온도가 180℃ 이상으로 상승하게 되어 CPP를 실란트로 사용할 경우 음식물에 녹아 들어가는 등의 문제가 발생될 우려가 있으며, 내유성이 부족하여 음식물이 실란트 내부로 침투되는 경향이 있었다.However, in the case of conventional non-stretched polypropylene (CPP, cast polypropylene) melting point is less than 160 ℃ when used in food cooked in a microwave oven was not enough heat resistance. In particular, when the content of fat is high, the viscosity is high, the dryness is strong, or the spicy taste is strong, the temperature at the interface between food and packaging material rises to 180 ° C or more, and when CPP is used as a sealant, it dissolves in food. There is a possibility that a problem may occur, and there is a tendency for food to penetrate into the sealant due to lack of oil resistance.

또한, 레토르트용 식품 포장재의 구성요소인 산소 차단(barrier) 필름으로서 알루미늄 호일이나 증착을 이용할 수 없는 전자레인지용 포장재의 경우 투명증착 필름을 이용하고 있는데, 이 경우 포장재 구성시 적층되는 CPP 실란트의 높은 헤이즈(haze)로 인하여 내용물이 보이는 투명 포장재로 제조되기 힘들뿐만 아니라 재활용 시에도 서로 다른 재질이 적층된 구성으로 인해 어려움이 있다. In addition, as an oxygen barrier film that is a component of a retort food packaging material, a transparent packaging film is used in the case of a microwave packaging material in which aluminum foil or vapor deposition cannot be used. In this case, a high CPP sealant laminated in the packaging material is used. Due to the haze (haze) is not only difficult to manufacture the transparent packaging material visible content, there is a difficulty due to the configuration in which different materials are laminated at the time of recycling.

종래의 폴리올레핀계 열접착 필름으로서, 한국 특허공개 제2007-0089820호에 레토르트 포장용 폴리올레핀계 접착필름이 개시되어 있다. 그러나 상기 필름은 열수축률 및 접착강도 면에서는 우수하나 앞서 말한 바와 같이 내열성이 160℃ 미만이므로 전자레인지에서 가열시 용융되는 문제가 있어 식품 포장용도로 사용하기에는 적당하지 않다.As a conventional polyolefin thermal adhesive film, Korean Patent Publication No. 2007-0089820 discloses a polyolefin adhesive film for retort packaging. However, the film is excellent in terms of heat shrinkage and adhesive strength, but as mentioned above, since the heat resistance is less than 160 ° C., there is a problem that the film melts when heated in a microwave oven, and thus it is not suitable for use in food packaging.

물질의 특성상 폴리에스터는 폴리올레핀계에 비해 높은 내열성을 가지고 있지만 종래에는 대개 금속 라미네이션이나 박리성(easy-peel) 필름으로 자가 접착강도가 강하게 요구되지 않는 용도에만 적용되어 왔다. 한국 특허공개 제1999-0065023호에는 금속 라미네이션용 열접착 공중합 폴리에스터 필름이 개시되어 있으며, 한국 특허공개 제2001-0002729호에는 공압출 2층 폴리에스터 접착 필름이 개시되어 있다. 그러나, 상기 금속라미네이션용 필름은 포장재(pouch) 제조공정 온도에서 자가 접착강도가 충분하지 않고, 상기 공압출 필름은 레토르트 살균 처리 후에 공압출 층이 분리되는 현상이 발생하며 무정형인 접착층의 낮은 접착 개시 온도 때문에 레토르트 살균 처리 중에 접착이 발생하는 등 실란트 용도로 이용되기에는 어려움이 있다. Due to the nature of the material, polyester has a higher heat resistance than polyolefins, but conventionally, it has been applied only to applications in which self adhesive strength is not strongly required as a metal lamination or an easy-peel film. Korean Patent Laid-Open Publication No. 1999-0065023 discloses a heat-bonded copolymer polyester film for metal lamination, and Korean Patent Publication No. 2001-0002729 discloses a coextruded two-layer polyester adhesive film. However, the metal lamination film does not have sufficient self-adhesive strength at the pouch manufacturing process temperature, the co-extruded film is a phenomenon that the co-extruded layer is separated after the retort sterilization treatment, and low adhesion start of the amorphous adhesive layer It is difficult to be used for sealant applications such as adhesion occurs during retort sterilization due to temperature.

따라서, 본 발명의 목적은 내열성 및 투명성이 개선되고 조성 및 접착조건에 따라 박리성 접착 및 영구 접착이 가능한 자가접착용 이축연신 폴리에스터 열접착 필름을 제공하는 것이다. Accordingly, it is an object of the present invention to provide a self-adhesive biaxially stretched polyester thermal adhesive film capable of improved heat resistance and transparency and peelable adhesion and permanent adhesion according to composition and adhesion conditions.

상기 목적에 따라, 본 발명은 결정성의 폴리에스터 및 무정형 공중합 폴리에스터를 포함하며, 헤이즈가 10% 이하이고 용융온도가 200℃ 초과이며, 기재층과 적층 후에 200 내지 250 ℃에서 1초간 자가 접착했을 때의 접착강도가 1.5 내지 5.0 kgf/15mm인, 이축연신 폴리에스터 열접착 필름을 제공한다.In accordance with the above object, the present invention comprises crystalline polyester and amorphous copolyester, having a haze of 10% or less, a melting temperature of more than 200 ° C., and self-adhesion at 200 to 250 ° C. for 1 second after lamination with a base layer. It provides a biaxially stretched polyester thermal adhesive film having an adhesive strength of 1.5 to 5.0 kgf / 15 mm.

본 발명의 이축연신 폴리에스터 열접착 필름은, 종래의 폴리올레핀계 열접착 필름에 비해 내열성 및 투명성이 우수하고 기존의 폴리에스터계 열접착 필름에 비하여 접착강도가 향상되어 전자레인지용 레토르트 식품 포장재의 실란트로서 활용될 수 있다.The biaxially stretched polyester heat-adhesive film of the present invention is excellent in heat resistance and transparency compared to the conventional polyolefin-based heat-adhesive film, and has improved adhesive strength as compared to the conventional polyester-based heat-adhesive film, resulting in a sealant for a retort food packaging material for a microwave oven. It can be utilized as.

이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

고온에서 충분한 접착강도를 가지는 열접착 필름을 제조하기 위해서는 비결정질 성분의 공중합율을 높여 무정형이 되도록 하는 것이 유리하다. 그러나 무정 형 공중합 폴리에스터의 경우 이축연신시 열고정을 하더라도 수축되는 경향이 강하다. 반면에, 결정성 폴리에스터의 경우 이축연신을 실시하더라도 열고정을 통해 열수축율을 감소시킬 수 있으나, 열경화로 인해 접착성을 잃게 되는 것이 일반적이다. 이와 같이, 무정형 공중합 폴리에스터는 접착성을, 결정성 폴리에스터는 치수안정성 및 유연성을 향상시키는 역할을 하므로, 접착성과 열안정성 및 충격강도를 모두 만족시키기 위해서는 무정형 공중합 폴리에스터와 결정성 폴리에스터를 적당한 비율로 혼합하여 사용하여야 한다. In order to produce a thermal adhesive film having sufficient adhesive strength at high temperature, it is advantageous to increase the copolymerization rate of the amorphous component to be amorphous. However, amorphous copolyester has a strong tendency to shrink even if heat-setting during biaxial stretching. On the other hand, in the case of crystalline polyester, even if biaxial stretching is performed, heat shrinkage can be reduced through heat setting, but it is common to lose adhesiveness due to thermal curing. As such, the amorphous copolymer polyester serves to improve adhesion and the crystalline polyester improves the dimensional stability and flexibility. The mixture should be used in an appropriate ratio.

예를 들어, 상기 결정성 폴리에스터는 전체 필름의 중량을 기준으로 10 내지 60 중량%로 함유되고, 상기 무정형 공중합 폴리에스터는 40 내지 90 중량%로 함유되는 것이 좋다.For example, the crystalline polyester is contained in 10 to 60% by weight based on the weight of the entire film, the amorphous copolymer polyester is preferably contained in 40 to 90% by weight.

본 발명의 필름에 사용되는 결정성 폴리에스터는, 융점이 낮고 유연성을 증가시키기 위해 폴리부틸렌테레프탈레이트(PBT), 폴리트리메틸렌테레프탈레이트(PTT), 또는 이의 혼합수지를 사용하는 것이 바람직하다.In the crystalline polyester used in the film of the present invention, it is preferable to use polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), or a mixed resin thereof in order to have a low melting point and increase flexibility.

또한, 본 발명의 필름에 사용되는 무정형 공중합 폴리에스터는, 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트(PBT), 및 폴리트리메틸렌테레프탈레이트(PTT) 중 1종 이상의 폴리에스터에 2가알콜 또는 2가산이 공중합된 무정형의 수지인 것이 바람직하다. 이 때, 상기 2가알콜 또는 2가산의 공중합율은 전체 무정형 공중합 폴리에스터 수지를 기준으로 10 내지 25 mol%인 것이 좋다.In addition, the amorphous copolyester used in the film of the present invention is a dihydric alcohol in at least one polyester of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT). Or an amorphous resin copolymerized with diacids. At this time, the copolymerization rate of the dihydric alcohol or diacid is preferably 10 to 25 mol% based on the total amorphous copolymerized polyester resin.

또한, 공중합되는 2가알콜 또는 2가산으로서는 네오펜틸글리콜, 1-4-시클로헥산디메탄올, 이소프탈산, 및 디메틸이소프탈산으로 이루어진 군으로부터 선택되 는 1종 이상을 사용할 수 있으며, 바람직하게는 방향족 디카복실산을 사용할 수 있고, 특히 디메틸이소프탈레이트인 것이 좋다. As the dihydric alcohol or diacid to be copolymerized, one or more selected from the group consisting of neopentyl glycol, 1-4-cyclohexanedimethanol, isophthalic acid, and dimethylisophthalic acid can be used, and preferably aromatic Dicarboxylic acid can be used and it is especially preferable that it is dimethyl isophthalate.

이 때, 상기 결정성 폴리에스터 및 무정형 공중합 폴리에스터는 식품적합성 촉매를 사용하여 중합된 것이 바람직하며, 예를 들어 Ti 또는 Ge를 이용하는 것이 좋다.At this time, the crystalline polyester and the amorphous co-polyester is preferably polymerized using a food compatible catalyst, for example, it is preferable to use Ti or Ge.

또한, 본 발명의 열접착 필름은 열고정 이후의 비중이 1.30 내지 1.36의 범위인 것이 바람직하며, 상기 범위 내에서 접착성과 치수안정성이 더욱 우수해질 수 있다.In addition, the heat-adhesive film of the present invention preferably has a specific gravity after heat setting in the range of 1.30 to 1.36, it can be more excellent in adhesion and dimensional stability within the above range.

또한, 본 발명의 열접착 필름은, 종방향으로 2.5 내지 3.5 배 연신되고, 횡방향으로 2.5 내지 4.5 배 연신되는 것이 바람직하다. 열고정은 190 내지 250 ℃에서 실시할 수 있으며, 횡방향의 치수안정성을 부여하기 위해서는 텐터 내의 열고정 이후에 3 내지 5 % 이완을 주는 것이 바람직하다.Moreover, it is preferable that the heat-adhesive film of this invention is extended | stretched 2.5 to 3.5 times in the longitudinal direction, and extends 2.5 to 4.5 times in the lateral direction. The heat setting can be carried out at 190 to 250 ℃, in order to give the dimensional stability in the transverse direction, it is preferable to give 3 to 5% relaxation after heat setting in the tenter.

본 발명의 열접착 필름은, 기본적으로 단일층의 구조를 가질 수 있으며, 실란트 용도로 사용하기 위해서는 두께가 20 내지 80 ㎛인 것이 바람직하다.The heat-adhesive film of the present invention may basically have a single layer structure, and in order to use it for sealant use, the thickness is preferably 20 to 80 μm.

본 발명의 필름은 폴리에스터계 수지를 원료로 하고 있기 때문에 200℃ 초과의 용융온도을 가질 수 있어서 내열성이 우수하며, 이에 따라 내열성이 요구되는 레토르트 식품 포장재의 실란트로서 사용하는데 적합하고, 특히 최근 수요가 급증하는 전자레인지용 레토르트 식품 포장재의 실란트로서 사용하는데 무리가 없다.Since the film of the present invention is made of polyester-based resin, it can have a melting temperature of more than 200 ° C., which is excellent in heat resistance, and thus suitable for use as a sealant of a retort food packaging material requiring heat resistance. It is easy to use it as a sealant for a rapidly increasing retort food packaging material for microwave ovens.

또한, 기재필름과 적층 후에 200 내지 250 ℃에서 1초간 자가 접착했을 때의 접착강도가 1.5 내지 5.0 kgf/15mm이므로 열접착 필름으로 사용하는데 손색이 없으 며, 원료 수지의 배합 비율 및 접착 조건에 따라 박리성(easy-peel) 접착과 영구 접착을 모두 구현할 수 있다. 결정성 폴리에스터의 함량이 높을수록 접착온도가 낮을수록 박리성 접착이 되고, 결정성 폴리에스터의 함량이 낮을수록 접착온도가 높을수록 영구 접착이 이루어진다.In addition, since the adhesive strength is 1.5 to 5.0 kgf / 15mm when self-adhesive for 1 second at 200 to 250 ° C after lamination with the base film, there is no problem in using it as a thermal adhesive film. Both easy-peel adhesion and permanent adhesion can be achieved. The higher the content of crystalline polyester, the lower the adhesion temperature, the peelable adhesion, and the lower the content of the crystalline polyester, the higher the adhesion temperature, the permanent adhesion is achieved.

또한 본 발명의 필름은 헤이즈가 10% 이하이므로 종래의 불투명한 폴리올레핀계 열접착 필름에 비하여 포장재 용도로 특히 적합하다.In addition, since the film of the present invention has a haze of 10% or less, the film of the present invention is particularly suitable for use as a packaging material as compared with the conventional opaque polyolefin-based thermal adhesive film.

또한, 본 발명의 필름은, 120 내지 150 ℃의 온도 및 20 내지 40 분의 조건에서의 열수축율이 종방향 및 횡방향 각각 5% 미만인 것이 바람직하다.Moreover, it is preferable that the film of this invention is less than 5% of heat shrink rates in the temperature of 120-150 degreeC, and the conditions of 20-40 minutes, respectively in a longitudinal direction and a lateral direction.

본 발명의 열접착 필름이 포장재의 실란트로 사용될 경우, 포장재 적층구조의 가장 내면에 위치될 수 있다. 예를 들어, 일반 레토르트 식품 포장재 용도로 사용할 경우에는 폴리에스터 // 알루미늄 호일 // 나일론 // 실란트의 층 순으로 구성할 수 있고, 전자레인지용 식품 포장재로 사용할 경우에는 투명증착 폴리에스터 // 나일론 혹은 폴리에스터 // 실란트의 층 순으로 구성할 수 있으며, 그 외의 다양한 층구성 조합이 가능하다. 전자레인지용 식품 포장재의 경우에는 적층구조의 전 층을 폴리에스터로 조합이 가능하여 재활용 측면에서 환경적으로도 도움이 될 수 있다. When the heat-adhesive film of the present invention is used as a sealant of a packaging material, it may be located on the innermost surface of the packaging material laminate structure. For example, it can be configured in the order of polyester // aluminum foil // nylon // sealant for general retort food packaging applications, or transparent vapor-deposited polyester // nylon for food packaging materials for microwave ovens. Alternatively, polyester // sealant can be configured in layer order, and various other combinations of layers can be made. In the case of a food packaging material for a microwave oven, all layers of the laminated structure can be combined with polyester, which may be environmentally helpful in terms of recycling.

이하, 본 발명을 실시예에 의해 보다 상세히 설명하지만, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following Examples.

열접착 필름의 제조Preparation of Heat Adhesive Film

비교예 1 Comparative Example 1

도레이(Toray)사의 CPP 필름(TORAYFAN* NO) 중 두께 70㎛의 ZK99S를 사용하였다.ZK99S having a thickness of 70 μm was used in a CPP film (TORAYFAN * NO) manufactured by Toray.

비교예 2 Comparative Example 2

한국 특허공개 제2001-0002729호에서 개시된 실시예 2의 조건으로 두께 50㎛의 공압출 2층 폴리에스터 열접착 필름을 제조하였다.A coextruded two-layer polyester thermal adhesive film having a thickness of 50 μm was prepared under the conditions of Example 2 disclosed in Korean Patent Publication No. 2001-0002729.

실시예 1 Example 1

결정성 폴리에스터로서 Ti 촉매로 중합한 폴리부틸렌테레프탈레이트(LG화학, 제품명: LUPOX HV1010)를 사용하였다. 무정형 공중합 폴리에스터로서 Ti 촉매로 중합되고 주성분이 에틸렌테레프탈레이트이며 디메틸이소프탈레이트가 18mol%로 공중합된 폴리에스터를 사용하였다. 결정성 폴리에스터와 무정형 공중합 폴리에스터를 40/60의 중량비로 블렌딩하고 T-다이(T-die)에서 280℃의 온도에서 압출한 뒤, 종방향에 대하여 70℃에서 3.0배 연신하고 횡방향에 대하여 95~110℃에서 4.2배로 연신하여 50㎛의 필름을 제조하였다. 이를 200℃에서 열고정한 후 횡방향 치수안정성을 높이기 위해 4.5% 이완을 주어, 비중이 1.34인 2축연신 폴리에스터 열접착 필름을 완성하였다.Polybutylene terephthalate (LG Chemical, product name: LUPOX HV1010) polymerized with a Ti catalyst was used as the crystalline polyester. As an amorphous copolymer polyester, a polyester polymerized with a Ti catalyst, a main component of ethylene terephthalate and a dimethyl isophthalate copolymerized with 18 mol% was used. The crystalline polyester and the amorphous copolyester are blended at a weight ratio of 40/60 and extruded at a temperature of 280 ° C. in a T-die, followed by stretching 3.0 times at 70 ° C. in the longitudinal direction and in the transverse direction. It stretched by 4.2 times at 95-110 degreeC with respect to the film of 50 micrometers. After heat setting at 200 ° C., 4.5% relaxation was given to increase lateral dimensional stability, thereby completing a biaxially stretched polyester thermal adhesive film having a specific gravity of 1.34.

실란트로서의 응용Application as sealant

상기 비교예 1 내지 2 및 실시예 1에서 제조된 열접착 필름을 실란트로서 사용하여, 폴리에스터(12㎛)//나일론(15㎛)//실란트(50㎛)의 구조로 적층시키고 드라이라미네이션(dry lamination) 방법으로 우레탄계 접착제를 형성시켰다. Using the heat-adhesive films prepared in Comparative Examples 1 and 2 and Example 1 as sealants, laminated in a structure of polyester (12 μm) // nylon (15 μm) // sealant (50 μm) and dried lamination ( The urethane-based adhesive was formed by dry lamination method.

시험예Test Example

상기 비교예 및 실시예의 열접착 필름에 대해 다음과 같이 물성을 평가하여 하기 표 1에 정리하였다. The physical properties of the thermal adhesive films of Comparative Examples and Examples were evaluated as follows, and summarized in Table 1 below.

접착강도를 제외한 모든 물성은 열접착 필름 단독으로 측정하였고, 접착강도는 PET와 나일론과의 적층 후에 측정한 수치이다. All physical properties except the adhesive strength were measured by the heat-bonded film alone, and the adhesive strength was measured after lamination of PET and nylon.

a. 헤이즈a. Haze

상기 비교예 및 실시예에서 제조된 열접착 필름의 헤이즈를 JIS K7136에 준 거해서 측정하였다.The haze of the heat adhesive film manufactured by the said comparative example and the Example was measured based on JISK7136.

b. 파단강도, 파단신도, 영률b. Breaking strength, elongation at break, Young's modulus

상기 비교예 및 실시예에서 제조된 열접착 필름에 대하여, ASTM D 882에 의거하여 측정하였으며, 인스트론(INSTRON)사의 만능시험기(UTM, 모델명 4206-001)를 이용하여 각각의 필름을 길이 약 100 mm 폭 15 mm로 재단한 후 척간 간격이 50 mm가 되도록 장착하여 인장속도 200 mm/분의 속도로 측정하였다.The thermal adhesive films prepared in Comparative Examples and Examples were measured according to ASTM D 882, and each film was about 100 lengths using a universal testing machine (UTM, model name 4206-001) manufactured by INSTRON. After cutting to 15 mm mm width, it was mounted so that the interval between chucks was 50 mm and measured at a speed of 200 mm / min of tensile speed.

c. 접착강도 c. Adhesive strength

상기 비교예 및 실시예의 열접착 필름을 실란트로서 사용하여 PET 및 나일론과 적층하여 제조한 우레탄계 접착제를, 230℃에서 0.2MPa로 1초간 열밀봉바(heat seal bar)에서 접착한 후 만능재료시험기로 300m/분의 속도로 180도 방향으로 측정하였다. The urethane-based adhesive prepared by laminating with PET and nylon using the heat-adhesive films of Comparative Examples and Examples was bonded to a heat seal bar at 0.2 ° C for 1 second at 230 ° C., followed by a universal testing machine. It measured in the 180 degree direction at the speed of 300 m / min.

d. 수축율 d. Shrinkage

상기 비교예 및 실시예에서 제조된 열접착 필름의 10 x 10 cm 시편을 레토르트 처리 조건(120℃, 30분)으로 오토클레이브 내에서 방치한 후 종방향과 횡방향의 길이 변화를 측정하였다. After the 10 x 10 cm specimens of the heat-adhesive film prepared in Comparative Examples and Examples were left in the autoclave under retort treatment conditions (120 ° C., 30 minutes), the length change in the longitudinal direction and the transverse direction was measured.

e. 용융온도(내열온도)e. Melting temperature (heat resistance temperature)

상기 비교예 및 실시예에서 제조된 열접착 필름에 대하여, 퍼킨엘머(Perkin-Elmer)사의 시차주사형열분석기(DSC)를 이용하여 승온 속도 20℃/분으로 측정하여 나타나는 흡열곡선의 피크점을 기준으로 설정하였다. For the heat-adhesive film prepared in Comparative Examples and Examples, using the Perkin-Elmer differential scanning thermal analyzer (DSC) to measure the peak point of the endothermic curve which is measured at a temperature increase rate of 20 ℃ / min Standard was set.

Figure 112009081817648-PAT00001
Figure 112009081817648-PAT00001

상기 표 1을 볼 때, 실시예 1의 필름의 용융온도는 220℃ 정도로서, 비교예 1 및 2에 따르는 종래의 열접착 필름에 비하여 내열성이 우수한 것을 알 수 있다. 또한, 헤이즈면에서 매우 우수하므로 포장 필름으로서 적합하다. 그리고, 레토르트 조건하(120℃ 및 30분)에서 종방향과 횡방향 각각에 대한 열수축율 평가 결과 실란트가 갖추어야 할 5% 미만의 열수축율과 레토르트 포장용 접착강도 허용수준인 3.5kgf/15mm 이상의 충분한 접착강도를 나타내었다. 이로써 종래의 폴리에스터계 열접착 필름에 비해서 접착강도가 높고 폴리올레핀계 열접착 필름보다 내열성 및 투명성이 우수하여, 전자레인지용 레토르트 식품 포장재(pouch)에 적합하다고 볼 수 있다. Looking at the above Table 1, the melting temperature of the film of Example 1 is about 220 ℃, it can be seen that the heat resistance is superior to the conventional thermal adhesive film according to Comparative Examples 1 and 2. Moreover, since it is very excellent in terms of a haze, it is suitable as a packaging film. And under the retort conditions (120 ℃ and 30 minutes), the heat shrinkage evaluation results in the longitudinal and transverse directions, respectively, less than 5% of the sealant must have sufficient adhesion and 3.5kgf / 15mm of sufficient adhesive strength for retort packaging Strength is shown. As a result, the adhesive strength is higher than that of the conventional polyester thermal adhesive film, and the heat resistance and transparency are superior to the polyolefin thermal adhesive film, and thus, it may be considered to be suitable for a retort food pouch for a microwave oven.

이상, 본 발명을 상기 실시예를 중심으로 하여 설명하였으나 이는 예시에 지나지 아니하며, 본 발명은 본 발명의 기술분야에서 통상의 지식을 가진 자에게 자명한 다양한 변형 및 균등한 기타의 실시예를 이하에 첨부한 청구범위 내에서 수행할 수 있다는 사실을 이해하여야 한다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, It is to be understood that the invention may be practiced within the scope of the appended claims.

Claims (11)

결정성 폴리에스터 및 무정형 공중합 폴리에스터를 포함하며, 헤이즈가 10% 이하이고 용융온도가 200℃ 초과이며, 기재층과 적층 후에 200 내지 250 ℃에서 1초간 자가 접착했을 때의 접착강도가 1.5 내지 5.0 kgf/15mm인, 이축연신 폴리에스터 열접착 필름.It includes crystalline polyester and amorphous copolyester, has a haze of 10% or less, a melting temperature of more than 200 ° C, and an adhesion strength of 1.5 to 5.0 when self-bonding at 200 to 250 ° C for 1 second after lamination with a base layer Biaxially stretched polyester thermal adhesive film, which is kgf / 15mm. 제1항에 있어서, The method of claim 1, 상기 열접착 필름의 총중량을 기준으로, 상기 결정성 폴리에스터는 10 내지 60 중량%로 함유되고, 상기 무정형 공중합 폴리에스터는 40 내지 90 중량%로 함유되는 것을 특징으로 하는, 열접착 필름.Based on the total weight of the heat-adhesive film, the crystalline polyester is contained in 10 to 60% by weight, the amorphous co-polyester is characterized in that it is contained in 40 to 90% by weight, the heat-adhesive film. 제1항에 있어서, The method of claim 1, 상기 결정성 폴리에스터는, 폴리부틸렌테레프탈레이트(PBT), 폴리트리메틸렌테레프탈레이트(PTT), 또는 이들의 혼합수지를 포함하는 것을 특징으로 하는, 열접착 필름.The crystalline polyester, polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), or a heat-adhesive film, characterized in that it contains a mixed resin thereof. 제1항에 있어서, The method of claim 1, 상기 무정형 공중합 폴리에스터는, 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트(PBT), 및 폴리트리메틸렌테레프탈레이트(PTT) 중에서 선택되는 폴리에스터에 2가알콜 또는 2가산이 10 내지 25 mol%의 공중합율로 공중합된 수지인 것을 특징으로 하는, 열접착 필름.The amorphous copolyester is 10 to 25 mol% dihydric alcohol or diacid in a polyester selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT). It is resin copolymerized by the copolymerization ratio of the heat-adhesive film. 제1항에 있어서, The method of claim 1, 상기 무정형 공중합 폴리에스터는, 네오펜틸글리콜, 1-4-시클로헥산디메탄올, 이소프탈산, 및 디메틸이소프탈산으로 이루어진 군으로부터 선택된 1종 이상이 공중합된 폴리에스터인 것을 특징으로 하는, 열접착 필름.The amorphous copolyester is a heat-adhesive film, characterized in that at least one selected from the group consisting of neopentyl glycol, 1-4-cyclohexanedimethanol, isophthalic acid, and dimethylisophthalic acid is copolymerized polyester. 제1항에 있어서, The method of claim 1, 상기 무정형 공중합 폴리에스터는, 디메틸이소프탈레이트가 공중합된 폴리에스터인 것을 특징으로 하는, 열접착 필름.The amorphous copolymer polyester is a heat-adhesive film, characterized in that the dimethyl isophthalate is copolymerized polyester. 제1항에 있어서, The method of claim 1, 상기 열접착 필름은, 단일층의 구조를 갖는 것을 특징으로 하는, 열접착 필 름.The heat-adhesive film, characterized in that it has a single layer structure. 제1항에 있어서, The method of claim 1, 상기 결정성 폴리에스터 및 무정형 공중합 폴리에스터는, Ti 및 Ge 중 하나 이상을 사용하여 중합된 것을 특징으로 하는, 열접착 필름.The crystalline polyester and the amorphous copolyester, the heat-adhesive film, characterized in that polymerized using at least one of Ti and Ge. 제1항에 있어서, The method of claim 1, 상기 열접착 필름은, 120 내지 150 ℃의 온도 및 20 내지 40 분의 조건에서의 종방향 및 횡방향의 열수축율이 각각 5% 미만인 것을 특징으로 하는, 열접착 필름.The heat-adhesive film is characterized in that the heat shrinkage in the longitudinal and transverse directions at a temperature of 120 to 150 ° C. and 20 to 40 minutes is less than 5%, respectively. 제1항에 있어서,The method of claim 1, 상기 열접착 필름의 비중은 1.30 내지 1.36인 것을 특징으로 하는, 열접착 필름.Specific gravity of the heat-adhesive film is 1.30 to 1.36, the heat-adhesive film. 제1항에 있어서, The method of claim 1, 상기 열접착 필름은, 레토르트(retort) 식품 포장재의 실란트(sealant)로서 사용되는 것을 특징으로 하는, 열접착 필름.The heat-adhesive film is used as a sealant of a retort food packaging material.
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KR102620810B1 (en) 2023-06-09 2024-01-03 제이케이머티리얼즈(주) Biaxially Oriented High-density Polyethylene Film with an Excellent Heat-Sealable and Method for Manufacturing by Thereof
KR102648996B1 (en) 2023-06-09 2024-03-19 제이케이머티리얼즈(주) Biaxially Oriented High-density Polyethylene Film with an Excellent Heat-Resistance and Transparency and Method for Manufacturing by Thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102620810B1 (en) 2023-06-09 2024-01-03 제이케이머티리얼즈(주) Biaxially Oriented High-density Polyethylene Film with an Excellent Heat-Sealable and Method for Manufacturing by Thereof
KR102648996B1 (en) 2023-06-09 2024-03-19 제이케이머티리얼즈(주) Biaxially Oriented High-density Polyethylene Film with an Excellent Heat-Resistance and Transparency and Method for Manufacturing by Thereof

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