KR100212919B1 - Process for preparing biaxial oriented polyamide film having excellent oxygen non-permeability - Google Patents

Process for preparing biaxial oriented polyamide film having excellent oxygen non-permeability Download PDF

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KR100212919B1
KR100212919B1 KR1019930027906A KR930027906A KR100212919B1 KR 100212919 B1 KR100212919 B1 KR 100212919B1 KR 1019930027906 A KR1019930027906 A KR 1019930027906A KR 930027906 A KR930027906 A KR 930027906A KR 100212919 B1 KR100212919 B1 KR 100212919B1
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polyamide
film
biaxially stretched
oxygen barrier
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KR950018158A (en
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차종원
송기상
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구광시
주식회사코오롱
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    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • 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
    • 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

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

Abstract

본 발명은 산소차단성이 우수한 이축연신 폴리아미드 필름의 제조방법에 관한 것으로, 폴리아미드-6 호모폴리머, 탄소수 2-12개를 갖는 디아민과 방향족 디카르복실산으로부터 중합되는 비정성 폴리아미드, 및 헥사메틸렌디아민과 아디프산으로부터 중합되는 폴리아미드-66을 일정 비율로 혼합한 후 압출 및 연신 공정을 거쳐 이축연신 폴리아미드 필름을 제조하는 것으로, 본 발명에 의해 제조된 필름은 용융상태에서의 흐름성이 좋아져 필름의 두께가 균일하며 물성 및 산소차단성이 우수한 이축연신 폴리아미드 필름이다.The present invention relates to a method for producing a biaxially stretched polyamide film having excellent oxygen barrier properties, comprising: polyamide-6 homopolymer, amorphous polyamide polymerized from diamine having 2 to 12 carbon atoms and aromatic dicarboxylic acid, and Polyamide-66 polymerized from hexamethylenediamine and adipic acid is mixed at a predetermined ratio, followed by an extrusion and stretching process to produce a biaxially stretched polyamide film. It is a biaxially stretched polyamide film having excellent properties, uniform film thickness, and excellent physical and oxygen barrier properties.

Description

산소차단성이 우수한 이축연신 폴리아미드 필름의 제조방법Method for producing biaxially stretched polyamide film having excellent oxygen barrier property

본 발명은 산소차단성이 우수한 이축연신 폴리아미드 필름의 제조방법에 관한 것으로서, 상세하게는 부패하기 쉬운 식품의 포장에 적합한 산소차단성이 우수한 이축연신 폴리아미드 필름의 제조방법에 관한 것이다.The present invention relates to a method for producing a biaxially stretched polyamide film having excellent oxygen barrier properties, and more particularly, to a method for producing a biaxially stretched polyamide film having excellent oxygen barrier properties suitable for packaging of perishable food.

이축연신 폴리아미드 필름은 기계적 강도가 우수하고, 내충격성, 내핀흘성, 산소차단성 등이 우수하여 식품포장재로서 널리 사용되고 있다.Biaxially oriented polyamide films are widely used as food packaging materials because of their excellent mechanical strength, excellent impact resistance, pin resistance, and oxygen barrier properties.

종래, 이축연신 폴리아미드 필름은 호모폴리머인 폴리아미드-6(소위, 나일론-6)을 이용하여 압출, 연신하여 제조되었는데, 이러한 폴리아미드 필름은 폴리아미드-6 사슬간의 수소결합에 의한 결정성에 의해 타 필름에 비해서는 높은 산소차단성을 가지나, 부패하기 쉬운 식품의 포장용으로는 만족스럽지 못하였으므로 이에 대한 개선이 요구되었다.Conventionally, biaxially stretched polyamide films have been prepared by extrusion and stretching using a homopolymer, polyamide-6 (so-called nylon-6), and these polyamide films are produced by crystallinity by hydrogen bonding between polyamide-6 chains. Compared with other films, it has high oxygen barrier property, but it was not satisfactory for packaging of perishable foods, and thus improvement was required.

이러한 개선 요구를 해결하는 방법으로 이축연신 폴리아미드 필름을 제조한 후에, 이를 기재로 사용하여 폴리염화비닐리덴(이하 PVDC라 약칭함)을 도포시킴으로써 산소차단성을 향상시키는 방법이 이용되어왔다. 그러나, 이러한 방법은 산소차단성을 향상시키기 위해 폴리아미드 필름의 제조공정 및 PVDC를 도포하는 공정 등 이중의 공정을 거쳐야 하므로 제조원가가 상승하는 문제점이 있으며 환경문제로 인한 PVDC의 사용에 대한 규제가 점점 강화되고 있는 실정이므로 근본적인 해결 방법이 되지 못하였다.After producing a biaxially stretched polyamide film as a method to solve this improvement demand, a method of improving oxygen barrier property by applying polyvinylidene chloride (hereinafter abbreviated as PVDC) using this as a substrate has been used. However, this method has to go through a double process such as a polyamide film manufacturing process and a PVDC coating process in order to improve oxygen barrier properties, which leads to a problem in that the manufacturing cost increases, and regulations on the use of PVDC due to environmental problems are gradually increasing. As it is being strengthened, it was not a fundamental solution.

또한, PVDC를 사용하지 않고 폴리아미드-6의 수소결합을 유지한 채, 산소차단성을 향상시킬 수 있는 방법으로 주사슬에 방향족 고리를 일정량 도입시키는 방법이 강구되었으나, 방향족 고리를 일정량 주사슬에 도입시킬 경우 필름의 기계적 물성이 저하되는 단점이 있었다.In addition, a method of introducing a certain amount of aromatic rings into the main chain has been devised to improve the oxygen barrier properties while maintaining hydrogen bonds of polyamide-6 without using PVDC. When introduced, there was a disadvantage that the mechanical properties of the film is lowered.

따라서, 본 발명은 상기한 바와 같은 선행기술에서의 제반 문제점을 감안하여, 공정의 단순화에 의한 제조원가 절감뿐만 아니라 필름의 기본 물성을 저하시키지 않고 우수한 산소차단성을 갖는 이축연신 폴리아미드 필름을 제공하는 것을 과제로 한다.Accordingly, the present invention provides a biaxially stretched polyamide film having excellent oxygen barrier properties without reducing the basic physical properties of the film as well as reducing the manufacturing cost by simplifying the process in view of the above problems in the prior art as described above. Let's make it a task.

상기한 과제를 해결하기 위하여 제공되는 본 발명은 이축연신 폴리아미드 필름의 제조시에, 폴리아미드-6, 탄소수 2∼12개를 갖는 디아민과 방향족 디카르복실산으로부터 중합되는 비정성(非晶性) 폴리아미드, 그리고 헥사메틸렌디아민과 아디프산으로부터 중합되는 폴리아미드-66(소위, 나일론-66)을 일정 비율로 혼합한 후, 압출, 연신 및 열처리 공정을 거쳐 이축연신 폴리아미드 필름을 제조하는 것을 특징으로 한다.In order to solve the above problems, the present invention provides a non-crystalline polymer that is polymerized from polyamide-6, diamine having 2 to 12 carbon atoms, and aromatic dicarboxylic acid in the production of a biaxially stretched polyamide film. ) Polyamide, and polyamide-66 (so-called nylon-66) polymerized from hexamethylenediamine and adipic acid were mixed at a predetermined ratio, and then a biaxially stretched polyamide film was prepared by extrusion, stretching and heat treatment. It is characterized by.

보다 구체적으로, 본 발명은 이축연신 폴리아미드 필름의 제조시에 하기 구조식(Ⅰ)의 폴리아미드-6, 탄소수 2∼12개를 갖는 디아민과 방향족 디카르복실산의 중합생성물인 하기 구조식(Ⅱ)의 비정성 폴리아미드, 및 헥사메틸렌디아민과 아디프산의 중합생성물인 하기 구조식(Ⅲ)의 폴리아미드-66을 다음의 식 ①, ②를 만족시키는 범위로 혼합한 후, 압출, 연신 및 열처리 공정을 거쳐 이축연신 폴리아미드 필름을 제조하는 것을 특징으로 한다.More specifically, the present invention provides the following structural formula (II) which is a polymerization product of polyamide-6 of the following structural formula (I), diamine having 2 to 12 carbon atoms, and aromatic dicarboxylic acid in the production of a biaxially stretched polyamide film. Amorphous polyamide and polyamide-66 of the following structural formula (III), which is a polymerization product of hexamethylenediamine and adipic acid, are mixed in a range satisfying the following formulas ① and ②, followed by extrusion, stretching and heat treatment steps It is characterized by producing a biaxially stretched polyamide film through.

위 식에서, n은 100 이상의 정수Where n is an integer greater than or equal to 100

위 식에서, R은 탄소수 2-12개의 알킬기, R'은 치환된 또는 비치환된 방향족기, n은 100 이상의 정수Wherein R is an alkyl group having 2-12 carbon atoms, R 'is a substituted or unsubstituted aromatic group, n is an integer of 100 or more

위 식에서, n은 100 이상의 정수Where n is an integer greater than or equal to 100

위 식 ①, ②에서, [Ⅰ]는 폴리아미드[Ⅰ]의 무게[g],In the above formulas ① and ②, [Ⅰ] is the weight of polyamide [Ⅰ] [g],

[Ⅱ]는 폴리아미드[Ⅱ]의 무게[g][II] is the weight of polyamide [II] [g]

[Ⅲ]는 폴리아미드[Ⅲ]의 무게[g]를 나타냄.[III] shows the weight [g] of polyamide [III].

본 발명에 따르는 폴리아미드의 혼합 비율에서([Ⅱ]+[Ⅲ])/[Ⅰ]가 0.1보다 작으면 필름에 효과적인 산소차단성을 부여할 수 없고, 1보다 크면 필름의 기본 물성인 강도, 모듈러스 등이 저하되어 포장재로서 사용하기에 적당하지 않다. 뿐만 아니라 [Ⅱ]/[Ⅲ]가 1보다 작으면 필름의 산소차단성이 저하되는 문제점이 있으며, 5보다 크면 필름의 기본 물성이 저하되는 문제점이 있다. 즉, 폴리아미드(Ⅱ)를 배제하게 되면 우수한 산소차단성을 기대할 수 없게 되며, 폴리아미드(Ⅲ)를 배제할 경우에는 폴리아미드(Ⅰ)를 단독으로 사용한 필름에 비하여 필름의 강도, 모듈러스 등이 저하되는 문제점이 발생하게 된다.If ([II] + [III]) / [I] is less than 0.1 in the mixing ratio of the polyamide according to the present invention, it is impossible to impart effective oxygen barrier properties to the film, and if it is greater than 1, the strength, which is the basic physical property of the film, Modulus, etc. are lowered and are not suitable for use as a packaging material. In addition, when [II] / [III] is less than 1, there is a problem that the oxygen barrier property of the film is lowered, and when it is greater than 5, there is a problem that the basic physical properties of the film are lowered. That is, when the polyamide (II) is excluded, excellent oxygen barrier properties cannot be expected. When the polyamide (III) is excluded, the strength, modulus, etc. of the film is lower than that of the film using the polyamide (I) alone. The problem of degradation occurs.

상기 3종의 폴리아미드의 혼합은 혼합기에서 2∼4시간 동안 균일하게 혼합하는 것이 적합하며, 압출기에서의 온도는 220∼290가 적합하다.Mixing of the three polyamides is suitably mixed for 2 to 4 hours in a mixer, the temperature in the extruder is 220 to 290 Is suitable.

이와 같이 3종류의 폴리아미드를 압출시에 일정 비율로 혼합하여 압출하게 되면, 압출기내에서의 높은 온도에 의한 아미드 교환반응에 의해 3종류의 폴리아미드가 무질서하게 교환반응에 참여함으로써 랜덤 코폴리아미드(random copolyamide)를 형성하게 되어 용융상태에서의 흐름성이 좋아져 필름의 두께 균일화를 동시에 만족하게 되며, 기존의 PVDC 도포에 의한 산소차단성과 동등한 수준의 산소차단성을 갖는 이축연신 폴리아미드 필름을 제조할 수 있게 된다.In this way, when three types of polyamides are mixed and extruded at a predetermined ratio during extrusion, the three types of polyamides randomly participate in the exchange reaction due to the amide exchange reaction caused by the high temperature in the extruder. (random copolyamide) is formed to improve the flowability in the molten state to satisfy the film uniformity at the same time, to prepare a biaxially stretched polyamide film having the same level of oxygen barrier properties as oxygen barrier by conventional PVDC coating You can do it.

이하, 본 발명을 실시예를 통하여 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[제조예 1][Production Example 1]

가압이 가능한 중합관에 카프로락탐(113.2g)과 순수(4.53g)를 투입하고 275, 가압 하에서 4시간 동안 중합한 후, 열수에서 24시간 동안 추출하고, 이를 다시 110, 진공 하에서 건조하여 폴리아미드-6(폴리아미드 Ⅰ)을 중합하였다.275 g of caprolactam (113.2 g) and pure water (4.53 g) were added to the polymerizable tube. , Polymerization for 4 hours under pressure, followed by extraction for 24 hours in hot water, which was again 110 And dried under vacuum to polymerize polyamide-6 (polyamide I).

[제조예 2][Production Example 2]

헥사메틸렌디아민(116.21g)과 테레프탈산(99.68g), 이소프탈산(66.45g), 그리고 순수(7g)를 투입한 후 260, 가압 하에서 5시간동안 중합한 후, 추출 및 건조 공정을 거쳐 비정성 폴리아미드(Ⅱ)를 중합하였다.Hexamethylenediamine (116.21g), terephthalic acid (99.68g), isophthalic acid (66.45g), and pure water (7g) After polymerization for 5 hours under pressure, the amorphous polyamide (II) was polymerized through an extraction and drying process.

[제조예 3][Manufacture example 3]

헥사메틸렌디아민과 아디프산염을 70함유하는 수용액 250g을 가압중합관에 투입한 후, 255, 가압 하에서 중합하여 폴리아미드-66(폴리아미드 Ⅲ)을 수득하였다.Hexamethylenediamine and adipate 70 250 g of aqueous solution was added to the pressure polymerization tube, and then 255. And polymerization under pressure afforded polyamide-66 (polyamide III).

[필름의 제조][Manufacture of Film]

[실시예 1∼4]EXAMPLES 1-4

제조예 1∼3에서 제조한 폴리아미드(Ⅰ)∼(Ⅲ)를 하기의 표 1의 비율로 혼합기에 투입하고 3시간 동안 균일하게 혼합한 다음, 압출 및 연신공정을 거쳐 이축연신 폴리아미드 필름을 제조하였다. 연신된 필름을 200∼210에서 30초 동안 열처리하여 필름을 제조하였다.The polyamides (I) to (III) prepared in Production Examples 1 to 3 were added to the mixer at the ratio of the following Table 1, mixed uniformly for 3 hours, and then subjected to an extrusion and stretching process to obtain a biaxially stretched polyamide film. Prepared. 200-210 stretched film The film was prepared by heat treatment for 30 seconds at.

[비교예 1]Comparative Example 1

제조예 1에서 중합한 폴리아미드(Ⅰ)를 이용하여 압출, 연신, 열처리 공정을 거쳐 필름을 제조한 후, 이 필름을 기재로 하여 폴리염화비닐리덴을 3μm 두께로 도포시켜 필름을 제조하였다.Using polyamide (I) polymerized in Preparation Example 1, a film was prepared by extrusion, stretching, and heat treatment, and then polyvinylidene chloride was applied to a thickness of 3 μm to form a film.

[비교예 2]Comparative Example 2

제조예 1에서 중합한 폴리아미드(Ⅰ)를 단독으로 사용하여 압출, 연신, 열처리 공정을 거쳐 필름을 제조하였다.Using polyamide (I) polymerized in Preparation Example 1 alone, a film was prepared by extrusion, stretching, and heat treatment.

[비교예 3]Comparative Example 3

제조예 1과 제조예 2에서 중합한 폴리아미드(Ⅰ) 및 폴리아미드(Ⅱ)를 투입비가 (Ⅰ):(Ⅱ)=85:15가 되도록 투입한 후 혼합, 압출, 연신, 열처리 공정을 거쳐 필름을 제조하였다.The polyamide (I) and the polyamide (II) polymerized in Production Example 1 and Production Example 2 were added so as to have an input ratio of (I) :( II) = 85: 15, followed by mixing, extrusion, stretching and heat treatment. A film was prepared.

[비교예 4][Comparative Example 4]

제조예 1과 제조예 3에서 중합한 폴리아미드(Ⅰ) 및 폴리아미드(Ⅲ)를 투입비가 (Ⅰ):(Ⅲ)=85:15가 되도록 투입한 후 혼합, 압출, 연신, 열처리 공정을 거쳐 필름을 제조하였다.Polyamide (I) and polyamide (III) polymerized in Preparation Example 1 and Preparation Example 3 were added so that the input ratio was (I) :( III) = 85: 15, followed by mixing, extrusion, stretching, and heat treatment. A film was prepared.

실시예 및 비교예에서 제조한 필름의 물성 및 효과를 다음의 방법으로 측정하고 그 결과를 표 2에 나타내었다.The physical properties and effects of the films prepared in Examples and Comparative Examples were measured by the following method and the results are shown in Table 2.

[물성 측정 방법][Measurement Method]

산소투과도:필름을 가로, 세로 각각 20cm가 되도록 취한 후, 가스투과도 측정기(일본 Toyoseiki 제품, Model No.M-150Ⅱ PVD-18OK)를 이용하여 측정하였다.Oxygen permeability: The film was taken to be 20 cm in length and width, and then measured using a gas permeability meter (Model No.M-150II PVD-18OK, manufactured by Toyoseiki, Japan).

기계적 물성:필름을 가로 및 세로가 20cmx1cm가 되도록 취한 후, 인스트롱을 이용하여 25, 50상대습도에서 5회 반복하여 측정한 후, 최대값과 최소값을 버리고 나머지 값을 평균하여 구하였다.Mechanical properties: Take the film so that it is 20cmx1cm in width and length, and then use instron 25 , 50 After measuring 5 times at relative humidity, the maximum and minimum values were discarded and the remaining values were averaged.

Claims (1)

이축연신 폴리아미드 필름의 제조에 있어서, 하기 구조식(Ⅰ)의 폴리아미드-6, 탄소수 2~12개를 갖는 디아민과 방향족 디카르복실산의 중합생성물인 하기 구조식(Ⅱ)의 비정성 폴리아미드, 및 헥사메틸렌디아민과 아디프산의 중합생성물인 하기 구조식(Ⅲ)의 폴리아미드-66을 다음의 식 ①, ②를 만족시키는 범위로 혼합한 후, 압출, 연신 및 열처리 공정을 거치는 것을 특징으로 하는 산소차단성이 우수한 이축연신 폴리아미드 필름의 제조방법:In the production of the biaxially stretched polyamide film, polyamide-6 of the following structural formula (I), amorphous polyamide of the following structural formula (II) which is a polymerization product of diamine having 2 to 12 carbon atoms and aromatic dicarboxylic acid, And mixing polyamide-66 of the following structural formula (III), which is a polymerization product of hexamethylenediamine and adipic acid, in a range satisfying the following formulas ① and ②, followed by extrusion, stretching and heat treatment. Process for producing biaxially stretched polyamide film having excellent oxygen barrier property: 위 식에서, n은 100 이상의 정수Where n is an integer greater than or equal to 100 위 식에서, R은 탄소수 2-12개의 알킬기, R'은 치환된 또는 비치환된 방향족기, n은 100 이상의 정수Wherein R is an alkyl group having 2-12 carbon atoms, R 'is a substituted or unsubstituted aromatic group, n is an integer of 100 or more 위 식에서, n은 100 이상의 정수Where n is an integer greater than or equal to 100 위 식 ①, ②에서, [Ⅰ]는 폴리아미드[Ⅰ]의 무게[g],In the above formulas ① and ②, [Ⅰ] is the weight of polyamide [Ⅰ] [g], [Ⅱ]는 폴리아미드[Ⅱ]의 무게[g],[II] is the weight of polyamide [II] [g], [Ⅲ]는 폴리아미드[Ⅲ]의 무게[g]를 나타냄.[III] shows the weight [g] of polyamide [III].
KR1019930027906A 1993-12-15 1993-12-15 Process for preparing biaxial oriented polyamide film having excellent oxygen non-permeability KR100212919B1 (en)

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