EP0247203A1 - Materiau d'emballage en polyamide - Google Patents

Materiau d'emballage en polyamide

Info

Publication number
EP0247203A1
EP0247203A1 EP86906444A EP86906444A EP0247203A1 EP 0247203 A1 EP0247203 A1 EP 0247203A1 EP 86906444 A EP86906444 A EP 86906444A EP 86906444 A EP86906444 A EP 86906444A EP 0247203 A1 EP0247203 A1 EP 0247203A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
acid
packaging material
layer
gas barrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP86906444A
Other languages
German (de)
English (en)
Inventor
Seiichi Yamashiro
Tooru Matsubayashi
Kouichi Sakai
Hiroshi Toyao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
Original Assignee
Teijin Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP24411085A external-priority patent/JPS62106926A/ja
Priority claimed from JP60244111A external-priority patent/JPS62109738A/ja
Application filed by Teijin Ltd filed Critical Teijin Ltd
Publication of EP0247203A1 publication Critical patent/EP0247203A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2377/00—Polyamides
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the present invention relates to a packaging material made of a polyamide, more particularly, it relates to a packaging material made of a copolymerized polyamide having excellent gas barrier properties, strength and heat resistance.
  • a material having high gas barrier properties is required in packaging, especially in food packaging to elongate the shelf life of the food or to keep the freshness of the food.
  • a packaging material having excellent oxgen barrier property is desired to prevent the progress of the deterioration of the food caused by the transmission of oxygen.
  • a packaging material having excellent barrier property to carbon dioxide gas is desired for the container of a carbonated beverage, etc. to keep its refreshness.
  • Various materials have been developed to meet the above requirements, for example, polyvinylidene chloride, ethylene-vinyl alcohol copolymer, polyamide, polyethylene terephthalate, etc., and various methods have been proposed.
  • a gas barrier material such as polyvinylidene chloride or a saponified ethylene/vinyl acetate copolymer (vide; Japanese Unexamined Patent Publications No. 117565/79 and No.
  • a further object of the present invention is to provide a packaging material suitable for a multi-layer structure composed of the polyamide component and polyethylene terephthalate component.
  • This invention is directed to a polyamide packaging material exellent in the resistance to the permeation of oxygen and carbon oxide gases, which comprises a copolymerized polyamide comprising tetramethylene adipamide unit and tetramethylene isophthalamide unit.
  • a copolymerized polyamide comprising tetramethylene adipamide unit and tetramethylene isophthalamide unit.
  • Best Mode of Carrying out the Invention Copolymerized polyamide valuably used for the packaging material of the present invention comprises 10 to 90 mole% of tetramethylene adipamide units and 90 to 10 mole% of tetramethylene isophthalamide units. It has been unexpectedly found that by copolymerizing polytetramethylene adipamide with the isophthalic acid, the gas barrier property is highly improved as well as moldability.
  • the ratio of tetramethylene adipamide unit and tetramethylene isophthalamide unit is preferably 20:80 to 80:20.
  • the copolymerized polyamide layer having a tetramethylene adipamide content of not more than 90 has a rate of crystallization suitable for the drawing or stretching of said multi- layer structure.
  • the ratio of tetramethylene adipamide unit exceeds 90, the rate of crystallization of the polymer becomes extremely high, and the clouding phenomenon tends to occur in the obtained molded article such as preform.
  • the preform comprising the multi-layer structure above-mentioned must be preheated at the vicinity of 150°C in the drawing step, therefore, the clouding or crystallization of polyethylene terephthalate layer cannot be avoided.
  • the copolymerized polyamide may comprises other comonomer component, so far as the characteristic properties are not degraded.
  • the polyamide of the present invention contains other comonomer units in an amount of less than 20% of the whole recurring units, and a part of the tetramethylenediamine and a part of adipic acid or isophthalic acid are substituted with one or more kinds of other diamines, aminocarboxylic acids, lactam or dicarboxylic acids.
  • the comonomer components are aliphatic diamines such as ethylenediamide, trimethylenediamine, hexamethylenediamine, etc.; aromatic diamines such as phenylenediamine, xylylene- diamine, 3,6-diaminoacridine, N-methyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, tolylenediamine, etc.; alicyclic diamines such as 1,2-diaminocylobutane, etc.; aliphatic aminocarboxylic acids such as glycine, alanine, valine, etc.; aromatic aminocarboxylic acids such as phenylalanine, amino- benzoic acid, etc.; alicyclic aminocarboxylic acids such as aminocyclohexanecarboxylic acid, etc.; lactam such as ⁇ propiolactam, r-butyrolactam, ⁇ -caprolactam
  • the relative viscosity (r)rel; 1.0 wt% solution using 96% sulfuric acid as the solvent; measured at 20°C) of the polyamide of the present invention is preferably 2.0 or higher from the viewpoint of the strength of the obtained film or article.
  • the copolymerized polyamide can be produced by the conventional method known as the process for the production of polyamide. For example, it can be produced by condensing tetramethylenediamine with isophthalic acid, and tetramethylenediamine with adipic acid to form respective salts, and subjecting the resultant reaction product to the polycondensation reaction.
  • Various polycondensation catalysts, stabilizers, etc. can be used in the above production process. If necessary, other additives such as colorants fluorescent blighteners, oxidation stabilizers, ultraviolet absorbing agents, antistatic agents, flameretardants, etc. may be used in the process.
  • the polyamide packaging material of the present invention is, for example, a film and a container such as bottle, cup, etc. produced by a molding method accompanying with the drawing process.
  • the film or the sheet can be manufactured by the conventional methods known as the film-forming or sheet- forming methods.
  • the resin is dried at a temperature not lower than 80°C for 30 minutes of more, melted and extruded with an extruder furnished with a T-die or I-die, etc., and quenched to obtain an undrawn film or sheet, which may be further drawn along uniaxial or biaxial directions to obtain a drawn film or sheet.
  • the polyamide packaging material of the present invention is used for one component of a multi-layer structure.
  • the multi-layer structure comprises a layer of self-supportable polymer component, such as polyethylene terephthalate, and a layer of the copolymerized polyamide component.
  • the weight ratio of the copolymerized polyamide layer is preferably 5 to 50 wt%, especially 10 to 30 wt% to keep the physical properties and to attain high gas barrier properties of the obtained multi-layer drawn polyester sheet or bottle. Any combination of two of more polymers including the copolymerized polyamide may have an integral structure of a polymer-blend. The integral structure has also excellent gas barrier properties.
  • the polyethylene terephthalate that can be used in combination with the polyamide packaging material of the present invention is a polyester comprising at least 80 mole% of ethylene terephthalate units based on the total recurring units.
  • a part of the terephthalic acid component may be replaced by at least one member selected from bifunctional carboxylic acids; for example; aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl etherdicarboxylic acid, diphenylsulfonedicarboxylic acid; alicyclic carboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and azelaic acid; and hydroxyacids such as p- ⁇ -hydroxyethoxybenzoic acid,
  • the packaging material of the present invention there can be mentioned a container formed by the molding method including the drawing steps, such as a cup or bottle. Furthermore, the material may be a container obtained by the deep drawing of undrawn laminated sheet or a container obtained by drawing a bottom-closed laminated pipe. Moreover, a tray manufactured by the vaccum forming or the air pressure forming of a sheet is one of embodiments of the present invention.
  • the multi-layer drawn bottle of the present invention is manufactured basically by the hitherto developed process for the forming of polyester bottles, that is, by the process comprising the forming of a multi-layer preform and the orientation blow-molding of the preform.
  • the multi-layer preform can be formed e.g. by forming a multi-layer pipe composed of a polyetylene terephthalate layer and a copolymerized polyamide layer by the multi-layer co-extrusion technique, cutting the pipe to a prescribed length, and forming both ends in the desired forms of mouth and bottom by thermal forming.
  • a preform having multi-layer structure can be manufactured by the multi-layer injection molding process wherein the copolymerized polyamide is injected successively to the inner surface, outer surface or between the layers of polyethylene terephthalate.
  • the draw ratio of the bottle at the barrel portion in the drawing of the blow expansion of the multi-layer preform is preferably 1.2 or more, especially 2 or more in terms of areal ratio.
  • the packaging material of the present invention made of a polyamide has excellent gas barrier properties.
  • the carbon dioxide gas permeability constant of the material is 1/5 to 1/10 of that of nylon 6 and accordingly the material is extremely useful for the packaging of a material to which high gas barrier properties are especially required.
  • an advantage of the present invention is that a multi-layer structure having good processability is prepared by using the conventional methods and equipments.
  • nylon 46 A polytetramethylene adipamide (hereinafter referred to as nylon 46) having an rel of 3.5 was prepared from tetramethylenediamine and adipic acid according to the method disclosed in the specification of Japanese Patent Unexamined Publication No. 149430/81.
  • the nylon 46 was dried by a vacuum drier at 100°C for 24 hours, and a single-layer film having a thickness of about 100 ⁇ m was manufactured by using a 30mm-diameter extruder at cylinder temperature of 300°C and a casting roll temperature of about 20°C.
  • the obtained film had an opaque white appearance.
  • nylon 46 has excellent gas barrier properties, however, nylon 46 is not formed into a transparent film. Examples 1 and 2, Comparative Examples 4 and 5
  • Polyamides were prepared by the polycondensation of tetramethylenediamine, adipic acid and isophthalic acid. The rel, appearances and gas barrier properties of the polyamides are shown in Table 2.
  • PET Polyethylene terephthalate
  • the copolymerized polyamide shown in the table 3 was dried at 100°C for 24 hours in vacuum.
  • the polyethylene terephthalate and the polyamide were supplied to the cylinders A and B of the ASB-50EX-T-type one-stage multilayer biaxial orientation stretch blow-molding machine made by Nissei ASB Machine Co.
  • a preform having a weight ratio of the intermediate layer of 20 wt% was manufactured by this process.
  • the preform had a cylindrical form closed at one end and having an outer diameter of 25 to 26 mm, a thickness of 3.5 mm and a total length of 155 mm.
  • the preform was pre-heated at a temperature of 120 to
  • the preform was drawn axially in a bottle-shaped mold and expanded laterally with compressed air to form a bottle having an outer body diameter of 82 mm, a total height of 280 mm, a barrel portion thickness of 250 to 360 ⁇ m , and an inner volume of 1040 - 1050 ml.
  • the drawability (blow-moldability) of the preform in the above procedure and the gas barrier properties measured by using the test pieces prepared by cutting the barrel of the bottle are shown in the table 3.
  • Preforms were manufactured by using the copolymerized polyamide used in the Example 4, by the method similar to the Example 4 except for the thickness relationship between the polyamide layer and the PET layer, which was varied in a manner shown in the table 4, and the drawabilities and the gas barrier properties of the preforms were measured.
  • the bottle of the present invention has excellent moldability and gas barrier properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Polyamides (AREA)

Abstract

Un matériau d'emballage en polyamide comprend un polyamide copolymérisé comprenant entre 10 et 90 mole% unités d'adipamide tétraméthylène et entre 90 et 10 mole% d'unités d'isophthalamide de tétraméthylène. Le polyamide copolymérisé a d'excellentes propriétés de barrière aux gaz et une bonne aptitude au moulage.
EP86906444A 1985-11-01 1986-10-28 Materiau d'emballage en polyamide Withdrawn EP0247203A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP24411085A JPS62106926A (ja) 1985-11-01 1985-11-01 ポリアミド製包装材料
JP244111/85 1985-11-01
JP60244111A JPS62109738A (ja) 1985-11-01 1985-11-01 多層延伸ポリエステルボトル
JP244110/85 1985-11-01

Publications (1)

Publication Number Publication Date
EP0247203A1 true EP0247203A1 (fr) 1987-12-02

Family

ID=26536577

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86906444A Withdrawn EP0247203A1 (fr) 1985-11-01 1986-10-28 Materiau d'emballage en polyamide

Country Status (3)

Country Link
EP (1) EP0247203A1 (fr)
KR (1) KR880700003A (fr)
WO (1) WO1987002680A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908272A (en) * 1987-04-27 1990-03-13 Mitsubishi Gas Chemical Company, Inc. Gas-barrier multilayered structure
KR930010631B1 (ko) * 1989-08-05 1993-11-02 디에스엠 엔. 브이. 폴리아미드 조성물
DE4137430A1 (de) * 1991-11-14 1993-05-19 Huels Chemische Werke Ag Mehrschichtiges kunststoffrohr
DE4137431A1 (de) * 1991-11-14 1993-05-19 Huels Chemische Werke Ag Mehrschichtiges kunststoffrohr
US20060093772A1 (en) * 2004-10-27 2006-05-04 Fish Robert B Jr Multilayered pipes comprising hydrolysis resistant polyamides
US7696301B2 (en) * 2004-10-27 2010-04-13 E.I. Du Pont De Nemours And Company Marine umbilical comprising hydrolysis resistant polyamides
EP2724860B1 (fr) * 2011-06-27 2019-02-06 Mitsubishi Gas Chemical Company, Inc. Corps moulé par injection multicouche
US9718955B2 (en) * 2011-06-27 2017-08-01 Mitsubishi Gas Chemical Company, Inc. Injection-molded body
MX2014000044A (es) * 2011-06-27 2014-07-09 Mitsubishi Gas Chemical Co Pelicula y recipiente de envasado de pelicula.

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4229340A (en) * 1979-08-27 1980-10-21 Celanese Corporation Glass fiber-reinforced polyethylene terephthalate/polyamide blends
NL8104639A (nl) * 1981-10-13 1983-05-02 Stamicarbon Werkwijze voor het maken van polytetramethyleenadipamide.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8702680A2 *

Also Published As

Publication number Publication date
WO1987002680A3 (fr) 1988-03-24
KR880700003A (ko) 1988-02-15
WO1987002680A2 (fr) 1987-05-07

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Inventor name: MATSUBAYASHI, TOORU

Inventor name: TOYAO, HIROSHI

Inventor name: YAMASHIRO, SEIICHI

Inventor name: SAKAI, KOUICHI