WO1998047704A1 - Film polyamide retrecissable multicouche - Google Patents

Film polyamide retrecissable multicouche Download PDF

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Publication number
WO1998047704A1
WO1998047704A1 PCT/JP1998/001796 JP9801796W WO9847704A1 WO 1998047704 A1 WO1998047704 A1 WO 1998047704A1 JP 9801796 W JP9801796 W JP 9801796W WO 9847704 A1 WO9847704 A1 WO 9847704A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
heat
polyamide
weight
multilayer film
Prior art date
Application number
PCT/JP1998/001796
Other languages
English (en)
Japanese (ja)
Inventor
Hiroki Kuriu
Hidekazu Biwaki
Osamu Niwa
Original Assignee
Gunze Limited
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
Application filed by Gunze Limited filed Critical Gunze Limited
Priority to AU68544/98A priority Critical patent/AU6854498A/en
Publication of WO1998047704A1 publication Critical patent/WO1998047704A1/fr

Links

Classifications

    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/58—Cuttability
    • B32B2307/581—Resistant to cut
    • 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
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable

Definitions

  • the present invention relates to a polyamide-based multilayer shrink film.
  • the film of the present invention is applied to applications requiring gas barrier uniformity, such as shrink packs and lid materials for tray containers.
  • LLDPE adhesive resin EV0 adhesive resin LLDPE which is made by sandwiching EVOH (genide of ethylene-vinyl acetate copolymer) with LLDPE (linear low-density polyethylene) Film is used.
  • This film suffers from poor pinhole resistance and transparency.
  • a multilayer film including a polyamide resin layer is known (JP-A-4-59244, JP-A-4-185322, US Pat. No. 5,562,996).
  • This film has improved pinhole resistance and transparency, but has room for improvement in the adhesion to the tray.
  • An object of the present invention is to provide a heat-shrinkable multilayer film having excellent pinhole resistance, transparency, and adhesion to a tray.
  • the present invention relates to the following heat-shrinkable multilayer film.
  • a heat-shrinkable multilayer film including five layers of a polyamide layer / EVOH layer / polyamide layer and an adhesive resin layer Z, wherein the polyamide layer is made of 6 nylon and / or 6-66 copoly nylon.
  • the EVOH layer contains a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 65 mol%; the polyolefin layer contains a linear low-density 70 to 95% by weight and amorphous nylon 30 to 5% by weight.
  • a heat-shrinkable multilayer film comprising polyethylene (LLDPE) and / or low-density polyethylene (LDPE); wherein the adhesive resin is a resin capable of bonding a polyamide layer and a polyolefin layer.
  • the EVOH layer is ethylene-vinyl acetate with ethylene content of 25-50 mol% Item 2.
  • LL DPE linear low density polyethylene
  • Item 3 The heat-shrinkable multilayer film according to Item 1, wherein the polyamide layer is 1 to 15 m; the EVOH layer is 2 to 15 m; the adhesive resin layer is 1 to 5 / m; and the polyolefin layer is 2 to 40.
  • Item 4 The heat-shrinkable multilayer film according to Item 1 or 2, wherein the film has a heat shrinkage of 2 to 50% in the vertical direction and 2 to 50% in the horizontal direction when the film is treated with boiling water for 30 seconds.
  • Item 5. The heat-shrinkable multilayer film according to items 1 to 4, wherein an antifogging agent is added.
  • Item 6 The heat-shrinkable multilayer film according to Item 1, wherein the two polyamide layers contain 70 to 95% by weight of 6-66 copolynylon and 30 to 5% by weight of amorphous nylon.
  • Item 7 Co-extrusion film formation in a flat shape using a T-die, followed by sequential biaxial stretching of about 1.2 to 5.0 times in the longitudinal direction and about 2.5 to 5.0 times in the horizontal direction.
  • a method for producing a film including five layers, namely, a polyamide layer, a ZEVOH layer, a Z polyamide layer, a Z adhesive resin layer, and a polyolefin layer.
  • Clause 8 The method of clause 7, wherein the two polyamide layers comprise 70-95% by weight of 6-66 copolynairon and 30-5% by weight of amorphous nylon.
  • the heat-shrinkable multilayer film of the present invention is preferably a film having a five-layer structure of a polyamide layer, an EOH layer, a polyamide layer, an adhesive resin layer and a polyolefin layer, but a polyolefin layer, an adhesive resin layer, and a polyamide layer.
  • Layer Polyamide layer Adhesive resin layer Polyolefin layer may be a seven-layer film.
  • the polyamide layer comprises 70-95% by weight, preferably 80-90% by weight, and 30-5% by weight, preferably 20-10% by weight, of nylon 6 and nylon 6-copolynylon.
  • 6-66 copolynylon is a copolymer of 6-nylon (poly- ⁇ -force prolactam) and 66-nylon (polyhexamethylene adipamide). It is preferably at least 50%, more preferably at least 70 mol%.
  • Nylon has a molecular weight (weight average molecular weight) of about 13,000-33,000.
  • the two polyamide layers may be the same or different as long as they contain the above components.
  • Polyamide layer thickness is l ⁇ 15m Degree, preferably about 3 to 11 ⁇ ⁇ .
  • Amorphous polyamides include copolymers or terpolymers of dicarboxylic acids such as terephthalic acid and isophthalic acid with diamines such as hexamethylenediamine.
  • the EVOH layer is a genoide of an ethylene-vinyl acetate copolymer, and the ethylene content is usually about 20 to 65 mol%, preferably about 25 to 50 mol%, more preferably about 25 to 45 mol%. is there.
  • the degree of genification is about 90% or more, preferably about 95% or more.
  • the thickness of the EVOH layer is about 2 to 15 m, preferably about 3 to 10 m.
  • the adhesive resin layer is not particularly limited as long as the EVOH layer and the polyolefin layer can be adhered, but is preferably LLDPE treated by a graft reaction.
  • the thickness of the adhesive resin layer is about l to 5 m, preferably about 2 to 5 m.
  • the polyolefin layer comprises a polyolefin, such as polyethylene or polypropylene, preferably linear low density polyethylene (LLDPE) and / or low density polyethylene (LDPE), especially LLDPE.
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • the thickness of the polyolefin layer is about 2 to 40 m, preferably about 5 to 20 m.
  • the total thickness of the laminated film of the present invention is about 6 to 75 m, preferably about 20 to 40 m.
  • an antifogging agent is preferably added to the polyolefin layer.
  • Known antifogging agents are widely used, such as fatty acid esters of polyhydric alcohols, amines of higher fatty acids, amides of higher fatty acids, and ethylene oxide in amine amides of higher fatty acids. An added anti-fogging agent may be mentioned.
  • the polyamide-based multilayer shrinkable film of the present invention is preferably a flat film.
  • This film may be co-extruded in a flat shape from a T-die and sequentially biaxially stretched.
  • the film formation is not particularly limited, but can be generally performed by extrusion casting on a cooled chill roll.
  • the film of the present invention is obtained by successively biaxially stretching the film thus formed. The stretching is carried out, for example, by longitudinal stretching using a roll stretching machine and transverse stretching using a tenter stretching machine.
  • the stretching ratio is preferably about 1.2 to 5 times in the vertical direction and about 2.5 to 5 times in the horizontal direction. Degrees.
  • the stretching temperature is about 60 to 120 ° C in the longitudinal direction, preferably about 70 to 100 ° C, and about 70 to 100 in the horizontal direction; about L80 ° C, preferably about 100 ° C. It is about 160 ° C.
  • the heat treatment method is not particularly limited, but is generally performed in a continuous process following the transverse stretching using a tenter stretching machine.
  • the force can be reduced (relaxed) within 20%, preferably 3 to 10% in the width direction.
  • the width may be set to be the same as the width in the horizontal stretching.
  • the width may be set to be equal to or greater than the width at the time of stretching.
  • the heat treatment conditions are, for example, less than 150 ° C., preferably about 80 to 130 ° C. by a tenter stretching machine, and if necessary, within about 20% in the width direction, preferably 3 to It can be performed with the size reduced to about 10%.
  • the heat treatment is performed for the purpose of preventing natural shrinkage.
  • Applications of the multilayer film according to the present invention include meat, processed meat, retort foods, water foods, microwave oven products, food packaging materials such as frozen foods, and other various packaging materials. Etc. can also be processed.
  • packaging form examples include overwrap packaging, sleeve packaging, and the like.
  • the packaging may be made into a bag by heat sealing, and is not particularly limited. Can be used as a packaging material simply by cutting it to a predetermined size.
  • Polyamide layer 6-66 copoly nylon (80% by weight) and amorphous nylon (20% by weight)
  • the polyolefin layer was mixed with an anti-fogging agent at 5000 ppm.
  • Pinhole test I Torsion bending test: A film formed into a cylindrical shape with a folding diameter of 150i and a length of 300 mm was mounted on a gelbo flex tester (manufactured by RIKEN KOGYO CO., LTD.), And a twist angle of 440 ° was used. Repeat the bending linear motion of Ocm 1000 times at 25 ° C and 5 ° C each, and check the number of pinholes using the permeate. The measurement is performed at a position of 300 cm 2 at the center of the sample.
  • Pinhole test II (Rotating drum test): After wrapping the square cake in a film so that it fits, place the ten cakes in a hexagonal pillar-shaped drum that rotates 50 times a minute for 20 minutes. After rotating for 30 minutes, or after 30 minutes, count the number of samples that generate pinhole force.
  • Average thickness At regular intervals, measure the thickness using a pointer micrometer (Gugami Co., Ltd.) and average the measured values.
  • Lubricity Measure static friction Z dynamic friction according to ASTM D-1894.
  • Oxygen permeability Measure according to ASTM D-3985.
  • the components of the respective layers were co-extruded in a flat shape from a T-die and extruded on a chill roll to obtain a flat film.
  • the obtained film was successively biaxially stretched (3.0 times in the longitudinal direction, 3.4 times in the transverse direction) and heat-treated at 100 ° C for 20 minutes to obtain a film of the present invention.
  • Table 1 shows the physical property values of the obtained film.
  • Polyamide layer 6-nylon (80% by weight) and amorphous nylon (20% by weight)
  • Polyamide layer 6-66 copoly nylon (80% by weight) and amorphous nylon (20% by weight)
  • Adhesive resin layer LLDPE based, grafted and functional groups introduced
  • the polyolefin layer was mixed with an anti-fogging agent at 5000 ppm.
  • the shrinkage (heat shrinkage) when immersed in 100 ° C warm water for 30 seconds is It was 20.3% in the MD direction and 29.6% in the D0 direction.
  • LLDPE layer Z adhesive resin layer ZE V 0 H layer Z adhesive resin layer No. LLDPE layer 1 2/3/2/11 m Five-layer film (brand name: Ecorap; manufacturer Okura Industries Co., Ltd.) Manufactured in the same manner as 1.
  • Example 1 Physical properties of the films obtained in Example 1 and Comparative Example 1 were measured. Table 1 shows the results. In addition, the above films were subjected to pinhole tests I and II. The results are shown in Tables 1 and 2.
  • Polyamide ZEVOHZ Polyamide 3-layer laminated film (HEP TAX; manufactured by Gunze Co., Ltd.) is used as a seal layer.
  • a polyolefin layer composed of LL DP E is used as a seal layer. Bonding was performed with the above-mentioned adhesive resin introduced to obtain a laminated film having a five-layer structure.
  • a tray (125Mix200mni) is wrapped with the film obtained in Example 1 and Comparative Example 2 having a folded diameter of 155 and a length of 240 ⁇ , and the wrapped tray is passed through a tunnel at 120 ° C for 10 seconds to shrink the film. Then, the packaging condition was observed and evaluated.
  • Example 1 In the laminated film obtained in Example 1, the film adhered to the tray, and no excess film was formed in the square of the tray. In addition, the film was fitted on the tray, and the film on the top of the tray was in a stretched state.
  • the film of the present invention has good shrink properties, and a packaged product in which the film is in close contact can be easily obtained.
  • Example 2 Comparing the results of Example 1 and Example 2, it was found that the stretchability was improved by using two polyamide layers of 6-66 nylon.
  • the number of breaks during continuous operation for 8 hours was 0, the heat shrinkage was larger than that of the film of Example 2, and the adhesion to the tray was excellent. Therefore, as the crystalline polyamide component, 6-66 copolynylon is preferable to 6-nylon.

Landscapes

  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention concerne un film polyamide rétrécissable à la chaleur, multicouche, qui possède d'excellentes propriétés de résistance à la piqûre, de transparence et d'adhésion à un support. Spécifiquement, le film comprend cinq couches: une couche de polyamide, une couche de copolymère éthylène-alcool vinylique (EVOH), une couche de polyamide, une couche de résine adhésive et une couche de polyoléfine. La couche de polyamide renferme 70 à 95 % en poids de nylon 6 et/ou de copolynylon 6-66, et 30 à 5 % en poids de nylon non cristallin. La couche d'EVOH renferme un saponifié d'un copolymère éthylène-acétate de vinyle ayant une teneur en éthylène comprise entre 20 et 65 % par mole. La couche de polyoléfine renferme un polyéthylène linéaire de faible densité (LLDPE) et/ou un polyéthylène de faible densité (LPDE). La résine adhésive est une résine capable de coller la couche de polyamide sur la couche de polyoléfine. L'invention concerne également un procédé permettant de fabriquer ledit film.
PCT/JP1998/001796 1997-04-21 1998-04-20 Film polyamide retrecissable multicouche WO1998047704A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU68544/98A AU6854498A (en) 1997-04-21 1998-04-20 Multilayer shrinkable polyamide film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/103598 1997-04-21
JP9103598A JPH10291286A (ja) 1997-04-21 1997-04-21 ポリアミド系多層収縮フィルム

Publications (1)

Publication Number Publication Date
WO1998047704A1 true WO1998047704A1 (fr) 1998-10-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/001796 WO1998047704A1 (fr) 1997-04-21 1998-04-20 Film polyamide retrecissable multicouche

Country Status (3)

Country Link
JP (1) JPH10291286A (fr)
AU (1) AU6854498A (fr)
WO (1) WO1998047704A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001078980A1 (fr) * 2000-04-18 2001-10-25 Gunze Limited Film multicouche tendu anticondensation a action rapide, et son procede de production
EP1824677A4 (fr) * 2004-12-10 2009-09-23 Curwood Inc Films barrieres d'emballage multicouches comprenant des copolymeres d'ethylene alcool de vinyle

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4485659B2 (ja) * 2000-07-11 2010-06-23 ユニチカ株式会社 熱収縮性二軸延伸積層フィルムの製造方法
JP4719362B2 (ja) * 2001-02-22 2011-07-06 大倉工業株式会社 防曇性に優れたシーラントフィルム
JP4703055B2 (ja) * 2001-08-02 2011-06-15 グンゼ株式会社 防曇性に優れた多層延伸フィルム
JP4936847B2 (ja) * 2006-10-13 2012-05-23 グンゼ株式会社 ポリアミド系多層フィルム
US20110117341A1 (en) * 2008-06-06 2011-05-19 Gunze Limited Multilayered film with excellent antifogging property
JP5400646B2 (ja) * 2010-02-04 2014-01-29 グンゼ株式会社 二軸延伸多層フィルムを用いた食品用容器
CN103042791B (zh) * 2012-12-21 2015-04-08 江阴升辉包装材料有限公司 一种多层共挤抗凝血高阻隔热收缩薄膜及其制备方法
JP6365337B2 (ja) * 2015-02-16 2018-08-01 三菱ケミカル株式会社 ガス置換包装体トップシール用蓋材
JP6933242B2 (ja) * 2019-12-18 2021-09-08 住友ベークライト株式会社 多層フィルム

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59152853A (ja) * 1983-02-21 1984-08-31 住友ベークライト株式会社 熱収縮性多層フイルムの製造方法
JPS59212261A (ja) * 1983-05-17 1984-12-01 住友ベークライト株式会社 熱収縮性多層フイルム
JPH0459244A (ja) * 1990-06-27 1992-02-26 Gunze Ltd 多層フィルム及びその製造法
JPH04185322A (ja) * 1990-11-16 1992-07-02 Gunze Ltd 多層フィルム
JPH05309775A (ja) * 1992-05-01 1993-11-22 Okura Ind Co Ltd トレイ容器包装体用ポリアミド系熱収縮性積層フィルム
JPH0655711A (ja) * 1992-08-07 1994-03-01 Gunze Ltd 多層熱収縮性フィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59152853A (ja) * 1983-02-21 1984-08-31 住友ベークライト株式会社 熱収縮性多層フイルムの製造方法
JPS59212261A (ja) * 1983-05-17 1984-12-01 住友ベークライト株式会社 熱収縮性多層フイルム
JPH0459244A (ja) * 1990-06-27 1992-02-26 Gunze Ltd 多層フィルム及びその製造法
JPH04185322A (ja) * 1990-11-16 1992-07-02 Gunze Ltd 多層フィルム
JPH05309775A (ja) * 1992-05-01 1993-11-22 Okura Ind Co Ltd トレイ容器包装体用ポリアミド系熱収縮性積層フィルム
JPH0655711A (ja) * 1992-08-07 1994-03-01 Gunze Ltd 多層熱収縮性フィルム

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001078980A1 (fr) * 2000-04-18 2001-10-25 Gunze Limited Film multicouche tendu anticondensation a action rapide, et son procede de production
US7014920B2 (en) 2000-04-18 2006-03-21 Gunze Limited Anti-fogging, stretched, multilayer film excellent in quick-acting property and method for producing the same
EP1824677A4 (fr) * 2004-12-10 2009-09-23 Curwood Inc Films barrieres d'emballage multicouches comprenant des copolymeres d'ethylene alcool de vinyle
US8741433B2 (en) 2004-12-10 2014-06-03 Curwood, Inc. Packaging films comprising nylon blend compositions

Also Published As

Publication number Publication date
JPH10291286A (ja) 1998-11-04
AU6854498A (en) 1998-11-13

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