WO2018006251A1 - Film à barrière élevée modifié - Google Patents

Film à barrière élevée modifié Download PDF

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Publication number
WO2018006251A1
WO2018006251A1 PCT/CN2016/088464 CN2016088464W WO2018006251A1 WO 2018006251 A1 WO2018006251 A1 WO 2018006251A1 CN 2016088464 W CN2016088464 W CN 2016088464W WO 2018006251 A1 WO2018006251 A1 WO 2018006251A1
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WO
WIPO (PCT)
Prior art keywords
content
mxd6
rare earth
nucleating agent
barrier film
Prior art date
Application number
PCT/CN2016/088464
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English (en)
Chinese (zh)
Inventor
杜秀艳
Original Assignee
杜秀艳
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.)
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Publication date
Application filed by 杜秀艳 filed Critical 杜秀艳
Priority to PCT/CN2016/088464 priority Critical patent/WO2018006251A1/fr
Publication of WO2018006251A1 publication Critical patent/WO2018006251A1/fr

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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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives

Definitions

  • the present invention is in the field of biaxially oriented films, particularly in the field of barrier films.
  • MXD6 is a poly(adipicyl metaphenylene dimethylamine) obtained by polycondensation of m-xylylenediamine and adipic acid. It is an aromatic polyamide resin with excellent barrier properties, and its barrier properties are less affected by environmental humidity. , Recover quickly after cooking.
  • Chinese patent application CN 102837474 reports on a high barrier nylon film obtained by using MXD6 modified PA6, but under the existing production conditions, MXD6 phase usually exists in the form of large spherulites, while PA6 is relatively fine in crystallography, resulting in There are problems in the physical properties of the product, such as insufficient strength, high brittleness and high haze.
  • the present invention has proposed a method for solving the above problems through extensive research. technical problem
  • the inventors have surprisingly found that the addition of a nano rare earth nucleating agent to the formulation of a high barrier film can improve the crystallization behavior of MX D6 and PA6, and promote the crystals of the two materials in the film to be finer and more uniform;
  • a specific compatibilizer is added to the mixed system of D6 and PA6 to improve the compatibility of the two phases, thereby obtaining a film having excellent barrier properties, high mechanical strength and good transparency.
  • a modified high barrier film comprising a surface layer a, a core layer and a surface layer b, wherein: the content of MXD6 in the surface layer a is 10 ⁇ 30 ⁇ 3 ⁇ 4, and the content of PA6 is 63 ⁇ 84.9 ⁇ 3 ⁇ 4, characterized by: MX D6 content in surface layer a is 30 ⁇ 40%, PA6 content is 63 ⁇ 85%, anti-stick masterbatch content is 2 ⁇ 4 ⁇ 3 ⁇ 4, compatibilizer content is 3 ⁇ 8 %, the content of nano rare earth nucleating agent is 5.5 ⁇ 8 ⁇ 3 ⁇ 4; the content of MXD6 in the core layer is 95 ⁇ 99.9%, the content of nano rare earth nucleating agent is 0.1 ⁇ 5 ⁇ 3 ⁇ 4; in the surface b, MXD6 The content is 10 ⁇ 30 ⁇ 3 ⁇ 4, the content of PA 6 is 63 ⁇ 85%, the content of anti-stick masterbatch is 2-4%, the content of compatibilizer is 8.5-12%, and the content of nano rare earth nucleating agent is 2. ⁇ 4.5%.
  • the content of the nano rare earth nucleating agent in the surface layer a is 6.0 to 7.5%; the content of the nano rare earth nucleating agent in the core layer is 1.5 to 3.5%.
  • the content of the nano rare earth nucleating agent in the surface layer b is 3.0%.
  • the nano rare earth nucleating agent is one or a mixture of barium stearate, barium chloride, barium fumarate, tungsten oxide, and barium oxide.
  • the nano rare earth nucleating agent has a particle diameter of 90-400 nm, more preferably 150-250 nm, a specific surface area of 10 to 100 m 2 /g, and a bulk specific gravity of 0.5 to 2.0 g/cm 3 .
  • the compatibilizing agent is polyethylene glycol 400 grafted with MXD6; preferably, the content of the compatibilizer is 4-6 ⁇ 3 ⁇ 4; most preferably, the content of the compatibilizer is 5.5%.
  • the high barrier film is characterized in that: the content of MXD6 in the surface layer a is 30%, the content of PA6 is 64.5%, and the content of the anti-stick masterbatch is 2 ⁇ 3 ⁇ 4,
  • the content of the agent is 3 ⁇ 3 ⁇ 4, the content of the nano rare earth nucleating agent is 6.0%; the content of MXD6 in the core layer is 99.5%, the content of the nano rare earth nucleating agent is 6.0%; the content of MXD6 in the surface layer b is 30%
  • the content of PA6 is 64.5 ⁇ 3 ⁇ 4, the content of anti-stick masterbatch is 2%, the content of compatibilizer is 3%, and the content of nano rare earth nucleating agent is 0.5%.
  • the high barrier film is characterized by: MXD6 content in the surface layer a is 30%, PA6 content is 55%, anti-stick masterbatch content is 2%, compatibilizer
  • the content of the nano rare earth nucleating agent is 8 ⁇ 3 ⁇ 4, the content of MXD6 in the core layer is 95%, the content of the nano rare earth nucleating agent is 5%, and the content of MXD6 in the surface layer b is 30%.
  • the content of PA6 is 55 ⁇ 3 ⁇ 4, the content of the anti-stick masterbatch is 2%, the content of the compatibilizer is 8%, and the content of the nano rare earth nucleating agent is 5%.
  • the high barrier film is characterized by: MXD6 content in the surface layer a is 30%, PA6 content is 60.5%, anti-stick masterbatch content is 2%, compatibilizer
  • the content of the nano rare earth nucleating agent is 2%; the content of MXD6 in the core layer is 98%, the content of the nano rare earth nucleating agent is 2%; the content of MXD6 in the surface layer b is 30%,
  • the content of PA6 is 60.5 ⁇ 3 ⁇ 4, the content of the anti-stick masterbatch is 2%, the content of the compatibilizer is 5.5%, and the content of the nano rare earth nucleating agent is 2%.
  • the invention increases the tensile strength of the film and reduces the haze of the film by adding a nano rare earth nucleating agent and a compatibilizing agent, and the addition of the nano rare earth nucleating agent has no effect on the barrier property of the film. Adding a nano rare earth nucleating agent, the crystal form of MXD6 is fine and uniform.
  • the high barrier film of the following examples was prepared by the method of Chinese Patent Application No. CN 201210250206.0.
  • the high barrier film was prepared according to the following formula: The content of MXD6 in the surface layer a was 30%, the content of PA6 was 64.5%, the content of the anti-stick masterbatch was 2%, and the content of the polyethylene glycol 400 grafted MXD6. 3%, the content of barium stearate is 6.0%; the content of MXD6 in the core layer is 99.5%, the content of barium stearate is 2.0%; the content of MXD6 in the surface layer b is 30%, and the content of PA6 is 64.5. %, the content of the anti-stick masterbatch is 2%, the content of the polyethylene glycol 400 grafted MXD6 is 3%, and the content of the barium stearate is 3.0%.
  • the high barrier film was prepared according to the following formula:
  • the content of MXD6 in the surface layer a was 30%, the content of PA6 was 55%, the content of the anti-stick masterbatch was 2%, and the content of the polyethylene glycol 400 grafted MXD6 was 8%, the content of cerium oxide is 6.5%; the content of MXD6 in the core layer is 95%, the content of cerium oxide is 2.0%; the content of MX D6 in the surface layer b is 30%, the content of PA6 is 55%, anti-sticking
  • the content of the master batch was 2%, the content of the polyethylene glycol 400 grafted MXD6 was 8%, and the content of cerium oxide was 3.0%.
  • the high barrier film was prepared according to the following formula: The content of MXD6 in the surface layer a was 30%, the content of PA6 was 60.5%, the content of the anti-stick masterbatch was 2%, and the content of the polyethylene glycol 400 grafted MXD6 was 5.5%, the content of tungsten oxide is 6.0%; the content of MXD6 in the core layer is 98%, the content of tungsten oxide is 2%; the content of MXD6 in the surface layer b is 30%, the content of PA6 is 60.5%, anti-sticking mother The content of the material was 2%, the content of the polyethylene glycol 400 grafted MXD6 was 5.5%, and the content of the tungsten oxide was 3.0%.
  • a high barrier film according to the following formula: in the surface layer a MXD6 content of 30%, PA6 content of 68 ⁇ 3 ⁇ 4, anti-stick masterbatch content of 2%; MXD6 content of the core layer is 100%; MXD6 in surface b The content of the content is 30%, the content of PA6 is 68%, and the content of the anti-stick masterbatch is 2%.
  • Examples 1-3 added a nano rare earth nucleating agent and a compatibilizer, which have a better effect on the tensile strength and haze of the film, and the addition of nano rare earth nucleation
  • the agent has no effect on the barrier properties of the film.
  • the addition of nano rare earth nucleating agent has obvious improvement effect on the crystallization of MXD6.
  • the core layer can see obvious crystals with large spherulitic morphology, and the nano rare earth nucleating agent is added, and the crystal form is fine and uniform. .

Abstract

L'invention concerne un film à barrière élevée modifié, ledit film comprenant une couche superficielle (a), une couche centrale et une couche superficielle (b), et étant caractérisé en ce que : dans la couche superficielle (a), la teneur en MXD6 est de 30 à 40 %, la teneur en PA6 est de 63 à 85 %, la teneur en mélange maître anti-collant est de 2 à 4 %, la teneur en agent de compatibilité est de 3 à 8 % et la teneur en agent de nucléation de terres rares nanométrique est de 5,5 à 8 % ; dans la couche centrale, la teneur en MXD6 est de 95 à 99,9 % et la teneur en agent de nucléation de terres rares nanométrique est de 0,1 à 5 % ; dans la couche superficielle (b), la teneur en MXD6 est de 10 à 30 %, la teneur en PA6 est de 63 à 85 %, la teneur en mélange maître anti-collant est de 2 à 4 %, la teneur en agent de compatibilité est de 8,5 à 12 % et la teneur en agent de nucléation de terres rares nanométrique est de 2 à 4,5 %. Le film à barrière élevée modifié présente un allongement à la rupture amélioré et un trouble réduit.
PCT/CN2016/088464 2016-07-04 2016-07-04 Film à barrière élevée modifié WO2018006251A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/088464 WO2018006251A1 (fr) 2016-07-04 2016-07-04 Film à barrière élevée modifié

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/088464 WO2018006251A1 (fr) 2016-07-04 2016-07-04 Film à barrière élevée modifié

Publications (1)

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WO2018006251A1 true WO2018006251A1 (fr) 2018-01-11

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365248B1 (en) * 1998-07-15 2002-04-02 Idemitsu Petrochemical Co., Ltd. Easily tearable laminated barrier film and bag product using the same
EP1541340A1 (fr) * 2003-12-09 2005-06-15 Amcor Flexibles Europe A/S Stratifiés autoclavables avec barrière anti-migration
JP2006040595A (ja) * 2004-07-23 2006-02-09 Showa Denko Packaging Co Ltd 電子部品ケース用包材及び電子部品用ケース並びに電子部品
CN102837474A (zh) * 2011-06-20 2012-12-26 厦门长塑实业有限公司 一种高阻隔性薄膜及其制作方法
CN102896849A (zh) * 2012-07-19 2013-01-30 厦门长塑实业有限公司 高阻隔尼龙薄膜及其制备方法
CN103254635A (zh) * 2013-03-15 2013-08-21 东风(十堰)非金属部件有限公司 一种稀土改性增韧尼龙材料及其制备方法
CN104354411A (zh) * 2014-10-28 2015-02-18 厦门长塑实业有限公司 一种纳米稀土成核剂改性的高阻隔薄膜

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365248B1 (en) * 1998-07-15 2002-04-02 Idemitsu Petrochemical Co., Ltd. Easily tearable laminated barrier film and bag product using the same
EP1541340A1 (fr) * 2003-12-09 2005-06-15 Amcor Flexibles Europe A/S Stratifiés autoclavables avec barrière anti-migration
JP2006040595A (ja) * 2004-07-23 2006-02-09 Showa Denko Packaging Co Ltd 電子部品ケース用包材及び電子部品用ケース並びに電子部品
CN102837474A (zh) * 2011-06-20 2012-12-26 厦门长塑实业有限公司 一种高阻隔性薄膜及其制作方法
CN102896849A (zh) * 2012-07-19 2013-01-30 厦门长塑实业有限公司 高阻隔尼龙薄膜及其制备方法
CN103254635A (zh) * 2013-03-15 2013-08-21 东风(十堰)非金属部件有限公司 一种稀土改性增韧尼龙材料及其制备方法
CN104354411A (zh) * 2014-10-28 2015-02-18 厦门长塑实业有限公司 一种纳米稀土成核剂改性的高阻隔薄膜

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