WO2018006251A1 - Modified high barrier film - Google Patents
Modified high barrier film Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- content
- mxd6
- rare earth
- nucleating agent
- barrier film
- 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.)
- Ceased
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
-
- 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. .
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
说明书 发明名称：一种改性的高阻隔薄膜 Specification Name of Invention: A modified high barrier film
技术领域 Technical field
[0001] 本发明属于双向拉伸薄膜领域， 特别是阻隔性薄膜领域。 [0001] The present invention is in the field of biaxially oriented films, particularly in the field of barrier films.
背景技术 Background technique
[0002] MXD6是由间苯二甲胺和己二酸缩聚得到的聚己二酰间苯撑二甲胺， 是一种具 有优异阻隔性能的芳香族聚酰胺树脂， 阻隔性能受环境湿度影响较小， 蒸煮处 理后恢复快。 中国专利申请 CN 102837474报道了采用 MXD6改性 PA6得到的高阻 隔尼龙薄膜中， 但在现有的生产工艺条件下， MXD6相通常以大球晶形态存在 ， 而 PA6相对结晶比较细致， 由此造成产品物性上存在不足， 强度不高， 脆性较 大， 雾度高的问题。 本发明通过大量研究， 提出一种解决上述问题的方法。 技术问题 [0002] 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
[0003] 本发明人惊讶的发现在高阻隔薄膜的配方中加入纳米稀土成核剂可以改善 MX D6与 PA6的结晶行为， 促使薄膜中两种材料的晶体更为细致且均匀； 同吋在 MX D6与 PA6的混合体系中加入特定的相容剂， 提高两相的相容性， 进而获得具有 优异阻隔性能， 力学强度高， 透明性良好的薄膜。 [0003] 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.
问题的解决方案 Problem solution
技术解决方案 Technical solution
[0004] 一种改性的高阻隔薄膜， 所述薄膜包括表层 a、 芯层、 表层 b， 其特征是： 表层 a中 MXD6的含量为 10~30<¾， PA6的含量为 63~84.9<¾， 其特征在于： 表层 a中 MX D6的含量为 30~40%， PA6的含量为 63~85%， 防粘母料的含量为 2~4<¾， 相容剂 的含量为 3~8%， 纳米稀土成核剂的含量为 5.5~8<¾； 芯层中 MXD6的含量为 95~99 .9% , 纳米稀土成核剂的含量为 0.1~5<¾； 在表层 b中 MXD6的含量为 10~30<¾， PA 6的含量为 63~85%， 防粘母料的含量为 2~4%， 相容剂的含量为 8.5-12%， 纳米稀 土成核剂的含量为 2~4.5%。 [0004] 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%.
[0005] 在一个实施方案中， 表层 a中所述纳米稀土成核剂的含量为 6.0~7.5%； 芯层中 所述纳米稀土成核剂的含量为 1.5-3.5% ； 表层 b中所述纳米稀土成核剂的含量为 3.0%。 [0005] In one embodiment, 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%.
[0006] 所述的纳米稀土成核剂是硬脂酸铈、 氯化铈、 富马酸镧、 氧化钨、 氧化镨中的 一种或几种混合物。 [0006] The nano rare earth nucleating agent is one or a mixture of barium stearate, barium chloride, barium fumarate, tungsten oxide, and barium oxide.
[0007] 所述的纳米稀土成核剂， 其粒径为 90-400nm， 更优选 150-250nm， 比表面积为 1 0~100m2/g, 松装比重为 0.5~2.0g/cm3。 [0007] 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 .
[0008] 所述的相容剂为聚乙二醇 400接枝 MXD6; 优选地， 相容剂的含量为 4~6<¾； 最 优选地， 相容剂的含量为 5.5%。 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%.
[0009] 在一个实施方案中， 所述的高阻隔薄膜， 其特征在于： 在表层 a中 MXD6的含 量为 30%， PA6的含量为 64.5%， 防粘母料的含量为 2<¾， 相容剂的含量为 3<¾， 纳 米稀土成核剂的含量为 6.0%; 芯层中 MXD6的含量为 99.5%， 纳米稀土成核剂的 含量为 6.0%; 在表层 b中 MXD6的含量为 30%， PA6的含量为 64.5<¾， 防粘母料的 含量为 2%， 相容剂的含量为 3%， 纳米稀土成核剂的含量为 0.5%。 [0009] In one embodiment, 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%.
[0010] 在一个实施方案中， 所述的高阻隔薄膜， 其特征在于： 在表层 a中 MXD6的含 量为 30%， PA6的含量 55%， 防粘母料的含量为 2%， 相容剂的含量为 8<¾， 纳米 稀土成核剂的含量为 5%; 芯层中 MXD6的含量为 95%， 纳米稀土成核剂的含量 为 5%; 在表层 b中 MXD6的含量为 30%， PA6的含量为 55<¾， 防粘母料的含量为 2 %, 相容剂的含量为 8%， 纳米稀土成核剂的含量为 5%。 [0010] In one embodiment, 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%.
[0011] 在一个实施方案中， 所述的高阻隔薄膜， 其特征在于： 在表层 a中 MXD6的含 量为 30%， PA6的含量 60.5%， 防粘母料的含量为 2%， 相容剂的含量为 5.5<¾， 纳 米稀土成核剂的含量为 2%; 芯层中 MXD6的含量为 98%， 纳米稀土成核剂的含 量为 2%; 在表层 b中 MXD6的含量为 30%， PA6的含量为 60.5<¾， 防粘母料的含量 为 2%， 相容剂的含量为 5.5%， 纳米稀土成核剂的含量为 2%。 [0011] In one embodiment, 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%.
发明的有益效果 Advantageous effects of the invention
有益效果 Beneficial effect
[0012] 本发明通过添加纳米稀土成核剂及相容剂， 提高了薄膜的拉伸强度， 降低了薄 膜的雾度， 同吋添加纳米稀土成核剂对薄膜的阻隔性能并没有什么影响。 添加 纳米稀土成核剂， MXD6的结晶形态明细细致且均匀。 本发明的实施方式 [0012] 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. Embodiments of the invention
[0013] 为了使本领域的技术人员更好地理解本发明的技术方案， 下面进一步披露一些 非限制实施例对本发明作进一步的详细说明。 [0013] In order to make those skilled in the art better understand the technical solutions of the present invention, the present invention will be further described in detail below by way of non-limiting embodiments.
[0014] 下面实施例中的高阻隔薄膜采用中国专利申请 CN 201210250206.0公幵的方法 制备。 [0014] The high barrier film of the following examples was prepared by the method of Chinese Patent Application No. CN 201210250206.0.
[0015] 实施例 1 [0015] Example 1
[0016] 按照以下配方进行制备高阻隔薄膜： 在表层 a中 MXD6的含量为 30%， PA6的含 量为 64.5%， 防粘母料的含量为 2%， 聚乙二醇 400接枝 MXD6的含量为 3%， 硬脂 酸铈的含量为 6.0%; 芯层中 MXD6的含量为 99.5%， 硬脂酸铈的含量为 2.0%; 在 表层 b中 MXD6的含量为 30%， PA6的含量为 64.5%， 防粘母料的含量为 2%， 聚乙 二醇 400接枝 MXD6的含量为 3%， 硬脂酸铈的含量为 3.0%。 [0016] 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%.
[0017] 实施例 2 [0017] Example 2
[0018] 按照以下配方进行制备高阻隔薄膜： 在表层 a中 MXD6的含量为 30%， PA6的含 量 55%， 防粘母料的含量为 2%， 聚乙二醇 400接枝 MXD6的含量为 8%， 氧化镧的 含量为 6.5%; 芯层中 MXD6的含量为 95%， 氧化镨的含量为 2.0%; 在表层 b中 MX D6的含量为 30%， PA6的含量为 55%， 防粘母料的含量为 2%， 聚乙二醇 400接枝 MXD6的含量为 8%， 氧化镧的含量为 3.0%。 [0018] 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%.
[0019] 高阻隔薄膜的制备过程同实施例 1。 [0019] The preparation process of the high barrier film is the same as in Example 1.
[0020] 实施例 3 Embodiment 3
[0021] 按照以下配方进行制备高阻隔薄膜： 在表层 a中 MXD6的含量为 30%， PA6的含 量 60.5%， 防粘母料的含量为 2%， 聚乙二醇 400接枝 MXD6的含量为 5.5%， 氧化 钨的含量为 6.0%; 芯层中 MXD6的含量为 98%， 氧化钨的含量为 2%; 在表层 b中 MXD6的含量为 30%， PA6的含量为 60.5%， 防粘母料的含量为 2%， 聚乙二醇 400 接枝 MXD6的含量为 5.5%， 氧化钨的含量为 3.0%。 [0021] 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%.
[0022] 高阻隔薄膜的制备过程同实施例 1. [0022] The preparation process of the high barrier film is the same as in the embodiment 1.
[0023] 比较例 1 Comparative Example 1
[0024] 按照以下配方进行制备高阻隔薄膜： 在表层 a中 MXD6的含量为 30%， PA6的含 量 68<¾， 防粘母料的含量为 2%; 芯层中 MXD6的含量为 100%; 在表层 b中 MXD6 的含量为 30%， PA6的含量为 68%， 防粘母料的含量为 2%。 [0024] Preparation of 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%.
[0025] 高阻隔薄膜的制备过程同实施例 1。 [0025] The preparation process of the high barrier film is the same as in Example 1.
[0026] 表 1 Table 1
[0027] 项目 实施例 1 实施例 2 实施例 3 比较例 1 [0027] Item Embodiment 1 Example 2 Example 3 Comparative Example 1
[0028] 拉伸强度 /MPa MD/TD 202/184 235/250 220/270 171/168 Tensile strength / MPa MD / TD 202 / 184 235 / 250 220 / 270 171 / 168
[0029] 断裂伸长率 /<¾MD/TD 114/108 105/95 160/90 49/35 Elongation at break /<3⁄4MD/TD 114/108 105/95 160/90 49/35
[0030] 雾度 /% 6.0 5.2 3.9 13.0 [0030] Haze /% 6.0 5.2 3.9 13.0
[0031] 氧气透过率 /cm3/m2.day.atm 7.3 7.6 7.2 7.2 [0031] Oxygen transmission rate /cm3/m2.day.atm 7.3 7.6 7.2 7.2
[0032] 从上表可以看出， 实施例 1-3添加有纳米稀土成核剂及相容剂， 对薄膜的拉伸 强度及雾度有较好的改善作用， 同吋添加纳米稀土成核剂对薄膜的阻隔性能并 没有什么影响。 添加纳米稀土成核剂， 对于 MXD6的结晶具有明显的改善作用， 未添加前， 芯层可以看到明显的大球晶形态的晶体， 而添加有纳米稀土成核剂 ， 结晶形态明细细致且均匀。 [0032] As can be seen from the above table, 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. Before the addition, 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. .
[0033] [0033]
[0034] 本发明的方法已经通过较佳实施例进行了描述， 相关人员明显能在本发明内容 、 精神和范围内对本文所述的方法和应用进行改动或适当变更与组合， 来实现 和应用本发明技术。 本领域技术人员可以借鉴本文内容， 适当改进工艺参数实 现。 特别需要指出的是， 所有类似的替换和改动对本领域技术人员来说是显而 易见的， 它们都被视为包括在本发明内。 The method of the present invention has been described in terms of preferred embodiments, and it is obvious that those skilled in the art can modify or appropriately modify and combine the methods and applications described herein to implement and apply the present invention. The technology of the present invention. Those skilled in the art can learn from the contents of this document and appropriately improve the implementation of process parameters. It is to be understood that all such alternatives and modifications are obvious to those skilled in the art and are considered to be included in the present invention.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2016/088464 WO2018006251A1 (en) | 2016-07-04 | 2016-07-04 | Modified high barrier film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2016/088464 WO2018006251A1 (en) | 2016-07-04 | 2016-07-04 | Modified high barrier film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018006251A1 true WO2018006251A1 (en) | 2018-01-11 |
Family
ID=60901495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2016/088464 Ceased WO2018006251A1 (en) | 2016-07-04 | 2016-07-04 | Modified high barrier film |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2018006251A1 (en) |
Citations (7)
| 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 (en) * | 2003-12-09 | 2005-06-15 | Amcor Flexibles Europe A/S | Migration-barrier retort laminates |
| JP2006040595A (en) * | 2004-07-23 | 2006-02-09 | Showa Denko Packaging Co Ltd | Electronic component case packaging material, electronic component case and electronic component |
| CN102837474A (en) * | 2011-06-20 | 2012-12-26 | 厦门长塑实业有限公司 | High barrier film and manufacturing method thereof |
| CN102896849A (en) * | 2012-07-19 | 2013-01-30 | 厦门长塑实业有限公司 | High-barrier nylon film and preparation method thereof |
| CN103254635A (en) * | 2013-03-15 | 2013-08-21 | 东风(十堰)非金属部件有限公司 | Rare earth modified toughening nylon material and its preparation method |
| CN104354411A (en) * | 2014-10-28 | 2015-02-18 | 厦门长塑实业有限公司 | High-barrier thin film modified by nano rare earth nucleating agent |
-
2016
- 2016-07-04 WO PCT/CN2016/088464 patent/WO2018006251A1/en not_active Ceased
Patent Citations (7)
| 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 (en) * | 2003-12-09 | 2005-06-15 | Amcor Flexibles Europe A/S | Migration-barrier retort laminates |
| JP2006040595A (en) * | 2004-07-23 | 2006-02-09 | Showa Denko Packaging Co Ltd | Electronic component case packaging material, electronic component case and electronic component |
| CN102837474A (en) * | 2011-06-20 | 2012-12-26 | 厦门长塑实业有限公司 | High barrier film and manufacturing method thereof |
| CN102896849A (en) * | 2012-07-19 | 2013-01-30 | 厦门长塑实业有限公司 | High-barrier nylon film and preparation method thereof |
| CN103254635A (en) * | 2013-03-15 | 2013-08-21 | 东风(十堰)非金属部件有限公司 | Rare earth modified toughening nylon material and its preparation method |
| CN104354411A (en) * | 2014-10-28 | 2015-02-18 | 厦门长塑实业有限公司 | High-barrier thin film modified by nano rare earth nucleating agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Polylactide/halloysite nanotube nanocomposites: Thermal, mechanical properties, and foam processing | |
| CN104479205B (en) | A kind of injection molding forming method of graphene modified poly ethylene high-strength composite thin products | |
| Montes et al. | Synergistic reinforcement of poly (vinyl alcohol) nanocomposites with cellulose nanocrystal-stabilized graphene | |
| Ljungberg et al. | Nanocomposites of isotactic polypropylene reinforced with rod-like cellulose whiskers | |
| CN103097445B (en) | Comprise the polymer nanocomposite of the poly(lactic acid) strengthened with modified sheet silicate | |
| Bindhu et al. | Boron Nitride reinforced polylactic acid composites film for packaging: Preparation and properties | |
| JP6746911B2 (en) | Ethylene-vinyl ester copolymer saponified composition pellets and method for producing the same | |
| McCardle et al. | Effect of Reinforcement Orientation on the Mechanical Properties of Microfibrillar PP/PET and PET Single‐Polymer Composites | |
| CN103640290B (en) | Completely biodegradable composite membrane with high barrier property | |
| CN105835491B (en) | A kind of ageing-resistant copolyester film of way contracting and preparation method thereof | |
| US20130085212A1 (en) | Procedure for the obtainment of nanocomposite materials | |
| Luna et al. | Polymer nanocomposites for food packaging | |
| CN105189633B (en) | PET nano composite materials and container prepared therefrom | |
| Xu et al. | Highly efficient three-dimensional gas barrier network for biodegradable nanocomposite films at extremely low loading levels of graphene oxide nanosheets | |
| CN104877317A (en) | Preparation method of full-bio-based composite material capable of being rapidly composited stereoscopically after melting | |
| CN104448491A (en) | Extrusion molding method of graphene modified polyethylene high-strength composite thin products | |
| CN104354411B (en) | The high-isolation film that a kind of nano rare earth is nucleater modified | |
| Baouz et al. | Effects of mixing protocols on impact modified poly (lactic acid) layered silicate nanocomposites | |
| CN103540113A (en) | Method for improving mechanical properties of polypropylene carbonate (PPC) through calcium carbonate filled modification | |
| Nuruddin et al. | Processing and characterization of food-grade plasticizer-compatibilized cellulose nanocrystals and ethylene vinyl alcohol copolymer nanocomposites | |
| CN112739779A (en) | Resin composition, molded body, and application thereof | |
| WO2018006251A1 (en) | Modified high barrier film | |
| JP2018095863A (en) | Biaxially stretched polyamide resin film and laminate using the same | |
| CN104194016B (en) | A kind of nanometer peanut protein polymer compound film and preparation method thereof | |
| EP3587478A1 (en) | Process for obtaining a bioplastic film and graphene oxide and/or graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16907756 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 13/03/2019) |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 16907756 Country of ref document: EP Kind code of ref document: A1 |