CN112041387A - 疏液层形成用树脂组合物、以及使用其的疏液性薄膜、疏液性层叠体、包装材料及容器 - Google Patents
疏液层形成用树脂组合物、以及使用其的疏液性薄膜、疏液性层叠体、包装材料及容器 Download PDFInfo
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- CN112041387A CN112041387A CN201980028798.1A CN201980028798A CN112041387A CN 112041387 A CN112041387 A CN 112041387A CN 201980028798 A CN201980028798 A CN 201980028798A CN 112041387 A CN112041387 A CN 112041387A
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Abstract
一种疏液层形成用树脂组合物,其包含(A)聚烯烃树脂、(B)甲硅烷基化聚烯烃、以及具有与(A)聚烯烃树脂相容的部位及与(B)甲硅烷基化聚烯烃相容的部位的(C)增容剂,且(B)甲硅烷基化聚烯烃的聚烯烃部位与(A)聚烯烃树脂是不相容的。
Description
技术领域
本公开涉及疏液层形成用树脂组合物、以及使用其的疏液性薄膜、疏液性层叠体、包装材料及容器。
背景技术
以往,对于食品、饮料、医药品、化学品等许多的商品,开发出对应于各自的内容物的包装材料。特别地,作为液体或半固体、凝胶状物质等内容物的包装材料,使用耐水性、耐油性、阻气性、轻量性、可挠性、设计性等优异的塑料材料。
另外,作为液体或半固体、凝胶状物质等内容物的包装材料,以提供更高功能为目的,有提出层叠有多种塑料基材的塑料层叠体;或纸、金属箔、无机材料等与塑料基材的复合层叠体;以及对于塑料基材施有利用功能性组合物的处理的复合体等。
作为上述的高功能之一,例如要求抑制液体或半固体、凝胶状物质等内容物对于包装材料内表面的附着,即抑制在包装体内部的残留的功能。更具体而言,对于酸奶、果冻、糖浆等的容器的盖材、粥、汤、咖哩、意大利面酱等的杀菌(retort)食品包装材料、化学品或医药品等的液体、半固体、凝胶状物质等的保存容器用薄膜材料等,要求可抑制下述问题的高的疏液性:在其内表面附着内容物,无法完全地用完内容物而发生浪费;或因内容物的附着而发生污染;内容物的排出作业耗费工夫。
对于这些要求,例如专利文献1中提出一种疏水性包装材料,其在包装材料的内表面设置有含有聚硅氧烷粒子等疏水性微粒的聚硅氧烷树脂组合物层。另外,专利文献2中提出一种包装材料,其以添加有球状硅的树脂层作为最内层,且具有内容物疏水性、脱模性。
现有技术文献
专利文献
专利文献1:日本特开2013-23224号公报
专利文献2:日本特开平8-337267号公报
发明内容
发明所要解决的课题
作为包装材料内表面的树脂层的材料,聚乙烯或聚丙烯等聚烯烃树脂被使用作为赋予热封性、耐热性及耐冲击性等功能的材料。然而,为了赋予疏液性,在聚烯烃树脂中添加有上述的聚硅氧烷粒子时,也容易发生树脂层内的聚硅氧烷粒子的凝聚或聚硅氧烷粒子从树脂层游离,抑制内容物对于包装材料内表面的附着的效果未必充分。
本公开为鉴于上述现有技术所具有的课题而完成者,目的在于提供可形成能充分地抑制内容物的附着的疏液层的树脂组合物、以及使用其的疏液性薄膜、疏液性层叠体、包装材料及容器。
用以解决课题的手段
为了达成上述目的,本公开提供一种疏液层形成用树脂组合物,其包含(A)聚烯烃树脂、(B)甲硅烷基化聚烯烃、以及具有与上述(A)聚烯烃树脂相容的部位及与上述(B)甲硅烷基化聚烯烃相容的部位的(C)增容剂,且上述(B)甲硅烷基化聚烯烃的聚烯烃部位与上述(A)聚烯烃树脂是不相容的。
根据上述疏液层形成用树脂组合物,由于并用(A)聚烯烃树脂、聚烯烃部位与(A)聚烯烃树脂不相容的(B)甲硅烷基化聚烯烃、及(C)增容剂,可形成能充分地抑制内容物的附着的疏液层。(B)甲硅烷基化聚烯烃为将疏液性赋予至疏液层的成分,但在(A)聚烯烃树脂中仅添加聚烯烃部位与(A)聚烯烃树脂不相容的(B)甲硅烷基化聚烯烃时,在所形成的疏液层中,(B)甲硅烷基化聚烯烃彼此会凝聚,分散性差且不易集中存在于疏液层表面,难以得到充分的疏液性。相对于此,通过将(C)增容剂与(B)甲硅烷基化聚烯烃并用,可提高(B)甲硅烷基化聚烯烃的分散性,同时(B)甲硅烷基化聚烯烃的聚烯烃部位介由(C)增容剂而与(A)聚烯烃树脂相容,由此(B)甲硅烷基化聚烯烃的聚硅氧烷部位变得容易集中存在于疏液层表面,可有效率地将疏液性赋予至疏液层。由此,可形成一种疏液层,其具有比以往使用聚硅氧烷粒子的情况更优异的疏液性。
在上述疏液层形成用树脂组合物中,上述(C)增容剂可包含选自丙烯与乙烯的嵌段共聚物、及乙烯与乙烯·丁烯共聚物的嵌段共聚物中的至少一种。通过使用这些(C)增容剂,例如可在(A)聚烯烃树脂及(B)甲硅烷基化聚烯烃的聚烯烃部位中的一者使用聚丙烯,另一者使用聚乙烯。由此,变得容易将热封性、耐热性及耐冲击性等功能赋予至疏液层,或赋予对于如杀菌食品包装材料的施予隔水加热等加热处理的包装材料用途的适应性。另外,在(A)聚烯烃树脂及(B)甲硅烷基化聚烯烃的聚烯烃部位中的一者使用聚丙烯、另一者使用聚乙烯时,通过使用上述(C)增容剂,可更有效率地将疏液性赋予至疏液层。
在上述疏液层形成用树脂组合物中,上述(C)增容剂的含量相对于上述(B)甲硅烷基化聚烯烃的含量的质量比((C)增容剂的质量/(B)甲硅烷基化聚烯烃的质量)可为0.05~20。通过此含量的比为上述范围内,所形成的疏液层可更充分地抑制内容物的附着。
另外,本公开提供一种疏液层形成用树脂组合物,其包含(A)聚烯烃树脂及(B)甲硅烷基化聚烯烃,且上述(B)甲硅烷基化聚烯烃的聚烯烃部位与上述(A)聚烯烃树脂是相容的。
根据上述疏液层形成用树脂组合物,由于并用(A)聚烯烃树脂、及聚烯烃部位与(A)聚烯烃树脂相容的(B)甲硅烷基化聚烯烃,在所形成的疏液层中提高(B)甲硅烷基化聚烯烃的分散性,同时因(B)甲硅烷基化聚烯烃的聚烯烃部位与(A)聚烯烃树脂是相容的,由此(B)甲硅烷基化聚烯烃的聚硅氧烷部位变得容易集中存在于疏液层表面,可有效率地将疏液性赋予至疏液层,可充分地抑制内容物对于疏液层的附着。
上述疏液层形成用树脂组合物可进一步包含(D)聚硅氧烷。通过进一步包含(D)聚硅氧烷,可在所形成的疏液层中增加表面的Si存在量,因此可更提高疏液性。
另外,本公开提供一种疏液性薄膜,其具备使用上述本公开的疏液层形成用树脂组合物所形成的疏液层。根据如此的疏液性薄膜,由于具备使用上述本公开的疏液层形成用树脂组合物所形成的疏液层,可充分地抑制内容物对于疏液层的附着。另外,根据上述疏液性薄膜,不仅对于水或油,且对于咖哩或意大利面酱等水包油分散型内容物也可显现良好的疏液性。
上述疏液性薄膜可进一步具备在上述疏液层的一个主面上设置的1层以上的树脂层。通过将疏液性薄膜作成具备除疏液层以外的树脂层的多层结构,除了疏液性之外,也可赋予进一步的功能性(耐热性、耐冲击性等)。另外,疏液层的薄膜化成为可能,成本降低也成为可能。
当疏液性薄膜具备除疏液层以外的树脂层时,上述疏液层中的上述(A)聚烯烃树脂的熔点T1(℃)、及上述1层以上的树脂层中与上述疏液层相接的树脂层所包含的树脂的熔点T2(℃)可满足T1<T2的关系。通过满足上述关系,从结晶化度的观点来看,可抑制疏液层中的(B)甲硅烷基化聚烯烃转移至第2树脂层,由于可提高(B)甲硅烷基化聚烯烃往疏液层表面的集中存在化或渗出(bleed out)的效率,故有更提高疏液性的倾向。
另外,本公开提供一种疏液性层叠体,其具备基材及在该基材上设置的上述本公开的疏液性薄膜,且上述疏液层配置于至少一侧的最表面。根据如此的疏液性层叠体,由于具备上述本公开的疏液性薄膜,可充分地抑制内容物对于疏液层的附着。另外,由于将疏液性薄膜与具有所期望的功能的基材进行层叠,可将机械强度或阻隔性、遮光性等功能赋予至疏液性层叠体。
另外,本公开提供一种包装材料,其为使用上述本公开的疏液性层叠体而形成的。根据如此的包装材料,由于使用上述本公开的疏液性层叠体而形成,可充分地抑制内容物对于疏液层的附着。
上述包装材料可使用于施予80℃以上的加热处理的用途。根据本实施方式的包装材料,即使在使用于如此的用途时,在加热处理后也可抑制内容物对于包装材料内表面的附着。
进而,本公开提供一种容器,其至少在内表面具有使用上述本公开的树脂组合物所形成的疏液层。根据如此的容器,由于具备使用上述本公开的疏液层形成用树脂组合物所形成的疏液层,可充分地抑制内容物对于疏液层的附着。
发明的效果
根据本公开,可提供能形成可充分地抑制内容物的附着的疏液层的树脂组合物、以及使用其的疏液性薄膜、疏液性层叠体、包装材料及容器。
附图说明
图1为本公开的一个实施方式的疏液性层叠体的概略剖面图。
图2为本公开的一个实施方式的疏液性层叠体的概略剖面图。
图3为说明疏液性层叠体的疏液性的评价方法的示意图。
图4为说明疏液性层叠体的疏液性的评价方法的示意图。
具体实施方式
以下,一边参照附图,一边详细地说明本公开的合适的实施方式。此外,附图中,对于相同或相当部分附上相同符号,省略重复的说明。另外,附图的尺寸比率不限定于图示的比率。
[疏液性层叠体]
本实施方式的疏液性层叠体具备基材及在该基材上设置的疏液性薄膜,且具有疏液层配置于至少一侧的最表面的结构。图1及图2为本实施方式的疏液性层叠体的概略剖面图。本实施方式的疏液性层叠体可以如图1所示的疏液性层叠体1那样,具有包含疏液层11的疏液性薄膜10与基材14隔着粘接剂13层叠的结构。另外,本实施方式的疏液性层叠体可以如图2所示的疏液性层叠体2那样,具有包含疏液层11及第2树脂层12的疏液性薄膜10与基材14隔着粘接剂13层叠的结构。当疏液性薄膜10具备第2树脂层12时,疏液性薄膜10为以疏液层11成为疏液性层叠体2的最表面的方式,以第2树脂层12与基材14相向的方式配置。
<疏液层11>
疏液层11为具有疏液性的层。疏液层11也可为通过加热能显现热封性的层。此处,所谓的疏液性为包含疏水性及疏油性的两特性的概念,具体而言,为对液体状、半固体状或凝胶状的水性或油性材料疏液的特性。作为水性或油性材料,可举出水、油、酸奶、果冻、布丁、糖浆、粥、汤、咖哩、意大利面酱等食品、洗手液、洗发水等洗剂、医药品、化妆品、化学品等。另外,所谓的热封性,作为一例,为指能在100~200℃、0.1~0.3MPa、1~3秒的条件下热封的性质。热封的条件可根据疏液性层叠体的热封所需要的条件而容易地变更。
疏液层11的厚度优选为0.1~100μm,更优选为1~70μm,进一步优选为3~50μm,特别优选为5~30μm。通过疏液层11的厚度为上述下限值以上,有变得容易得到良好的疏液性及热封性的倾向。另一方面,通过厚度为上述上限值以下,可减薄疏液性层叠体整体的厚度。
疏液层11可使用包含下述成分的疏液层形成用树脂组合物而形成。以下,说明疏液层形成用树脂组合物。
<疏液层形成用树脂组合物>
本公开的一个实施方式的疏液层形成用树脂组合物包含(A)聚烯烃树脂(以下也称为“(A)成分”)、(B)甲硅烷基化聚烯烃(以下也称为“(B)成分”)、以及具有与上述(A)聚烯烃树脂相容的部位及与上述(B)甲硅烷基化聚烯烃相容的部位的(C)增容剂(以下也称为“(C)成分”),且上述(B)甲硅烷基化聚烯烃的聚烯烃部位与上述(A)聚烯烃树脂是不相容的。
本公开的另一实施方式的疏液层形成用树脂组合物包含(A)聚烯烃树脂及(B)甲硅烷基化聚烯烃,且上述(B)甲硅烷基化聚烯烃的聚烯烃部位与上述(A)聚烯烃树脂是相容的。
即,疏液层形成用树脂组合物当(B)甲硅烷基化聚烯烃的聚烯烃部位与(A)聚烯烃树脂不相容时,含有(C)增容剂作为必要成分,当(B)甲硅烷基化聚烯烃的聚烯烃部位与(A)聚烯烃树脂相容时,不需要(C)增容剂。另外,疏液层形成用树脂组合物可进一步包含(D)聚硅氧烷。以下,详细说明各成分。
((A)聚烯烃树脂)
作为聚烯烃树脂,并没有特别的限制,例如可举出低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、乙烯-α烯烃共聚物、均聚、嵌段或无规聚丙烯、丙烯-α烯烃共聚物等。作为α烯烃成分,可例示乙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、4-甲基-1-戊烯等。共聚物可为无规共聚物,也可为嵌段共聚物。除上述以外,聚烯烃树脂也可为聚降冰片烯等环状聚烯烃。另外,从密封性及强度物性(拉伸强度、冲击强度等)的观点来看,上述聚烯烃树脂优选为线状聚烯烃,线状聚烯烃可为直链状,也可为分支状。
将疏液性层叠体使用于如杀菌食品包装材料的施予隔水加热等加热处理的包装材料用途时,聚烯烃树脂优选含有聚丙烯树脂。通过聚烯烃树脂含有聚丙烯树脂,变得容易防止袋状的包装材料因隔水加热等加热处理而破袋。
作为聚丙烯树脂,可举出均聚聚丙烯、嵌段聚丙烯、无规聚丙烯以及如上述的除乙烯及丙烯以外的α-烯烃与丙烯的共聚物(丙烯系共聚物)。此处所谓的嵌段聚丙烯与作为后述的(C)增容剂的乙烯-丙烯嵌段共聚物不同,一般而言为具有对于聚合阶段的均聚聚丙烯使EPR(橡胶成分)及聚乙烯分散的结构者。在这些中,聚丙烯树脂优选包含无规聚丙烯或嵌段聚丙烯。通过包含无规聚丙烯,有低温·短时间下的热封变得容易的倾向。通过包含嵌段聚丙烯,耐热性及耐冲击性提高,有变得容易防止因热而袋状的包装材料破袋的倾向。
聚烯烃树脂的熔点可根据最终用途而适宜调整。例如,若为杀菌食品包装材料用途,则聚烯烃树脂的熔点优选为130~170℃。
聚烯烃树脂也可为经规定的酸所改性的改性聚烯烃。改性聚烯烃例如通过利用从不饱和羧酸、不饱和羧酸的酸酐、不饱和羧酸的酯等所衍生的不饱和羧酸衍生物成分来将聚烯烃进行接枝改性而得到。另外,作为聚烯烃树脂,也可使用羟基改性聚烯烃或丙烯酸改性聚烯烃等改性聚烯烃。
上述的聚烯烃树脂可单独使用一种或组合二种以上使用。
((B)甲硅烷基化聚烯烃)
甲硅烷基化聚烯烃为将疏液性赋予至疏液层11的成分。甲硅烷基化聚烯烃为在聚烯烃单元中具有聚硅氧烷部位者。
作为甲硅烷基化聚烯烃,例如可举出作为PE-Si接枝共聚物的Dow Corning Toray股份有限公司制的制品、作为PE-Si嵌段共聚物的MITSUI FINE CHEMICALS股份有限公司制的Exfola、作为PP-Si接枝共聚物的Dow Corning Toray股份有限公司制的制品等。
作为甲硅烷基化聚烯烃,从更提高疏液层11的疏液性的观点来看,比起接枝共聚物,更优选嵌段共聚物。这是因为嵌段共聚物具有容易集中存在化于或渗出至疏液层11表面的倾向。
上述的甲硅烷基化聚烯烃可单独使用一种或组合二种以上使用。
甲硅烷基化聚烯烃可为其聚烯烃部位与(A)聚烯烃树脂相容者,也可为不相容(非相容)者。只是在使用聚烯烃部位与(A)聚烯烃树脂不相容的甲硅烷基化聚烯烃时,必须并用以下的(C)增容剂。此外,使用聚烯烃部位与(A)聚烯烃树脂不相容的甲硅烷基化聚烯烃时,虽然必须并用(C)增容剂,但是具有下述优点:(A)聚烯烃树脂及(B)甲硅烷基化聚烯烃的材料的组合的选项增加,根据目的·用途的设计成为可能,同时具有容易更提高疏液性的倾向。
((C)增容剂)
使用聚烯烃部位与(A)聚烯烃树脂不相容的甲硅烷基化聚烯烃作为(B)甲硅烷基化聚烯烃时,使用增容剂。增容剂为具有与(A)聚烯烃树脂相容的部位及与上述(B)甲硅烷基化聚烯烃相容的部位的成分。通过使用增容剂,可提高聚烯烃部位与(A)聚烯烃树脂不相容的(B)甲硅烷基化聚烯烃与(A)聚烯烃树脂的相容性。
作为与(A)聚烯烃树脂相容的部位,可举出与(A)聚烯烃树脂能相容的聚烯烃结构,优选为具有与(A)聚烯烃树脂同种的聚烯烃结构的部位。即,当(A)聚烯烃树脂为聚乙烯树脂时,(C)增容剂优选具有聚乙烯结构,当(A)聚烯烃树脂为聚丙烯树脂时,(C)增容剂优选具有聚丙烯结构。另外,当(A)聚烯烃树脂为乙烯-α烯烃共聚物、丙烯-α烯烃共聚物等包含2种以上的烯烃的共聚物时,(C)增容剂优选至少具有使与构成上述共聚物的烯烃中成为主成分的烯烃同种的烯烃发生聚合或共聚而成的结构。
作为与(B)甲硅烷基化聚烯烃相容的部位,可举出与(B)甲硅烷基化聚烯烃的聚烯烃部位能相容的聚烯烃结构,优选为具有与(B)甲硅烷基化聚烯烃的聚烯烃部位同种的聚烯烃结构的部位。即,当(B)甲硅烷基化聚烯烃的聚烯烃部位具有聚乙烯结构时,(C)增容剂优选具有聚乙烯结构,当(B)甲硅烷基化聚烯烃的聚烯烃部位具有聚丙烯结构时,(C)增容剂优选具有聚丙烯结构。另外,当(B)甲硅烷基化聚烯烃的聚烯烃部位具有以乙烯-α烯烃共聚物、丙烯-α烯烃共聚物等包含2种以上的烯烃的共聚物为基础的结构时,(C)增容剂优选至少具有使与构成上述共聚物的烯烃中成为主成分的烯烃同种的烯烃发生聚合或共聚而成的结构。
作为(C)增容剂,例如可使用由聚乙烯或乙烯·α-烯烃共聚物构成的聚乙烯单元与由聚丙烯或丙烯·α-烯烃共聚物构成的聚丙烯单元所构成的嵌段共聚物;或者由聚乙烯单元与乙烯·丁烯共聚物单元所构成的嵌段共聚物。如此的嵌段共聚物为二嵌段共聚物、三嵌段共聚物、多嵌段共聚物中的任一结构皆无妨。此时,如果(A)聚烯烃树脂或(B)甲硅烷基化聚烯烃的聚烯烃部位为聚乙烯,则该部位与(C)增容剂的聚乙烯部位(聚乙烯单元)相容,如果(A)聚烯烃树脂或(B)甲硅烷基化聚烯烃的聚烯烃部位为聚丙烯,则该部位与(C)增容剂的聚丙烯部位(聚丙烯单元)或乙烯·丁烯共聚物部位(乙烯·丁烯共聚物单元)相容。
上述的增容剂可单独使用一种或组合二种以上使用。
((D)聚硅氧烷)
聚硅氧烷为更提高疏液层11的疏液性的成分。作为聚硅氧烷,例如可举出硅油、硅树脂、聚硅氧烷寡聚物、硅粉等。在这些中,从容易得到更良好的疏液性来看,优选硅油。
作为硅油,可举出二甲基硅油、甲基苯基硅油、甲基氢硅油、环状二甲基硅油、烷基改性硅油、长链烷基改性硅油、高级脂肪酸改性硅油等。
作为硅油,例如可举出Wacker Asahikasei Silicone股份有限公司制的制品、信越化学工业股份有限公司制的制品、Momentive Performance Materials公司制的制品、Dow Corning Toray股份有限公司制的制品等。
作为硅树脂,可举出信越化学工业股份有限公司制的制品、Wacker AsahikaseiSilicone股份有限公司制的制品等。
作为聚硅氧烷寡聚物,可举出信越化学工业股份有限公司制的制品、Dow CorningToray股份有限公司制的制品等。
作为硅粉,可举出信越化学工业股份有限公司制的制品、Dow Corning Toray股份有限公司制的制品等。
上述的聚硅氧烷可单独使用一种或组合二种以上使用。
疏液层形成用树脂组合物中的(A)成分的含量以疏液层形成用树脂组合物的固体成分全量为基准,优选为50.0~99.9质量%,更优选为55.0~99.0质量%,进一步优选为60.0~98.0质量%。若(A)成分的含量为上述下限值以上,则有容易得到良好的热封性的倾向。另一方面,若(A)成分的含量为上述上限值以下,则由于(B)成分及(C)成分的含量相对地增加,故有疏液性容易提高的倾向。
疏液层形成用树脂组合物中的(B)成分及(C)成分的合计含量以疏液层形成用树脂组合物的固体成分全量为基准,优选为0.1~50.0质量%,更优选为1.0~45.0质量%,进一步优选为2.0~40.0质量%。若(B)成分及(C)成分的合计含量为上述下限值以上,则有疏液性容易提高的倾向。另一方面,若(B)成分及(C)成分的合计含量为上述上限值以下,则由于(A)成分的含量相对地增加,故有容易得到良好的热封性的倾向。
当疏液层形成用树脂组合物包含(C)成分时,(C)成分的含量相对于(B)成分的含量的质量比((C)成分的质量/(B)成分的质量)可为0.01~50,优选为0.05~30,更优选为0.05~20。若此含量的比为上述下限值以上,则可使(B)甲硅烷基化聚烯烃充分地分散于疏液层中,有能得到更良好的疏液性的倾向。另一方面,若此含量的比为上述上限值以下,则防止因过剩的(C)增容剂而被覆(B)甲硅烷基化聚烯烃,有能得到更良好的疏液性的倾向。另外,即使添加(C)增容剂至含量的比超出上述上限值,(B)甲硅烷基化聚烯烃也成为无法更多分散的状态,有变得看不到疏液性的提高效果的倾向。
当疏液层形成用树脂组合物包含(D)成分时,以疏液层形成用树脂组合物全量为基准,其含量优选为0.1~20.0质量%,更优选为1.0~15.0质量%,进一步优选为2.0~10.0质量%。若(D)成分的含量为上述下限值以上,则有疏液性容易提高的倾向。另一方面,若(D)成分的含量为上述上限值以下,则由于(A)成分的含量相对地增加,故有容易得到良好的热封性的倾向。另外,若(D)成分的含量超过上述上限值,则有变得容易发生(D)成分从疏液层游离的倾向。
疏液层形成用树脂组合物在不损害疏液性的程度的范围内,根据需要也可包含其它的添加剂。作为其它的添加剂,例如可举出阻燃剂、增滑剂(slipping agent)、抗黏连剂(antiblocking agent)、抗氧化剂、光稳定剂、增黏剂等。
疏液层11可通过将上述疏液层形成用树脂组合物制膜而形成。
<第2树脂层12>
第2树脂层12是为了提高热封性、耐热性及耐冲击性、氧·水蒸气阻隔性等而设于疏液层11与基材14之间的层。第2树脂层12优选包含具有热封性的热塑性树脂。
作为第2树脂层12所用的热塑性树脂,并没有特别的限定,可举出聚烯烃树脂、乙烯-α,β不饱和羧酸共聚物或其酯化物或离子交联物、乙烯-乙酸乙烯酯共聚物或其皂化物、聚乙酸乙烯酯或其皂化物、聚碳酸酯树脂、热塑性聚酯树脂、ABS树脂、聚缩醛树脂、聚酰胺树脂、聚苯醚(polyphenylene oxide)树脂、聚酰亚胺树脂、聚氨酯(polyurethane)树脂、聚乳酸树脂、呋喃树脂及聚硅氧烷树脂等。这些热塑性树脂可单独使用一种或组合二种以上使用。
第2树脂层12所用的上述热塑性树脂从热封性、耐热性及耐冲击性容易提高来看,优选包含聚烯烃树脂。作为聚烯烃树脂,可使用与疏液层11所用的(A)聚烯烃树脂同样者。
当第2树脂层12与疏液层11相接时,疏液层11中的(A)聚烯烃树脂的熔点T1(℃)与第2树脂层12中的上述热塑性树脂的熔点T2(℃)优选满足T1<T2的关系。通过满足上述关系,从结晶化度的观点来看,可抑制疏液层11中的(B)甲硅烷基化聚烯烃转移至第2树脂层12,可提高(B)甲硅烷基化聚烯烃对于疏液层11表面的集中存在化或渗出的效率,故有更提高疏液性的倾向。从相同的观点来看,熔点T2优选比熔点T1更高1℃以上,更优选高3℃以上。
第2树脂层12的厚度可根据使用该疏液层形成用树脂组合物的商业材料的最终用途而适宜设定。第2树脂层12的厚度例如优选为0.1~300μm,更优选为1~200μm,进一步优选为5~150μm,特别优选为10~100μm。
<疏液性薄膜10>
通过上述的疏液层11单层、或疏液层11及第2树脂层12的2层,而形成具有疏液性的疏液性薄膜10。疏液性薄膜10为以覆盖基材14的表面的一部分或全部的方式形成。此外,疏液性薄膜10可根据用途,不与基材14层叠,而以疏液性薄膜10单独使用。
疏液性薄膜10可进一步包含1层以上的除疏液层11及第2树脂层12以外的其它树脂层。其它树脂层的组成可与第2树脂层12的组成同样,也可不同。
<基材14>
基材14只要成为支撑体,则没有特别的限制,例如可举出纸、树脂薄膜、金属箔等。作为纸,可举出上等纸、特殊上等纸、涂布纸、铜版纸、高光泽印刷纸(cast-coated paper)、仿造纸、牛皮纸等。作为树脂薄膜,可举出包含聚烯烃(例如聚乙烯(PE)、聚丙烯(PP)等)、酸改性聚烯烃、聚酯(例如聚对苯二甲酸乙二醇酯(PET)等)、聚酰胺(PA)、聚氯乙烯(PVC)、乙酸纤维素、赛璐玢树脂中的至少一种的薄膜。此薄膜可为拉伸薄膜,也可为非拉伸薄膜。作为金属箔,例如可举出铝箔、镍箔等。基材14也可为层叠有材质不同的多个基材者。
基材14的厚度没有特别的限定,可根据用途而适宜调整,但通常为1~500μm,优选为10~100μm。
作为基材14与疏液性薄膜10的贴合方法,可举出如以下的利用粘接剂的层合方法及利用热处理的层合方法等,但不受它们所限定。
(利用粘接剂的层合方法)
作为利用粘接剂的层合方法,可使用干式层合、湿式层合、无溶剂层合等各种众所周知的层合方法。作为这些层合方法所用的粘接剂13,可举出以下者。
<粘接剂13>
粘接剂13为粘接疏液性薄膜10与基材14者。作为粘接剂13,例如可举出对于聚酯多元醇、聚醚多元醇、丙烯酸多元醇、碳酸酯多元醇等主剂、使2官能以上的异氰酸酯化合物作用而成的聚氨酯树脂等。上述的各种多元醇可单独使用一种或组合二种以上使用。
粘接剂13可以促进粘接为目的,进一步在上述的聚氨酯树脂中配合碳二亚胺化合物、噁唑啉化合物、环氧化合物、磷化合物、硅烷偶合剂等。
另外,根据对于粘接剂13所要求的性能,也可在上述的聚氨酯树脂中配合其它的各种添加剂、稳定剂。
粘接剂13的厚度没有特别的限定,但从得到所期望的粘接强度、追随性及加工性等的观点来看,例如优选为1~10μm,更优选为3~7μm。
(利用热处理的层合方法)
作为利用热处理的层合方法,可大致举出以下的方法。
(1)将粘接性树脂挤出至经预先制膜的疏液性薄膜10与基材14之间,进行层合的方法。
(2)将构成疏液性薄膜10的树脂层与粘接性树脂共挤出,与基材14层合的方法。
(3)将上述(1)或(2)的方法所得的层合基材进一步以热辊进行加热·加压、由此使其粘接的方法。
(4)将上述(1)或(2)的方法所得的层合基材进一步在高温气体环境下保管,或者使其通过高温气体环境下的干燥·烘烤炉的方法。
作为利用热处理的层合方法所用的粘接性树脂,可举出酸改性聚烯烃等。另外,上述的方法为通过挤出层合而将基材14与疏液性薄膜10层叠,但也可不进行挤出层合,而预先将酸改性聚烯烃系涂布剂(溶解型、分散型)涂覆形成在基材14上后,通过热处理层叠疏液性薄膜10。
另外,在基材14上也可设置粘接性底漆(锚涂层(anchor coat))。作为其材料,可使用聚酯系、聚氨酯系、聚烯丙胺系、聚乙烯亚胺系、聚丁二烯系、乙烯-乙酸乙烯酯共聚物、氯-乙酸乙烯酯系等。在粘接性底漆中,根据需要也可配合能作为粘接剂13使用的上述的各种硬化剂、添加剂。
[包装材料]
本实施方式的包装材料为使用上述的疏液性层叠体而形成者。作为包装材料,具体而言可举出酸奶、果冻、糖浆等的容器的盖材、粥、汤、咖哩、意大利面酱等的杀菌食品包装材料(杀菌袋(retort pouch))等。通过以在包装材料的内表面(内容物侧)配置疏液层的方式形成包装材料,由此可抑制液体或半固体、凝胶状物质等内容物对于包装材料内表面的附着或残留。另外,在如杀菌食品包装材料的袋状包装材料中,有因包装材料的最内层彼此黏连而内容物变得难以排出的情况,但根据本实施方式的包装材料,作为最内层的疏液层彼此不易黏连,可有效率地排出内容物。
上述包装材料可为使用于施予80℃以上的加热处理的用途者。具体而言,可为使用于如杀菌食品包装材料的施予隔水加热等加热处理的包装材料用途者。根据本实施方式的包装材料,即使在使用于如此的用途时,在加热处理后也可抑制内容物对于包装材料内表面的附着或残留。
[容器]
本实施方式的容器为至少在内表面(内容物侧)具有使用上述的疏液层形成用树脂组合物所形成的疏液层的容器。作为容器,具体而言可举出化学品或医药品等液体、半固体、凝胶状物质等的保存容器、容纳洗手液或洗发水等的瓶等。通过以在容器的内表面(内容物侧)配置疏液层的方式形成容器,由此可抑制液体或半固体、凝胶状物质等内容物对于容器内表面的附着或残留。
实施例
以下,基于实施例及比较例更具体地说明本公开,但本公开不受以下的实施例所限定。
[实施例1]
<疏液层形成用树脂组合物的制作>
混合作为(A)成分的直链状低密度聚乙烯(LLDPE,商品名“Evolue”,PrimePolymer股份有限公司制)与作为(B)成分的甲硅烷基化聚乙烯(PE-Si的接枝共聚物,DowCorning Toray股份有限公司制),调制疏液层形成用树脂组合物。各成分的含量以(A)成分及(B)成分的总量为基准,以(B)成分成为5质量%、剩余部分成为(A)成分的方式调整。
<疏液性层叠体的制作>
使用三层共挤出机,挤出疏液层形成用树脂组合物而制膜,得到包含厚度为100μm的疏液层的疏液性薄膜。使用聚氨酯系粘接剂(三井化学股份有限公司制),将所得的疏液性薄膜与作为基材的厚度为38μm的PET薄膜(商品名“Emblet”,UNITIKA股份有限公司制)进行干式层合,在50℃下熟化5日,得到疏液性层叠体。
[实施例2~10]
除了如表1所示地变更疏液层形成用树脂组合物中的(A)成分及(B)成分的种类、以及(B)成分的含量((A)成分的含量为其剩余部分)以外,与实施例1同样地制作疏液层形成用树脂组合物、疏液性薄膜及疏液性层叠体。
[实施例11]
<疏液层形成用树脂组合物的制作>
混合作为(A)成分的直链状低密度聚乙烯(LLDPE,商品名“Evolue”,PrimePolymer股份有限公司制)、作为(B)成分的甲硅烷基化聚乙烯(PE-Si-PE的三嵌段共聚物,商品名“Exfola”,MITSUI FINE CHEMICALS股份有限公司制)与作为(D)成分的硅油(二甲基聚硅氧烷,Dow Corning Toray股份有限公司制),调制疏液层形成用树脂组合物。各成分的含量为以(A)成分、(B)成分及(D)成分的总量为基准,以(B)成分成为5质量%、(D)成分成为5质量%、剩余部分成为(A)成分的方式调整。
<疏液性层叠体的制作>
除了使用上述疏液层形成用树脂组合物以外,与实施例1同样地制作疏液性薄膜及疏液性层叠体。
[实施例12~13]
除了如表1所示地变更疏液层形成用树脂组合物中的(A)成分及(B)成分的种类以外,与实施例11同样地制作疏液层形成用树脂组合物、疏液性薄膜及疏液性层叠体。
[实施例14]
<疏液层形成用树脂组合物的制作>
与实施例1同样地制作疏液层形成用树脂组合物。
<疏液性层叠体的制作>
将作为(A)成分的直链状低密度聚乙烯(LLDPE,商品名“Evolue”,Prime Polymer股份有限公司制)当作第2树脂层形成用树脂组合物。使用三层共挤出机,将疏液层形成用树脂组合物与第2树脂层形成用树脂组合物共挤出而制膜,得到包含厚度为15μm的疏液层与厚度为85μm的第2树脂层的疏液性薄膜。使用聚氨酯系粘接剂(三井化学股份有限公司制),将所得的疏液性薄膜的第2树脂层与作为基材的厚度为38μm的PET薄膜(商品名“Emblet”,UNITIKA股份有限公司制)进行干式层合,得到疏液性层叠体。
[实施例15]
除了如表1所示地变更第2树脂层形成用树脂组合物中的(A)成分的种类以外,与实施例14同样地制作疏液层形成用树脂组合物、第2树脂层形成用树脂组合物、疏液性薄膜及疏液性层叠体。
[实施例16]
<疏液层形成用树脂组合物的制作>
混合作为(A)成分的无规聚丙烯(丙烯-乙烯无规共聚物,商品名“PrimePolypro”,Prime Polymer股份有限公司制)、作为(B)成分的甲硅烷基化聚乙烯(PE-Si-PE的三嵌段共聚物,商品名“Exfola”,MITSUI FINE CHEMICALS股份有限公司制)与作为(C)成分的PP-PE的嵌段共聚物,调制疏液层形成用树脂组合物。各成分的含量为以(A)成分、(B)成分及(C)成分的总量为基准,以(B)成分成为5质量%、(C)成分成为0.1质量%、剩余部分成为(A)成分的方式调整。
<疏液性层叠体的制作>
除了使用上述疏液层形成用树脂组合物,且如表1所示地变更第2树脂层形成用树脂组合物中的(A)成分的种类以外,与实施例14同样地制作疏液性薄膜及疏液性层叠体。
[实施例17~56]
除了如表1及表2所示地变更疏液层形成用树脂组合物中的(A)成分、(B)成分及(C)成分的种类、以及(B)成分及(C)成分的含量((A)成分的含量为它们的剩余部分)、第2树脂层形成用树脂组合物中的(A)成分的种类以外,与实施例16同样地制作疏液层形成用树脂组合物、第2树脂层形成用树脂组合物、疏液性薄膜及疏液性层叠体。此外,在实施例25中,如表1所示,在疏液层形成用树脂组合物中进一步添加(D)成分。
[比较例1]
除了在疏液层形成用树脂组合物中不添加(B)成分以外,与实施例14同样地制作疏液层形成用树脂组合物、第2树脂层形成用树脂组合物、疏液性薄膜及疏液性层叠体。
[比较例2]
除了如表2所示地变更疏液层形成用树脂组合物中的(A)成分的种类及第2树脂层形成用树脂组合物中的(A)成分的种类以外,与比较例1同样地制作疏液层形成用树脂组合物、第2树脂层形成用树脂组合物、疏液性薄膜及疏液性层叠体。
[比较例3~4]
除了如表2所示地变更疏液层形成用树脂组合物中的(A)成分及(B)成分的种类、以及(B)成分的含量((A)成分的含量为其剩余部分)、第2树脂层形成用树脂组合物中的(A)成分的种类以外,与实施例14同样地制作疏液层形成用树脂组合物、第2树脂层形成用树脂组合物、疏液性薄膜及疏液性层叠体。
[比较例5]
除了在疏液层形成用树脂组合物中不添加(B)成分以外,与实施例24同样地制作疏液层形成用树脂组合物、第2树脂层形成用树脂组合物、疏液性薄膜及疏液性层叠体。
表1及表2中,各成分的详细如下。表1及表2中的“-”意指不使用相当于其的成分。另外,表1及表2中,示出疏液层中的(C)成分的含量相对于(B)成分的含量的质量比((C)成分的质量/(B)成分的质量)。另外,表1及表2中,示出疏液层所用的作为(A)成分的树脂的熔点T1(℃)与第2树脂层所用的作为(A)成分的树脂的熔点T2(℃)的大小关系。进而,表1及表2中,示出疏液层中的(A)成分与(B)成分(聚烯烃部位)的相容性。
[(A)聚烯烃树脂]
A1:直链状低密度聚乙烯(LLDPE),商品名“Evolue”,熔点为116℃,Prime Polymer股份有限公司制
A2:无规聚丙烯(丙烯-乙烯无规共聚物),商品名“Prime Polypro”,熔点为134℃,Prime Polymer股份有限公司制
A3:嵌段聚丙烯,商品名“Novatec”,熔点为165~166℃,Japan Polypropylene股份有限公司制
A4:直链状低密度聚乙烯(LLDPE),商品名“Novatec LL”,熔点为122℃,JapanPolyethylene股份有限公司制
[(B)甲硅烷基化聚烯烃]
B1:PE-Si的接枝共聚物,Dow Corning Toray股份有限公司制
B2:PE-Si-PE的三嵌段共聚物,商品名“Exfola”,MITSUI FINE CHEMICALS股份有限公司制
B3:PP-Si的接枝共聚物,Dow Corning Toray股份有限公司制
[(C)增容剂]
C1:丙烯与乙烯的嵌段共聚物
C2:乙烯与乙烯·丁烯共聚物的嵌段共聚物
[(D)聚硅氧烷]
D1:硅油(二甲基聚硅氧烷),Dow Corning Toray股份有限公司制
[疏液性评价]
<实施例1~6、11、14~15、34~40及比较例1:无热处理下的疏液性>
关于使用直链状低密度聚乙烯(LLDPE)作为疏液层形成用树脂组合物中的(A)成分的实施例1~6、11、14~15、34~40及比较例1,通过图3所示的方法,进行无热处理下的疏液性的评价。首先,将实施例及比较例所得的疏液性层叠体切割成纵210mm×横300mm的样品100,以疏液层成为内侧的方式,折叠两半成为纵210mm×横150mm的尺寸(参照图3的(a)),以热封口机,在190℃、0.03MPa、2sec的条件下,以10mm宽度热封合纵向端部的1边与横向端部的1边(与折回的边为相反侧的边),形成密封部51,制作纵向端部的一边开口的袋(pouch)(参照图3的(b))。接着,从袋的开口部注入100g的色拉油52(商品名“日清色拉油”,Nisshin Oillio公司制)(参照图3的(c))。然后,以热封口机,在190℃、0.03MPa、2sec的条件下,以10mm宽度热封合开口部而形成密封部51,将袋密闭(参照图3的(d))。对于密闭的袋的折回边的某个角部,以排除密封部51的尺寸计,切断成为纵3cm×横3cm的三角形的部分,形成注入口(参照图3的(e))。手持与注入口在对角线上的角部53,将袋颠倒而保持30秒,使色拉油52排出至容器56,通过秤57来称量排出量(g)(参照图3的(f))。从所称量的排出量,通过下述式求出残液量(%)。
残液量(%)={(100-排出量)/100}×100
测定进行3次,从3次的平均残液量,依据下述评价基准来评价疏液性。表3及表4中示出平均残液量(%)及疏液性的评价结果。
◎:平均残液量小于2.0%
○:平均残液量为2.0%以上且小于2.5%
△:平均残液量为2.5%以上且小于3.5%
×:平均残液量为3.5%以上
<实施例7~10、12~13、16~33、41~56及比较例2~5:隔水加热处理后及杀菌处理后的疏液性>
关于使用无规聚丙烯(PP-PE无规共聚物)或嵌段聚丙烯作为疏液层形成用树脂组合物中的(A)成分的实施例7~10、12~13、16~33、41~56及比较例2~5,通过图4所示的方法,进行隔水加热处理后及杀菌处理后的疏液性的评价。首先,准备2片将实施例及比较例所得的疏液性层叠体切割成纵210mm×横150mm的样品200。将2片的样品200以各自的疏液层成为内侧的方式重叠,以热封口机,在190℃、0.03MPa、2sec的条件下,以10mm宽度热封合纵向端部的1边与横向两端部的2边,形成密封部51,制作纵向端部的一边开口的袋(参照图4的(a))。接着,从袋的开口部注入100g的水包油分散型液体54(商品名“BonCurry”,大冢食品公司制)(参照图4的(b))。然后,以热封口机,在190℃、0.03MPa、2sec的条件下,以10mm宽度热封合开口部而形成密封部51,将袋密闭(参照图4的(c))。
在隔水加热处理时,将密闭的袋在100℃下隔水加热处理5分钟。另一方面,在杀菌处理时,将密闭的袋投入至高温高压调理杀菌装置(Hitachi Capital股份有限公司制)后,以高温的水蒸气、在压力为0.2MPa的条件下、在121℃进行30分钟的杀菌处理,然后进行上述的隔水加热处理。
在上述处理后立即切断密闭的袋的上部而形成注入口(参照图4的(d))。接着,手持与注入口相反侧的密封部51,将袋颠倒而保持30秒,使水包油分散型液体54排出至容器56,通过秤57来称量排出量(g)(参照图4的(e))。从所称量的排出量,通过下述式求出残液量(%)。
残液量(%)={(100-排出量)/100}×100
测定进行3次,从3次的平均残液量,依据下述评价基准来评价疏液性。表3及表4中示出平均残液量(%)及疏液性的评价结果。
◎:平均残液量小于8.0%
○:平均残液量为8.0%以上且小于10.0%
△:平均残液量为10.0%以上且小于13.0%
×:平均残液量为13.0%以上
[外观评价]
在上述疏液性评价中,以目视观察从袋内排出液体时的液体的排出行为,依据下述评价基准进行外观评价。表3及表4中示出结果。
○:看到排斥液体的样子,对于疏液性层叠体的附着少。
△:看到排斥液体的样子,但是附着于疏液性层叠体。
×:看不到排斥液体的样子。
表1
表2
表3
表4
如由表3及表4所示的结果可知,确认到根据实施例1~56的疏液性层叠体,与比较例1~5的疏液性层叠体相比,可提高疏液性。
另外,对于实施例41~56的疏液性层叠体,疏液层中的树脂的熔点T1与第2树脂层中的树脂的熔点T2满足T1<T2的关系,可知得到特别良好的疏液性。
此外,实施例16的疏液性层叠体为(C)成分/(B)成分的质量比低至0.02者,另外,实施例17的疏液性层叠体为(C)成分/(B)成分的质量比高至25者,它们与(C)成分/(B)成分的质量比为0.05~20的范围内的其它实施例的疏液性层叠体相比,为疏液性稍低的结果。但若与比较例的疏液性层叠体相比,确认到实施例16及17的疏液性层叠体可提高疏液性。
符号说明
1、2 疏液性层叠体
11 疏液层
12 第2树脂层
13 粘接剂
14 基材
51 密封部
52 色拉油
53 角部
54 水包油分散型液体
56 容器
57 秤
100、200 疏液性层叠体的评价用样品
Claims (12)
1.一种疏液层形成用树脂组合物,其包含(A)聚烯烃树脂、(B)甲硅烷基化聚烯烃、以及具有与所述(A)聚烯烃树脂相容的部位及与所述(B)甲硅烷基化聚烯烃相容的部位的(C)增容剂,且所述(B)甲硅烷基化聚烯烃的聚烯烃部位与所述(A)聚烯烃树脂是不相容的。
2.如权利要求1所述的树脂组合物,其中,所述(C)增容剂包含选自丙烯与乙烯的嵌段共聚物、及乙烯与乙烯·丁烯共聚物的嵌段共聚物中的至少一种。
3.如权利要求1或2所述的树脂组合物,其中,所述(C)增容剂的含量相对于所述(B)甲硅烷基化聚烯烃的含量的质量比、即(C)增容剂的质量/(B)甲硅烷基化聚烯烃的质量为0.05~20。
4.一种疏液层形成用树脂组合物,其包含(A)聚烯烃树脂及(B)甲硅烷基化聚烯烃,且所述(B)甲硅烷基化聚烯烃的聚烯烃部位与所述(A)聚烯烃树脂是相容的。
5.如权利要求1至4中任一项所述的树脂组合物,其进一步包含(D)聚硅氧烷。
6.一种疏液性薄膜,其具备使用权利要求1至5中任一项所述的树脂组合物形成的疏液层。
7.如权利要求6所述的疏液性薄膜,其进一步具备在所述疏液层的一个主面上设置的1层以上的树脂层。
8.如权利要求7所述的疏液性薄膜,其中,所述疏液层中的所述(A)聚烯烃树脂的熔点T1、及所述1层以上的树脂层中与所述疏液层相接的树脂层所包含的树脂的熔点T2满足T1<T2的关系,所述T1、T2的单位为℃。
9.一种疏液性层叠体,其具备基材及在该基材上设置的权利要求6至8中任一项所述的疏液性薄膜,且所述疏液层配置于至少一侧的最表面。
10.一种包装材料,其为使用权利要求9所述的疏液性层叠体而形成的。
11.如权利要求10所述的包装材料,其使用于施予80℃以上的加热处理的用途。
12.一种容器,其至少在内表面具有使用权利要求1至5中任一项所述的树脂组合物形成的疏液层。
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JP6829613B2 (ja) * | 2017-01-30 | 2021-02-10 | 三井化学株式会社 | 樹脂組成物およびその成形体 |
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2019
- 2019-06-07 US US16/973,679 patent/US20210115231A1/en active Pending
- 2019-06-07 EP EP19820607.0A patent/EP3816225A4/en active Pending
- 2019-06-07 JP JP2020525539A patent/JP7383233B2/ja active Active
- 2019-06-07 CN CN201980028798.1A patent/CN112041387A/zh active Pending
- 2019-06-07 WO PCT/JP2019/022824 patent/WO2019240056A1/ja active Application Filing
- 2019-06-07 KR KR1020207028227A patent/KR20210019988A/ko not_active Application Discontinuation
- 2019-06-13 TW TW108120440A patent/TWI819003B/zh active
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CN101815754A (zh) * | 2007-08-31 | 2010-08-25 | 荷兰聚合物学会基金会 | 相容化聚烯烃组合物 |
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JP7383233B2 (ja) | 2023-11-20 |
TWI819003B (zh) | 2023-10-21 |
WO2019240056A1 (ja) | 2019-12-19 |
TW202003785A (zh) | 2020-01-16 |
EP3816225A4 (en) | 2022-03-09 |
US20210115231A1 (en) | 2021-04-22 |
EP3816225A1 (en) | 2021-05-05 |
JPWO2019240056A1 (ja) | 2021-07-15 |
KR20210019988A (ko) | 2021-02-23 |
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