CN1011131B - 聚缩醛树脂薄膜制造方法 - Google Patents
聚缩醛树脂薄膜制造方法Info
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Abstract
一种聚缩醛树脂薄膜通过下列改进方法而制得,即在处于下述公式所表示的挤出树脂温度范围之内,通过吹胀法将熔体指数为0.3~5.0的聚缩醛树脂加工成薄膜,熔点(℃)<挤出树脂温度(℃)≤熔点+100-8×(熔体指数)(℃)。
Description
本发明涉及一种由聚缩醛树脂制造薄膜的方法。特别是本发明的方法可制得无论横向还是纵向均具有低撕裂强度的特征的薄膜,但该薄膜可按直线方式被撕裂,容易沿一条直线撕裂开。
图1是表示在树脂可进行本发明的吹胀模塑的挤出阶段所使用的树脂温度范围的示图。在图中,可采用的薄膜成型范围是由下列四条直线所限定区域的范围,四条直线是:T=MP+100-8·MI,T=MP,MI=0.3,MI=5.0。可采用较佳的范围是由下列四条直线所限定区域的范围,四条直线是:T=MP+80-8MI,T=MP,MI=0.3,MI=5.0。(其中MP为熔点)。图2表示本发明的吹胀阶段。图2中〔1〕表示模头,〔2〕管状物,〔3〕开始变形点,〔4〕鼓泡状物。
聚缩醛树脂或具有-CH2-O-键作为重复单元的聚合物化合物是众所熟知的,并且已被广泛用作典型的工程塑料。
可是它们大多数仅仅被用于注塑,而很少用于挤出成型,并且特别是很少用于制造薄膜。其原因是加工这类树脂成薄膜十分困难。
通常,两类薄膜制造方法是大家熟知的,即T型模头方法和吹胀方法。T型模头法通常是使引入的塑料熔体流由一点扩展达到所需的薄膜宽度,以便使熔体流转变成厚度尽可能更均匀的薄膜,再把熔体流通过一滑片型喷嘴(Slip-shaped nozzle)以薄膜的型式挤出,然后冷却制得薄膜。吹胀法是聚乙烯薄膜成型经常采用的方法。该方法是先把熔融的塑体通过一环形挤出喷嘴以管状型式挤出,向管内吹入空气或其它类似的流体,藉此把该管状物吹胀成管状薄膜。T型模头法和吹脂法各有自己的优缺点。与T型模头法相比较,吹胀法通常生产率高并且更经济,适用于厚度小的薄膜成型但另一方面取决于原材料树脂的不同,它的适应性差别很大。因此不能说吹胀法可以适用于所有各类树脂。对聚缩醛树脂来说,采用吹胀法制造该树脂的薄膜,还有各种技术问题尚待解决。因此,聚缩醛树脂薄膜的制造至今未被工业化。
鉴于上述情况,为了能用吹胀法来制造聚缩醛树脂薄膜,本发明者进行了一系列的研究。其结果他们发现只要选择恰当的聚缩醛树脂和恰当的温度条件,就可以用吹胀法来制造聚缩醛薄膜,并且这个发现构成了本发明。
因此,本发明提供了一种聚缩醛树脂薄膜的制造方法,其特征在于处于下述公式所表示的挤出树脂温度范围之内,通过吹胀法将熔体指数为0.3~5.0的聚缩醛树脂加工成薄膜。
熔点(℃)<挤出树脂温度(℃)≤熔点+100-8×(熔体指数)(℃)。
本发明是基于这样一个发现,即只有聚缩醛树脂的熔体指数为0.3~5.0时,通过安排以使挤出树脂温度处在上述公式表示的温度范围之内,才有可能用吹塑法将该树脂加工成薄膜。
本发明中所用的熔体指数(以下简称MI)是按照美国材料试验学会的ASTM D-1238标准测定的值。熔点是由差热分析测出的吹热峰的温度值来表示的。
上述这样的聚缩醛树脂相当于那些具有较低MI和较高平均分子量的聚缩醛树脂市售品。更准确地说,MI在0.5~3.0范围的聚缩醛树脂,无论是均聚物还是共聚物则更合适。MI低于0.3的树脂吹胀加工十分困难,而MI高于5.0的树脂也不合适,因为由于在吹塑操作阶段易于发生垂伸而造成薄膜
成型十分困难。
具有交联或支链分子结构的聚缩醛树脂则最为合适。这样的聚缩醛树脂可以通过使一种具有一个以上能生成支链或交联分子结构的官能团的化合物与聚合好的线型聚缩醛树脂进行反应而制得。这样的树脂也可以通过将一种具有一个以上能产生支链或交联反应的官能团的单体加进一种单体组份之中以便进行共聚合而制得。例如三 烷与一种具有一个缩水甘油基的单体共聚合作为一个组份所得的缩醛共聚物就是这种树脂的一个例子。当然加进诸如环醚之类常用的共聚单体所得的多组份共聚物,根据需要也可使用。
在吹胀模塑方法中,当采用吹胀技术将具有上述专门指定MI数值的聚缩醛树脂从环形喷嘴熔融挤出时,重要的是树脂温度必须保持在按下列公式表示的温度范围之内:
熔点(℃)<挤出树脂温度(℃)≤熔点+100-8×(熔体指数)(℃)。
树脂温度最好保持在按下述公式表示的温度范围之内:
熔点+10(℃)≤挤出树脂温度(℃)≤熔点+80-8×(熔体指数)(℃)。
适用于吹胀模塑的这些树脂温度范围如图1中所示。如果树脂温度太高,熔体粘度变低,由于垂伸效应使薄膜成型变得困难了。如果树脂温度太低,则熔体粘度变高,在模头处产生的压力损失就大,导致增加挤出机操作的功率消耗,并且因以降低了生产率。另外,这种较高树脂温度还容易产生薄膜厚度的不均匀性。
通过保持上述必须达到的条件,这种聚缩醛树脂采用本发明的吹胀法进行薄膜成型就变得实际可行了。至于其它条件,只需达到吹胀技术的一般条件即可。也就是采用一种直角模头,将聚缩醛树脂熔体向上或向下挤出成管状,并且该管状挤出树脂的一端在夹辊之间被夹紧,而且吹进空气以使该管状物被充气吹胀到所需的尺寸,该薄膜被连续导出。同时将该机头旋转或转向,由此可防止任何薄膜的厚度不均匀性。管状薄膜在两端切断,把一端封上该薄膜就可形成一个薄膜袋。或者可将管状薄膜恰当拉伸成片状薄膜,并且经热固化或其它方式提供了一种利用聚缩醛树脂特征和各种适用于不同最终用途的性能的薄膜。本发明所制得的薄膜可以按照吹胀技术的通常标准调节厚度。这种调节一般可在0.005~0.1毫米范围之内。
此外,本发明者发现采用本发明的吹胀法制得的聚缩醛树脂薄膜具有优异的特性,即纵向撕裂强度和横向撕裂强度都小,并且撕裂方向的直线性也很好。
一般来说,由挤出模塑法制得的塑料薄膜,在挤出方向(以下称之为纵向方向)具有分子取向,因此沿纵向方向容易撕裂。然而,沿横向方向就难撕裂。进一步来说,在挤出方向挤出的薄膜有较高的纵向拉伸强度,可是沿着纵向方向的撕裂倾向也增强了。
然后尚未公开过有纵向和横向方向都容易被撕裂的薄膜。
本发明者发现在纵向和横向方向撕裂强度都小的薄膜可以采用吹胀法,在前述的各种条件下,制备聚缩醛树脂薄膜而制得。特别是可以采用吹胀法在下列条件制得横向方向撕裂强度小以及撕裂方向的直线性好的聚缩醛树脂薄膜,例如吹胀比为1.2~6.0,拉伸比为1.0~12.0,吹胀比和拉伸比两者之比表示在下式中:
0.1≤吹胀比/拉伸比≤6.0。
本发明中,吹胀比和拉伸比定义如下:
在图2中,从模头〔1〕挤出的熔体树脂保持几乎同一直径进行传送从而形成管状物〔2〕,随后从开始变形点〔3〕处发生膨胀。当在开始变形点〔3〕处管状物的直径为D时,它的速度为V,变形后鼓泡状物〔4〕的直径是DE,它的速度是V,那么:
吹胀比=DE(毫米)/D(毫米)
拉伸比=V(米/分)/V(米/分)。
按照本发明可以制得一种聚缩醛树脂薄膜,该薄膜在挤出方向和直角方向的撕裂强度均为50公斤/厘米或更低,抗撕裂蔓延强度为10公斤/厘米或更低,并且撕裂方向直线性很好。但是吹胀比与拉伸比之比的数值变得低于上述范围时,横向方向(直角方向)的撕裂强度就变得大于纵向方向(挤出方向)的撕裂强度,而且撕裂方向直线性就变小。相反,吹胀比与拉伸比之比的数值变得高于上述范围,则横向方向的撕裂强度就变得小于纵向方向的撕裂强度,并且撕裂方向直线性就变大。
采用本发明的吹胀法制备的薄膜,其撕裂强度在挤出方向和直角方向均为50公斤/厘米或更低,抗
撕裂蔓延强度为10公斤/厘米或更低,并且撕裂方向直线性很好,因以该薄膜可被很好撕裂而不起毛,可很好用于未密封的制品等。
实施本发明所用的聚缩醛树脂,可以根据用于薄膜的性能要求,加进一些通常可用于热塑性和热固性树脂中的已知物质,包括稳定剂例如增塑剂、抗氧剂和紫外光吸收剂;抗静电剂;表面活性剂;着色剂例如染料和颜料;改善流动性的润滑剂;结晶加速剂(成核剂)。再有,按照薄膜使用的用途还可以附加地加进少量其它一些热塑性树脂或无机填料。
如上所述,按照本发明的方法,能够采用吹胀法制备聚缩醛树脂薄膜,并且与通常的T型模头相比较,本发明改进了生产率和经济性。通过采用已知技术,本发明可允许容易制备比较薄的薄膜。所得薄膜具有聚缩醛树脂的优良特性,例如优良的机械、物理、化学和热性能,并且它还具有不透氧的特殊性能。因此,用于包装或能发挥其特性之长处的各种其它最终用途,该薄膜既可以如此单独使用也可以与其它一些薄膜或金属箔层压使用。本发明制得的薄膜的上述用途就是它很容易一下撕开,因为该薄膜在纵向和横向方向的撕裂强度都小,并且撕裂方向的直线性很好。
实施例1
使用一种缩醛共聚物树脂P(MI为2.5,熔点为165℃),其中其甲醛部分和其乙醛部分之间的重量比为98∶2。通过利用一台直径40毫米的挤出机和一个其模头直径为50毫米以及模唇间隙为3毫米的模头,在200℃的树脂温度、拉伸比为8.0以及吹胀比为2.4的条件下,挤出形成管状薄膜。以21米/分的引出速度在空气冷却条件下将薄膜引出。因此制得了厚度为25微米的薄膜。
制得25微米厚的薄膜的性能如下列表1中所示。
树脂性能和薄膜性能按下列方式测定:
MI:按照ASTM D1238,负荷重2160克,在190℃下测定。
熔点:用示差扫描量热仪(DSC)测定(加热速度5℃/分),以吸热峰位置的温度值表示。
拉伸强度/伸长率:按照ASTM D882测定。
氧气透过率:按照ASTM D1434测定。
撕裂强度:按照JIS Z埃尔曼多夫(Elmendorf)撕裂试验测定,但对样品不作起始切割。
撕裂蔓延强度:按照JIS Z Elmendorf撕裂试验测定
撕裂方向直线性:从300毫米的样品的一边沿直角方向用手撕,并且测定撕开线的直线性。撕开线偏离直角方向的多少如下进行评价,
低于10毫米 ○
10~50毫米 △
高于50毫米 ×
实施例2
使用一种缩醛接枝共聚物树脂Q(MI为0.8,熔点为166℃),其中其甲醛部分、其乙醛部分和六氧亚甲基二醇缩水甘油基三者间的重量比为97.2∶2∶0.8。通过利用一台直径50毫米挤出机和一个其模头直径为120毫米以及模唇间隙为1毫米的模头,在树脂温度210℃、拉伸比为2.0,吹胀比为1.2~3.6的条件下挤出形成管状薄膜。以25~40米/分的引出速度在空气冷却下进行引出。因此,制得厚度为8~50微米的薄膜。
所得薄膜的性能,厚度为25和50微米的两种薄膜,如下列的表2中所示。(见表1、2)
比较例1
使用一种缩醛共聚物树脂(MI为9.0,熔点为165℃),其中其甲醛部分和其乙醛部分的重量比为98∶2。打算在不同的挤出树脂温度下仍按实施例1中相同的方式进行吹胀模塑,但不能达到稳定的薄膜成型。
实施例3和4,比较例2和3
使用在实施例1和2中相同的聚缩醛共聚物P和Q,并在不同的挤出树脂温度下,试图进行薄膜成型。其结果示于表3和表4中。(见表3、4)
实施例5,比较例4
在与实施例1类似的条件下形成厚度为25微米的薄膜,但设定吹胀比为3.6和拉伸比为2.0。并且该薄膜的性能按同样方法测定。其结果示于表5中。作为一个比较例,在相同条件下形成厚度为25微米的低密度聚乙烯薄膜(MI0.2)并且其结果也示于表5中。(见表5)
表1
挤出方向 直角方向
拉伸强度(公斤/厘米2) 567 683
拉伸伸长率9%) 76 3
氧气透过率 342
(厘米3/米2·天·大气压)
撕裂强度(公斤/厘米) 6.0 20.5
撒裂蔓延强度(公斤/厘米) 2.2 5.7
撒裂方向直线性 0 0
表2
25微米厚 50微米厚
挤出方向 直角方向 挤出方向 直角方向
拉伸强度(公斤/厘米) 553 680 600 700
拉伸伸长率(%) 103 3.5 107 3.7
氧气透过率
(厘米3/米3·天·大气压) 364 181
表3
实施例3 比较例2
(共聚物P) (共聚物P)
树脂温度(℃) 180 220 240 260
不好
薄膜成型条件 稳定 稳定 稍不稳定 (垂伸)
拉伸强度 挤出方向 561 533 - -
(公斤/厘米2) 直角方向 672 633 - -
拉伸伸长率 挤出方向 63 72 - -
(%) 直角方向 3.2 3.2
表4
实施例4 比较例3
(共聚物a) (共聚物Q)
树脂温度(℃) 180 220 240 260
薄膜成型条件 稳定 稳定 稳定 不稳定
拉伸强度 挤出方向 540 622 533 -
(公斤/厘米2) 直角方向 667 720 634 -
拉伸伸长率 挤出方向 101 108 85 -
(%) 直角方向 3.5 3.7 3.2 -
表5
挤出方向 | 直角方向 | ||
实施例5 | 拉伸强度(公斤/厘米2) | 668 | 683 |
撕裂蔓延强度(公斤/厘米) | 4.2 | 4.0 | |
撕裂方向直线性 | ○ | ○ | |
比较例4 | 拉伸强度(公斤/厘米2) | 220 | 210 |
撕裂蔓延强度(公斤/厘米) | 26.3 | 23.7 | |
撕裂方向直线性 | × | × |
Claims (5)
1、一种聚缩醛树脂薄膜的制造方法,该方法包括在处于下述公式所表示的挤出树脂温度范围之内,通过吹胀法将熔体指数为0.3~5.0的聚缩醛树脂加工成薄膜:
熔点(℃)<挤出树脂温度(℃)≤熔点+100-8×(熔体指数)(℃)。
2、按照权利要求1所述的聚缩醛树脂薄膜的制造方法,其中聚缩醛树脂的熔体指数为0.5~3.0。
3、按照权利要求1所述的聚缩醛树脂薄膜的制造方法,其中挤出树脂温度满足下述条件:
熔点+10(℃)≤挤出树脂温度(℃)≤熔点+80-8×(熔体指数)(℃)。
4、按照权利要求1-3之一所述的聚缩醛树脂薄膜的制造方法,其中聚缩醛树脂具有交联或支链的分子结构。
5、按照权利要求1所述的聚缩醛树脂薄膜的制造方法,其中在吹胀工艺中,吹胀比为1.2~6.0,拉伸比为1~12;并且吹胀比与拉伸比两者之比为0.1≤吹胀比/拉伸比≤6.0。
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JP62155057A JPH0822564B2 (ja) | 1987-04-01 | 1987-06-22 | ポリアセタ−ル樹脂フィルムの製造法 |
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JPH09147626A (ja) * | 1995-11-22 | 1997-06-06 | Nippon Zeon Co Ltd | 樹脂組成物、および成形品 |
CN101863121B (zh) * | 2009-04-14 | 2012-09-05 | 杨庆理 | 纳米孔膜及制造方法 |
JP5551662B2 (ja) * | 2011-08-23 | 2014-07-16 | 旭化成ケミカルズ株式会社 | ポリアセタールの製造方法 |
CN109280321B (zh) * | 2018-08-07 | 2020-01-21 | 唐山开滦化工科技有限公司 | 一种聚甲醛薄膜及其制备方法 |
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US3980734A (en) * | 1972-07-06 | 1976-09-14 | Hoechst Aktiengesellschaft | Thermoplastic moulding compositions based on poly (oxymethylene) |
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DE3880187T2 (de) | 1993-07-29 |
JPH0822564B2 (ja) | 1996-03-06 |
US4879085A (en) | 1989-11-07 |
KR910005207B1 (ko) | 1991-07-23 |
EP0285291A2 (en) | 1988-10-05 |
DE3880187D1 (de) | 1993-05-19 |
CN88101745A (zh) | 1988-11-23 |
KR880012337A (ko) | 1988-11-26 |
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