CN1014064B - 生产多孔薄膜的方法 - Google Patents
生产多孔薄膜的方法Info
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Abstract
一种生产具有足够的机械强度、柔韧性好、微气孔均匀、水蒸汽渗透性高的多孔薄膜和极薄的多孔薄膜的方法，该方法包括将30～80份重量的比表面为15米2/克或15米2/克以下和平均颗粒大小为0.4～4微米的无机细粉末与20～70份重量的聚烯烃树脂掺合，接着将得到的掺合物用熔融模塑法制成薄膜，然后，将薄膜至少在一个轴向拉伸，使其长度达到原长度的2～7倍。
Description
本发明是关于生产一种多孔薄膜的方法，该多孔薄膜具有柔韧性和均匀的微气孔结构，并因而具有优良的水蒸汽渗透性和防水性，适用于防水衣、防水罩、包装材料等。
迄今已知的生产多孔薄膜的方法是使用一种非相容物质，例如无机细粉与聚烯烃树脂按特定的比例掺合，接着将所得的掺合物进行熔融模塑，使之形成薄膜或薄片，然后将薄膜或薄片进行单轴或双轴拉伸。
但是，这种加工方法有缺点，因为树脂受到拉伸并由于拉伸而定向，从而使薄膜或薄片的硬度提高，柔韧性降低。
为克服此缺点，有人推荐了下述生产多孔薄膜的方法：①使热塑性高弹体与聚烯烃树脂和一种填料掺合（日本专利公报NOSho59-30833/1984）;
②使液体或蜡状的烃聚合物与聚烯烃树脂和一种填料掺合（美国专利NO4，472，328）;和
③用硫酸钡作为无机细粉与聚烯烃树脂掺合（英国专利NO2，151，538）。
然而，按照这些生产方法制得的多孔薄膜在实际使用中有以下缺点：
按照方法（1）制得的薄膜其多孔性是不够的，水蒸汽的渗透性差。按照方法（2）制得的多孔薄膜在高温大气中或经过很长时间后，会有烃聚合物在生成的薄膜表面渗出，使表面发粘。按照方法（3）制得的多孔薄膜具有优良的柔韧性和足够的水蒸汽渗透性，但其拉伸稳定性即高度拉促能力差。而且，这些方法存在着一个共同的问题，即不能生产极薄的约20μ的薄膜。此外，掺合第三种组分的方法，会导致成本大大提高。
本发明的目的是提供一种生产多孔薄膜的方法，该方法制得的多孔薄膜含有具有优良耐化学性的聚烯烃树脂，具有对于实际应用来说足够的机械强度和优良的柔韧性，也具有均匀的微气孔和高的水蒸汽渗透性，该方法还制得极薄的多孔薄膜。
本发明属于一种制造多孔薄膜的方法，该方法包括将30%～80%重量的无机细粉（其比表面积为15米2/克或15米2/克以下，平均颗粒大小为0.4～4微米）与20～70%重量的聚烯烃树脂掺合，接着将所得的掺合物熔融模塑成薄膜，然后，至少在一个轴向拉伸薄膜，使其伸长到原来长度的2～7倍。
本发明使用的聚烯烃树脂的例子有聚丙烯，低密度聚乙烯，线型低密度聚乙烯、高密度聚乙烯及其掺合物，其中，线型低密度聚乙烯和含有线型低密度聚乙烯的掺合物是特别好的。适用于线型低密度聚乙烯的共聚用单体组份的例子一般有丁烯、4-甲基戊烯、己烯、辛烯、癸烯等，其中，以4-甲基戊烯和辛烯的可塑性和其产品的物理性能为最好。
本发明使用的无机细粉末是比表面积为15米2/克或15米2/克以下和平均颗粒大小为0.4到4微米的细颗粒。本发明使用的无机细粉末的例子是碳酸钙、碳酸镁、氧化镁、硫酸钡、二氧化硅、氢氧化铝、氧化铝等，其中，以沉淀碳酸钙和沉淀硫酸钡为最好，因为这些材料具有均匀的颗粒直径和均匀的比表面积，当它们与树脂组份掺合和在得到的掺合物成型时，它们具有优良的分散性，同时掺合物具有优质的加工成型性能。而且，无机细粉末以呈球型的为最好。沉淀硫酸钡是通过例如硫化钡与硫酸钠的水溶液的反应或硫化钡与硫酸的反应而得到。形状包括无定形、锭状、片状、菱形、球形等。在特定的条件下确定硫化钡和SO2- 4的浓度，反应的物理条件和反应温度，便能得到具有所希望的平均颗粒直径。
沉淀碳酸钙通常是通过将二氧化碳通入氢氧化钙的水悬浮液而生成的，它是立方形，平均颗粒大小为1微米或1微米以下;或呈锭形或针状，平均
颗粒大小为1微米或1微米以上。在特定的条件下确定氧化钙水悬浮液的反应温度、所加具体盐的种类和反应终止时间，便可获得具有所要求的平均颗粒大小的球形沉淀碳酸钙。无机细粉末的比表面积为15米2/克或15米2/克以下，最好为0.5～5米2/克。如果比表面积超过15米2/克，无机细粉末的形状便变为无定形、片状或针状，使颗粒大小分布变宽，并使所得薄膜的拉伸性能降低，因而不可能获得好的多孔性。而且，细粉末表面的多孔性增加，并由于有挥发组份（如附着在气孔上的水分，在熔融模塑时可看到发泡现象，生成的薄膜的气孔直径增加而且它的耐水压力大大降低。
无机细粉末的平均颗粒大小为0.4～4微米为宜，尤以0.6～2微米为最好，如果平均颗粒大小超过4微米，薄膜的拉伸性能差，在均匀变白之前出现拉伸断裂。因此，操作的稳定性差，不可能形成均匀的气孔。
另一方面，如果平均颗粒大小小于0.4微米，那末无机细粉末不能高度填充，不能生成多孔薄膜。
在本发明的树脂组合物中，按掺合物重为100份计，无机细粉末的量在30～80份重量范围内，最好为30～70份重量。小于30份重量时，就拉伸薄膜而言，多孔性不好。如果其量超过80份重量，捏和性、分散性和拉伸性差，自然，水蒸汽渗透性也差，而且，柔韧性降低。
下面要叙述本发明的生产多孔薄膜的方法。首先，使无机细粉末按特定比例与聚烯烃树脂混合。对混合方法没有特别的限制。一般是用掺合器之类使这些材料混合，接着是用班伯里（Banbury）混合机使混合物掺合，或先用另一个熔融捏和器，然后，将掺合物制粒或不制粒，然后用通常的片材成型机制成片材，可随意加入各种添加剂，例如，润滑剂（如硬脂酸钙），颜料稳定剂（起耐热耐光作用），增塑剂，抗静电剂等。
薄膜通常是用压延、浇铸或挤出等方法制造的，其中，以采用圆形模头或T-模头的挤出法为最好。然后将挤出的薄片用已知的方法，在聚烯烃树脂的软化温度或低于该温度下至少在单轴向拉伸，拉伸比达2～7倍。在以上拉伸比范围中尤以4～6倍的拉伸比为最好。如果拉伸比小于2倍，难以获得足够的水蒸汽渗透性，而拉伸比超过7倍时会发生拉伸断裂，不可能进行稳定的生产。
下面用实施例对本发明进行更详细的叙述。薄膜的物理性能是用下列方法评定的：
比表面积（米2/克）：按照BEF吸附法测定。
平均颗粒大小（微米）：用测定粉末表面积的仪器测定（岛津（Shimazu）制造），即将样品（3克）装入2厘米2×1厘米的样品管中，在50mm水压下测定空气渗透时间（5cc）。
断裂时的拉伸强度（公斤）采用25毫米宽×100毫米长的薄膜试片，采用Tensilon拉伸试验机（日本Toyosokki.K.K制造的试验机商标）以200毫米/分拉伸速度进行试验，分别在MD（塑流方向）和在TD（垂直于塑流的方向）测定断裂强度。
水蒸汽的渗透性：按照ASTM-E-96-66测定。
柔韧性：根据手感评定如下：
A：很柔韧
B：有点柔韧
C：不柔韧
实施例1～9
将具有表1所示比表面积和平均颗粒大小的无机细粉末[沉淀钡（实施例1～4和8～9）]沉淀硫酸钙（实施例5和6）或氧化镁（实施例7）按表1所示的量加到MI＝2[L-LDPE（实施例1～7）]的线型低密度聚乙烯，MI＝5[LDPE（实施例8）]的低密度聚乙烯或MI＝1.5[PP（实施例9]的聚丙烯中，接着用Henschcl混合器（商标）使混合物掺合，将混合物制粒，用挤出的方法将混合物制成薄膜，然后在50℃下用辊单轴拉伸薄膜，使其长度达原长度的2～7倍以得到20微米厚的多孔薄膜。然后测定薄膜的物理性能，表1中列出其结果。
实施例10
将由实施例2的组分制得的薄膜在70℃下用双轴拉伸机同时在纵向和横向进行拉伸（3×3）倍，以得到20微米厚的多孔薄膜。表1中列出其物理性能的测定结果。
实施例11
按实施例1的方法将占60%重量的比表面积为4.1米2/克和平均颗粒大小为0.8微米的沉淀硫
酸钡与20%重量的MI＝2的线型低密度聚乙烯（L-LDPE）和20%重量的MI＝5的低密度聚乙烯（LDPE）进行掺合以得到多孔薄膜。
表1列出其物理性能的测定结果。
比较实施例1～6
按实施例1的方法制备多孔薄膜，但与不同量的L-LDPE掺合的无机细粉末（沉淀硫酸钡（比较实施例1～3和5～6）或碳酸钙（比较实施例4））的种类和用量不同，拉伸条件也不同，如表1所示，表1列出其物理性能的测定结果，在比较实施例1中，由于加入的无机细粉末的数量小于30%，多孔性降低，同时水蒸汽渗透性小。在比较实施例2中，由于加入的无机细粉末的量超过80%，拉伸能力下降，在按1.5的拉伸比进行拉伸时发生拉伸断裂。在比较实施例3和4中，由于无机细粉末的比表面积超过15米2/克，拉伸能力下降，同时用片材成型机进行挤出时可看到发泡，并开裂。在比较实施例5中，由于无机细粉末的平均颗粒直径超过4微米，拉伸能力下降，因而不可能进行拉伸比为2的稳定生产。在比较实施例6中，由于拉伸比小于2，不可能获得足够的水蒸汽渗透性。
由于本发明的薄膜的多孔程度是足够的，水蒸汽的渗透性和空气渗透性是好的，同时耐水性也是优良的。特别是由于它的柔韧性好，有柔软的手感，适合于做衣服，特别适用于卫生方面。与先有技术不同，本发明的方法能生产非常薄的（厚度为20微米或20微米以下）薄膜;所得的多孔薄膜几乎不是单独使用的，其主要用途是层合在非织布、纸、尼龙塔夫绸等上。薄膜越薄，成本越低，而且在做衣服时还有一个特点，即并不会由于叠层厚而感到不舒服。
Claims (2)
1、一种制备多孔薄膜的方法，该方法包括掺合30-80份重量的比表面不大于15米2/克，平均颗粒大小为0.4-4微米的球形颗状的无机粉末和20-70份重量的聚烯烃树脂，然后，熔融所得掺合物使成薄膜并至少在单轴方向拉伸该薄膜至原长度的2-7倍，所说的无机粉末选自沉淀碳酸钙、硫酸钡、沉淀硫酸钡、碳酸镁、氧化镁、二氧化硅、氢氧化铝和氧化铝。
2、权利要求1的方法，其中所说的聚烯烃树脂是线型低密度聚乙烯树脂或含有线型低密度聚乙烯树脂的掺合物。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP287909/1985 | 1985-12-23 | ||
| JP60287909A JPS62148537A (ja) | 1985-12-23 | 1985-12-23 | 多孔性フイルムの製造法 |
| JP287909/85 | 1985-12-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86108657A CN86108657A (zh) | 1987-09-09 |
| CN1014064B true CN1014064B (zh) | 1991-09-25 |
Family
ID=17723294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86108657A Expired CN1014064B (zh) | 1985-12-23 | 1986-12-23 | 生产多孔薄膜的方法 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4921652A (zh) |
| EP (1) | EP0227037B1 (zh) |
| JP (1) | JPS62148537A (zh) |
| KR (1) | KR900003046B1 (zh) |
| CN (1) | CN1014064B (zh) |
| AU (1) | AU595565B2 (zh) |
| CA (1) | CA1305300C (zh) |
| DE (1) | DE3680493D1 (zh) |
| NO (1) | NO169080C (zh) |
| NZ (1) | NZ218669A (zh) |
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| CN100349731C (zh) * | 2002-10-30 | 2007-11-21 | 戈尔企业控股股份有限公司 | 多孔高分子膜的增韧复合材料 |
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| MX2012006109A (es) | 2009-12-10 | 2012-07-20 | Sca Hygiene Prod Ab | Articulos absorbentes como sumideros de carbono. |
| CN102275297A (zh) * | 2011-08-05 | 2011-12-14 | 大连方盛塑料有限公司 | 一种制造多孔薄膜的方法 |
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-
1985
- 1985-12-23 JP JP60287909A patent/JPS62148537A/ja active Granted
-
1986
- 1986-12-17 EP EP86117615A patent/EP0227037B1/en not_active Expired - Lifetime
- 1986-12-17 NZ NZ218669A patent/NZ218669A/xx unknown
- 1986-12-17 DE DE8686117615T patent/DE3680493D1/de not_active Expired - Lifetime
- 1986-12-17 CA CA000525608A patent/CA1305300C/en not_active Expired - Fee Related
- 1986-12-18 NO NO865156A patent/NO169080C/no unknown
- 1986-12-22 AU AU66825/86A patent/AU595565B2/en not_active Ceased
- 1986-12-23 KR KR1019860011146A patent/KR900003046B1/ko not_active IP Right Cessation
- 1986-12-23 CN CN86108657A patent/CN1014064B/zh not_active Expired
-
1988
- 1988-08-08 US US07/229,797 patent/US4921652A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349731C (zh) * | 2002-10-30 | 2007-11-21 | 戈尔企业控股股份有限公司 | 多孔高分子膜的增韧复合材料 |
| CN1314734C (zh) * | 2003-01-30 | 2007-05-09 | 上海杰事杰新材料股份有限公司 | 防水透气微孔膜、其制备方法及用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO169080B (no) | 1992-01-27 |
| EP0227037B1 (en) | 1991-07-24 |
| CA1305300C (en) | 1992-07-21 |
| EP0227037A3 (en) | 1988-07-06 |
| CN86108657A (zh) | 1987-09-09 |
| JPH0580502B2 (zh) | 1993-11-09 |
| NO169080C (no) | 1992-05-06 |
| KR870005779A (ko) | 1987-07-07 |
| NO865156D0 (no) | 1986-12-18 |
| US4921652A (en) | 1990-05-01 |
| DE3680493D1 (de) | 1991-08-29 |
| KR900003046B1 (ko) | 1990-05-04 |
| NZ218669A (en) | 1989-01-27 |
| AU595565B2 (en) | 1990-04-05 |
| AU6682586A (en) | 1987-07-02 |
| EP0227037A2 (en) | 1987-07-01 |
| NO865156L (no) | 1987-06-24 |
| JPS62148537A (ja) | 1987-07-02 |
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