CN87104709A - 封接膜 - Google Patents
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Abstract
一种具有优良封接强度的薄膜,其基层由70~90wt%的聚烯烃(如:聚丙烯)和10~30wt%分子量低于聚烯烃的树脂(如:氢化石油树脂)组成。至少在基层的一个表面上有一个相对于基层重量1~20wt%的无规共聚物膜层,该膜层由80~99wt%的丙烯和1~20wt%的乙烯组成,如:全同丙烯—乙烯共聚物。
Description
本发明介绍一种以聚丙烯为基础的薄膜、其中包括可热封接的聚丙烯薄膜。
以往的发明描述过多种聚丙烯薄膜(如在GB2028168A,EP135178和DE3247988中所提到的薄膜的心层或基层即为聚丙烯)及添加于薄膜中的各种添加剂(如某些模量改进剂,抗静电介质,硅氧烷及颜料等)。然而,没有一件发明对明显提高聚烯烃薄膜的封接强度作过阐述。
本发明涉及的是仅具有一个组分的聚丙烯薄膜,其封接强度高于以往的仅具有一个组分封接层的聚丙烯薄膜的封接强度,即在相同的封接温度下,本发明薄膜的封接强度明显提高,或在封接强度相同时,本发明薄膜仅需较低的封接温度即可。
本发明薄膜(特别是可封接薄膜)的基层由70~97Wt%,最好是70~90Wt%的聚烯烃和3-10Wt%,最好是10-30Wt%,分子量低于聚烯烃的树脂组成。至少在基层的一个表面上有一个相对于基层重量1-20Wt%的无规共聚物膜层。该膜层由80-99Wt%的丙烯和1-20Wt%的乙烯组成。
这种薄膜可用于包装工业、並能适应高标准的使用要求,如高模量,高透明度的要求。另外,这种薄膜还具有良好的隔离性,即指对水蒸汽和气体(尤其是氧)的低渗透性。薄膜具有优异的接封接性,並专用于热封接包装。当然也可用于传统使用玻璃纸封口的包装,如:烟卷包装。
这种薄膜的基层由聚烯烃和低分子量树脂组成。聚烯烃最好是每个分子中包含2-8个碳原子(特殊情况,每个分子包含2-4个碳原子)的单α烯烃聚合物。该聚合物可以是乙烯、丙烯、丁烯-1和4-甲基戊烯或己烯之一的一个均聚物,或是上述两个或两个以上烯烃的一个共聚物。聚丙烯,尤其是高分子量有规立构占优势的丙烯晶态聚合物特别适宜作这种薄膜的基层材料。另外,丙烯和含量高达20Wt%的其它烯烃(如乙烯)的共聚物也可用作基层材料。最合适的聚丙烯是一种全同聚丙烯,其密度范围0.86-0.92g/CC(按ASTMD 1505,在23℃测定),其熔体流动指数为1-15g/10min(按ASTMD1238,在230℃,2.16Kg条件下测定)。这种全同聚丙烯可通过使用齐格勒(Ziegler)催化剂(如:AlCl3和TiCl4)的聚合法制取。
基层的其它组分是低分子量树脂,最好是氢化树脂。这种树脂的分子量低于聚烯烃的分子量,且一般小于5000,最好小于1000(如:500-1000)。这种树脂可以是天然树脂或合成树脂,而且可具有60-180℃的软化点温度范围(按ASTME28测定),例如:软化点范围80℃-150℃,最好是100℃-140℃,特殊情况下可为120℃-140℃。
适宜于氢化的树脂是烃类树脂,酮类树脂,酰胺树脂,松香,苯并呋喃树脂、萜烯树脂,氯化脂族烃或芳香烃树脂。烃类树脂是焦炉气,裂化石脑油,气油和萜烯油的聚合物。
最优选的氢化树脂是氢化石油树脂。通常,这些氢化石油树脂是通过催化加氢裂介石油馏分的热聚合蒸汽而制备的,馏分的沸点范围在20℃-280℃之间。这些馏分一般是分子中有一个或多个不饱和环的化合物,例如:环二烯,环烷和环茚。通过不饱和烃的催化聚合制备氢化树脂也是可行的。
氢化之前,聚合树脂通常熔解在一种饱和烃熔剂中,如:庚烷。使用的加氢催化剂可以是镍、还原镍或硫化钼。单级氢化在温度为200℃-330℃(最好210℃-230℃),压力20-120大气压(最好30-90大气压)的条件下持续5-7小时。氢化之后,滤出溶剂中的催化剂,利用蒸馏回收溶剂供循环使用。在EP0082726(申请号82306853、1)中所描述並要求保护的一种改进的氢化处理方法可提高优质氢化烃树脂的产量。
在基层中,聚烯烃对低分子量树脂的比率是70-97(最好是70-90)Wt%的聚烯烃以及3-30(最好是10-30)Wt%的低分子量树脂。最佳的相对量分别为75-85Wt%对15-25Wt%,例如:80Wt%的聚烯烃对20Wt%的低分子树脂。
薄膜的基层或心层的一个或最好是两个表面上具有相对于基层重量1-20Wt%(最好1-10Wt%,特殊情况下5Wt%)的共聚物,该共聚物由80~99Wt%的丙烯和1-20Wt%的乙烯组成,这种共聚物常被称为无规共聚物。这个组成膜层的共聚物中丙烯最好占90-99Wt%(特殊情况占94-98Wt%,如95.5Wt%),其余部分是乙烯。这个共聚物膜层专用于热封接。
这种丙烯和乙烯的无规共聚物通常是一个全同丙烯-乙烯共聚物,其密度范围0.86-0.92g/CC,(按ASTMD 1505,在23℃测定),熔体流动指数范围2-15g/10min(按ASTM D1238,在230℃,2.16Kg条件下确定)。这种全同丙烯-乙烯共聚物可通过使用众所周知的齐格勒催化剂(如AlCl3和TiCl4)的聚合法制取。
本发明的薄膜是由基层、表面层等多重组分(如果需要,这些组分可包括其它成分,如:抗静电介质,遮光剂及滑动助剂),用一种简便的方式恰当地组合而成的一种多层膜,其最好的组合途径是采用同步复合挤压技术。
该多层膜的拉伸可以是非定向或单轴定向的,但最好是在膜平面上沿两个相互垂直方向进行双轴定向拉伸,以便使膜具有一定的强度可采用展幅机进行平面膜的定向拉伸。管形膜的定向拉伸则是由复合在一起的聚合材料以多层管的形式从一个环形模口挤压而过,冷却受挤压管(模管),利用所谓“气泡”法重新加热,並膨胀模管,导致横定向,同时沿纵向拉伸横管,导致纵定向。定向之后最好对多层膜进行“热定形”(即通过加热多层膜来改善多层膜的尺寸稳定性,以防止热缩)。“热定形”温度在聚合物玻璃化温度之上,熔点之下范围内。
薄膜厚度视使用目的之不同而不等,一般以2-150μm为宜,用于包装时其厚度多为10-60μm。薄膜的一个或多个外层膜的厚度通常为0.05-2.5μm。
实例:
本实例中,对由不同组分组成的两种复合薄膜的封接性、韧性、光学特性及隔离特性作一比较。
这两种复合薄膜均是在膜平面沿互相垂直的两个方向通过双轴定向而获得强度的。展幅机给予复合薄膜的定向比,在纵向是500%,在横向是900%。每种薄膜均有两个1μm厚的封接层且两种薄膜的总厚度均约为22μm。
1号薄膜(对比薄膜)由一个基层和它的两表面上的表面膜层组成。基层是全同聚丙烯,其密度约0.90g/cc(按ASTM D1505,在23℃测定),熔体流动指数2.8g/10Min(按ASTM D1238,在230℃和2.16Kg条件确定)。基层两表面上的表面膜层是一种由95.5Wt%的丙烯和4.5Wt%的乙烯组成的无规共聚物。这是一种全同共聚物,其密度为0.90g/cc(按ASTM D1505,在23℃测定),熔体流动指数6.5g/10Min(按ASTM D1238。在230℃和2.16Kg条件测定)。
2号薄膜(本发明薄膜)也是由一个基层和两个表面膜组成,且其表面膜与1号薄膜的表面膜相同。其基层由80Wt%的(与1号薄膜基层相同的)全同聚乙烯和20Wt%的氢化石油树脂混合而成。所述的树脂是通过催化加氢裂介石油的蒸汽馏分而制备的,该蒸汽馏分的沸点在20℃-280℃范围之间。氢化过程按EP0082726(申请号82306853、1)中描述的步骤进行,由此制备的树脂其软化点温度为125℃。
附图1-7表示由实验得出的1号薄膜和2号薄膜的封接强度、热粘着性、混浊度,光泽、韧度和隔离特性。
这些特性试验按下述步骤进行:
封接强度
这是指薄膜的“常温”热封接强度。它是在薄膜的封接部位冷却到环境温度,並充分显现其潜在强度之后而进行测定的。
采用瑞典Bromma AB设计和实验的结果做成的一种Packforsk 52-B型热封接测试仪进行薄膜的热封接。将一个宽15mm,长280mm的窄条对折,並夹在热粘接测试仪的夹板之间,把它封接在一起。薄膜的封接面积约为15×15mm2。封接的保压条件是恒压5bar,保持0.5秒。为了测量封接强度,在封接的夹板打开时,不进行热粘着性测定的自动剥离动作。待封接区冷却到环境温度后,将薄膜条未封接的两端夹在拉力试验机夹板中进行剥离,在剥离率为508mm/Min时,拉力试验机记录拉裂时所需的力,並用Kg/15Min为单位表示。
热粘接性
热粘接性是在薄膜热封接之后而用来进行热封接的热能散失之前所测得的热封接强度。测试设备也是Packforsk 52-B型热粘接检验器,热封接的形成如同前述。在热封接检验器完成热封接,並打开其夹板的瞬间,剥离动作便自动开始,热粘接检验器自动记录拉裂封接的力,並以Kg/15mm为单位表示薄膜的热粘接性。剥离操作在可控延时(等于夹板打开到剥离开始之间的时间)和可控剥离率的条件下进行。以估用于各和热粘接试验的常用条件是:可控延时时间=0.9S,剥离率=100mm/S。
混浊度和光泽
薄膜的这两项光学特性使用加德纳(Gardner)薄膜混浊度测量仪测试。混浊度测试依据ASTM D1003,光泽测试依据ASTM D523进行。
弹性模量
弹性模量是对薄膜韧度的一种量度。用15mm宽的薄膜试样,依据DIN53457进行薄膜拉力试验而获得其弹性模量值。
隔离特性
隔湿、隔氧特性是通过测量薄膜的水蒸汽透过率(WVTR)和氧气透过率(OTR)而确定的。WVTR值是依据ASTM F372,在37.4℃和100%相对湿度条件下,使用“Modern Controls Incorporated”的Permetran仪器进行测量。OTR值是依据ASTM D3985,在27℃条件下,使用上述公司的Oxtran Twln仪器进行测量。
图1表示,在温度100℃-110℃之间和130℃以上时,2号薄膜的封接强度明显高于1号薄膜的封接强度。在温度110℃-130℃之间,2号薄膜的封接强度近似,或高于1号薄膜的封接强度。
图2表示,在温度约110℃以下时,2号薄膜的热粘接性(Kg/15Min)优于1号薄膜。
图3、4表示,2号薄膜的混浊度小于1号薄膜,而光泽大于1号薄膜。
图5表示,(用弹性模量表示)2号薄膜的韧度明显高于1号薄膜。
图6、7表示,2号薄膜的隔离特性超过1号薄膜一倍。
在薄膜的基层中加入较少量(20Wt%)的氢化树脂即可得到性能如此优于已有技术的薄膜,这一结果是令人吃惊的。
Claims (15)
1、一种薄膜,其特征是基层由70-97Wt%的聚烯烃和3-30Wt%,分子量低于聚烯烃的树脂组成,至少在基层的一个表面上有一个相对于基层重量1-20Wt%的共聚物膜层。该共聚物膜层由80-99Wt%的丙烯和1-20Wt%乙烯组成。
2、按权利要求1所述的薄膜,其特征是基层由70-90Wt%的聚烯烃和10-30Wt%的树脂组成。
3、按权利要求1或权利要求2所述的薄膜,其特征是薄膜中的共聚物是一种无规共聚物。
4、按上述任一权利要求所述的薄膜,其特征是基层中的聚烯烃是一种每个分子中含2-4个碳原子的单α烯烃聚合物,最好是聚丙烯。
5、按权利要求4所述的薄膜,其特征是薄膜中的聚丙烯是一种全同聚丙烯,其密度范围是0.86-0.92g/cc(按ASTMD1505,在23℃测定),熔体流动指数范围1-15g/10Min(按ASTM D1238,在230℃,2.16Kg条件下确定)。
6、按以上任一权利要求所述的薄膜,其特征是薄膜中的树脂是氢化树脂。
7、按权利要求6所述的薄膜,其特征是基层中的氢化树脂是一种氢化石油树脂。
8、按权利要求7所述的薄膜,其特征是薄膜中的氢化树脂是在200℃-330℃温度下,使用一种氢化催化剂,通过催化加氢裂介石油的蒸汽馏分而制备,或在催化剂作用下聚合不饱和烃馏分而制备的。
9、按上述任一权利要求所述的薄膜,其特征是薄膜中树脂的软化点温度范围是100℃-140℃(按ASTM E28测定)。
10、按上述任一权利要求所述的薄膜,其特征是基层由75-85Wt%的聚烯烃和15-25Wt%的树脂组成。
11、按上述任一权利要求所述的薄膜,其特征是基层的每个表面上有相对于该基层重量1-10Wt%的无规共聚物膜层。
12、按上述任一权利要求所述的薄膜,其特征是无规共聚物由94-98Wt%的丙烯和2-6Wt%的乙烯组成。
13、按上述任一权利要求所述的薄膜,其特征是无规共聚物是一种全同丙烯一乙烯共聚物,其密度范围为0.86-0.92g/cc(按ASTM D1505,在23℃测定),其熔体流动指数范围为2-15g/10Min(按ASTM,D1238,在230℃和2.16Kg条件下确定)。
14、按上述任一权利要求所述的薄膜,其特征是薄膜是双轴定向的。
15、按上述任一权利要求所述的薄膜,其特征是薄膜的厚度是10-60μm,薄膜的一个或多个外层膜的厚度是0.05-2.5μm。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB868613161A GB8613161D0 (en) | 1986-05-30 | 1986-05-30 | Sealable films |
GB8613161 | 1986-05-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN87104709A true CN87104709A (zh) | 1988-03-02 |
Family
ID=10598680
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN198787104709A Pending CN87104709A (zh) | 1986-05-30 | 1987-05-29 | 封接膜 |
Country Status (14)
Country | Link |
---|---|
US (1) | US4921749C1 (zh) |
EP (1) | EP0247898B2 (zh) |
JP (1) | JP2933625B2 (zh) |
KR (1) | KR940004025B1 (zh) |
CN (1) | CN87104709A (zh) |
AU (1) | AU603112B2 (zh) |
BR (1) | BR8707325A (zh) |
CA (1) | CA1296853C (zh) |
DE (1) | DE3766290D1 (zh) |
ES (1) | ES2019938B3 (zh) |
FI (1) | FI880423A (zh) |
GB (1) | GB8613161D0 (zh) |
IN (1) | IN167765B (zh) |
WO (1) | WO1987007215A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1067017C (zh) * | 1992-09-18 | 2001-06-13 | 克里奥瓦克公司 | 防湿薄膜 |
CN108859356A (zh) * | 2018-06-25 | 2018-11-23 | 上海若祎新材料科技有限公司 | 多层共挤流延聚乙烯薄膜组合物和薄膜及其应用 |
CN114148065A (zh) * | 2021-12-01 | 2022-03-08 | 广东德冠包装材料有限公司 | 一种阻湿双拉聚丙烯珍珠标签基膜及其制备方法 |
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-
1986
- 1986-05-30 GB GB868613161A patent/GB8613161D0/en active Pending
-
1987
- 1987-01-01 IN IN461/DEL/87A patent/IN167765B/en unknown
- 1987-05-29 CA CA000538377A patent/CA1296853C/en not_active Expired - Lifetime
- 1987-05-29 WO PCT/GB1987/000374 patent/WO1987007215A1/en active Application Filing
- 1987-05-29 JP JP62503336A patent/JP2933625B2/ja not_active Expired - Lifetime
- 1987-05-29 CN CN198787104709A patent/CN87104709A/zh active Pending
- 1987-05-29 EP EP87304792A patent/EP0247898B2/en not_active Expired - Lifetime
- 1987-05-29 KR KR1019880700103A patent/KR940004025B1/ko not_active IP Right Cessation
- 1987-05-29 ES ES87304792T patent/ES2019938B3/es not_active Expired - Lifetime
- 1987-05-29 BR BR8707325A patent/BR8707325A/pt not_active Application Discontinuation
- 1987-05-29 DE DE8787304792T patent/DE3766290D1/de not_active Expired - Lifetime
- 1987-05-29 AU AU74866/87A patent/AU603112B2/en not_active Ceased
-
1988
- 1988-01-29 FI FI880423A patent/FI880423A/fi not_active Application Discontinuation
- 1988-03-17 US US07150408 patent/US4921749C1/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1067017C (zh) * | 1992-09-18 | 2001-06-13 | 克里奥瓦克公司 | 防湿薄膜 |
CN108859356A (zh) * | 2018-06-25 | 2018-11-23 | 上海若祎新材料科技有限公司 | 多层共挤流延聚乙烯薄膜组合物和薄膜及其应用 |
CN108859356B (zh) * | 2018-06-25 | 2019-06-28 | 上海若祎新材料科技有限公司 | 多层共挤流延聚乙烯薄膜组合物和薄膜及其应用 |
CN114148065A (zh) * | 2021-12-01 | 2022-03-08 | 广东德冠包装材料有限公司 | 一种阻湿双拉聚丙烯珍珠标签基膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
BR8707325A (pt) | 1988-09-13 |
ES2019938B3 (es) | 1991-07-16 |
AU7486687A (en) | 1987-12-22 |
IN167765B (zh) | 1990-12-15 |
FI880423A0 (fi) | 1988-01-29 |
US4921749C1 (en) | 2001-02-27 |
WO1987007215A1 (en) | 1987-12-03 |
CA1296853C (en) | 1992-03-10 |
KR880701181A (ko) | 1988-07-26 |
AU603112B2 (en) | 1990-11-08 |
DE3766290D1 (de) | 1991-01-03 |
EP0247898B1 (en) | 1990-11-22 |
GB8613161D0 (en) | 1986-07-02 |
EP0247898A1 (en) | 1987-12-02 |
FI880423A (fi) | 1988-01-29 |
JPH01500102A (ja) | 1989-01-19 |
KR940004025B1 (ko) | 1994-05-11 |
JP2933625B2 (ja) | 1999-08-16 |
US4921749A (en) | 1990-05-01 |
EP0247898B2 (en) | 2004-07-21 |
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