CN1089629A - 可热缩的共挤压成型薄膜及其制造方法 - Google Patents
可热缩的共挤压成型薄膜及其制造方法 Download PDFInfo
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Abstract
本发明公开了一种三层可热缩的共挤压成型的
薄膜,其中间层由添加有氢化碳氢树脂或其它树脂或
低分子量聚乙烯或聚丙烯蜡的线性低密度聚乙烯或
线性中密度聚乙烯构成,两个外层由添加有同用于中
间层同组的树脂或石蜡添加剂的聚丙烯或乙烯-丙
烯共聚物构成。
Description
制造单层或多层热缩薄膜的双膜泡共挤压技术是公知的。这种薄膜尤其是在包装行业中得到广泛应用。
例如,美国专利4,863,760(Viskora)公开了一种热缩薄膜的生产工艺,这种由线性低密度聚乙烯和α-烯烃组成的薄膜是通过沿纵向和横向两个轴间拉伸定向的。
所述薄膜可以是单层的,也可与含有乙烯-乙酸乙酯共聚物或线性低密度聚乙烯的混合物共挤压而成。
美国专利4,532,189(Grace)公开了一种三层或五层的薄膜,其中间层由线性低密度聚乙烯或线性中密度聚乙烯加乙烯-乙酸乙酯共聚物或乙烯-丙烯共聚物组成,外层由乙烯-丙烯共聚物添加聚丙烯或线性低密度聚乙烯组成。这种薄膜具有良好的抗撕裂强度和抗热封性能。
使用碳氢树脂改善聚丙烯和乙烯-丙烯共聚物的性能也是公知技术。
欧洲专利00,210,750(Hercules)要求保护一种抗静电的聚丙烯薄膜,由于使用了碳氢树脂,这种薄膜可以在低温下热密封。
虽然利用现有技术已获得性能良好的产品,但是对薄膜的机械、光学和热封性能的改进仍是需要的,特别是在包装行业中。
意外地发现,将三层聚烯烃同适合的添加剂相混合,在简便的条件下便可以获得具有改进性能的三层热缩共挤压成形薄膜。上述薄膜的中间层由添加有树脂的线性低密度聚乙烯或线性中密度聚乙烯组成,其中的树脂从由氢化的碳氢树脂、萜烯树脂、苯酚树脂、松脂、聚环戊二烯、低分子乙烯或石蜡、线性甚低密度聚乙烯、马来酐聚合物以及丙烯酸酯聚合物、乙烯-丙烯酸酯-马来酐三元共聚物组成的组中选取。
所述的薄膜的两个外层由添加有中间层属同组的树脂或石蜡的聚丙烯或乙烯-丙烯共聚物组成。
制备所述薄膜的方法包括下列步骤:
a)用传统的干搅拌器搅拌颗粒的原料,以便生产出用于待制造的三个薄膜层的三种混合物。
b)对送入带有三个同心环状槽的模具中的三种混合物进行共挤压;
c)立即冷却该筒状薄膜,然后用红外线或热空气在接近其软化点温度下加热该薄膜;
d)通过双膜泡双轴拉伸对薄膜定向;
e)通过空气气流冷却薄膜;
f)切泡和滚卷薄膜。
按照本发明所获得的薄膜改善了热缩性(%)、机械阻力、韧性、透明度和光泽。
下面的详细说明描述了本发明的可热缩的共挤压的薄膜本身所具有的特性和优点以及有关的制备方法。
所述的薄膜是由三层组成,中间层是由添加有树脂的线性低密度的聚乙烯组成,其中的树脂是从氢化的碳氢树脂、萜烯树脂、苯酚树脂、松脂、聚环戊二烯、低分子乙烯或聚丙烯石蜡、线性甚低密度聚乙烯、马来酐聚合物、以及丙烯酸酯聚合物乙烯-丙烯酸酯-马来酐三元共聚物、乙烯-乙酸乙烯/乙烯-乙烯酯-马来酐三元共聚物构成的组中选取。
上述薄膜的两个外层是由添加有同中间层所具有的添加剂属于同一组的树脂或石蜡的丙烯单聚物或乙烯-丙烯共聚物组成。
所用的这些物质具有下列特性:
线性低密度聚乙烯和线性中密度聚乙烯是由乙烯和最多为8%的丁烯和或辛烯或乙烯或α-甲基戊烯组成;线性甚低密度聚乙烯是由添加最多为10%的辛烯和四甲基戊烯或丙烯(密度为0.890-0.910)的乙烯组成。
聚丙烯是密度约为0.90的丙烯均聚物;乙烯-丙烯共聚物是由乙烯和丙烯组成的共聚物,而主要组分为后者。
氢化碳氢树脂包含氢化芳烃碳烃树脂、氢化萜烯树脂等,例如通过把各种未饱和的芳烃碳氢化合物(例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基二甲苯、茚乙基和或甲基茚、萜烯)聚合生成的树脂氢化所获得的树脂。
这个树脂组还包括通过使部分石油裂化的副产品(其沸点从150℃至300℃(范围内)聚合而获得的氢化树脂。聚乙烯和聚丙烯的分子量在1800至8000范围,这类聚乙烯和聚丙烯是属于可乳化型的,并可以是氧化的或不是氧化的。
添加在中间层的线性低密度聚乙烯或线性中密度聚乙烯中的树脂或蜡的重量百分数为1.0至35。
添加在两个外层的聚丙烯或乙烯-丙烯共聚物中的树脂或蜡的重量百分数为2至35。
这种薄膜的制备方法包括下列步骤:
使适当比例的颗粒状的组成成分(按每层所需要的基体聚合物和添加剂)进行混合;
通过三个进料器将聚合物送入带有三个同心环状狭缝的单一模具中。
使熔融的聚合物脱离模具而形成一个三层筒状薄膜毛坯。
使这个仍处在热态的筒状薄膜通过被液体冷却介质(例如15-30℃和水)冷却的外环和也被液体介质(例如15-30℃的水)冷却的内模之间的间隙定形。
外环对筒状薄膜的圆周冷却是均匀的,沿圆周的最大温度偏差为1℃。
筒状薄膜经内外冷却8-25秒后从大约210℃降低到30℃。离开外环的水作为一层液体薄膜附着在筒状薄膜的外表面上,并流入下面的容器中。
在下一步中,利用双膜泡技术将筒状薄膜通过在纵横两个方向上双轴拉伸定向。具体操作如下:
冷的筒状薄膜送入红外线辐射炉或热空气炉中,在那里被加热到接近软化的温度。筒状薄膜被压缩空气膨胀并沿横向扩展如此导致分子的横向取向。同时,通过引起炉子的拉滚上升气流及在不同速度下进行的最终拉滚,使筒状薄膜在纵向上得到拉伸。
薄膜经受双轴热拉伸后,急剧被冷却,使分子内部取向稳定。冷却是通过吹入5℃至15℃的空气实现的。
初级筒状薄膜的冷却、定形、膜泡膨胀,以及薄膜的稳定化的操作条件,是本发明要求保护的具有所希望性能的薄膜的生产方法和基本特征。
根据本申请专利的方法所得到的薄膜,其厚度为8-60,其性能与按已有技术生产的薄膜相比较有所改进。
特别是,本发明的薄膜具有如下的性能:
120℃下的收缩:41%到53%
机械阻力:100 N/mm2至150 N/mm2
韧性:500 N/mm2至700 N/mm2
透明度:90%至94%
光泽度:100至115光电池单位
撕裂扩张(tearing propagation):12g至18g
收缩强度:15g/cm至35g/cm
图1是收缩-温度曲线图,它示出了例3所述产品的横向收缩百分比,也给出了供比较用的商品薄膜MD的相应曲线。
薄膜的物理和机械性能的改进带来改进的技术特性:
较好的方向性(在较低温度下的较高拉伸百分比);
纵横两个方向上更加均衡;
甚至在高收缩百分比之下也有较低的收缩强度;
各层之间较好的粘着带来较高的热封阻力;
卓越的方向性带来的较好的机械性能;
良好的光学性能。
由于具有以上性能,本发明的薄膜适用于一般的包装业,特别在那些要求薄膜与产品良好附着的应用中(箱盒、书籍、杂志、食物、蔬菜以及多包装产品),该薄膜显示出比已有产品更为完美的特性。下面举例说明(未穷尽所有情况)。
例1(比较)
制备三层(A/B/A)薄膜(其中A为外层,B为内层)。总厚度15μ;A厚度2μ;B厚度11μ。A层由丙烯单聚物[HIMONT生产的Moplen S 38 FT,熔化指数1.8(230℃,2.15kg)]添加微粉化了的二氧化硅(0.5%)和完全饱和的氢化碳氢树脂(2%)(分子量=900;Brookfield 粘性=1000)组成。
所用树脂为由Eastman kodak生产的Eastotac H 130。
B层由线性低密度聚乙烯(由Dow Chemical生产的Dowlex NG5060)组成熔化指数为1(190℃,2.16 kg),密度为0.923。这一聚合物添加了1%的芥酰胺(erucamide,光滑剂)。特别是采用了由Constab Co.生产的Constab GL 6004。脱离模具的熔化了的材料的温度接近190℃(对A层)和接近200℃(对B层)。筒状薄膜的中间冷却水温度为24℃,而外膜冷却水温度为30℃。脱离模具的筒状薄膜直径为180 mm。然后,将薄膜在下列条件下,在纵横两个方向定向:
温度为170℃
腔拉滚速度:5m/min
炉拉滚速度:5.2m/min
卷绕机拉滚速度:26m/min
膨胀泡直径:900mm
平面薄膜宽度:1415mm
因此,拉伸比是对称的:长×宽=5×5
根据本发明得到的薄膜与按现有方法制造的薄膜比较,显示出更好的性能,特别是:
厚度更均匀
收缩百分比更高,且纵横双向更均衡
抗拉强度和拉长破裂强度更高
抗撕裂强度更高
薄膜特性列于表1、2和3。
例2
重复例1的工艺过程,但以线性中密度聚乙烯取代线性低密度聚乙烯作为中间层,并且在线性中密度聚乙烯中添加2%氢化碳氢树脂Eastotac H 130。
线性中密度聚乙烯的熔化指数约为1(190℃,2.16kg),密度为0.94。
薄膜特性列于表1和3。
例3
重复例1工艺过程,但有小的改变:中间层由线性低密度聚乙烯添加2%碳氢树脂组成。碳氢树脂为由Eastman Kodak生产的Eastotac H 130型碳氢树脂。
脱离模具的熔化材料温度为190℃(B层),而泡的定向温度约为162℃。
薄膜特性列于表1、2和3。特别指出,各层之间的粘附性能改善了。
例4
重复例2的工艺过程,中间层使用添加了4%的氢化碳氢树脂(Estotac H 130型,由Eastman Kodak生产)的线性中密度聚乙烯。
薄膜特性列于表1。
例5
重复例3 工艺过程,但中间层使用乙烯-丙烯共聚物和任一种熔化指数为3到4(230℃,2.16kg)、软化点Vicat约为110℃的丙烯-乙烯(约为5%)共聚物,并添加2%的Eastotac H 130碳氢树脂。
特别是使用了由HIMONT生产的Moplen SYL7008。
薄膜特性列于表1和2。
例6
重复例4工艺过程,外层使用乙烯-丙烯共聚物,特别是由HIMONT生产的Moplen SYL 7008作为外层。
薄膜特性列于表1。
例7
重复例1工艺过程。中间层使用了100份线性低密度聚乙烯(Dowlex NG 5006型)和10份线性甚低密度聚乙烯(DSM的TeamXTMX 100F型)的混合物,密度为0.9,熔化指数为1.5。
薄膜特性列于表1、2和3。
例8
重复例7的工艺过程,使用乙烯-丙烯共聚物作外层。特别是使用添加了2% Eastotac H 130 和1% Constab GL 6001的Moplen SYL 7008。
薄膜特性列于表1。
例9
重复例1的工艺过程,中间层使用线性低密度聚乙烯和乙烯-丙烯酸酯-马来酸酐三元聚合物的混合物。
特别是,混合物由100份线性低密度聚乙烯(Dowlex NG 5056)和10份三元共聚物(Enichem Polimeri生产的Lotader 2308)组成,其熔化指数为2(190℃,2.16 kg),密度为0.94。
薄膜特性列于表1。
例10
重复例9的工艺过程,外层使用添加了2% Eastotac H 130的乙烯-丙烯共聚物。
薄膜特性列于表1、2和3。
例11
重复例9工艺过程,内层由100份线性低密度聚乙烯和10份乙烯-乙酸乙烯-马来酸酐三元聚合物,特别是Dupont的Bynel E 361熔化指数为1)混合而成。
薄膜特性列于表1。
例12
重复例11的工艺过程,外层使用添加了2% Eastotac H 130的乙烯-丙烯共聚物。
薄膜特性列于表1、2和3。
例13
重复例5的工艺过程。在本例中,在由线性低密度聚乙烯Eni-chem的Clearflex FG 308组成的中间层中,按1.5%的比例,添加了密度为0.93、分子量为4500的聚丙烯石蜡,代替碳氢树脂。
特别是添加了Epolene E 43石蜡(Eastam Chemical)。
薄膜特性列于表1。
表1
试验 单位 例1 例2 例3 例4 例5 例6
测量参数
透光率 ASTM % 94 94 92 92 92 92
D 1033
光泽度 D 2457 Photoelec. 115 115 115 115 105 105
cell units
120℃下 - % L40 44 44 43 45 45
的收缩 T46 50 52 50 51 51
收缩强度 D 2838 N/mm270 70 60 62 58 60
弹性模量 D 882 N/mm2650 680 660 600 600 610
抗拉强度 D 882 N/mm2120 125 120 105 115 118
拉伸破坏 D 882 % 110 110 105 95 105 100
抗撕裂 D 1938 g 9 9 10 10 13 12
强度
在全部例中膜厚度均为 15μ
*参照商品薄膜
表2 层间的粘接强度
试验方法(非标准的)。从膨胀之前的共挤压的筒状薄膜沿横向切下若干个20 mm宽的条,在用手工使这些条的内层剥离后,用测力计从已剥离端测量使这些层分开所需要的力。
例1 例3 例5 例7 例10 例12 对照例*
g 350 570 600 540 710 730 200
*对照例=由包括聚丙烯单聚物/线性低密度聚乙烯/丙烯单聚物的按照例1中所描述的工艺获得的层构成的作为参考的共挤压薄膜,它同例1的不同在于没有碳氢树脂添加剂。
层间粘接强度的提高可使耐热封性能获得改善。
表3 耐热封性能
这个方法(非标准的)是对200 mm宽的热封薄膜试样作拉伸破坏试验。热封是借助于热金属丝或条完成的。
例1 例2 例3 例7 例10 例12 E*
N/mm 60 78 83 66 81 80 72
E*用于对照的商品薄膜-Cryovac MD薄膜(W.R.Grace)。
Claims (12)
1、一种三层可热收缩的共挤压成形薄膜,它的两个外层由添加有树脂的聚丙烯(PP)或乙烯-丙烯共聚物(EPC)构成,所述的树脂是从由氢化碳氢树脂、萜烯树脂、酚醛树脂、松脂树脂、聚环戊二烯、低分子量聚乙烯或聚丙烯石蜡、线性甚低密度聚乙烯(VLDPE)、马来酸酐(MA)、丙烯酸酯(AE)聚合物、乙烯-丙烯酯-马来酸酐三元共聚物,以及乙烯-乙酸-乙烯酯马来酐(EVA/MA)三元共聚物组成的组中选取;其中间层由添加有同两个外层所用的树脂或石蜡属相同组的树脂或石蜡的线性低密度的聚乙烯(LLDPE)或线性中密度的聚乙烯(LMDPE)构成。
2、如权利要求1所述的薄膜,其中,所述的线性低密度聚乙烯和线性中密度聚乙烯由乙烯和至多含有8%的丁烯或辛烯或己烯或α-甲基戊烯组成。
3、如权利要求1所述的薄膜,其中,所述的线性甚低密度乙烯是由乙烯至多添加10%的辛烯和四甲基戊烯或丙烯组成,其密度为0.890至0.910。
4、如权利要求1所述的薄膜,其中,所述的聚丙烯是一种密度约为0.90的丙烯单聚物。
5、如权利要求1所述的薄膜,其中,所述的乙烯-丙烯共聚物是一种由乙烯和丙烯组成的共聚物;其中丙烯是主要组分。
6、如权利要求1所述的薄膜,其中,添加于外层的聚丙烯或乙-丙烯共聚物中的树脂或石蜡的重量百分数在2至35的范围内。
7、如权利要求1所述的薄膜,其中,添加于中层的线性低密度聚乙烯或线性中密度聚乙烯中的树脂或石蜡的重量百分数在1.0至35的范围内。
8、如权利要求1所述的薄膜,其中,薄膜在120℃下的收缩范围为41至53%,机械阻力为从100至150N/mm2,韧性为从500至70mm2,透明度从90至93%,光泽度为从100至115光电池单位,撕张为从12至18克,收缩强度为从15至35g/cm。
9、一种制备三层可热收缩的共挤压成形的薄膜的方法,其中,两外层是由添加有树脂的聚丙烯或乙烯-丙烯共聚物组成,所述的树脂是从由氢化碳氢树脂、萜烯树脂、苯酚树脂、松脂、聚环戊二烯、低分子量聚乙烯或聚丙烯石蜡、线性甚低密度聚乙烯、马来酐共聚物和丙烯酸酯聚合物、乙烯-丙烯酸酯-马来酐三元共聚物、以及乙烯-乙酸乙烯/马来酐三元共聚物组成的组中选取;其中间层是由添加有同两外层相同的添加剂组中的树脂或石蜡的线性低密度聚乙烯或线性中密度聚乙烯构成;其中,
a)将这些原料干燥搅拌以便制得待获得的三层薄膜所用的三种混合物;
b)将这三种混合物同时共挤压成形并输送到一具有三个同心环状狭缝的模具中;
c)对所获得的筒状薄膜立即冷却后,加热到靠近其软化点的温度;
d)通过双膜泡伸展使筒状薄膜定向;
e)用空气流冷却所获得的薄膜。
10、如权利要求9所述的方法,其中使所述的筒状薄膜在一外环和一内模之间通过冷却,外环和内模由15℃至30℃的液体冷却介质冷却,沿筒状薄膜圆周的最大温度差为1℃。
11、如权利要求9所述的方法,其中,使所述的筒状薄膜以8至25秒从210℃冷却到30℃(步骤C)。
12、如权利要求9所述的工艺,其中所述的筒状薄膜的冷却是由5℃至15℃空气流完成的。
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN1315642C (zh) * | 1999-02-12 | 2007-05-16 | 株式会社吴羽 | 包装用复合体 |
CN101318577B (zh) * | 2008-07-07 | 2011-08-17 | 苏州天加新材料有限公司 | 用于带骨肉包装的热收缩片状薄膜 |
CN101003720B (zh) * | 2007-01-22 | 2012-07-18 | 白山市喜丰塑业有限公司 | 聚乙烯三层复合多功能防雾棚膜 |
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Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CA2664910A1 (en) * | 2006-12-15 | 2008-07-03 | Fina Technology, Inc. | Polypropylene blown film |
WO2011009165A1 (en) * | 2009-07-23 | 2011-01-27 | Tristano Pty Ltd | Multilayer film |
BR112012010897B1 (pt) | 2009-11-17 | 2019-09-10 | Basell Poliolefine Italia Srl | "filmes termorretráteis" |
FR2996162B1 (fr) * | 2012-10-02 | 2015-11-27 | Ceisa Packaging | Complexe multicouche associant une couche centrale a base de polyethylene et deux couches externes a base de polypropylene |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4532189A (en) * | 1982-02-19 | 1985-07-30 | W. R. Grace & Co., Cryovac Div. | Linear polyethylene shrink films |
CA1340037C (en) * | 1985-06-17 | 1998-09-08 | Stanley Lustig | Puncture resistant, heat-shrinkable films containing very low density polyethylene copolymer |
GB2221649B (en) * | 1988-08-11 | 1992-04-29 | Okura Industrial Co Ltd | Heat shrinkable composite film and packaging method using same |
US5023143A (en) * | 1989-03-14 | 1991-06-11 | W. R. Grace & Co.-Conn. | Low shrink force shrink film |
US5298302A (en) * | 1992-08-21 | 1994-03-29 | W. R. Grace & Co.-Conn. | Film with improved lap seal |
-
1992
- 1992-10-30 IT ITMI922506A patent/IT1256051B/it active IP Right Grant
-
1993
- 1993-10-25 US US08/142,697 patent/US5472791A/en not_active Expired - Fee Related
- 1993-10-26 EP EP93117306A patent/EP0595252A1/en not_active Withdrawn
- 1993-10-26 CA CA002109278A patent/CA2109278A1/en not_active Abandoned
- 1993-10-29 TW TW082109037A patent/TW294626B/zh active
- 1993-10-29 CN CN93119808A patent/CN1089629A/zh active Pending
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CN103788492B (zh) * | 2014-02-13 | 2016-01-06 | 福建师范大学 | 一种三层结构的高韧性高透光聚烯烃薄膜的制备方法 |
CN105882078A (zh) * | 2014-10-08 | 2016-08-24 | 山东中塑泰富科技有限公司 | 新型树脂poe在pof聚烯烃收缩膜中的应用技术 |
CN105882078B (zh) * | 2014-10-08 | 2017-10-10 | 山东中塑泰富科技有限公司 | 树脂poe应用在pof聚烯烃收缩膜中的方法 |
CN105949594A (zh) * | 2016-05-20 | 2016-09-21 | 苏州倍力特物流设备有限公司 | 一种拉伸缠绕膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US5472791A (en) | 1995-12-05 |
ITMI922506A1 (it) | 1994-04-30 |
EP0595252A1 (en) | 1994-05-04 |
IT1256051B (it) | 1995-11-21 |
CA2109278A1 (en) | 1994-05-01 |
ITMI922506A0 (it) | 1992-10-30 |
TW294626B (zh) | 1997-01-01 |
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