CN1122073C - 用于防护气候的抗紫外线塑料薄膜或涂层 - Google Patents
用于防护气候的抗紫外线塑料薄膜或涂层 Download PDFInfo
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Abstract
叙述了抗紫外线塑料薄膜或在其它承载体上的涂层,被设计为例如与植物生长有关的特别是温室门帘、温室薄膜和室外植物生长的覆盖材料、遮篷之类的气候防护体。塑料薄膜或涂层完全或部分含有含硅烷基的交联聚烯烃,硅烷基是用共聚合引入的。
Description
本发明涉及抗紫外线(UV)的塑料薄膜或在其它承载材料上的涂层。特别是用作例如与植物生长有关特别是温室门帘、温室薄膜和室外生长用覆盖材料、遮篷等的气候防护体。这些薄膜的主要问题是它们的使用寿命,因为薄膜要暴露于阳光和一些化学品,例如用于植物生长的化学品下。
为了提高这种薄膜的寿命,使用阻止胺的光稳定剂(HALS-位阻胺光稳定剂)是已知的。这种光稳定剂叙述于例如EP-A 0,214,507中。有一些很好的稳定剂可使薄膜的使用寿命增长。它们常常与其它类型的稳定剂结合使用,也与UV-吸收剂结合使用,以进一步增加使用寿命。位阻胺非常活泼并且能很快地清除掉形成的降解产物,而且它们是碱性的。这使它们容易与和薄膜接触的外来物质进行反应,特别是酸性物质,例如基于硫-、氯-和溴-的化合物。在一些温室里这类化学品是广泛用来保护植物不受各种病虫害侵袭的。当位阻胺与这些化学品反应时,它们的作用受到损失,薄膜的UV-保护被破坏。一些温室薄膜生产商限制了他们的与下列各组物质、杀虫剂、杀霉菌剂等有关的或长期暴露于下列各组物质、杀虫剂、杀霉菌剂等的薄膜寿命保证期,更具体的是含溴、氯、氟、碘、硫的物质、石油产品和含铜的木材保护剂。
也已知道,当薄膜和涂层暴露于所谓的酸雨中时,它们只有较短的寿命。因此可在空气污染严重的环境中应用于遮篷。HALS-稳定剂生产商将一些类型的适合于这种环境使用的稳定剂投入了市场,即所谓的“抗酸雨剂”,但试验表明,它们的效果与其它的HALS-稳定剂相差不多。
从JP-A-5245987中已知一种用于温室和类似环境的叠层薄膜。据说它有高的拉伸强度并且是透明和耐热的。薄膜用EVA制成,在过氧化物的帮助下有不饱和烷氧基硅烷接枝于其上,此后聚合物进行交联。在接枝时聚合物链用过氧化物打开,在此处连结了硅烷,然后进行交联。该薄膜没有任何抗UV的资料,在发明人自己的实验中(见下述)显示,此硅烷接枝的聚烯烃没有所要求的抗UV性。
温室门帘结构内可产生火灾并且能迅速蔓延。因此希望能得到温室门帘防火材料,它也必须满足诸如防护UV、长使用寿命等其它要求。
本发明的目的是制取适合于温室门帘、温室薄膜和室外生长覆盖材料的塑料薄膜或其它承载材料上的涂层的材料。如上所述这种材料也可以在其它产品中使用,例如遮篷和软百页窗,因为它们也可暴露于有酸性的环境中,这种材料应是UV稳定的,并且暴露于化学品不受影响或只有程度很小的影响。它们通常是在温室环境中使用并在一些情况下也是耐火的。
本发明的目的是用完全或部分含交联聚烯烃-硅烷共聚物的薄膜或涂层达到的,即在聚合过程中将硅烷基团置于聚烯烃链中的共聚物,它不同于接枝的聚合物是聚烯烃链例如被过氧化物打开,然后接枝硅烷基并进行交联。
聚烯烃-硅烷共聚物的交联最好是在水和硅烷缩合催化剂的影响下进行。
聚烯烃最好是聚乙烯,例如低密度聚乙烯LDPE或其某些共聚物,例如EVA或EBA。它们的较高的UV稳定性是使人惊异的,因为这种材料几乎是一种普通的聚烯烃共聚物,不同的只是其分子是互相交联的,但其性能(诸如结晶性)几乎是不变的。聚烯烃(最好是基团聚乙烯)除了硅烷基外也可含一个或多个其它的共聚单体,这样的共聚单体的实例是乙酸乙烯酯、丙烯酸丁酯、1-丁烯和1-辛烯。
在多层膜中,至少有一层是由本发明的交联的聚烯烃-硅烷共聚物形成的,但其它的层可由其它材料形成,诸如热辐射吸收材料。其它层至少有一层含吸热材料,例如EVA、EBA、PET或PA。
薄膜或涂层也可加入添加剂,这样的添加剂的实例是颜料(使能透过阳光的某些波长)和诸如硬脂酸甘油酯、甘油酯之类的消雾剂或其它产品以避免水滴凝结。消雾剂只能加在外层。薄膜也可以是多孔型,在生产薄膜时将无机或有机的发酵剂或发泡剂混合入塑料,当发泡剂作用时形成了闭合或连通的孔穴。其它的添加剂的实例是可切碎的热塑性塑料、稳定剂、润滑剂和阻燃剂。
聚烯烃-硅烷共聚物交联时,建立了连续的三维分子结构,此结构使材料具有一些优点,诸如:
·较强的抗UV辐射性;
·较高的抗化学品能力;
·较高的抗热性;
·材料的存储性,产生较少的收缩和较低的形成永久褶皱的趋向;
·较高的断裂强度;
·较好的低温性能;以及
上述各种性能的结合。
聚合物主链的组成包括含可水解硅烷基的聚烯烃共聚物。这样的聚合物组成叙述于例如SE-B 462 752中。
理想的阻燃性是在塑料薄膜中或其产品带条中加入阻燃剂得到的,阻燃剂可包括含卤素或磷的化合物。使用这些化合物不降低防护UV的水平。当使用所谓的HALS-稳定剂以得到满意的使用寿命时就是这一情况。另一办法是用含卤素或含磷化合物的塑料薄膜或塑料薄膜的条带形成承载材料,再用一层交联聚烯烃-硅烷共聚物进行处理。
在下面所述的实验中,使用了用乙烯基三甲氧基硅烷交联的LDPE。此聚合物在挤塑性能上象“常规”的低密度聚乙烯。这就是说聚合物可在通常的挤塑机中挤塑成薄膜而不需要特别的设备改装或添加剂,交联是在水和催化剂存在下在挤塑后得到的。现将薄膜的生产叙述于下列的实施例中。
实施例1
含交联聚乙烯的吹膜的生产
所用的交联聚合物是得自Borealis的硅烷交联的LDPE-LE4421,再加入母料形式的催化剂LE 4436。LE 4421是商品共聚物,在链中有乙烯基三甲氧基硅烷聚合。我们使用的是5%催化剂母料。聚合物和催化剂是在刚要挤塑前分别混合的,虽然也可以使用通常装在挤塑机上的常规混合设备进行混合。但使用这种方法的好处是可以减少聚合物和催化剂的接触时间,由此而最大限度地减少了过早交联的危险,过早交联使薄膜中产生凝胶。
聚合物和催化剂母料的贮存是在约20℃下并防止潮湿和水汽,以减少过早交联的危险。
实验使用密度923Kg/m3的薄膜材料,熔体流速(MFR2)为0.9g/分钟,挤塑机加热区的温度设定为150-170℃。螺杆速度为112rpm,产生工作力52Amp、熔融压力266巴和熔融温度178℃。
为了得到有适合性能的薄膜,所使用的吹胀率为1∶2。熔融温度保持在180℃以下以避免有凝胶形成产生的问题。在挤塑过程中用抗氧化剂形式的加工稳定剂防止聚合物降解。
实施例2
此实验是进行不同塑料薄膜的寿命试验,薄膜暴露于UV辐射和硫/硫化合物。
试验的进行尽可能反映温室的真实条件。样品首先在硫下暴露一天一夜,使用所谓的硫灯,然后暴露在Atlas氙老化试验仪Ci35A下。老化试验仪的条件如下:0.35W/m2(波长340nm),23.h照射/24h。不进行喷水。条件需反映在佛罗里达所使用的条件。按有规律的时间间隔从老化试验仪取出样品在拉伸试验仪(拉伸速度100mm/min)上进行试验并在FT-IR(傅里叶转换红外光谱仪-译注)中进行对照,看到于1718cm上-1处有羰基积累。
受试薄膜是:
70微米LDPE+HALS
70微米交联LDPE-硅烷共聚物
下面是基于拉伸强度测定得到的结果
表1相对伸长50%的时间
1 | 2 | |
A | 1400h | >1500h |
B | 470h | >1500h |
实验A中的薄膜样品只暴露于老化试验仪;实验B中的样品先暴露于硫灯24小时,然后再暴露于老化试验仪。
从实验可知,交联薄膜对UV是非常稳定的,不管它是否暴露于硫;非交联的聚合物当其未暴露在硫下时有很好的UV稳定性,但暴露于硫后薄膜的UV稳定性呈指数幂降低。如果希望增加交联聚合物的寿命,自然也可加入HALS-稳定剂。然而此稳定剂在酸性环境下的效果是需要考虑的。
实施例3
此实验对暴露于UV辐射下的HDPE、硅烷接枝的HDPE和乙烯/乙烯基硅烷共聚物塑料薄膜的寿命进行比较。
将各薄膜暴露于Atlas氙老化试验仪Ci35A,条件如下:0.35W/m2(340nm),23小时照射/24小时,不进行喷水。在样品的老化过程中连续进行一简单机械试验,即将它们取出进行弯曲。只要薄膜样品不断裂或破碎成块,老化继续进行。样品断裂或变成碎块所需的时间示于表2。
受试薄膜是:
A:50微米HDPE
B:50微米HDPE+HALS
C: 50微米硅烷接枝的HDPE
D:50微米硅烷接枝的HDPE+HALS
E:70微米乙烯/乙烯基硅烷共聚物
F:50微米乙烯/乙基基硅烷共聚物+HALS
G:50微米50/50(乙烯/乙烯基硅烷共聚物+HDPE)
H:50微米50/50(乙烯/乙烯基硅烷共聚物+HDPE)+HALS
所得结果如下:
表2样品变成碎块所需时间
A | B | C | D | E | F | G | H |
1000h | 1450h | 1300h | 1300h | >5000h | >5000h | >2000h | >2000h |
从表可见,与用硅烷接枝的聚乙烯相比,用乙烯/乙烯基硅烷共聚物得到了令人惊异的好结果。
如已述及,本发明的材料可以是薄膜形式或在其它承载材料上的涂层形式,其厚度最好<500微米。此处的薄膜是指连续的薄膜和可用于温室门帘的小薄膜条带。薄膜可以是多层类型的,其中至少一层是由本发明的交联聚烯烃-硅烷共聚物形成的,其它各层可以是其它的材料,例如吸热材料。这样的材料的实例是聚乙烯的共聚物EVA和EBA。承载材料可以是完全或部分由含卤素-或磷的聚合物诸如PVC、PVDC、PCTFE、PVF、PVDF、PEB、PTFE或E/TFE组成。
薄膜可以加颜料以对阳光进行筛选而对植物生长产生作用。这种颜料仅对阻光中的一些波长是透明的。这种颜料的实例是干涉颜料,如在WO 95/05727中所述。加入UV吸收剂特别是二苯酮或苯并***型吸收剂也是可以的。薄膜中也可含所谓的消雾剂以避免水滴的凝聚。消雾剂只可加入薄膜的表面层中。
薄膜也可以是所谓的微孔型,即当生产薄膜时在塑料中混合有机或无机发酵或发泡组分,当发泡组分破裂时产生闭合或连通的孔穴或气泡。
使用薄膜的一例是由这种薄膜制成的可折叠式气候防护帘或遮篷,包括互相连结的条带,条带可以是有褶裥的,或是互相连结和/或通过纱线***连结的,例如通过针织或编织的方法。这种气候防护帘的例子叙述于例如EP 0 109 951中。条带至少是部分含有本发明的抗UV塑料薄膜的。
使用本发明薄膜的另一实例是这种薄膜制成的可折叠的防水的气候防护帘或遮篷,包括互相连结的条带、纱线或条带和纱线的组合,帘的至少一面具有全部或部分由本发明的抗UV塑料薄膜形成的防水层。
气候防护帘或遮篷中的条带至少有一部分是能透光的。条带可含有阻燃剂的添加剂。
本发明当然是不只限于所述的实施例的,但一些修改是可能在本发明范围之内的。
Claims (22)
1.抗紫外线的塑料薄膜或其它承载材料上的涂层,作为气候防护用于与植物生长有关的温室门帘、温室薄膜和室外植物生长覆盖材料、遮篷,其特征在于它全部或部分是用含共聚合引入的硅烷基的交联聚烯烃形成。
2.权利要求1所述的塑料薄膜或涂层,其特征在于交联聚烯烃由聚乙烯或任何其共聚物组成。
3.权利要求2所述的塑料薄膜或涂层,其特征在于聚乙烯为LDPE和/或HDPE,其共聚物为EVA或EBA。
4.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于它是多层型的薄膜,其中至少一层含交联的聚烯烃-硅烷共聚物。
5.权利要求4所述的塑料薄膜或涂层,其特征在于其它层至少有一层含吸热材料。
6.权利要求5所述的塑料薄膜或涂层,其特征在于吸热材料为EVA、EBA、PET或PA。
7.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于聚烯烃-硅烷共聚物是在水和硅烷缩合催化剂影响下交联的。
8.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于用交联聚烯烃生产的塑料薄膜/涂层和/或承载材料是提供了阻燃添加剂。
9.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于承载材料完全或部分由含卤素-或磷的聚合物组成。
10.权利要求9所述的塑料薄膜或涂层,其特征在于聚合物为PVC、PVDC、PCTFE、PVF、PVDF、PEB、PTFE或E/TFE组成。
11.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于它是加颜料以产生选择性太阳光线屏蔽的。
12.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于它含有作为添加剂的硬脂酸甘油酯、甘油酯类型的消雾剂以防止水滴凝聚。
13.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于它是多孔型的,即薄膜具有闭合或开放的孔穴/气泡。
14.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于交联聚烯烃是与非交联聚烯烃和/或聚烯烃共聚物混合的。
15.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于它含有一紫外线稳定剂作为添加剂。
16.权利要求15所述的塑料薄膜或涂层,其特征在于紫外线稳定剂为HALS稳定剂。
17.前述任一项权利要求所述的塑料薄膜或涂层,其特征在于它含有二苯酮或苯并***类型的紫外线吸收剂作为添加剂。
18.一种可折叠的气候防护帘或遮篷,它包括互相连结的条带,其特征在于该条带至少部分是由抗紫外线的塑料薄膜组成,它完全或部分是含共聚合引入的硅烷基的交联聚烯烃。
19.一种可折叠的防水气候防护帘或遮篷,它包括相互连结的条带和/或纱线,其特征在于帘的至少一个面上具有完全或部分含有含硅烷基的交联聚烯烃的防水层,硅烷基是用共聚合引入的。
20.权利要求18或19所述的气候防护帘,其特征在于至少其中的一些条带是透光的。
21.权利要求18、19或20所述的气候防护帘,其特征在于其条带是由有阻燃剂添加剂的抗紫外线塑料薄膜生产的。
22.权利要求18-21任一项或若干项所述的气候防护帘,其特征在于其条带是用纱线连结的。
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SE96014998 | 1996-04-17 | ||
SE9601499A SE506736C2 (sv) | 1996-04-17 | 1996-04-17 | UV-resistent plastfilm eller beläggning och dess användning som klimatskydd |
SE9601499-8 | 1996-04-17 |
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CN (1) | CN1122073C (zh) |
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SE (1) | SE506736C2 (zh) |
TR (1) | TR199802090T2 (zh) |
WO (1) | WO1997039058A1 (zh) |
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ES2161134B1 (es) * | 1999-04-21 | 2002-06-16 | Solplast S A | Metodo para la obtencion de una lamina de cubrimiento para evitar el ennegrecimiento de los bordes de los petalos de las rosas rojas y la propagacion de ciertos virus que puedan afectar las plantas en cultivo,y lamina obtenida segun este metodo. |
NL1014360C2 (nl) * | 2000-02-11 | 2001-08-16 | Weterings B V H | Ruit, voorzien van een aanslag en/of aantasting tegengaande bekleding alsmede werkwijze voor het vervaardigen daarvan. |
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ES2303484B2 (es) | 2007-10-15 | 2010-03-08 | Universidad Complutense De Madrid | Material de cobertura, revestimiento o pantalla para la proteccion y terapia de ojos contra los efectos de la luz azul. |
TWI523607B (zh) * | 2010-04-15 | 2016-03-01 | 陶氏農業科學公司 | 使用含有聚二氯乙烯(pvdc)蒸氣障壁之多層薄膜的農用薰蒸技術 |
CN102756522B (zh) * | 2012-06-28 | 2015-12-16 | 上海普拉斯克塑料有限公司 | 紫外线阻隔温室膜 |
CN102977407B (zh) * | 2012-11-27 | 2014-08-06 | 广州嘉德乐生化科技有限公司 | 一种含有单硬脂酸甘油酯和稀土脂肪酸皂的组合物及制备方法 |
JP6251956B2 (ja) * | 2013-01-22 | 2017-12-27 | セイコーエプソン株式会社 | 光学素子収納用パッケージ、光学フィルターデバイス、光学モジュール、および電子機器 |
CN103953127B (zh) * | 2014-05-15 | 2016-03-30 | 精碳伟业(北京)科技有限公司 | 带功能层的钢结构防火卷材及其制备方法 |
CN106550800B (zh) * | 2015-09-30 | 2020-04-14 | 中国石油化工股份有限公司 | 聚烯烃大棚膜及其制备方法 |
EP3621807B1 (en) * | 2017-05-11 | 2022-08-24 | Dow Global Technologies LLC | Multilayer polyolefin greenhouse films with high transparency |
CA3065680A1 (en) | 2017-07-17 | 2019-01-24 | Ab Ludvig Svensson | Greenhouse screen |
CN108274786A (zh) * | 2018-01-19 | 2018-07-13 | 全椒光太胶粘制品有限公司 | 一种车用隔离膜材料快速成型制造工艺 |
CN108966946B (zh) * | 2018-07-27 | 2021-03-23 | 山东隆昌塑业有限公司 | 一种可以特定过滤390nm以下光波的农用蔬菜大棚薄膜 |
CN109403058B (zh) * | 2018-09-05 | 2021-12-14 | 苏州意诺工业皮带有限公司 | 一种轻型门帘带及其制备方法 |
CN109483996A (zh) * | 2018-10-29 | 2019-03-19 | 苏州福慧材料科技有限公司 | 一种三层复合农膜的生产工艺 |
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US5367025A (en) * | 1991-10-08 | 1994-11-22 | Wedtech, (Usa) Inc. | Crosslinkable polyethylene-based composition for rotational molding |
Also Published As
Publication number | Publication date |
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IL126543A (en) | 2004-01-04 |
PT888404E (pt) | 2001-03-30 |
PL188984B1 (pl) | 2005-05-31 |
BR9708711A (pt) | 1999-08-03 |
DE69703203T2 (de) | 2001-02-01 |
SE506736C2 (sv) | 1998-02-09 |
AU2419897A (en) | 1997-11-07 |
ES2153764A1 (es) | 2001-03-01 |
DE888404T1 (de) | 1999-07-22 |
CZ294164B6 (cs) | 2004-10-13 |
WO1997039058A1 (en) | 1997-10-23 |
ES2153764B1 (es) | 2001-09-01 |
EP0888404A1 (en) | 1999-01-07 |
JP2000508689A (ja) | 2000-07-11 |
SE9601499D0 (sv) | 1996-04-17 |
SE9601499L (sv) | 1997-10-18 |
PL329389A1 (en) | 1999-03-29 |
DE69703203D1 (de) | 2000-11-02 |
IL126543A0 (en) | 1999-08-17 |
CN1219185A (zh) | 1999-06-09 |
AU719162B2 (en) | 2000-05-04 |
RU2195468C2 (ru) | 2002-12-27 |
ES2152665T3 (es) | 2001-02-01 |
EP0888404B1 (en) | 2000-09-27 |
HK1021383A1 (en) | 2000-06-09 |
CZ333598A3 (cs) | 2000-02-16 |
TR199802090T2 (xx) | 1999-01-18 |
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