CN108025534B - 具有优良防滴落性能的多层温室膜 - Google Patents
具有优良防滴落性能的多层温室膜 Download PDFInfo
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Abstract
公开一种多层膜,包含:a)第一层,所述第一层包含i)聚烯烃组分;和ii)亲水‑亲油平衡值在2至6范围内的聚环氧乙烷/聚乙烯共聚物;b)第二层,所述第二层包含i)聚烯烃组分;ii)1至5重量%的选自脱水山梨糖醇酯、聚氧乙烯酯、甘油酯、聚甘油酯、氟基化合物以及其组合组成的组的添加剂,其中所述添加剂的亲水‑亲油平衡值在7至18范围内;和iii)无机填料;其中所述第二层与所述第一层相邻;以及c)包含聚烯烃组分的表层。所述多层膜用于温室应用。
Description
技术领域
本发明涉及聚烯烃膜。更具体地说,本发明涉及用于温室应用的聚烯烃膜。
背景技术
滴落是由于“封闭体”的内部气氛和外部气氛的温差以及界面处的局部冷却而经常发生的现象。由农业膜包围的温室内的气氛饱和了从土壤或植物蒸发的水蒸气,因为水的表面张力非常高(约72mN/m),并且通常由聚乙烯(PE)、乙烯-乙酸乙烯酯(EVA)或聚氯乙烯(PVC)构成的温室膜的表面能低,水蒸气在冷膜的内表面上逐滴凝结而引起水滴落。由于不规则的反射,膜上的水滴大大减少了入射的阳光,并且落在植物上的液滴可能导致作物的物理损伤。
因此,为了避免滴落,使用防滴落处理来使温室膜的内表面在性质上亲水,或通过添加表面活性剂来降低水的表面张力。这两种方法都可以使蒸汽凝结的液滴在表面上散开并且排走,确保阳光传输到温室中,并且减少对植物的物理损害。
目前,市场上可买到的大多数防滴落膜都含有低分子量的添加剂(例如非离子表面活性剂,如脱水山梨糖醇酯、聚氧乙烯酯、甘油酯以及聚甘油酯),所述添加剂从主体膜基质迁移到塑料膜表面。表面上的这些低分子量的表面活性剂可以溶解在水中,降低水的表面张力,使“改性水”可以铺展在膜上。典型的防滴落添加剂浓度范围是1至5重量%。多层膜,特别是3层膜已被广泛用于温室应用。对于市场上的大多数3层膜,低分子量添加剂掺入到膜的内层和中间层中,在这两层中具有相同的防滴落调配物。中间层充当防滴落添加剂的储集层。然而,通常这些市售表面活性剂添加剂中的大多数与非极性聚乙烯膜基质没有良好的亲和力。这些添加剂能快速扩散出膜,并且容易被冷凝水从膜表面冲走,导致防滴落作用时间缩短,并且膜的防滴落性能在较短时间内下降。
因此,期望具有较长作用时间的防滴落添加剂。
发明内容
在本发明的一个实施例中,公开了一种多层膜,包含:a)第一层,所述第一层包含i)聚烯烃组分;和ii)具有选自CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的组的结构的聚环氧乙烷/聚乙烯共聚物,其中a是9至25并且b是1至10;并且其中所述聚环氧乙烷/聚乙烯共聚物具有2至6范围内的亲水-亲油平衡值;b)第二层,所述第二层包含i)聚烯烃组分;ii)1至5重量%的选自脱水山梨糖醇酯、聚氧乙烯酯、甘油酯、聚甘油酯、氟基化合物以及其组合组成的组的添加剂,其中所述添加剂的亲水-亲油平衡值在7至18范围内;和iii)无机填料;其中所述第二层与所述第一层相邻,以及c)包含聚烯烃组分的表层。
附图说明
为了说明本发明,附图示出了目前优选的本发明的形式。然而,应理解,本发明不限于附图中所示出的实施例。
图1显示了在80天的实地测试之后拍摄的实例1膜的照片(左:从内向外拍摄的照片;右:从外向内拍摄的照片)。
图2显示了在80天的实地测试之后拍摄的比较实例A膜的照片(左:从内向外拍摄的照片;右:从外向内拍摄的照片)。
图3显示了在80天的实地测试之后拍摄的比较实例B膜的照片(左:从内向外拍摄的照片;右:从外向内拍摄的照片)。
图4显示了在80天的实地测试之后拍摄的比较实例C膜的照片(左:从内向外拍摄的照片;右:从外向内拍摄的照片)。
图5显示了比较实例D膜的照片(左:从内向外拍摄的照片;右:从外向内拍摄的照片)。
具体实施方式
本发明的一个广泛的方面包含以下,由以下组成,或基本上由以下组成:a)第一层,所述第一层包含i)聚烯烃组分;和ii)具有选自CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的组的结构的聚环氧乙烷/聚乙烯共聚物,其中a是9至25并且b是1至10
其中所述聚环氧乙烷/聚乙烯共聚物具有2至6范围内的亲水-亲油平衡值;b)第二层,所述第二层包含i)聚烯烃组分;ii)1至5重量%的选自脱水山梨糖醇酯、聚氧乙烯酯、甘油酯、聚甘油酯以及其组合组成的组的添加剂,其中所述添加剂的亲水-亲油平衡值在7至18范围内;和iii)无机填料;其中所述第二层与所述第一层相邻,以及c)包含聚烯烃组分的表层。
第一层包含至少一种聚烯烃组分。聚烯烃的实例包括但不限于单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚异戊二烯或聚丁二烯,以及环烯烃的聚合物,如环戊烷或降冰片烯,聚乙烯,例如高密度聚乙烯(HDPE)、高密度和高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)以及线性低密度聚乙烯(LLDPE)。
可以使用上述聚烯烃的混合物,例如聚丙烯与聚异丁烯的混合物、聚丙烯与聚乙烯(例如PP/HDPE)的混合物以及不同类型的聚乙烯(例如LDPE/HDPE)的混合物。
聚烯烃组分的其它实例包括单烯烃和二烯烃彼此或与其它乙烯基单体的共聚物,例如乙烯/丙烯共聚物、LLDPE以及其与LDPE的混合物、丙炔/丁-1-烯共聚物、丙烯/异丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烷共聚物、丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/甲基丙烯酸烷基酯共聚物、乙烯/乙酸乙烯酯共聚物以及其盐,以及乙烯与丙烯和二烯的三元共聚物,所述二烯如己二烯、二环戊二烯或亚乙基-降冰片烯;以及此类共聚物与彼此或与上文提及的其它聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙酸乙烯酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA以及其混合物。
第一层还包含与疏水性聚环氧乙烷/聚乙烯共聚物的共聚物。此共聚物通常具有选自CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和
CH3CH2(CH2CH2)aCO(OCH2CH2)bOH组成的组的结构,其中a是9至25并且b是1至10。
疏水性聚环氧乙烷/聚乙烯共聚物的亲水-亲油平衡(HLB)值通常在2至6的范围内。本文包括并且本文公开2至6内的任何范围,例如,HLB值可以是2至5、3至5或4至6。
聚环氧乙烷/聚乙烯共聚物通常以1至5重量%范围内的量存在于第一层中。1与5重量%内任何和所有范围均并入本文并且在本文中公开,例如共聚物能以1至4重量%、1至3重量%、或2至3重量%、或3至5重量%范围内的量存在于第一层中,。
-组分(b)-第二层
第二层膜与第一层相邻。第二层包含聚烯烃组分。聚烯烃可以选自上文列出的任何聚烯烃。在各种实施例中,聚烯烃组分可以是LDPE或LLDPE。
第二层还含有亲水性添加剂。这一添加剂选自脱水山梨糖醇酯、聚氧乙烯酯、甘油酯、聚甘油酯、氟基化合物以及其组合组成的组。这些添加剂具有相对较小的分子量(通常分子量低于500)。市售防滴落剂的一个实例是来自临安助剂(Lin'an auxiliary)的LY-6。
亲水性添加剂的HLB值通常在7至18的范围内。7至18内的任何范围包括于本文并且公开于本文中,例如HLB值可以是8至16、10至15或11至14。
添加剂一般以1至5重量%范围内的量存在于第二层中。1与5重量%内的任何和所有范围都并入本文并且公开于本文中,例如添加剂能以1至4重量%、1至3重量%、或2至3重量%、或3至5重量%范围内的量存在于第二层中。
第二层进一步包含无机填料。填料可以具有多孔结构。可以使用的无机填料的实例包括但不限于硅藻土、沸石、多孔二氧化硅、多孔二氧化钛、多孔氧化铝以及绿坡缕石。将无机填料掺入这一层中以控制和/或降低亲水性添加剂的迁移速率。
无机填料通常以0.5至5重量%范围内的量存在于第二层中。0.5与5重量%内的任何和所有范围都并入本文并且公开于本文中,例如无机填料能以0.5至4重量%、1至4重量%、1至3重量%或2至3重量%范围内的量存在于第二层中。
-组分(c)-表层
膜的外层或表层包含聚烯烃组分。聚烯烃可以选自上文列出的任何聚烯烃。在各种实施例中,聚烯烃组分可以是LDPE或LLDPE。
所述膜可以进一步包含另外的具有聚烯烃组分的1至4个层。聚烯烃可以选自上文列出的那些聚烯烃。这些附加层介于第二层与表层之间。1至4范围内的任何值并入本文中并且公开于本文中;例如可以存在1、2、3或4个附加层。
任选的组分
在一些实施例中,抗氧化剂可以存在于膜中。抗氧化剂的实例包括但不限于烷基化单酚、烷基化氢醌、羟基化硫代二苯基醚、次烷基双酚、苯甲基化合物、酰氨基酚、b-(3,5-二叔丁基-4-羟基苯基)-丙酸与一元醇或多元醇的酯、b-(5-叔丁基-4-羟基-3-甲基苯基)-丙酸与一元醇或多元醇的酯、b-(3,5-二叔丁基-4-羟基苯基)羟苯基)-丙酸的酰胺以及其组合。
在一些实施例中,UV稳定剂可以存在于膜中。UV稳定剂的实例包括但不限于2-(2'-羟基苯基)-苯并三唑、2-羟基-二苯甲酮、经取代的苯甲酸的酯、丙烯酸酯、丙二酸酯、位阻胺、羟基苯基-s-三嗪以及其组合。
生成组合物的方法
本发明的多层膜优选在如本领域中通常已知的吹塑膜方法中形成,但是也可以使用其它方法,如流延膜或层压。
实例
所用原料在表1示出。
表1.原料信息。
膜制备方法:
混配
首先,通过使用双螺杆挤出机制备UV 944和AO B900在LLDPE树脂中的母料。以相同的方法制备防雾(TS-403)母料。将这些粒料形式的母料以及防滴落剂和无机填料(如果调配物中有填料)与LDPE粉末混合在一起。最终膜调配物中UV 944和AO B900的含量分别为1.0和0.2重量%。然后在40mm双螺杆挤出机上进行混配。LLDPE由一个进料器进料,并且LDPE粉末和所有其它添加剂从另一个进料器进料。温度设定在180℃左右,并且螺杆速度为250rpm。在约230℃下测量熔体温度。
来自混配工艺的粒料在吹膜工艺之前完全干燥。
吹膜
这些膜在3层吹塑膜生产线上制备。吹胀比(BUR)在2.5左右。膜厚度控制在100μm左右。层厚度为1/1/1。
表2总结了本发明的所有调配物。实例1使用疏水性PEO-PE(Unithox 420)作为内层添加剂。1.0%的C18-EO9和1.0%的Unithox450也掺入内层中以进一步增加表面亲水性。将低分子量添加剂LY-6与硅藻土混合以掺入中间层。
比较实例A在内层和中间层都具有与实例1相同的防滴落调配物,但在中间层没有硅藻土。比较实例B、C以及D的内层和中间层具有相同的添加剂和添加剂量。比较实例B具有与实例1相同的内层添加剂。比较实例C具有与实例1的中间层相同的防滴落添加剂。比较实例D在内层/中间层中具有添加剂和填料两者。比较实例E具有与实例1相同的中间层,但在内层中没有疏水性PEO-PE。
表2.膜的不同层的调配物。
光学性质测试:
在BYK Gardner雾度计上测试膜样品的雾度。在光学测试之前,使用乙醇来清洁在膜表面上膨胀出的添加剂。
膜加速防滴落测试:
按照中国国家标准GB 4455-2006对膜的防滴落性能进行测试。将膜夹在水浴笼上形成一个封闭的空间,由压锥产生的膜倾斜角度为15度。将水浴中的水加热至60℃,并且水蒸气冷凝,并且在PE膜上形成一层薄薄的水。冷凝水回流到水浴中,并且防滴落剂逐渐被冲走。在膜的内表面上形成不透明的水滴和/或透明的水片/流,并且失去防滴落性能。
失败的标准设定为:
1.不透明水滴面积大于总膜面积的30%。
2.水片/水流面积大于总膜面积的50%。
当防滴落性能失效时记录防滴落作用时间(天)。
防滴落性能实地测试:
通过使用来自本发明研究的膜建立温室。在中国北方进行实地测试。温室长60m,宽8m,并且高3m。在2015年4月至6月进行测试,环境温度在-2至35℃范围内变化经记录温室内的湿度在30%至80%范围内。
结果:
所有膜样品的防滴落性能总结在表3中。
表3.不同膜的防滴落测试和光学测试结果。
经过80天的实地测试,不同膜样品的防滴落性能展示于图1-5中。实例1显示出良好的防滴落性能。来自实例1的膜在整个测试时间中保持良好的透明度,在膜表面上没有发现水滴或雾。
比较实例A在中间层不添加硅藻土的情况下,在80天实地试验后也显示出优异的防滴落性能。但从加速测试结果来看,本发明实例显然具有长得多的防滴落寿命。硅藻土的加入可以封装LY-6并且减缓扩散,产生长得多的防滴落性能。
对于比较实例B、C以及D,小液滴在内表面上冷凝。这些水滴导致膜的透明度大大降低。
对于比较实例E,当亲水性表面活性剂(LY-6)代替内层中的疏水性PEO/PE共聚物时,在5天的加速测试之后发现水滴,而我们的发明实例1保持透明性,没有水滴形成,持续>27天。
本发明研究的另一个优点是在中间层中添加填料减少了对光学性质的负面影响(由填料添加引起)。如表3所示,与比较实例A(膜中不含填料)相比,实例1的雾度稍微增加。在表层(内层)中添加了填料的比较实例D的雾度上升幅度大。
Claims (4)
1.一种多层膜,包含:
a)第一层,所述第一层包含
i)聚烯烃组分;和
ii)具有以下组合的聚环氧乙烷/聚乙烯共聚物:CH3CH2(CH2CH2)aCH2CH2(OCH2CH2)bOH和
CH3CH2(CH2CH2)aCO(OCH2CH2)bOH,其中a是9至25并且b是1至10;并且其中所述聚环氧乙烷/聚乙烯共聚物具有2至6范围内的亲水-亲油平衡值,其中所述聚环氧乙烷/聚乙烯共聚物以1重量%至5重量%的范围存在于所述第一层中;
b)第二层,所述第二层包含
i)聚烯烃组分;
ii)1至5重量%的选自脱水山梨糖醇酯、聚氧乙烯酯、甘油酯、聚甘油酯、氟基化合物以及其组合组成的组的添加剂,其中所述添加剂的亲水-亲油平衡值在7至18范围内;和
iii)无机填料;
其中所述第二层与所述第一层相邻,以及
c)包含聚烯烃组分的表层,其中所述无机填料选自硅藻土、沸石、多孔二氧化硅、多孔二氧化钛、多孔氧化铝以及绿坡缕石组成的组,并且以2重量%至5重量%的范围存在于所述第二层中,并且其中所述第一层为所述多层膜的内层并且所述表层为所述多层膜的外层。
2.根据权利要求1所述的多层膜,在所述第二层与所述表层之间进一步包含1至4个聚烯烃层。
3.根据权利要求1至2中任一项所述的多层膜,其中所述表层包含选自低密度聚乙烯、线性低密度聚乙烯以及其组合组成的组的聚烯烃组分。
4.一种由根据权利要求1至3中任一项所述的多层膜制备的温室膜。
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EP (1) | EP3349984A4 (zh) |
JP (1) | JP2018530455A (zh) |
CN (1) | CN108025534B (zh) |
AR (1) | AR106034A1 (zh) |
BR (1) | BR112018004216A2 (zh) |
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EP3645622A4 (en) * | 2017-06-28 | 2021-03-10 | Dow Global Technologies LLC | FORMULATIONS FOR USE FOR GREENHOUSE FILMS WITH HIGH TRANSPARENCY |
JP7018300B2 (ja) * | 2017-11-28 | 2022-02-10 | 旭化成株式会社 | 農業用ポリオレフィン系多層フィルム |
CN113787799A (zh) * | 2021-09-03 | 2021-12-14 | 富维薄膜(山东)有限公司 | 一种新型防水雾薄膜及其制备方法 |
CN116580631B (zh) * | 2023-05-18 | 2024-05-17 | 广东工业大学 | 一种应用于液滴展平的模内标签膜及其制备方法和应用 |
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- 2015-09-18 JP JP2018512154A patent/JP2018530455A/ja not_active Ceased
- 2015-09-18 CN CN201580082909.9A patent/CN108025534B/zh not_active Expired - Fee Related
- 2015-09-18 WO PCT/CN2015/089986 patent/WO2017045199A1/en active Application Filing
- 2015-09-18 US US15/751,247 patent/US10603877B2/en not_active Expired - Fee Related
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- 2015-09-18 BR BR112018004216A patent/BR112018004216A2/pt not_active Application Discontinuation
- 2015-09-18 MX MX2018003169A patent/MX2018003169A/es unknown
- 2015-09-18 CA CA2998401A patent/CA2998401A1/en not_active Abandoned
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AR106034A1 (es) | 2017-12-06 |
BR112018004216A2 (pt) | 2018-09-25 |
WO2017045199A1 (en) | 2017-03-23 |
CN108025534A (zh) | 2018-05-11 |
JP2018530455A (ja) | 2018-10-18 |
CA2998401A1 (en) | 2017-03-23 |
US20180244021A1 (en) | 2018-08-30 |
US10603877B2 (en) | 2020-03-31 |
MX2018003169A (es) | 2018-05-17 |
EP3349984A1 (en) | 2018-07-25 |
EP3349984A4 (en) | 2019-02-20 |
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