CN1198709A - 使用基于乙烯、(甲基)丙烯酸酯、和(甲基)丙烯酸的聚合物涂覆或密封层合安全玻璃板 - Google Patents
使用基于乙烯、(甲基)丙烯酸酯、和(甲基)丙烯酸的聚合物涂覆或密封层合安全玻璃板 Download PDFInfo
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Abstract
使用以下成分的聚合物A)30~90wt%的乙烯,B)0~10wt%的含有2~12个碳原子的、还可能带有卤原子的另外的α-烯烃,C)3~40wt%的一种或多种的丙烯酸酯或甲基丙烯酸酯,其中酯基由C1~C20烷基、C5~C18环烷基、或C7~C18芳烷基组成的,此处所说的酯基还可以带有卤原子,D)7~30wt%的丙烯酸和/或甲基丙烯酸,以及E)0~10wt%的另外的可共聚的单体来涂覆或密封层合安全玻璃板。
Description
本发明涉及使用基于乙烯、(甲基)丙烯酸酯、和(甲基)丙烯酸的聚合物来涂覆或密封层合安全玻璃板。本发明还涉及这些聚合物的水乳液和还涉及使用这些水乳液涂覆或密封层合安全玻璃板的方法。本发明还涉及根据本发明涂覆或密封的层合安全玻璃板。
对汽车具有特别意义的层合安全玻璃板通常是由两层硅酸盐玻璃,和在其间插入一层塑料组成的。为此目的还可以使用能滤除紫外线或红外线的其他光学上有效的材料层,所说的塑料层一方面将二块玻璃板固定在一起,另一方面当整体的玻璃板破碎时它被用来将碎片保持在一起。
对此塑料材料层在耐机械、热、和化学试剂方面具有高的要求。当今仍被通常使用的聚乙烯缩丁醛薄膜在适当的程度上是符合这些要求的。但是,特别在当来自空气中的水份和侵蚀性沾污物贯穿到此塑料层时,它将失去其无色-透明的外观并成为混浊的。
在被完全封闭的层合安全玻璃板的情况中,例如,通过在其四周达到某种程度的密封对汽车的挡风玻璃可能是有帮助的,但是,例如,在那些汽车的侧窗的情况中,仅在非常特殊的情况可能进行这样的封边,而要对中间的塑料层达到气密性封闭迄今仍是非常困难的。
汽车侧窗的封闭只能在使用无色-透明的密封剂情况下进行,这种密封剂是肉眼所不能察觉的。通常使用的有色的,即,深暗色到黑色的密封组合物,例如被用于汽车挡风玻璃的情况中是不合适的。
因此本发明的目的是提供一种适用于涂覆层合安全玻璃板并满足耐机械、热、和化学性的必要要求的材料。此材料还应该适用于这样玻璃板的无色-透明封边。
DE-A2136076(1)披露通过高压聚合制备的乙烯、醋酸乙烯、丙烯酸(2-乙己)酯、和甲基丙烯酸的共聚物。这些共聚物适用于将二块玻璃结合在一起而生产出汽车挡风玻璃。因此,它们是以熔膜或溶液形式被施用于玻璃的。
DE-4130667(2)披露α-烯烃例如乙烯和不饱和羧酸例如(甲基)丙烯酸的共聚物,这些共聚物可能还含有作为聚合单元的第三种单体组份诸如不饱和羧酸酯,例如,(甲基)丙烯酸(2-乙己)酯。这些共聚物适用于涂覆玻璃表面,例如,玻璃瓶表面。所说的共聚物以粉末形式被辊涂到玻璃表面,然后为了产生所述的保护涂层而被加热。
本发明涉及使用以下成分的聚合物
A)30~90wt%的乙烯,
B)0~10wt%的含有2~12个碳原子的、还可能带有卤原子的另外的α-烯烃,
C)3~40wt%的一种或多种的丙烯酸酯或甲基丙烯酸酯,其中酯基由C1~C20烷基、C5~C18环烷基、或C7~C18芳烷基组成的,此处所说的酯基还可以带有卤原子,
D)7~30wt%的丙烯酸和/或甲基丙烯酸,以及
E)0~10wt%的另外的可共聚单体
来涂覆或密封层合安全玻璃板。
除了作为组份A)的乙烯外还被使用的合适的组份B)是含具有2~12、特别是2~9个碳原子的亚乙烯基或者特别是乙烯基的α-烯烃,它们可以还带有卤原子诸如氯、溴或特别是氟原子。这样的α-烯烃的例子是丙烯、1-丁烯、异丁烯、1-丙烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一烯、1-十二烯、丁二烯、苯乙烯、α-甲基苯乙烯、乙烯基甲苯、单氟乙烯、1,1-和1,2-二氟乙烯、三氟乙烯、四氟乙烯、一氯三氟乙烯、1,1-二氯-2,2-二氟乙烯、3-氟丙烯、3,3-二氟丙烯和3,3,3-三氟丙烯。
α-烯烃B)起替代部分的乙烯A)的作用,以便改进所生成的聚合物的性质。
适用的组份C)是那些其中酯基是由线型或优选为支化链的C6~C18烷基,或C6~C12环烷基,或C7~C18芳烷基、特别是苯烷基组成的,此处所说的酯基还可以带有卤原子如氯、溴或特别是氟。组份C)的例子是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸(2-乙己)酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸异十三酯、(甲基)丙烯酸正十四酯、(甲基)丙烯酸正十六酯、(甲基)丙烯酸正十八酯、(甲基)丙烯酸正二十酯、(甲基)丙烯酸环戊酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸2-、3-和4-甲基环己酯、(甲基)丙烯酸2,3-、2,4-、2,5-、2,6-、3,4-和3,5-二甲基环己酯、(甲基)丙烯酸环庚酯、(甲基)丙烯酸环辛酯、(甲基)丙烯酸环己·甲酯、(甲基)丙烯酸2-(环己基)乙酯、(甲基)丙烯酸3-(环己基)丙酯、(甲基)丙烯酸4-(环己基)丁酯、(甲基)丙烯酸6-(环己基)己酯、(甲基)丙烯酸8-(环己基)辛酯、(甲基)丙烯酸12-(环己基)十二酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-苯基乙酯、(甲基)丙烯酸3-苯基丙酯、(甲基)丙烯酸4-苯基丁酯、(甲基)丙烯酸6-苯基己酯、(甲基)丙烯酸8-苯基辛酯、(甲基)丙烯酸12-苯基十二酯、(甲基)丙烯酸2-、3-、和4-甲基苄酯、(甲基)丙烯酸单-、二-、和三-氟甲酯、还有(甲基)丙烯酸一、二-、三-、和四-氟乙酯。
优选的组份D)是丙烯酸本身或丙烯酸含量为50~100wt%的丙烯酸与甲基丙烯酸的混合物。
组份E)起进一步改性所制得的聚合物的作用。作为组份E)此处例如可以使用的乙烯基酯是醋酸乙烯酯或丙酸乙烯酯。
以单体混合物的总量计,单体组份A)~E)的优选用量如下:A)50~75wt%,特别是55~70wt%B)0~8wt%,特别是0~5wt%C)10~25wt%,特别是13~22wt%D)15~25wt%,特别是17~23wt%E)0~5wt%,特别是0~3wt%
在优选的实施方案中使用由A)50~75wt%的乙烯,B)0~8wt%的具有2~9个碳原子的、还可带有卤原子的另外的α-烯烃,C)10~25wt%的一种或多种的丙烯酸酯或甲基丙烯酸酯,其中酯基部分是由C6~C18烷基、C6~C12环烷基或C7~C14芳烷基组成的,此处所说的酯基还可带有卤原子,D)15~25wt%的丙烯酸和/或甲基丙烯酸,E)0~5wt%的另外的可聚合单体组成的聚合物来涂覆或密封层合安全玻璃板。
所述的聚合物在本技术领域中是已知的、它们可以通过所有的常用聚合方法来合成,优选的聚合方法是乳液聚合和特别是在温度为150°~300℃以及压力为1200~3000巴的高压聚合。
为了增进对在本发明中使用的聚合物性质的控制,例如为了避免涉及粘性的问题,可以使用由单体A)~E)组成的聚合物的混合物以及还有这些聚合物与其他乙烯共聚物例如聚(乙烯-(甲基)丙烯酸)的混合物。
层合安全玻璃板被广泛地应用于许多工业应用中。例如,它们被用于住宅和其他建筑物结构中。然而,优选的应用领域是运载工具结构。因此,设计用于运载工具的层合安全玻璃板被应用于例如汽车,载重汽车,公共汽车,建筑工地运载工具如挖掘机和推土机,农用运载工具如拖拉机中,或应用于铁路运载工具如客车车厢和火车头中。
当所述的聚合物被用作层合安全玻璃板、特别是用于运载工具的层合安全玻璃板的涂料介质时,这主要指它们的用途是作为适于在两块这样玻璃板之间使用的涂料。然而,本发明的范围包括层合安全玻璃板,特别是在运载工具用的层合安全玻璃板的外表面上的涂料,例如使外表面成为防尘的或无划痕的涂料。
另外的可能用途是层合安全玻璃板、特别是用于运载工具的层合安全玻璃板的封边。这特别涉及可降低的侧窗的上边缘的封边问题,如以上所说,封边只能以无色-透明的方式来实现。
所述的聚合物可通过任何的常用工艺被施加到层合安全玻璃板,例如,通过涂粉沫或箔或薄膜并随后使其熔化来实现。然而,在优选的实施方案中,它们是以具有固体含量为5~40wt%、特别是10~35%的,并且其中10~100%、特别是40~100%的羧基是被氨(NH3)或低分子量胺所中和的水乳液形式被施加的。适用的低分子量胺主要是具有1~25个、特别是2~12个碳原子的伯胺、仲胺、和叔胺。这些胺还可以带有羟基或具有醚氧官能。此外,这些胺在分子中还可以带有羟酸酯基,特别有意义的代表性的羧酸酯是是含胺基的不饱和的羧酸酯,例如,(甲基)丙烯酸氨烷酯。这样的胺的例子是甲胺,二甲胺,三甲胺,乙胺,二乙胺,三乙胺,正丁胺,二正丁胺,三正丁胺,哌啶,吗啉,乙醇胺,二乙醇胺,三乙醇,单乙基乙醇胺,二甲基乙醇胺,异丙醇胺,二(异丙醇)胺,三(异丙醇)胺和丙烯酸(2-氨乙)酯。在玻璃上固化聚合物期间所说的胺是起有利作用的并且还影响所得到的塑料层的性质。
最好的是,上述的水乳液是无乳化剂的,因为本发明中所用的聚合物通常是自乳化性的,特别是当组份D)的含量为15%或以上时。所述的水乳液是通过在压力下使用常用方法被方便地制备的。
为了提高所说的水乳液在层合安全玻璃板的表面或边缘的粘合,可以对这些表面用常规的粘合促进剂进诸如底漆进行预处理。
于是本发明的另一目的是提供一种涂覆或密封层合安全玻璃板、特别是运载工具用的层合安全玻璃板的方法,该方法的特征在于将所说的水乳液施加到层合安全玻璃板并干燥之,而干燥是通过惯用的方法进行的。
因为所述的水乳液本身是新的,因此它们还构成本发明的另一个目的。
本发明还涉及根据本发明涂覆或密封的层合安全玻璃板。
使用本发明的聚合物在层合安全玻璃板上制备的涂层在机械、热、和化学方面是高度稳定的。特别是,以此方式生产的层合安全玻璃板由于来自空气的的水份或有害物质的影响而变成混浊的情况事实上几乎没有或仅仅很缓慢,甚至在不充分的封边或未封边的情况时也能做到这一点。于是,当使用本发明的聚合物时不进行迄今为止通常使用的封边是可能的。
此外,所说的聚合物还构成用于层合安全玻璃板、特别是汽车侧窗玻璃(汽车侧窗玻璃内部涂有、具有较少稳定性的惯用的涂层例如聚乙烯缩丁醛膜形成的涂层)的理想的封边组合物,因为它们在事实上的无限的时间内能保证气密性的密封、而仍保持是无色-透明的,并且作为密封组合物是肉眼所不能察觉的。
实施例1
被夹心在层合安全玻璃板之间的涂层
将由60wt%的乙烯、20wt%的丙烯酸(2-乙己)酯和20wt%的丙烯酸的三元共聚物组成的,具有固体含量为21wt%和相当于羧基的中和度为60%的二甲基乙醇胺含量的无乳化剂的水乳液施加到二层的硅酸盐玻璃之间并干燥之。所得的、未封边的层合安全玻璃板与类似的未封边的层合安全玻璃板(其中内层是由聚乙烯缩丁醛组成)一起受到正常的天候条件作用。当具有内部的聚乙烯缩丁醛薄膜涂层的板变成明显的混浊时,含有本发明涂层的板仍就是完全无色透明的。实施例2
层合安全玻璃板的封边
一种适用作汽车侧窗的层合玻璃板被用实施例1的无乳化剂的水乳液封边,其中乳液被施加到边表面并进行干燥。由此获得在正常的天候条件下不发生变化的、看不见的无色-透明的密封。
Claims (8)
1.一种使用以下成分的聚合物
A)30~90wt%的乙烯,
B)0~10wt%的含有2~12个碳原子的、还可能带有卤原子的另外的α-烯烃,
C)3~40wt%的一种或多种的丙烯酸酯或甲基丙烯酸酯,其中酯基由C1~C20烷基、C5~C18环烷基、或C7~C18芳烷基组成的,此处所说的酯基还可以带有卤原子,
D)7~30wt%的丙烯酸和/或甲基丙烯酸,以及
E)0~10wt%的另外的可共聚的单体
涂覆或密封层合安全玻璃板的方法。
2.一种使用以下成分的聚合物
A)50~75wt%的乙烯,
B)0~8wt%的具有2~9个碳原子的、还可带有卤原子的另外的α-烯烃,
C)10~25wt%的一种或多种的丙烯酸酯或甲基丙烯酸酯,其中酯基部分是由C6~C18烷基、C6~C12环烷基或C7~C14芳烷基组成的,此处所说的酯基还可带有卤原子,
D)15~25wt%的丙烯酸和/或甲基丙烯酸,
E)0~5wt%的另外的可聚合的单体
涂覆或密封层合安全玻璃板的方法。
3.一种使用权利要求1或2所规定的聚合物涂覆或密封层合安全玻璃板的方法。
4.一种使用权利要求1~3的任一项权利要求所规定的聚合物作为运载工具用的层合安全玻璃板的二层玻璃之间的涂料介质的方法。
5.一种使用权利要求1~3的任一项权利要求所规定的聚合物对运载工具用的层合安全玻璃板封边的方法。
6.一种如权利要求1或2所规定的聚合物的水乳液,具有固体含量为5~40wt%,其中10~100%的羧基被氨或低分子量胺所中和。
7.一种涂覆或封闭层合安全玻璃板的方法,其中如权利要求6所规定的聚合物的水乳液被施加到层合安全玻璃并被干燥。
8.一种层合安全玻璃板,其特征在于涂料或密封剂包含如权利要求1或2的聚合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19529445.9 | 1995-08-10 | ||
DE19529445A DE19529445A1 (de) | 1995-08-10 | 1995-08-10 | Verwendung von Polymerisaten auf Basis von Ethylen, (Meth)acrylsäureestern und (Meth)acrylsäure zum Beschichten oder Versiegeln von Verbundsicherheitsglasscheiben |
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Publication Number | Publication Date |
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CN1198709A true CN1198709A (zh) | 1998-11-11 |
Family
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Family Applications (1)
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CN96197414A Pending CN1198709A (zh) | 1995-08-10 | 1996-07-26 | 使用基于乙烯、(甲基)丙烯酸酯、和(甲基)丙烯酸的聚合物涂覆或密封层合安全玻璃板 |
Country Status (14)
Country | Link |
---|---|
US (1) | US6096148A (zh) |
EP (1) | EP0876252B1 (zh) |
JP (1) | JPH11510780A (zh) |
KR (1) | KR19990036221A (zh) |
CN (1) | CN1198709A (zh) |
AT (1) | ATE226141T1 (zh) |
AU (1) | AU6787196A (zh) |
BR (1) | BR9609900A (zh) |
CA (1) | CA2223856A1 (zh) |
DE (2) | DE19529445A1 (zh) |
ES (1) | ES2185794T3 (zh) |
MX (1) | MX9801092A (zh) |
WO (1) | WO1997006005A1 (zh) |
ZA (1) | ZA966746B (zh) |
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CN1852928B (zh) * | 2003-07-24 | 2010-06-09 | 纳幕尔杜邦公司 | 具有改善低温性能的乙烯/丙烯酸烷基酯无规共聚物及其混炼胶和弹性体组合物 |
CN103172279A (zh) * | 2011-12-23 | 2013-06-26 | 北京众智同辉科技有限公司 | 夹层玻璃的边部密封结构及密封方法 |
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US20060240105A1 (en) * | 1998-11-02 | 2006-10-26 | Elan Corporation, Plc | Multiparticulate modified release composition |
US20090149479A1 (en) * | 1998-11-02 | 2009-06-11 | Elan Pharma International Limited | Dosing regimen |
WO2000025752A1 (en) | 1998-11-02 | 2000-05-11 | Church, Marla, J. | Multiparticulate modified release composition |
GB9904122D0 (en) * | 1999-02-23 | 1999-04-14 | Bonar Polymers Limited | Glass coating |
BRPI0015284B8 (pt) | 1999-10-29 | 2021-05-25 | Euro Celtique S/A | formulações de hidrocodona de liberação controlada |
US10179130B2 (en) | 1999-10-29 | 2019-01-15 | Purdue Pharma L.P. | Controlled release hydrocodone formulations |
DE10000940B4 (de) * | 2000-01-12 | 2004-02-12 | Silu Verwaltung Ag | Einkomponentige Dichtmasse auf Basis einer Dispersion von Polyacrylaten, Verfahren zu deren Herstellung und System |
US6559230B2 (en) | 2000-09-29 | 2003-05-06 | Dupont Dow Elastomers L.L.C. | Thermosetting ethylene/alpha-olefin composition and safety glass interlayer film made from the composition |
IT249284Y1 (it) * | 2000-10-02 | 2003-04-08 | Fiat Auto Spa | Lastra di materiale trasparente. |
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US7143800B2 (en) * | 2003-03-20 | 2006-12-05 | Cardinal Lg Company | Non-autoclave laminated glass |
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WO2006063078A2 (en) * | 2004-12-08 | 2006-06-15 | Elan Corporation, Plc | Topiramate pharmaceuticals composition |
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WO2007037790A2 (en) * | 2005-06-08 | 2007-04-05 | Elan Corporation, Plc | Modified release famciclovir compositions |
US8637150B2 (en) * | 2007-10-01 | 2014-01-28 | E I Du Pont De Nemours And Company | Multilayer acid terpolymer encapsulant layers and interlayers and laminates therefrom |
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-
1995
- 1995-08-10 DE DE19529445A patent/DE19529445A1/de not_active Withdrawn
-
1996
- 1996-07-26 JP JP9508075A patent/JPH11510780A/ja active Pending
- 1996-07-26 MX MX9801092A patent/MX9801092A/es unknown
- 1996-07-26 ES ES96928376T patent/ES2185794T3/es not_active Expired - Lifetime
- 1996-07-26 DE DE59609804T patent/DE59609804D1/de not_active Expired - Lifetime
- 1996-07-26 AU AU67871/96A patent/AU6787196A/en not_active Abandoned
- 1996-07-26 WO PCT/EP1996/003289 patent/WO1997006005A1/de active IP Right Grant
- 1996-07-26 AT AT96928376T patent/ATE226141T1/de not_active IP Right Cessation
- 1996-07-26 BR BR9609900A patent/BR9609900A/pt not_active IP Right Cessation
- 1996-07-26 EP EP96928376A patent/EP0876252B1/de not_active Expired - Lifetime
- 1996-07-26 CN CN96197414A patent/CN1198709A/zh active Pending
- 1996-07-26 CA CA002223856A patent/CA2223856A1/en not_active Abandoned
- 1996-07-26 KR KR1019980700889A patent/KR19990036221A/ko not_active Application Discontinuation
- 1996-07-26 US US09/011,065 patent/US6096148A/en not_active Expired - Fee Related
- 1996-08-08 ZA ZA9606746A patent/ZA966746B/xx unknown
Cited By (2)
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CN1852928B (zh) * | 2003-07-24 | 2010-06-09 | 纳幕尔杜邦公司 | 具有改善低温性能的乙烯/丙烯酸烷基酯无规共聚物及其混炼胶和弹性体组合物 |
CN103172279A (zh) * | 2011-12-23 | 2013-06-26 | 北京众智同辉科技有限公司 | 夹层玻璃的边部密封结构及密封方法 |
Also Published As
Publication number | Publication date |
---|---|
JPH11510780A (ja) | 1999-09-21 |
AU6787196A (en) | 1997-03-05 |
EP0876252B1 (de) | 2002-10-16 |
CA2223856A1 (en) | 1997-02-20 |
ES2185794T3 (es) | 2003-05-01 |
ZA966746B (en) | 1998-02-09 |
MX9801092A (es) | 1998-04-30 |
DE59609804D1 (de) | 2002-11-21 |
BR9609900A (pt) | 1999-05-25 |
US6096148A (en) | 2000-08-01 |
EP0876252A1 (de) | 1998-11-11 |
KR19990036221A (ko) | 1999-05-25 |
WO1997006005A1 (de) | 1997-02-20 |
ATE226141T1 (de) | 2002-11-15 |
DE19529445A1 (de) | 1997-02-13 |
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