CN1282359A - 聚氨酯粘合剂对涂漆面附着力的改进方法 - Google Patents
聚氨酯粘合剂对涂漆面附着力的改进方法 Download PDFInfo
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Abstract
本发明的一方面是处理涂漆面或玻璃表面的方法,从而改进此后涂覆的聚氨酯粘合剂的附着力。此法包括用预擦拭溶液涂覆该表面,预擦拭溶液包括烃基取代的芳族磺酸和可以溶解该酸的溶剂,以及使溶剂蒸发。在本发明的第二方面,预擦拭组合物包括0.5—10.0%重量的酸和90.0—99.5%重量的该酸的溶剂。
Description
本发明涉及聚氨酯粘合剂对涂漆面附着力的改进方法及其所用的组合物。
在如汽车工业等行业中,玻璃有效地粘合于涂漆的基材是很重要的。例如,挡风玻璃必须有效地粘合与涂漆的汽车车身以便在撞击或翻转的情况下支撑汽车车顶。一般情况下,使用聚氨酯密封胶将玻璃表面连接在涂漆面上。但是,有时很难将聚氨酯密封胶直接满意地粘合在涂漆面上。
结果,为了得到满意程度的聚氨酯附着在汽车车身的涂漆面,汽车制造商常常在涂覆粘合剂之前要求在涂漆面上额外预先涂覆底漆。例如标题为“改进对涂漆面粘合的方法和组合物”的美国专利4,525,511中讨论了这种底漆和涂底漆的方法(在此引为参考)。只有通过涂上面漆才可以满意地使聚氨酯密封胶粘合和得到油漆-玻璃表面结合体。
颁发给Schurnacher的标题为“聚氨酯密封胶粘合于涂漆的或玻璃表面的方法”的美国专利4,857,366(′366专利)代表了在玻璃-涂漆面粘合领域的进展,因为取消了涂底漆步骤(在此引为参考)。′366专利讨论了涂漆面的处理方法以便使聚氨酯粘合于涂漆面。这里讨论的方法包括涂覆对甲苯磺酸和选自酮、醇和脂族酯的溶剂的溶液。但是,在′366专利中讨论的溶剂对环境是比较危险的。而且在′366专利中讨论的溶液常常在经处理的表面留下难看的酸残余物,从而对某些油漆的光泽产生不利的影响。
在粘合剂和密封胶领域提供处理涂漆面的方法和组合物以有效地改进聚氨酯和涂漆面之间的粘合力,是一项进展。在该领域提供比上述现有技术的组合物对环境更为友好的组合物也是一项进展。这种技术不会在涂漆面留下难看的残余物,对涂漆面的光泽也不会有不利的影响。
本发明一个方面是处理涂漆或玻璃表面的方法,从而改进以后的涂覆的聚氨酯粘合剂的附着力。此法包括用预擦拭溶液涂覆该表面,该预擦拭溶液包括烃基取代的芳族磺酸和磺酸的溶剂,以及使溶剂蒸发。
在本发明的第二个方面,预擦拭溶液包括0.5-10.0%重量的烃基取代的芳族磺酸和90.0-99.5%重量的磺酸的溶剂。
本发明的方法和组合物具有几个优点。首先,本发明的方法和组合物可以利用芳族或烷基芳族溶剂,这些溶剂比现有技术所用的大多数溶剂对环境更友好。本发明的组合物在基材表面不留下结晶的残余物。最后,本发明的组合物对特定类型的油漆光泽没有不利的影响。
本发明的方法一般包括在表面上涂覆预擦拭溶液以及使预擦拭溶液中的溶剂蒸发。在这里所用的名词“预擦拭”是指在将任何粘合剂或密封胶涂覆在表面之前将该溶液涂覆于表面上。换言之,在将任何的随后组合物涂覆之前用本发明的预擦拭溶液来处理该表面。
预擦拭溶液含有酸和溶剂。在预擦拭溶液中的酸必须能溶解于该溶剂。酸是芳族磺酸,其中芳族部分之一还可由一个或多个烃取代基取代。而且,芳族部分可以含一个或多个磺酸部分。这些取代基优选有6或更多的碳原子。这些取代基优选有20或更少的碳原子。烃取代基可以是烷基、芳基、链烯基、芳烷基或烷芳基。取代基更优选有6-12个碳原子,最优选为9-12个碳原子。烃取代基可含不影响本发明组合物中的酸官能的非烃部分。芳族部分可以是满足本发明规定的任何芳族部分,优选是苯或萘。优选酸的实例包括十二烷基苯磺酸、二壬基萘二磺酸和二壬基萘磺酸。最优选的酸是十二烷基苯磺酸。在预擦拭溶液中酸含量优选占溶液总重量的至少0.5%重量,更优选占至少1.0%重量,尤为优选占至少1.5%重量。在预擦拭溶液中酸量优选低于或等于10.0%重量,更优选低于或等于5.0%重量,尤为优选低于或等于3.5%重量,最优选低于或等于2.5%重量。
在本发明的预擦拭溶液中所用的溶剂可溶解酸,但并不妨碍粘合剂对基材表面的粘合或对基材表面涂层涂层造成损害。溶剂优选是烷基醇、芳族或烷基芳族溶剂。通常使用这些溶剂,并包括例如异丙醇、苯、甲苯、二甲苯、异丙苯和石脑油。优选的溶剂类型是烷基芳族溶剂和芳族溶剂。用在本发明的预擦拭溶液中的溶剂优选是具有下列组成的石脑油:10%重量的含乙苯、二甲苯、异丙苯、丙苯、乙基甲苯的溶液;45%重量的三甲苯;40%重量的四甲苯和5%重量的萘,如在Remhold PublishingCorp.(1950)出版的工业溶剂(Industral Solvents)第二版中所述的。
在预擦拭溶液中的溶剂用量优选为预擦拭溶液总重量的至少90.0%重量,更优选为至少95.0%重量,尤为优选至少96.5%重量,最优选为至少97.5%重量。在预擦拭溶液中溶剂含量优选低于或等于预擦拭溶液总重量的99.5%重量,更优选为低于或等于99.0%重量,尤为优选低于或等于98.5%重量。
本发明的预擦拭溶液可以通过用该领域已知的方法将各成分混合而配制成。一般是用适宜的混合器将各成分混合。这种混合优选在惰性气氛中进行。
使用本发明的预擦拭溶液改进了聚氨酯密封胶对涂漆面的附着力而不需要使用底漆。预擦拭溶液可以用另外的方法擦拭、喷涂或接触涂漆面或玻璃表面。预擦拭溶液只需要涂覆很薄的一层,刚刚将表面覆盖即可。如果需要,可以多涂一些,但只会造成浪费。
将预擦拭溶液涂于表面后,使溶剂蒸发。一般来说,溶剂将在几秒到10分钟蒸发,这取决于周围条件。
在优选实施方案中,本发明所用的酸在周围条件下是非晶液体。这样,使用这些酸,本发明的预擦拭溶液以后不会留下任何结晶残余物,这些残余物常常造成不美观的外观。大量使用本发明的组合物虽然对粘合有效,对会造成浪费。在组合物干燥后,聚氨酯密封胶可以直接涂在经处理的表面上,无需在涂覆聚氨酯密封胶之前在涂漆面涂底漆。
在优选的实施方案中,用预擦拭溶液处理玻璃和/或涂漆面后,本发明的方法包括使表面与未固化的聚氨酯粘合剂接触。在更优选的实施方案中,此方法还包括使未固化的聚氨酯粘合剂固化。
聚氨酯密封剂在本领域是众所周知的,这里有美国专利4,539,345和4,511,626为例,将其相关内容并入本文。适宜的聚氨酯密封胶包括一份热或湿气固化的体系和两份热或化学活化的聚聚氨酯体系。这里公开的处理涂漆面或玻璃表面的方法可以用于使用聚氨酯密封胶处理原件也可以处理替换的整套玻璃装置中。
为了涂覆聚氨酯密封胶,将密封胶组合物涂覆基材,此后,第一基材上的粘合剂同第二基材接触。然后将粘合剂曝露于固化条件下。在优选的实施方案中,一种基材是玻璃,另一种基材是塑料、金属、玻璃纤维或复合基材,这些基材可以任选涂漆。一般来说,聚氨酯涂覆是在常温下进行。密封胶的配制优选得到的操作时间为6分钟或更长,更优选为10分钟或更长。操作时间优选为15分钟或更少,更优选为12分钟或更少。
下面的实施例不是用来限制本发明的范围。所有的份,除非指出一般是指重量份。
实施例1
在玻璃瓶中将2份十二烷基苯磺酸(DDBSA)同98份石脑油混合。在室温下将溶液搅拌几分钟,使DDBSA完全溶解在石脑油中,从而生成2%DDBSA/石脑油溶液。用2%DDBSA/石脑油溶液将干酪包布弄湿,在涂以固化的汽车漆(Du Pont RKF45500/691R98770)的表面上擦拭。在几分钟后石脑油闪蒸出。在溶剂闪蒸出后,将未固化的一份湿气固化的聚聚氨酯粘合剂(Essex Specialty Products,Inc.的Betaseal 520聚氨酯粘合剂)的6.4毫米×6.4毫米的熔珠涂于擦拭过的表面。使聚氨酯在23℃和相对湿度50%下固化三天。固化后,将某些聚氨酯样品曝露于下列环境条件下:试验条件A,没有再曝露。试验条件B,将样品浸在32℃的水中10天。试验条件C,样品曝露于38℃和相对湿度100%下14天。试验条件D,将样品曝露在90℃下14天。
通过剪切固化熔珠边,观察粘合破裂的模式测定以固化密封胶的附着力。希望界面粘合强度(即油漆-聚氨酯或玻璃-聚氨酯)大于粘合剂本身(密封胶内)的内聚强度。因此,当对油漆-聚氨酯-玻璃结合进行试验时,内聚破裂(CF)优先于粘合破裂。样品都显示100%内聚破裂。在基材上没有酸的沉积或基材涂层的明显降解。
实施例2-6
用三种不同的酸重复实施例1。在实施例2中,酸是二壬基二磺酸(Nacure 155磺酸),从King Industries购得,为在异丙醇中的1%溶液。在实施例3和4中,各自为Nacure 1052磺酸(50%二壬基萘磺酸和50%庚烷)溶解于石脑油中的1%和5%的溶液。在实施例5和6中,各自为Nacure 1053磺酸(50%二壬基萘磺酸和40%二甲苯和10%乙苯)溶解于石脑油中的1%和5%的溶液。将所有的样品在条件A、B、C和D条件下处理,在所有情况下显示100%的内聚破裂。在基材上没有可见的酸沉积或基材涂层的明显降解。对比实施例1
未固化的1份湿气固化的聚聚氨酯粘合剂(Essex SpecialtyProducts Inc.的Betaseal 520聚氨酯粘合剂)的6.4毫米×6.4毫米熔珠涂覆于未用任何预擦拭溶液擦拭过的涂漆面。使聚氨酯在23℃和相对湿度50%下固化3天。固化后,某些聚氨酯按照A、B、C和D的条件进行试验,所有样品显示0%内聚破裂,(100%粘合破裂)。对比实施例2-7
用在异丙醇中的5%的下列酸:甲苯甲酸、丙酸、醋酸、富马酸、苯甲酸和2,2-双(羟甲基)丙酸重复实施例1。这些实施例的样品只曝露于试验条件A。样品都显示0%内聚破裂。对比实施例8
用对甲苯磺酸在异丙醇的0.5%溶液重复实施例1。固化后,将样品在实验条件A、B、C和D下进行试验。所有样品显示100%内聚破裂。在基材表面留下残余酸,涂层受到严重损伤。
Claims (10)
1.一种预擦拭组合物,包括:
0.5-10.0%重量的包括烃基取代的芳族磺酸的酸;以及
90.0-99.5%重量的能溶解该酸的溶剂。
2.权利要求1的组合物,其中溶剂是烷基醇、芳族或烷基芳族溶剂。
3.权利要求1或2的组合物,其中溶剂是苯、甲苯、二甲苯、异丙苯或石脑油。
4.权利要求1-3中任一项的组合物,其中烃部分有6-20个碳原子,芳族部分是苯或萘。
5.权利要求1-4中任一项的组合物,其中烃部分是C9-12烷基部分。
6.权利要求1-5的组合物包括:1.0-3.0%重量的酸:以及
97.0-99.0%重量的溶剂。
7.权利要求1-6中任一项的组合物,其中酸是十二烷基苯磺酸、二壬基萘二磺酸或二壬基萘磺酸。
8.处理涂漆面以改进此后涂覆的聚氨酯粘合剂的附着力的方法,此法包括:
在表面上涂覆包括权利要求1-7中任一项的的组合物的预擦拭溶液;和使溶剂蒸发。
9.权利要求8的方法,还包括将未固化的聚氨酯密封胶涂覆在该表面的步骤。
10.权利要求9的方法,还包括:
使未固化的聚氨酯粘合剂固化。
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JP4960242B2 (ja) * | 2004-10-08 | 2012-06-27 | ダウ グローバル テクノロジーズ エルエルシー | 低揮発性イソシアネートモノマー含有ポリウレタンプレポリマー及び接着剤システム |
KR101264450B1 (ko) | 2005-01-21 | 2013-05-15 | 더 보잉 컴파니 | 변형제를 이용한 활성화 방법 |
US7781493B2 (en) * | 2005-06-20 | 2010-08-24 | Dow Global Technologies Inc. | Protective coating for window glass |
EP1760129A1 (de) * | 2005-09-02 | 2007-03-07 | Sika Technology AG | Wässrige Haftreinigerzusammensetzung zur Erhöhung der Haftung von Klebstoffen und Dichtstoffen auf Lacken |
MX2009006626A (es) | 2006-12-19 | 2009-06-30 | Dow Global Technologies Inc | Aditivos activadors de adhesion y metodos para mejorar composiciones de recubrimiento. |
US9102854B2 (en) * | 2007-11-07 | 2015-08-11 | Dow Global Technologies Inc. | Polyurethane sealant compositions having high filler levels |
BRPI0913143A2 (pt) * | 2008-09-10 | 2016-01-05 | Dow Global Technologies Llc | sistema e método de ligação de um adesivo reativo à pelo menos um substrato |
JP5594004B2 (ja) * | 2010-09-14 | 2014-09-24 | 横浜ゴム株式会社 | ガラスの接着方法 |
JP5972910B2 (ja) | 2011-02-17 | 2016-08-17 | ダウ グローバル テクノロジーズ エルエルシー | カルシウムカーボネートを含有するアルコキシシラン含有ポリウレタン接着剤組成物 |
JP2014511931A (ja) | 2011-05-03 | 2014-05-19 | ダウ グローバル テクノロジーズ エルエルシー | イソシアネート官能性プレポリマーを含有する促進された硬化組成物 |
JP5805854B2 (ja) | 2011-05-03 | 2015-11-10 | ダウ グローバル テクノロジーズ エルエルシー | ガラスに対する接合のために有用なデュアルキュア接着剤 |
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US6053971A (en) | 2000-04-25 |
BR9815177B1 (pt) | 2008-11-18 |
KR100590437B1 (ko) | 2006-06-19 |
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ES2223145T3 (es) | 2005-02-16 |
EP1042419B1 (en) | 2004-08-11 |
ATE273357T1 (de) | 2004-08-15 |
CA2314924A1 (en) | 1999-06-24 |
ES2223145T5 (es) | 2008-02-01 |
DE69825627D1 (de) | 2004-09-16 |
DE69825627T2 (de) | 2005-09-22 |
AU741998B2 (en) | 2001-12-13 |
BR9815177A (pt) | 2000-10-10 |
JP2010280901A (ja) | 2010-12-16 |
KR20010033216A (ko) | 2001-04-25 |
JP2002508431A (ja) | 2002-03-19 |
AU1935199A (en) | 1999-07-05 |
DE69825627T3 (de) | 2008-05-21 |
CN1117128C (zh) | 2003-08-06 |
CA2314924C (en) | 2008-01-22 |
EP1042419A1 (en) | 2000-10-11 |
WO1999031191A1 (en) | 1999-06-24 |
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