CN101291886A - 包括含有双-硅烷的蒸溅层与含有氟化烷基硅烷的疏水层的疏水涂层 - Google Patents

包括含有双-硅烷的蒸溅层与含有氟化烷基硅烷的疏水层的疏水涂层 Download PDF

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CN101291886A
CN101291886A CNA2006800337447A CN200680033744A CN101291886A CN 101291886 A CN101291886 A CN 101291886A CN A2006800337447 A CNA2006800337447 A CN A2006800337447A CN 200680033744 A CN200680033744 A CN 200680033744A CN 101291886 A CN101291886 A CN 101291886A
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N·科达兹
A·休格纳德
A·B·德罗斯
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Abstract

本发明涉及玻璃基材、陶瓷、玻璃陶瓷的疏水涂层,其特征在于它包括两层:直接涂布在所述基材上的含有Si-R3-Si基团的蒸溅层,R3选自直链、支链或芳族烷基链,优选地直链烷基链,其中这些两个硅原子之间的成键碳数小于6,优选地1-4;与所述蒸溅层连接的、含有有疏水/疏油全氟末端的烷基硅烷的涂层的层。本发明还涉及在如前面描述的基材上获得这样一种涂层的方法,以及单层、层压或多层玻璃门窗类的基材本身,在其至少一个表面的至少一部分有所述的涂层。

Description

包括含有双-硅烷的蒸溅层与含有氟化烷基硅烷的疏水层的疏水涂层
本发明涉及基材的疏水/疏油处理,该基材特别地是由玻璃、陶瓷、玻璃陶瓷材料等组成的。
本发明的玻璃门窗例如是用玻璃制成的玻璃门窗。它们特别用于航空、铁路或汽车技术领域。它们还可以用于建筑业技术领域或建筑物内部布置技术领域,例如像室内家具、家用电器(冰箱门、拷炉、玻璃储窗)等的装饰板。
人们已知这类处理的目的是使该基材具有非-可润湿性特性,也称之防雨特性。
可润湿性应该理解是这种性质,按照这种性质一些极性液体或非极性液体粘附在该基材上,形成令人不舒服的薄膜,以及基材具有保留任何性质灰尘或污物、手指痕迹、昆虫等的趋势。
水和/或污物的存在对于主要用于运输领域的玻璃门窗类透明基材尤其是令人不舒服的。
亲水或亲油液体与一种基材之间的接触角越大,例如水至少90°,这种基材的非-可润湿性性质,更通常地称之疏水性/疏油性也就越高。如果该基材倾斜或车辆运动时在空气动力学力的作用下,这种液体这时在这种基材上通过单一重力易于以滴的形式流出。赋予这种疏水性/疏油性性质的已知剂例如是如在专利申请EP 0 492 417、EP 0 492 545和EP 0672 779中描述的含氟烷基硅烷。按照这些文件,将在非水有机溶剂中含有含氟有机硅烷的溶液涂敷在该基材表面上可以得到这层。作为非水有机溶剂,文件EP 0 492 545特别列举了n-十六烷、甲苯、二甲苯等。这些溶剂特别适合于含氟氯硅烷。按照这个文件,含氟硅烷为含氟烷氧基硅烷时,使用甲醇或乙醇作为溶剂也是可能的。
通常的疏水/疏油剂特别地是烷基硅烷,其中烷基基团有至少一个全氟化末端,即由F3C-(CF2)n-基团组成,其中n是正整数或零。对此,该专利申请EP 0 719 743指出全氟化碳化物作为合适的溶剂。
在本发明的范围内最尖锐地提出的其中一个问题首先是疏水/疏油涂层的磨损问题。特别为了恢复通过透明基材的令人满意视觉,在定期必不可少的清洁该基材的操作过程中或多或少产生了这种磨损。于是人们不断地寻求减慢渐进除去上述类型疏水/疏油涂层的速度,特别地在汽车挡风玻璃的情况下在刮水器的作用下会产生这种除去。另一方面,这样一种除去还可以是通过紫外辐射由降解造成的。
由上述申请EP 0 492 545 A2还知道,让这种基材在涂敷涂层前进行蒸溅处理,增加该疏水/疏油涂层的粘附性。这种处理在于由所述蒸溅或底漆剂形成中间薄层,这些剂是有至少两个可水解官能的硅化合物。人们熟知,其中一个可水解官能允许该基材通过与硅原子连接的氧原子的化学键;第二个可水解官能允许固定疏水/疏油剂。在申请EP 0 492 545A2中提到作为剂蒸溅的SiCl4、SiHCl3、SiH2Cl2和Cl-(SiCl2O)nSiCl3化合物,n是1-4的整数。
专利EP 944 687更具体地描述了采用液法生产的防雨涂层,它包括由Si(OEt)4或SiCl4类前体得到的二氧化硅溶胶-凝胶基底层或蒸溅层与全氟烷基硅烷基官能层。
为了还改进疏水涂层的机械性能,专利EP 1 102 825描述了在同一层中同时加入氟化烷基硅烷和双-硅烷的疏水/疏油涂层组合物。
然而,如果这样一些底层能够达到与大多数实际UV规格和机械强度一致的性能,例如像汽车制造者强制性规定的性能,特别地是磨损性能,它们一般不是足够化学惰性的,因此通常能够使它们满足耐盐腐蚀标准。
特别地,本申请人进行的试验证明了,在大多数情况下,这样一些涂层难以完成由汽车制造者以这种材料强制性规定的技术任务书,并且该技术任务书是例如根据标准NF ISO 9227通过Brouillard Salin Neutre(BSN)抗性试验测量的。因此,在申请EP 944 687和EP 1 102 825中描述的涂层抗UV性能和机械强度显示出是令人满意的,这些涂层不具有足够的盐腐蚀性能,例如通过BSN试验测量的。这种不充分会限制其发展,特别在这个领域里这些标准最严格的亚洲市场更是如此。
本发明的主要目的是不仅耐磨损和UV辐射,而且还具有高化学惰性的涂层,即它们通常能够满足汽车工业目前强制性规定的技术任务书,抗磨损、UV与盐腐蚀两者。本发明的涂层还具有与今天已知涂层基本相同的性能,有关它们不同用途所需要的其它规格,例如像机械强度、耐水性等。
为此,根据第一个方面,本发明的目的是在优选地由玻璃、陶瓷、或玻璃陶瓷材料构成的基材上得到疏水/疏油涂层的方法,所述方法的特征在于它包括:
a)第一个步骤,该步骤是在所述的基材上涂布由下式蒸溅剂得到的第一蒸溅层:
(X1)3-q(R1)qSi-R3-Si(X2)3-q′(R2)q′
式中:
-Si是硅;
-R3代表直链、支链或芳族碳链,优选地直链碳链,其中这些两个硅原子之间成键碳数小于6,优选地是1-4;
-R1和R2每个都代表烷基或氢原子;
-X1和X2是相同或不同的可水解基团;
-q和q′等于0或1,优选地是零以及
b)第二个步骤,该步骤是在所述第一层上沉积含有至少一种氟化烷基硅烷的疏水涂层。
在本说明书的意义中,两个硅原子成键碳数应该理解是允许两个硅原子间直接连接的最小碳原子数,不是置于该两个硅之间的总碳原子数。在它们之间有支链基团或芳族环时,这种定义是特别直接相关的。作为实例,这个碳数在实施例8描述的双-甲硅烷基乙基苯中等于8。
一般而言,X1和X2是烷氧基基团,优选地甲氧基或乙氧基,或卤化物基团。
例如使用由下述通式表示的这类全氟烷基硅烷得到的溶液实施该疏水涂层沉积步骤:
F3C-(CF2)m-(CH2)n-Si(X)3-P(R)P
式中:
-m=0-15,优选地5-9;
-n=1-5,优选地n=2;
-p=0、1或2,优选地0或1,非常优选地0;
-R是烷基或氢原子;以及
-X是可水解基团,例如卤基团或烷氧基基团。
根据另一种方式,使用由例如像专利EP 844 265、专利申请US2004/0247886或专利US 6 649 272 B2中描述的全氟聚醚硅烷类的全氟烷基硅烷得到的溶液实施疏水涂层沉积步骤。
优选地,所述的全氟聚醚硅烷是用通式表示的这类:
Figure A20068003374400081
或用以下通式表示
式中:
-m=2-30
-n=1-3,优选地n=1
-p=0、1或2,优选地0或1,非常优选地0;
-R是烷基或氢原子;以及
-X是可水解基团,例如卤基团或烷氧基基团。
根据第二个方面,本发明涉及能通过实施如前面描述方法得到的疏水涂层。
本发明更特别地涉及玻璃基材、陶瓷、玻璃陶瓷的疏水涂层,该涂层包括:
-直接涂布在所述基材上的含有Si-R3-Si基团的蒸溅层,R3选自直链、支链或芳族烷基链,优选地直链烷基链,其中这些两个硅原子之间的成键碳数小于6,优选地1-4,
-与所述蒸溅层连接的、含有有疏水/疏油全氟末端的烷基硅烷的涂层的层。
根据第一个方式,所述烷基硅烷是用下述通式表示的这类:
F3C-(CF2)m-(CH2)n-Si
式中:
-m=0-15,优选地5-9;
-n=1-5,优选地n=2。
根据第二个方式,所述烷基硅烷含有全氟聚醚类基团。优选地,所述烷基硅烷是用下述通式表示的这类:
Figure A20068003374400091
或用下述通式表示的这类:
Figure A20068003374400092
式中:
-m=2-30
-n=1-3,优选地n=1。
该疏水层还可以含有第一个方式的具有全氟末端的烷基硅烷和第二个方式的含有全氟聚醚基团的烷基硅烷的混合物或由其混合物组成,例如像申请EP 1 229 085中所描述的。
例如,该蒸溅层的厚度是1-20nm,优选地2-5nm。
该涂层层的厚度可以是1-10nm,优选地1-5nm。
本发明的另一个目的在于一种产品,其外表面往往由玻璃、陶瓷、玻璃陶瓷材料或天然矿物材料构成,该外表面至少部分地有如前面描述的或由如前面描述的方法得到的疏水/疏油涂层。
本发明的产品例如是单层、层压或多层玻璃门窗。
明确指出,应该理解:
″单层玻璃门窗″是由单个玻璃板构成的玻璃门窗。
″层压玻璃门窗″是多个彼此连接薄板的叠层,例如借助聚乙烯缩丁醛,聚氨酯等粘合层将彼此固定的玻璃或塑料板的叠层;以及
″多层玻璃门窗″是多个分开薄板的组合,即特别地通过空气层将彼此分开的多个薄板组合。
这类产品中本发明疏水/疏油涂层的优点是双重的。首先,任选地在空气动力学力的作用下,例如在运动车辆的情况下,它允许在垂直或倾斜表面上的水滴或其它液体滴流走。此外,这些流走液滴包含了这些污物并将它们带走。通过该玻璃门窗的可见度改善达到这样一种程度,以致在某些情况下能够免去清洁设备(洗玻璃机、刮水器)。
最后,本发明的另一个目的的上述产品的应用:
-作为运输车辆或建筑物的玻璃门窗(汽车侧向玻璃、航空或汽车挡风玻璃);
-作为玻璃陶瓷焙烧板,炉门;
-作为城市动产元件,特别地作为公共汽车候车亭的元件;以及
-作为家具构件,特别地如镜子、存放搁板、家用电器器具搁板(例如冰箱)、淋浴间构件、隔墙;
-作为显示屏,特别地电视显示屏、触摸显示屏、等离子体显示屏。
下面实施例用于说明本发明而所描述的任何方面都不限制其保护范围。
在这些实施例中,所有的百分数是以质量百分数给出的。
实施例1
根据这个实施例,制备本发明的第一个试样E1。
把0.3%双(三乙氧基甲硅烷基)乙烷(CH3O)3Si(CH2)2Si(OCH3)3加到含有90%异丙醇和10%0.3N盐酸的溶液中。
同时,制备3%全氟癸基三乙氧基硅烷CF3(CF2)7(CH2)2Si(OC2H5)3在异丙醇(90%)/0.3N盐酸(10%)混合物中的溶液。这两种溶液在搅拌下混合15分钟。
按照第一沉积步骤,然后采用涂布(4次交叉进行)方法将双(三乙氧基甲硅烷基)乙烷基溶液沉积在已预先用氧化铈溶液磨光的玻璃基材空气面上,然后用软化水充分漂洗。如此得到蒸溅层的厚度是约4nm。
一达到该底层沉积,就采用同样的涂布技术再次沉积全氟癸基三乙氧基硅烷溶液。在这个实施例与下述实施例中,采用人们熟知的涂布技术沉积不同的层,其中使用浸透的擦布沉积这种材料或其前体。当然,如果为此目的而采用该技术领域中任何其它已知技术,具体地采用喷射,它还能更好地控制一些层的厚度,采用离心(按照在技术中已知方法英语术语旋涂),采用浸涂(往往称之浸-涂方法)或采用喷淋(往往称之流-涂方法),也没有超出本发明的范围。
在室温下达到15分钟后,用异丙醇洗去过量的氟硅烷。得到的层厚度是约4nm。
在另一个具体方案中,使用同样试剂和采用同样技术制备另一个试样E2,其不同之处是这次在玻璃基材锡面上进行这些相继的沉积。
实施例2:
重复上述制备第二个试样E3的同样步骤,但这次在第一沉积步骤过程中,使用0.4重量%Si(OCH3)4在90重量%乙醇和10重量%水的溶液中的蒸溅溶液处理该玻璃基材空气面。
这时,让如此涂布底层的基材在室温下与3%CF3(CF2)7(CH2)2Si(OC2H5)3在90%乙醇和10%水的混合物中的溶液进行接触,该混合物已用0.3N HCl进行酸化。
实施例3:
根据与前面相同的方式和按照专利EP 1 102 825说明书制备第三个试样E4。
与上述实施例使用的相同玻璃基材在其空气面进行了同样准备,该玻璃基材使用0.4重量%Si(OCH3)4在90%乙醇和10%水的溶液中的蒸溅溶液进行处理。
这时,让这种基材及其蒸溅在室温下与CF3(CF2)7(CH2)2Si(OC2H5)3和(CH3O)3Si(CH2)2Si(OCH3)3(其各自比例为3和1重量%)在90%乙醇和10%水的混合物中的溶液进行接触,该混合物已用0.3N HCl进行酸化。
实施例4:
按照下述标准评价根据实施例1-3制备的四个试样E1、E2、E3和E4:
1°)测量初始水的接触角,它们提供了接枝基材疏水特性的参考指示。
2°)该接枝疏水/疏油涂层按照下述两个不同试验经受磨损后,通过测量残留水在该试样上的接触角所得到的耐磨强度:
a)使用硬度毡H1,在面积1.5cm2上的负荷0.4kg/cm2,移动速度50周/分钟与旋转速度6转/分钟对这些试样进行摩擦试验Opel
Figure A20068003374400111
。如果试样5000周后的接触角依然大于80°,则评定它是令人满意的;
b)在面积4cm2上的负荷0.3kg/cm2,移动速度40周/分钟,同时使用Daiei Kagaku Seiki公司生产的设备,根据标准TSR7503G进行的摩擦试验Toyota
Figure A20068003374400121
。如果试样1500周后的接触角依然大于80°,则评定它是令人满意的;
3°)使用发出UV辐射的氙灯,其300-400nm的整个照度是60W/m2,通过试样的连续照明试验所测量的耐UV-A辐射性。如果试样曝光2000小时后的接触角依然大于80°,则评定它是令人满意的;
4°)通过如根据标准NF ISO 9227描述的Brouillard Salin Neutre(BSN)试验所测量的耐盐腐蚀性。该试验是在温度35℃下喷射细盐水滴(50g/lNaCl溶液,pH=7)。将这些试样倾斜达到与垂直成20°。目前应用于汽车侧向玻璃的最严格现行标准要求在300小时试验后的接触角大于70°。
根据实施例1-3制备这些试样所得到的结果汇集于表1中。
表1
Figure A20068003374400122
表1中列出的数据比较表明,本发明下-蒸溅层的存在导致该处理表面的初始防雨性能与采用现有技术蒸溅所达到的性能相同。
同样地,耐磨强度和抗UV性能是基本相同的,如这些不同试样的Opel
Figure A20068003374400123
、Toyota
Figure A20068003374400124
和UV试验所得到的结果表明的。
包括本发明疏水/疏油涂层的试样E1和E2表明采用BSN试验所测量的耐盐腐蚀性比直到现在已知的涂层好得多。
实施例5-8:
在这些实施例中,证明了在蒸溅层使用的双-硅烷中在这些两个硅原子之间的R3烷基链的性质对最后得到疏水涂层性能的影响。该实验方案与实施例1描述的相同,但以下述方式代替用于得到该蒸溅层的前体:
实施例5:使用双(三乙氧基甲硅烷基)甲烷(CH3O)3Si(CH2)Si(OCH3)3制备试样E5
实施例6:使用双(三乙氧基甲硅烷基)己烷(CH3O)3Si(CH2)6Si(OCH3)3制备试样E6
实施例7:使用双(三乙氧基甲硅烷基)辛烷(CH3O)3Si(CH2)8Si(OCH3)3制备试样E7
实施例8:使用双(三乙氧基甲硅烷基乙基)苯(CH3O)3Si(CH2)2-φ-(CH2)2Si(OCH3)3制备试样E8,其中φ是苯环。
表2列出不同试验得到的结果。
表2
Figure A20068003374400131
可以看出增加R3烷基链的长度不影响耐盐腐蚀性的质量。相反地,该直链碳链含有6个碳原子或6个以上碳原子时,这些耐磨强度试验是不太有利的。

Claims (17)

1.在优选地由玻璃、陶瓷、或玻璃陶瓷材料构成的基材上得到疏水/疏油涂层的方法,所述方法的特征在于它包括:
a)第一个步骤,该步骤是在所述的基材上涂布由下式蒸溅剂得到的第一蒸溅层:
(X1)3-q(R1)qSi-R3-Si(X2)3-q′(R2)q′
式中:
-Si是硅;
-R3代表直链、支链或芳族碳链,优选地直链碳链,其中这些两个硅原子之间成键碳数小于6,且优选地是1-4;
-R1和R2每个都代表烷基或氢原子;
-X1和X2是相同或不同的可水解基团;
-q和q′等于0或1,且优选地是零以及
b)第二个步骤,该步骤是在所述第一层上沉积含有至少一种氟化烷基硅烷的疏水涂层。
2.根据权利要求1所述的方法,其中X1和X2是烷氧基基团,优选地甲氧基或乙氧基,或卤基团。
3.根据权利要求1或2所述的方法,其特征在于使用由下式全氟烷基硅烷得到的溶液实施该疏水涂层沉积步骤:
F3C-(CF2)m-(CH2)n-Si(X)3-P(R)P
式中:
-m=0-15,优选地5-9;
-n=1-5,优选地n=2;
-p=0、1或2,优选地0或1,非常优选地0;
-R是烷基或氢原子;以及
-X是可水解基团,例如卤基团或烷氧基基团。
4.根据权利要求1或2所述的方法,其特征在于使用全氟聚醚硅烷类的全氟烷基硅烷得到的溶液实施该疏水涂层沉积步骤。
5.根据权利要求4所述的方法,其中所述的全氟聚醚硅烷是下式:
或下式:
Figure A20068003374400032
式中:
-m=2-30
-n=1-3,优选地n=1
-p=0、1或2,优选地0或1,非常优选地0;
-R是烷基或氢原子;以及
-X是可水解基团,例如卤基团或烷氧基基团。
6.能通过实施权利要求1-5中任一项权利要求所述方法得到的疏水涂层。
7.玻璃、陶瓷、玻璃陶瓷基材的疏水涂层,其特征在于它包括:
-直接涂布在所述基材上的含有Si-R3-Si基团的蒸溅层,R3选自直链、支链或芳族烷基链,优选地直链烷基链,其中这些两个硅原子之间的成键碳数小于6,且优选地1-4,
-与所述蒸溅层连接的、含有有疏水/疏油全氟末端的烷基硅烷的涂层的层。
8.根据权利要求7所述的疏水涂层,其中所述具有全氟化末端的烷基硅烷是用下述通式表示的这类:
F3C-(CF2)m-(CH2)n-Si
式中:
-m=0-15,优选地5-9;
-n=1-5,优选地n=2。
9.根据权利要求7所述的疏水涂层,其中所述具有全氟化末端的烷基硅烷含有全氟聚醚类的基团。
10.根据权利要求9所述的疏水涂层,其中所述烷基硅烷是用下述通式表示的这类:
Figure A20068003374400041
或用下述通式表示的这类:
Figure A20068003374400042
式中:
-m=2-30
-n=1-3,优选地n=1。
11.根据权利要求7所述的疏水涂层,其中该疏水涂层的层含有根据权利要求8所述的烷基硅烷和根据权利要求9或10所述的烷基硅烷的混合物或由其混合物组成。
12.根据权利要求6-11中任一项权利要求所述的疏水涂层,其中该涂层的层的厚度是1-10nm,优选地1-5nm。
13.产品,其例如由玻璃、陶瓷或玻璃陶瓷材料构成外表面至少部分地有根据权利要求7-12中任一项权利要求所述的或采用根据权利要求1-5中任一项权利要求所述方法得到的疏水/疏油涂层。
14.根据权利要求13所述的产品,它是单层、层压或多层玻璃门窗。
15.根据权利要求13或14中任一项权利要求所述产品作为运输车辆的玻璃门窗或在建筑业中的用途。
16.根据权利要求13或14中任一项权利要求所述产品作为玻璃陶瓷焙烧板或炉门的用途。
17.根据权利要求13或14中任一项权利要求所述产品作为城市动产元件,特别地作为公共汽车候车亭的元件,作为家具构件,特别地如镜子、存放搁板、家用电器器具搁板,例如冰箱、淋浴间构件、隔墙或作为显示屏,特别地电视显示屏、触摸显示屏、等离子体显示屏的用途。
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CN104379633A (zh) * 2012-07-12 2015-02-25 道康宁公司 用于表面处理的组合物、制备经表面处理的制品的方法及经表面处理的制品

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WO2007012779A2 (fr) 2007-02-01
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JP2009502470A (ja) 2009-01-29
US8092913B2 (en) 2012-01-10
BRPI0614106A2 (pt) 2012-11-20
CN101291886B (zh) 2012-07-04
FR2889183A1 (fr) 2007-02-02
KR101321946B1 (ko) 2013-10-30
FR2889183B1 (fr) 2007-09-07
MX2008000999A (es) 2008-04-02
US20090214809A1 (en) 2009-08-27
EP1919836A2 (fr) 2008-05-14
JP5017267B2 (ja) 2012-09-05
KR20080027881A (ko) 2008-03-28
ES2633089T3 (es) 2017-09-19
BRPI0614106B1 (pt) 2017-01-03
PT1919836T (pt) 2017-07-11
WO2007012779A3 (fr) 2007-04-05

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