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Publication numberCN101233173 B
Publication typeGrant
Application numberCN 200680027374
PCT numberPCT/EP2006/004837
Publication date31 Aug 2011
Filing date22 May 2006
Priority date25 May 2005
Also published asCA2609542A1, CA2609542C, CN101233173A, DE602006002821D1, EP1726609A1, EP1883669A1, EP1883669B1, US8187707, US20090104347, WO2006125589A1
Publication number200680027374.6, CN 101233173 B, CN 101233173B, CN 200680027374, CN-B-101233173, CN101233173 B, CN101233173B, CN200680027374, CN200680027374.6, PCT/2006/4837, PCT/EP/2006/004837, PCT/EP/2006/04837, PCT/EP/6/004837, PCT/EP/6/04837, PCT/EP2006/004837, PCT/EP2006/04837, PCT/EP2006004837, PCT/EP200604837, PCT/EP6/004837, PCT/EP6/04837, PCT/EP6004837, PCT/EP604837
Inventors吉斯波特斯德威仕, 吴迪, 明伟华, 鲁道夫安东尼厄斯西奥多瑞斯玛丽亚范本特姆
Applicant帝斯曼知识产权资产管理有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Hydrophobic coating
CN 101233173 B
Abstract
The invention relates to a hydrophobic film or coating, comprising: a) primary particles, b) secondary particles, adhering to the surface of the primary particles and having an average diameter that is smaller than the average diameter of the primary particles, c) a hydrophobic layer covering at least partly the surface of the secondary particles and adhering to that surface, characterized in that the secondary particles are adhering to the surface of the primary particles by covalent chemical bonds.
Claims(17)  translated from Chinese
1.疏水膜或涂层,所述膜或涂层包括:a)初级微粒,b)次级微粒,所述次级微粒粘附到所述初级微粒的表面上,且平均直径小于所述初级微粒的平均直径,c)疏水上部表面层,所述表面层覆盖所述次级微粒的至少一部分表面,且粘附到所述表面上,其特征在于,所述次级微粒通过共价化学键粘附到所述初级微粒的表面上,并且所述次级微粒的平均直径为5至lOOOnm,比所述初级微粒的平均直径小至少5倍。 1. Hydrophobic film or coating, said film or coating comprising: a) primary particles, b) secondary particles, the secondary particles adhere to the surface of the primary particles, having an average diameter smaller than the primary The average diameter of the particles, c) an upper surface of the hydrophobic layer, at least a portion of the surface layer covering the surface of the secondary particles and adhering to said surface, characterized in that the secondary particles by covalent chemical bonds sticky attached to the upper surface of the primary particles and the average diameter of the secondary particles is 5 to lOOOnm, at least 5 times smaller than the average diameter of the primary particles.
2.涂层或膜,包括:a)初级微粒,b)次级微粒,所述次级微粒粘附到所述初级微粒的表面上,且平均直径小于所述初级微粒的平均直径,其中,所述次级微粒通过共价化学键粘附到所述初级微粒的表面上,并且所述次级微粒的平均直径为5至lOOOnm,比所述初级微粒的平均直径小至少5倍。 2. The coating or film, comprising: a) primary particles, b) secondary particles, the secondary particles adhere to the surface of the primary particles and the primary particles have an average diameter smaller than the average diameter, wherein, The secondary particles by covalent chemical bonds adhering to the surface of the primary particles and the average diameter of the secondary particles is 5 to lOOOnm, at least 5 times smaller than the average diameter of the primary particles.
3.如权利要求2所述的膜或涂层,其特征在于,所述涂层或膜还包括上部表面层,所述表面层覆盖所述次级微粒的至少一部分表面,且粘附到所述表面上。 3. The film or coating according to claim 2, characterized in that the coating or film also comprises an upper surface layer, said surface layer covering at least a portion of the surface of the secondary particles and adhering to the said upper surface.
4.如权利要求1或3中任意一项所述的涂层或膜,其特征在于,所述上部表面层通过共价化学键粘附到所述次级微粒的表面上。 1 or 3. The coating or film according to any one of the preceding claims, characterized in that the upper surface of the layer by covalent chemical bonds adhering the secondary particles to the surface.
5.如权利要求1或2所述的膜或涂层,其在初级微粒的平均直径小于300nm时为透明涂层。 5. A film or coating according to claim 1 or claim 2, which is a transparent coating average diameter of the primary particles is less than 300nm.
6.如权利要求1或2所述的涂层或膜,其特征在于,所述初级微粒或所述次级微粒通过共价化学键粘附到一基材上。 Coating or film according to 1 or 2 as claimed in claim wherein said primary particles or the secondary particles by covalent chemical bonds adhering to a substrate.
7.如权利要求1或2所述的涂层或膜,其特征在于,所述初级微粒或所述次级微粒通过共价化学键粘附到一支撑层上。 7. A coating or film according to claim 1 or claim 2, characterized in that the primary particles or the secondary particles by covalent chemical bonds adhering to a supporting layer.
8.如权利要求1或2所述的涂层或膜,其特征在于,所述初级微粒的平均直径为0. 1至20 μ m0 8. A coating or film according to claim 1 or claim 2, wherein said primary particles have an average diameter of 0. 1 至 20 μ m0
9.如权利要求1或2所述的涂层或膜,其特征在于,使次级微粒粘附到初级微粒表面的共价化学键通过在初级微粒表面上的反应性官能团I和在次级微粒表面上的反应性官能团II进行反应而形成,其中所述反应性官能团I与所述反应性官能团II互补。 9. A coating or film according to claim 1 or claim 2, characterized in that, to make the primary particles adhered to the surface covalently bond the reactive functional group through I on the surface of the primary particles and the secondary particles in the secondary particles reactive functional groups on the surface is formed by reacting II, wherein the reactive functional group I and II of the complementary reactive functional groups.
10.如权利要求4所述的涂层或膜,其特征在于,使上部表面层粘附到次级微粒表面的共价化学键通过在次级微粒表面上的反应性官能团II和在疏水层上的反应性官能团I或III进行反应而形成,其中所述反应性官能团II与所述反应性官能团I和III互补。 10. 4 wherein the coating or film on the secondary particle surface by a reactive functional group in the hydrophobic layer II and the claims, characterized in that the upper surface layer is adhered to the surface of the particles covalently bond the secondary reactive functional group I or III reacting form, wherein the reactive functional group II with the reactive functional groups I and III complementary.
11.如权利要求9所述的涂层或膜,其特征在于,所述反应性官能团和相应的互补反应性官能团选自由酸和环氧、胺和环氧、羟基和环氧、硅烷醇和环氧、硫醇和环氧、硫醇和异氰酸酯、羟基和异氰酸酯、胺和异氰酸酯、酸和吖丙啶、酸和碳酰亚胺、胺和酮、胺和醛组成的组。 11. A coating or film according to claim 9, wherein the reactive functional group and corresponding complementary reactive functional groups selected from acid and epoxy, amine and epoxy, hydroxyl and epoxy, silanol and ring group oxygen, thiol and epoxy, thiol and isocyanate, hydroxyl and isocyanate, amine and isocyanate, acid and aziridine, acid and carbon imide, amines and ketones, amines and aldehydes formed.
12.如权利要求11所述的涂层或膜,其特征在于,选择胺和环氧作为反应性官能团和互补反应性官能团。 12. A coating or film according to claim 11, characterized in that the selection amine and epoxy as a reactive functional group and the complementary reactive functional groups.
13.用于制备权利要求1和权利要求3至12中任意一项所述膜或涂层的部件工具包,所述工具包包括:1)包括初级微粒的组合物,所述初级微粒已与次级微粒发生反应从而其表面被次级微粒覆盖,2)疏水层用组合物,所述组合物包括疏水化合物或聚合物。 13. A preparation according to claim 1 and claims 3-12 in any one of the film or coating of parts kits, the kit includes: 1 primary particles) a composition comprising the primary particles, which have been and Secondary particles which react whereby the secondary particle surface is covered, 2) a hydrophobic layer composition, said composition comprising a hydrophobic compound or polymer.
14.用于制备权利要求7至12中任意一项所述膜或涂层的部件工具包,所述工具包包括:1)包括初级微粒的组合物,所述初级微粒已与次级微粒发生反应,从而其表面被次级微粒覆盖,2)支撑层用组合物,所述组合物包括能够与初级或次级微粒形成共价化学键的化合物。 14. A preparation as claimed in claim any one of claims 7-12 or a film coating member kit, said kit comprising: a) a composition comprising the primary particles, the primary particles and the secondary particles has occurred The reaction, so that its surface is covered with secondary particles, 2) a support layer with a composition, said composition comprising a compound capable of covalent bond formation with a primary or secondary particles.
15.用于涂敷权利要求1至12中任意一项所述涂层或膜的方法,所述方法包括如下步骤:1)将包括已与次级微粒反应从而表面被次级微粒覆盖的初级微粒的组合物涂敷到在基材或支撑层上并且固化,以使次级微粒与支撑层发生反应;2)涂敷上部表面层用涂层组合物并且固化,以使上部表面层粘附到次级微粒上。 15. A method for the coating of claims 1 to 12, or any one of the coating film, the method comprising the following steps: 1) have been reacted with secondary particles comprises a surface is covered with secondary particles so that the primary The composition was applied to the particles on a substrate or support layer and cured, so that the secondary particles to react with the supporting layer; 2) an upper surface coated with a layer of the coating composition and cured, adhered to the upper surface of the layer to the secondary particles.
16.如权利要求15所述的方法,其中,所述固化在10至250C的温度下进行。 16. The method of claim 15, wherein said cured at 250 C Temperature 10 to be.
17.如权利要求15或16所述的方法,其中,已与次级微粒反应从而表面被次级微粒覆盖的初级微粒是覆盆子型微粒。 17. A method as claimed in claim 15 or 16, wherein the secondary particle has reacted with the surface to be covered so that the primary particles are secondary particles raspberry-type microparticles.
Description  translated from Chinese

疏水涂层 Hydrophobic coating

[0001] 本发明涉及一种涂层,用于制备所述涂层的部件工具包和用于涂敷所述涂层的方法。 [0001] The present invention relates to a coating, for the preparation of the coating member kit and method for applying the coating. 优选地,根据本发明的涂层是疏水涂层,甚至可以是超疏水涂层。 Preferably, the coating of the present invention is a hydrophobic coating, or even a super-hydrophobic coating.

[0002] 疏水涂层在许多应用领域越来越受欢迎,例如在门窗、TV屏、DVD光盘、烹调器具、 服装、医学器械等中,这是因为所述疏水涂层易于清洁且具有低粘附性。 [0002] The hydrophobic coating increasingly popular in many applications, such as doors and windows, TV screens, DVD discs, cooking utensils, clothing, medical equipment, etc., this is because the hydrophobic coating is easy to clean and has a low viscosity attached sex. 一般而言,疏水材料或涂层的特征在于,静态水接触角(Θ)为90或更高。 Generally, a hydrophobic material or coating is characterized by static water contact angle (Θ) is 90 or greater. 近十年来,可用的疏水聚合材料例如为聚(四氟乙烯)(PTFE)或聚丙烯(PP)。 Over the past decade, available hydrophobic polymeric materials such as poly (tetrafluoroethylene) (PTFE) or polypropylene (PP). 这些材料的疏水性有限,另外与工程材料或高度交联的涂层相比具有较差的机械性质。 The hydrophobic material is limited, and additional engineering materials or highly crosslinked coating having inferior mechanical properties compared. 例如PP的静态水接触角约为100,而已知最为疏水的聚合材料PTFE具有约为112的静态水解触角。 E.g. PP static water contact angle of about 100 , while the most hydrophobic polymeric material known PTFE having a static hydrolysis of about 112 antennae.

[0003] 在本领域中,一些疏水涂层被称为超疏水涂层。 [0003] In the present art, some of the hydrophobic coating is called superhydrophobic coatings. 超疏水涂层通常被定义为静态水解触角大于140。 Superhydrophobic coating is usually defined as a static antennae hydrolysis greater than 140 .

[0004] 在自然界中发现了一些具有超疏水性质的表面,例如睡莲叶或甘蓝叶。 [0004] found some superhydrophobic properties of the surface in nature, such as water lily leaves or cabbage leaves. 在叶片粗糙表面上分泌出的蜡降低了水和污染颗粒对叶片的粘附性。 Rough surface on the blade secrete wax reduces the water and pollution particles adhesion to the blade. 堆积在叶片上的水滴完全滚落(roll off),同时收集污垢微粒并在该过程中清洁叶片。 Water droplets deposited on the blades fully rolled (roll off), while collecting the dirt particles and cleaning blade in the process.

[0005] 通过将微米尺寸级的球形微粒掺入硅酮基涂料或聚烯烃基喷雾中可以得到疏水性提高的涂层(BASF Press release October 28 2002,P345e, DrKarin Elbl-ffeiser, Lotusan,Nature news service/Macmillan Magazines Ltd2002) 。 [0005] by the level of micron-sized spherical particles incorporated into the silicone-based or polyolefin-based spray paint can be improved hydrophobic coating (BASF Press release October 28 2002, P345e, DrKarin Elbl-ffeiser, Lotusan, Nature news service / Macmillan Magazines Ltd2002). ;

用作喷雾,但是具有机械强度差的缺陷。 As spray, but has poor mechanical strength deficiencies. 这种涂层的耐磨性很低,因而在维持表面疏水功能一段时间后,需要重新涂敷该涂层。 The wear resistance of such coatings is low, thus maintaining the surface of the hydrophobic functional for some time, the need to re-applied coating. 另外,由于该涂层在可见光范围内使光线发生散射,因而使涂层昏暗且在光学上不透明。 Further, since the coating in the visible range so that scattering of light occurs, and thus the coating is optically opaque and dark.

[0006] 在US6068911中,Hitachi描述了一种超疏水涂层,该涂层也是基于通过UV固化含有非反应性纳米微粒和含氟聚合物的树脂来制备粗糙表面的原理。 [0006] In the US6068911, Hitachi described a superhydrophobic coating layer by UV curing resin also containing a non-reactive nano-particles and a fluorine-containing polymer is prepared based on the principle of a rough surface. 所述涂层配制品由至少两种溶剂组成,挥发性最强的溶剂的挥发驱使含氟聚合物聚集到表面,从而使表面疏水。 The coating formulation consisting of at least two solvents, the most volatile solvent volatilization driven to the surface of the fluoropolymer aggregate, so that the surface hydrophobic. 惰性非反应性纳米微粒的存在导致表面粗糙,从而整个涂层具有超疏水性。 Presence of an inert non-reactive nano-particles results in surface roughness, so that the entire coating has a superhydrophobic. 因为这项技术基于溶剂蒸发从而在该过程中产生表面粗糙度,所以动力学在该过程中起一定作用。 Because the technology is based on evaporation of the solvent to produce a surface roughness in the process, so the dynamics play a role in this process. 但涂层的硬度、持久性和耐磨性不令人满意。 But the coating hardness, durability and wear resistance is unsatisfactory.

[0007] 另一种途径是,使用非耐磨层,该层由在固定基质层上的移动含氟试剂库不断补充,其中在顶部,经气相沉积的无机材料顶层粗糙度很大且具有很多裂纹(W0 01/92179)。 [0007] Another approach is to use a non-wear-resistant layer which constantly replenished by a matrix layer on the fixed mobile fluorinated reagent storage, wherein at the top, the top layer by vapor deposition of an inorganic material and having a large number of roughness Crack (W0 01/92179). 该方法的思路在于,含氟聚合物通过无机层扩散,并覆盖在该层上,因而形成可再生的表面层。 Thinking of this method is that the fluoropolymer through the inorganic layer diffusion, and overlying the layer, thus forming the surface layer can be regenerated. 这使得硬质且在光学上清澈的表面具有高水接触角和非常低的滚落角(roll-off angle)。 This makes it hard and optically clear surface with a high water contact angle and very low sliding angle (roll-off angle). 然而通过气相沉积生成这种复杂结构的过程非常费时费力,并且可以涂敷的面积也很有限。 However, by vapor deposition process of generating such a complex structure it is very time-consuming, and the area can be applied is limited. 而且可移动含氟聚合物的释放和冲洗对环境不利。 And can release mobile fluoropolymer and rinse for the environment.

[0008] 本发明的目的在于,提供一种易于生产、可再生且具有非常良好机械性质的疏水涂层。 [0008] The object of the present invention is to provide an easy to produce, renewable and has very good mechanical properties of the hydrophobic coating.

[0009] 令人惊奇地,该目的通过如下膜或涂层来实现,所述疏水膜或涂层包括: [0009] Surprisingly, this object is achieved by the following film or coating is achieved, the hydrophobic film or coating comprising:

[0010] a)初级微粒, [0010] a) primary particles,

[0011] b)次级微粒,所述次级微粒粘附到所述初级微粒的表面上,且平均直径小于所述初级微粒的平均直径, [0011] b) secondary particles, the secondary particles adhere to the surface of the primary particles, having an average diameter smaller than the average diameter of the primary particles,

[0012] c)疏水上部表面层,所述表面层覆盖所述次级微粒的至少一部分表面,且粘附到所述表面上, At least a portion of the surface [0012] c) an upper surface of the hydrophobic layer, the surface layer covering the secondary particles and adhering to said surface,

[0013] 其中,所述次级微粒通过共价化学键粘附到所述初级微粒的表面上。 [0013] wherein, the secondary particles by covalent chemical bonds adhering to the surface of the primary particles.

[0014] 根据本发明涂层的优点在于,根据本发明制备的涂层规整且品质恒定。 [0014] An advantage of the present invention, the coating that regular and constant quality coating according to the present invention is prepared.

[0015] 根据本发明涂层的另一个优点在于,该涂层具有非常高的耐磨性和/或耐擦伤性。 [0015] According to another advantage of the invention is that the coating, the coating has a very high wear resistance and / or scratch resistance.

[0016] 根据本发明涂层的另一个优点在于,根据本发明的涂层易于生产。 [0016] Another advantage of the present invention, the coating that is easy to produce the coating according to the present invention.

[0017] 根据本发明涂层的另一个优点在于,该涂层不含任何氟原子。 [0017] Another advantage of the present invention is that the coating, the coating does not contain any fluorine atoms.

[0018] 在包括覆盆子型微粒的层面上,除了使用疏水上部表面层以外,还可以使用不同种类的上部表面层,例如亲水层、具有吸收性质的层(例如用于吸收气味或散发香味)、具有催化活性的层(例如用于氧化消除空气污染)等。 [0018] In the level raspberries type comprising fine particles, except that an upper surface of the hydrophobic layer, may be used in different types of upper surface layers, for example a hydrophilic layer, a layer having absorbing properties (e.g., for absorbing odor or scent ), catalytically active layer (e.g., for the elimination of air pollution oxide) and the like. 甚至还可以是,根本不存在任何粘附到次级微粒的表面的层。 Or it may also be simply adhered to the secondary layer of any particle surface does not exist.

[0019] 以上述方法得到一种新型、独一无二的涂层或膜,该涂层或膜具有各种应用潜力, 这是因为其特定结构以及初级微粒和次级微粒之间的共价化学键。 [0019] In the above-described method to obtain a new and unique coating or film, the coating or film has a variety of potential applications, because of its specific structure and the covalent primary particles and secondary particles between bond. 这种涂层或膜的优点之一是,由于具有覆盆子型微粒结构,因此得到的涂层具有高比表面积。 One advantage of this coating or film is that due to the particles having a raspberry-type structure, thereby obtaining a coating having a high specific surface area. 因此,本发明还涉及一种涂层或膜,所述涂层或膜包括: Accordingly, the present invention also relates to a coating or film, the coating or film comprising:

[0020] a)初级微粒 [0020] a) primary particles

[0021] b)次级微粒,所述次级微粒粘附到所述初级微粒的表面上,且平均直径小于所述初级微粒的平均直径, [0021] b) secondary particles, the secondary particles adhere to the surface of the primary particles, having an average diameter smaller than the average diameter of the primary particles,

[0022] 其中,所述次级微粒通过共价化学键粘附到所述初级微粒的表面上。 [0022] wherein, the secondary particles by covalent chemical bonds adhering to the surface of the primary particles.

[0023] 优选地,涂层或膜还包括上部表面层,所述上部表面层覆盖在所述次级微粒的至少一部分表面,且粘附到上述表面上。 [0023] Preferably, the coating or film also comprises an upper surface layer, the upper surface layer covering at least a portion of the surface of the secondary particles and adhering to said surface. 上部表面层是最后涂敷且形成涂层表面的层面。 The upper surface of the last layer is applied and the level of the coating surface is formed. 优选地,上部表面层的厚度很薄,以致于可在涂层的上部表面上至少部分观察微粒的结构。 Preferably, the thickness of the upper surface of the thin layer, so that at least part of the structure can be observed on the upper surface of the particles of the coating. 更优选地,上部表面层的厚度约等于或小于初级微粒平均直径的三倍,更优选地,该层的厚度等于或小于初级微粒平均直径。 More preferably, the thickness of the upper surface of the layer is about equal to or less than three times the average diameter of the primary particles, and more preferably, the layer has a thickness equal to or less than the average diameter of the primary particles. 最优选地,该层的厚度等于或小于初级微粒平均直径的0. 5 倍。 Most preferably, the layer has a thickness equal to or less than 0.5 times the average diameter of the primary particles. 厚度优选大于1纳米,更优选大于2纳米。 The thickness is preferably greater than 1 nm, more preferably greater than 2 nm.

[0024] 优选地,上部表面层也通过共价化学键粘附到次级微粒的表面上。 [0024] Preferably, the upper surface layer is also adhered by covalent chemical bonds to the surface of the secondary particles. 这进一步改善了本发明涂层的机械性质。 This further improves the mechanical properties of the coating of the present invention.

[0025] 更优选地,初级微粒或次级微粒通过共价化学键粘附到基材上。 [0025] More preferably, the primary particles or secondary particles by covalent chemical bonds adhering to the substrate. 以这种方式得到的涂层具有进一步改善的耐擦伤性和对基材较高的粘附性。 The coatings obtained in this manner have further improved scratch resistance and high adhesion to the substrate.

[0026] 最优选地,初级微粒或次级微粒通过共价化学键粘附到支撑层上。 [0026] Most preferably, the primary particles or secondary particles by covalent chemical bonds adhering to the support layer. 例如如果基材不包括能与微粒形成共价化学键的反应性官能团,那么基材可被支撑层覆盖。 For example if the substrate does not include the ability to form covalent chemical bonds with the particles of the reactive functional group, then the substrate support layer can be covered.

[0027] 如果次级微粒的平均直径比初级微粒的平均直径小至少5倍,则得到良好的结果。 [0027] If the average diameter of the secondary particles is smaller than the average diameter of the primary particles of at least 5 times, good results are obtained. 这使得静态水接触角较高且水滚落角较低,因而提供了改善的自清洁性质。 This makes the static water contact angle and high water sliding angle is low, thus providing an improved self-cleaning properties.

[0028] 优选地,次级微粒的平均直径比初级微粒的平均直径小8倍、更优选小10倍、甚至更优选小20倍,然而还要更优选小40倍。 [0028] Preferably, the average diameter of the secondary particles is 8 times smaller than the average diameter of the primary particles, more preferably 10 times smaller, even more preferably 20 times smaller, yet still more preferably 40 times smaller.

[0029] 初级微粒的平均直径可以在0. 1至20 μ m的范围内。 [0029] The average diameter of the primary particles can be in the range of 0. 1 至 of 20 μ m. 优选地,初级微粒的平均直径在0. 5至10 μ m的范围内,更优选在0. 6至5 μ m的范围内,最优选在0. 6至3 μ m的范围内。 Preferably, the average diameter of the primary particles in the range of 0. 5 至 10 μ m, and more preferably in the range of 0. 6 至 5 μ m, and most preferably in the range of 0. 6 至 of 3 μ m. 以这种方式得到有利的自清洁性质。 In this manner favorable self-cleaning properties.

[0030] 次级微粒的平均直径可以在5至IOOOnm的范围内。 [0030] The average diameter of the secondary particles may be in the range of 5 to IOOOnm. 优选地,次级微粒的平均直径在10至500nm的范围内,更优选在30至300nm的范围内,最优选在40至60nm的范围内。 Preferably, the average diameter of the secondary particles is in the range 10 to 500nm, more preferably in the range of 30 to 300nm, most preferably in the range of 40 to 60nm. 以这种方式得到透明的涂层。 In this manner a transparent coating.

[0031] 如果初级微粒的平均直径小于300nm,则得到理想的透明涂层。 [0031] If the average diameter of the primary particles is less than 300nm, preferably transparent coating is obtained.

[0032] 最优选地,初级微粒的平均直径在0. 3至3 μ m的范围内,次级微粒的平均直径在10至IOOnm的范围内。 [0032] Most preferably, the average diameter of the primary particles in the range of 0. 3 至 3 μ m, the average diameter of the secondary particles is within the range of 10 to IOOnm.

[0033] 用于测定微粒尺寸的方法包括:透射电子显微镜(TEM)成像、扫描电子显微镜(SEM)成像和原子力显微镜(AFM)成像。 Method [0033] for the determination of particle size comprising: a transmission electron microscope (TEM) imaging, scanning electron microscopy (SEM) and atomic force microscopy image (AFM) imaging.

[0034] 为了测量微粒的尺寸,将在非常稀释的混合物中的微粒涂敷到薄层的表面上,从而在薄层的TEM图像中仅可观察到单一微粒。 [0034] In order to measure the size of particles, in a very dilute mixture applied to the surface of the thin layer of fine particles, so that a thin layer in the TEM image can be observed in only a single particle. 然后对100颗随意选择的微粒的尺寸进行测量,并计算平均值。 Then the size of the 100 randomly selected particles are measured, and calculate the average. 在微粒并非为球形的情况下,对于直径,测量由微粒的一侧向另一侧画线得到的最长直线。 In the case where the particles are not spherical, the diameter of the particles measured by a side to the other side of the longest straight line drawing obtained.

[0035] 优选地,微粒的长径比小于2,优选小于1. 5,更优选小于1. 2,最优选小于1. 1。 [0035] Preferably, the aspect ratio, fine particles of less than 2, preferably less than 1.5, more preferably less than 1.2, most preferably less than 1.1. 长径比为dl (由微粒的一侧向另一侧画线得到的最长直线)与d2(由微粒的一侧向另一侧画线得到的最短直线)之间的比值。 The ratio aspect ratio dl (by the side of the microparticles get to the other side of the longest straight line drawing) and d2 (by the side of the microparticles get to the other side of the line drawing shortest straight line) between.

[0036] 优选地,至少80%微粒的直径为平均直径的50%至200%。 [0036] Preferably, at least 80% of the particles having a diameter of 50 to 200% of the average diameter.

[0037] 初级微粒和次级微粒可以是有机微粒或无机微粒。 [0037] The primary particles and secondary particles may be organic particles or inorganic particles. 有机微粒的实例为,碳纳米球。 Examples of the organic fine particles is carbon nanoparticles. 优选地,初级微粒和次级微粒是无机微粒。 Preferably, the primary particles and secondary particles are inorganic particles. 适当的无机微粒例如为氧化物微粒。 Suitable inorganic oxide fine particles such as fine particles. 优选的氧化物微粒是选自如下氧化物的微粒:氧化铝、氧化硅、氧化锆、氧化钛、氧化锑、氧化锌、氧化锡、氧化铟和氧化铈。 Preferred oxide particles are particles selected from the oxides: alumina, silica, zirconia, titania, antimony oxide, zinc oxide, tin oxide, indium oxide and cerium oxide. 还可以使用由不同氧化物得到的微粒的混合物,或使用混合氧化物得到的微粒。 You can also use a mixture of different oxide particles obtained, or get mixed oxide particles. 最优选地,微粒是氧化硅的微粒。 Most preferably, the particles are microparticles of silicon oxide.

[0038] 如果使次级微粒粘附到初级微粒表面的共价化学键通过在初级微粒表面上的反应性官能团I和在次级微粒表面上的反应性官能团II进行反应而形成,则得到良好的结果,其中所述反应性官能团I与反应性官能团II互补。 [0038] If the secondary particles adhering to the surface of primary particles covalent bond by a reactive functional group I and reactive functional groups on the surface of primary particles on the surface of the secondary particles are formed by reacting II, then get a good As a result, wherein the reactive functional group reactive functional groups I and II complementary. 这意味着,第一反应性官能团与第二反应性官能团发生反应,但是第一和第二反应性官能团自身不会发生反应。 This means that the first reactive functional group and a second reactive functional group reacts, but the first and the second reactive functional group reaction itself does not occur. 这使得次级微粒粘附到初级微粒上,而初级微粒不会粘附到初级微粒上并且次级微粒也不会粘附到次级微粒上。 This makes the secondary particles adhering to the primary particles, and primary particles do not adhere to the primary particles and the secondary particles does not adhere to the secondary particles. 以这种方式得到所谓的覆盆子型(raspberry)微粒,其中次级微粒以单层形式基本上覆盖初级微粒的表面。 In this manner a so-called raspberry-type (raspberry) particles, wherein the secondary particles form substantially a single layer to cover the surface of the primary particles. 这种覆盆子型结构非常有利于获得自清洁性质。 This raspberry-type structure is very beneficial to obtain self-cleaning properties.

[0039] 同样令人期望的是,使上部表面层粘附到次级微粒表面的共价化学键通过在次级微粒表面上的反应性官能团II和在疏水层上的反应性官能团I或III进行反应而形成,其中所述反应性官能团II与反应性官能团I和III互补。 [0039] It is also desirable that the upper surface of the layer of particles adhered to the surface of the secondary covalent chemical bonds on the secondary particle surface by a reactive functional group II and reactive functional groups on the hydrophobic layer I or III, formed by the reaction, wherein the reactive functional group reactive functional groups II and I and III complementary.

[0040] 使次级微粒粘附到支撑层的共价化学键通过在次级微粒表面上的反应性官能团II和在支撑层上互补的反应性官能团I或III或IV进行反应而形成,这也是令人期望的。 [0040] so that the support layer is adhered to the covalent bond is formed by the secondary particle surface reactive functional groups on the support layer II and the complementary reactive functional group I or III or IV reacting secondary particles, which is desirable.

[0041] 适用于在本发明的涂层中形成共价化学键的成对反应性官能团与相应的互补反应性官能团的实例由包括酸和环氧、胺和环氧、羟基和环氧、硅烷醇和环氧、硫醇和环氧、硫醇和异氰酸酯、羟基和异氰酸酯、胺和异氰酸酯、酸和吖丙啶、酸和碳酰亚胺、胺和酮、胺和醛的组组成。 [0041] Examples of suitable and appropriate complementary reactive functional groups covalently bond pairs of reactive functional groups in the coating of the present invention is formed by including acids and epoxy, amine and epoxy, hydroxyl and epoxy, silanol epoxy, thiol and epoxy, thiol and isocyanate, hydroxyl and isocyanate, amine and isocyanate, acid and aziridine, acid and carbon imides, amines and ketones, amines and aldehydes sets.

[0042] 如果环氧和胺官能团用于形成共价化学键,则得到非常好的结果。 [0042] If epoxy and amine functional groups to form a covalent bond, then get very good results. [0043] 作为疏水上部表面层,可用层包括含有氟原子的化合物、聚合物或经固化的聚合材料,所述化合物、聚合物或经固化的聚合材料的至少一部分通过共价化学键键合到次级微粒上。 [0043] As an upper layer of hydrophobic surface, can be used a compound containing a layer comprising a fluorine atom, polymers or cured polymeric material, the compound, the polymer or the cured polymeric material is at least a portion of chemically by covalent bonding to the secondary on the particle level. 例如上述化合物、聚合物或经固化的聚合材料包括-CF2-或-CF3基团。 Such as the aforementioned compounds, polymers or cured polymeric materials include -CF2- or -CF3 group.

[0044] 化合物的例子包括2-全氟辛基-乙醇、2-全氟己基-乙醇、2-全氟辛基-乙胺、 2-全氟己基-乙胺、2-全氟辛基-乙酸、2-全氟己基-乙酸、3-全氟辛基-环氧丙烷、3-全氟己基-环氧丙烷。 Examples of the compound [0044] include 2-perfluorooctyl - ethanol, 2-perfluorohexyl - ethanol, 2-perfluorooctyl - ethylamine, 2- perfluorohexyl - ethylamine, 2-perfluorooctyl - acid, 2-perfluorohexyl - acetic acid, 3-perfluorooctyl-- oxide, 3-perfluorohexyl - propylene oxide.

[0045] 聚合物的例子包括全氟聚醚(PFP)。 Examples [0045] polymers include perfluoropolyether (PFP).

[0046] 优选地,作为疏水上部表面层,可用层包括如下聚合物,该聚合物包括硅烷或硅氧烷单体单元,且所述聚合物的至少一部分通过共价化学键键合到次级微粒上。 [0046] Preferably, the hydrophobic surface as an upper layer, usable layer comprising the polymer comprises silane or siloxane monomeric units, and at least a portion of the polymer by covalent chemically bonded to the secondary particles on. 以这种方式得到的涂层非常耐擦伤,还具有非常良好的耐候性。 In this way, the resulting coating is very resistant to abrasion, but also has very good weather resistance. 上述单体单元的例子包括,二甲氧基硅氧烷、乙氧基硅氧烷、甲基辛基硅氧烷、甲基乙烯基硅氧烷、三甲基硅氧烷、二甲基硅氧烷、 甲基苯基硅氧烷、二乙基硅氧烷、三氟丙基甲基硅氧烷、甲基苯基硅烷。 Examples of the above monomer unit include, dimethoxy siloxane, siloxane ethoxylates, methyloctyl siloxane, methyl vinyl siloxane, trimethyl siloxane, dimethyl silicone siloxane, methylphenyl silicone, diethyl silicone, trifluoropropyl methyl siloxane, methylphenyl silane.

[0047] 聚合物的例子包括如下聚二甲基硅氧烷,其中该聚二甲基硅氧烷的端基采用反应性官能团官能化,优选采用环氧基或氨基官能化,诸如单(3-氨基丙基)-聚二甲基硅氧烷、 单(3-缩水甘油醚基丙基)聚二甲氧基硅氧烷、双(3-氨基丙基)-聚二甲基硅氧烷和双(3-缩水甘油醚基丙基)_聚二甲基硅氧烷。 Examples [0047] polymer comprises polydimethylsiloxane, wherein the polydimethylsiloxane reactive end group functionalized functional group, preferably an amino group or an epoxy-functional, such as mono (3 - aminopropyl) - polydimethylsiloxane, mono (3- propyl ether) poly dimethoxy silicone, bis (3-aminopropyl) - polydimethylsiloxane and bis (3-propyl glycidyl ether) _ polydimethylsiloxane.

[0048] 本领域技术人员了解如何制备初级和次级微粒,且如何为上述微粒的表面提供适于形成共价化学键的反应性官能团。 [0048] skilled in the art understand how to prepare the primary and secondary particles and how to provide the surface of the particles suitable for the formation of covalent chemical bonds reactive functional groups. Stdber等在J. Coll. Interface Sci. 1968,26,第62页中公开了非常适于制备本发明涂层的初级微粒和次级微粒的方法。 Stdber et al. Discloses a method of primary particles and secondary particles are very suitable for the preparation of the present invention is coated in J. Coll. Interface Sci. 1968,26, page 62. 该方法包括:将四烷氧基硅烷溶于诸如乙醇的适当溶剂中,然后在搅拌的同时,使硅烷与水在催化剂的存在下发生反应,从而形成微粒。 The method comprising: tetraalkoxysilane dissolved in a suitable solvent such as ethanol, and while stirring, the silane and water react in the presence of a catalyst, to form microparticles.

[0049] 此后,通过使微粒与例如官能化有机硅氧烷(例如3-缩水甘油醚基丙基三烷氧基硅烷或3-氨基丙基-三烷氧基硅烷)进行反应,从而使所述微粒具有反应性官能团。 [0049] Thereafter, for example, by reacting the particles with the functional organosiloxane (e.g., glycidyl propyl 3- trialkoxy silane or 3-aminopropyl - trialkoxysilane) to react, so that the said microparticles having a reactive functional group. 优选地,3-缩水甘油醚基丙基三甲氧基硅烷或3-氨基丙基-三乙氧基硅烷用于上述反应。 Preferably, 3-glycidyl propyl trimethoxy silane or 3-aminopropyl - triethoxysilane used in the above reaction.

[0050] 微粒,可选在电荷控制剂(例如酸、碱或表面活性剂)的协助下,分散在水中、乙醇中或水/乙醇混合物中,从而形成适于涂敷含有微粒的层的组合物。 [0050] particles, optionally with the assistance of the charge control agent (e.g. an acid, alkali or surfactant), and dispersed in water, ethanol, water / ethanol mixture or to form a suitable coating composition containing fine particles layer thereof. 该组合物优选不包括其它固体组分或仅包括有限量的其它固体组分,当制备本发明的涂层时,上述有限量使得微粒不会包埋在上述组分中或仅部分包埋在上述组分中。 The composition preferably does not include other solid components or include only a limited amount of other solid components, when the coating of the present invention may be prepared, so that a limited amount of the aforementioned fine particles in the above-described components will not be embedded or partially embedded only in the above-described components.

[0051] 本发明还涉及一种部件工具包,所述工具包包括: [0051] The present invention also relates to a parts kit, the kit includes:

[0052] 1)包括初级微粒的涂层组合物, [0052] 1) comprises primary particles of the coating composition,

[0053] 2)包括次级微粒的涂层组合物, [0053] 2) includes a secondary particle coating composition,

[0054] 3)疏水上部表面层用组合物,包括疏水化合物或聚合物。 [0054] 3) an upper surface of the hydrophobic layer composition comprising a hydrophobic compound or polymer.

[0055] 本发明还涉及一种部件工具包,所述工具包包括: [0055] The present invention also relates to a parts kit, the kit includes:

[0056] 1)包括初级微粒的组合物,所述初级微粒已与次级微粒发生反应,从而其表面被次级微粒覆盖, [0056] 1) a composition comprising the primary particles, said primary particles have been reacted with secondary particles, so that a secondary particle whose surface is covered,

[0057] 2)疏水层用组合物,包括疏水化合物或聚合物。 [0057] 2) a hydrophobic layer composition comprising a hydrophobic compound or polymer.

[0058] 本发明还涉及一种用于制备本发明膜或涂层(包括支撑层)的部件工具包,所述工具包包括: [0058] The present invention also relates to a kit for the preparation of the present invention means a film or coating (including support layer), said kit comprising:

[0059] 1)包括初级微粒的组合物,所述初级微粒已与次级微粒发生反应,从而其表面被 [0059] 1) a composition comprising the primary particles, the primary particles have been reacted with secondary particles, so that its surface is

7次级微粒覆盖, 7 secondary particles covered

[0060] 2)支撑层用组合物,所述组合物包括能够与初级或次级微粒形成共价化学键的化合物。 [0060] 2) a support layer with a composition, said composition comprising a compound capable of covalent bond formation with a primary or secondary particles.

[0061 ] 本发明还涉及用于涂敷本发明涂层的方法。 [0061] The present invention also relates to a method for applying a coating of the present invention.

[0062] 在一个实施方式中,所述方法包括如下步骤: [0062] In one embodiment, the method comprises the steps of:

[0063] 1)将包括初级微粒的组合物涂敷到基材或支撑层上并且固化,如果适当的话在高温下固化,以使微粒与支撑层反应; [0063] 1) The composition comprising the primary particles applied to the substrate or support layer and curing, if appropriate at elevated temperature cure, so that the particles react with the supporting layer;

[0064] 2)将包括次级微粒的组合物涂敷到初级微粒上并且固化,如果适当的话在高温下下固化,以使次级微粒粘附到初级微粒上; [0064] 2) The composition comprising the secondary particles is applied to the primary particles and curing, if appropriate at elevated temperature to cure, so that the primary particles adhered to the secondary particles;

[0065] 3)涂敷上部表面层用涂料组合物并且固化,如果适当的话在高温下固化,以使上部表面层粘附到次级微粒上。 [0065] 3) an upper surface coated with a layer of coating composition and curing, if appropriate at elevated temperature cure, so that the upper surface of the layer is adhered to the secondary particles.

[0066] 步骤1-3中的涂敷可以通过本领域技术人员已知的用于涂敷涂料组合物的方法来实施,例如通过旋转涂布、喷涂或辊涂。 [0066] steps 1-3 may be applied by those skilled in the known methods for applying a coating composition to the embodiment, for example, by spin coating, spray coating or roller coating. 步骤1和2后,未固定的微粒可通过液体(例如水或溶剂)最终冲洗掉,或可用机械力(例如通过超声波)去除。 Steps 1 and 2, the unfixed microparticles by a liquid (e.g., water or solvent) finally washed out, or may be a mechanical force (e.g., ultrasonic) removed.

[0067] 在优选的实施方式中,用于涂敷本发明涂层的方法包括如下步骤: Method [0067] In a preferred embodiment, the present invention for applying the coating comprising the steps of:

[0068] 1)将包括已与次级微粒反应从而表面被次级微粒覆盖的初级微粒(覆盆子型微粒)的组合物涂敷到在基材或支撑层上并且固化,如果适当的话在高温下下固化,以使次级微粒与支撑层发生反应; [0068] 1) including the secondary particles to react with the surface to be covered so that the primary particles of secondary particles (raspberry-type particles) in the composition is applied to the substrate or support layer and curing, if appropriate at elevated temperature Under cured, so that the secondary particles to react with the support layer;

[0069] 2)涂敷上部表面层用涂层组合物并且固化,如果适当的话在高温下下固化,以使上部表面层粘附到次级微粒上。 [0069] 2) an upper surface coated with a layer of the coating composition and curing, if appropriate at elevated temperature to cure, so that the upper surface of the layer is adhered to the secondary particles.

[0070] 将先前制备好的覆盆子型微粒直接用在涂层方法中也是非常有利的,因为以这种方式加快了涂布工艺。 [0070] The previously prepared raspberry-type particles directly in the coating process is also very advantageous because in this way to speed up the coating process.

[0071] 步骤1和2中的涂敷可以通过本领域技术人员已知的用于涂敷涂料组合物的方法来实施,例如通过旋转涂布、喷涂或辊涂。 [0071] Step 1 and 2 may be applied by those skilled in the known methods for applying a coating composition to the embodiment, for example, by spin coating, spray coating or roller coating. 步骤1后,未固定的微粒可通过冲洗或通过机械方式(例如通过超声波)去除。 After step 1, unfixed particles by washing or by mechanical means (e.g. by ultrasound) is removed.

[0072] 支撑层可以包括涂层常用的添加剂,诸如颜料和填料。 [0072] The support layer may comprise conventional coating additives, such as pigments and fillers.

[0073] 支撑层优选由包括两种组分的树脂混合物形成,所述两种组分具有互补的反应性官能团。 [0073] The support layer is preferably formed from a resin mixture comprising two components, said two components having complementary reactive functional groups. 支撑层本身仍是未经固化的、经部分固化的或经完全固化的。 The support layer itself is still uncured, partially cured or fully cured through. 优选地,组分中的其中一种过量,结果在形成支撑层以后,上述过量组分中的反应性官能团仍可用于与初级或次级微粒表面上的官能团进行反应。 Preferably, the components of one of excess, the result after forming the support layer, the excess component reactive functional groups can still be used with the primary or secondary particles on the surface of the functional group to react. 最优选地,支撑层在步骤1前部分固化,并在步骤1后完全固化。 Most preferably, the support layer is partially cured before step 1 and fully cured after step 1.

[0074] 初级微粒与次级微粒之间形成共价化学键(也被称为固化反应),次级微粒与支撑层和上部表面层之间形成共价化学键或者在支撑层中形成共价化学键在例如10至2500C,优选在20至200C的温度下进行例如2分钟至数小时。 [0074] is formed between the primary particles and secondary particles covalent chemical bonds (also referred to as curing reaction), is formed between the secondary particles and the supporting layer and the upper surface of the layer or the covalent chemical bonds are formed in the support layer in the covalent chemical bonds e.g., 10 to 2500C, preferably at a temperature of 20 to 200 C was 2 minutes to several hours, for example. 这依赖于例如反应性官能团和所选择的互补反应性官能团。 It depends, for example, a reactive functional group selected complementary reactive functional groups. 本领域技术人员能够非常恰当地选择上述反应条件。 Those skilled in the art can very appropriately selecting the reaction conditions.

[0075] 作为自清洁涂层,该涂层非常适用于作为建筑涂层。 [0075] As a self-cleaning coating which is very suitable for use as architectural coatings.

[0076] 本发明在如下实施例中进一步解释,但并不局限于此。 [0076] The present invention is further explained in the following examples, but is not limited to this.

[0077] 实施例中所用材料 Examples of materials used [0077] Example

[0078] TEOS :四乙氧基硅烷,得自ABCR。 [0078] TEOS: tetraethoxysilane, available from ABCR. [0079] DMS-A15 :经氨基丙基封端的聚二甲基硅氧烷,得自ABCR。 [0079] DMS-A15: over aminopropyl terminated polydimethylsiloxane, obtained from ABCR.

[0080] TPGE :三羟甲基丙烷三缩水甘油基醚(TPTGE),得自Aldrich。 [0080] TPGE: Trimethylolpropane triglycidyl ether (TPTGE), available from Aldrich.

[0081] GPS :3-缩水甘油醚基丙基三甲氧基硅烷(纯度98% ),得自Aldrich。 [0081] GPS: 3- glycidyl propyl trimethoxysilane (98% purity), from Aldrich.

[0082] APS :3-氨基丙基三乙氧基硅烷(纯度98% ),得自Aldrich。 [0082] APS: 3- aminopropyl triethoxysilane (98% purity), from Aldrich.

[0083] DMSE21 :经环氧丙氧基丙基封端的聚二甲基硅氧烷,得自Gelesthc。 [0083] DMSE21: by glycidoxypropyl terminated polydimethylsiloxane, obtained from Gelesthc.

[0084] Jeffamine D-230 :聚氧化丙烯二胺,氨基氢当量=60,得自Huntsman。 [0084] Jeffamine D-230: polyoxypropylene diamine, an amino hydrogen equivalent = 60, available from Huntsman.

[0085] 氨水溶液)购自Merk。 [0085] ammonia solution) available from Merk.

[0086] 所有这些化学品未经进一步纯化直接使用。 [0086] All of these chemicals without further purification.

[0087]腿 [0087] Legs

[0088] 透射电子显微镜(TEM)。 [0088] Transmission electron microscopy (TEM). 采用JEOL JEM-2000FX TEM,在80kV下进行TEM实验。 Using JEOL JEM-2000FX TEM, TEM experiments conducted at 80kV. 常用的负极板用于数据记录。 The negative electrode plate common for data recording. 负极利用以8比特/通道灰阶模式工作的扫描仪(Agfa DUO, Scanner)进行数字化。 Negative use 8 bits / channel grayscale mode scanner (Agfa DUO, Scanner) digitizes. 样品通过如下方法制备:将硅石颗粒分散在乙醇中,将一滴稀释悬浮液沉积在经碳膜涂布的铜网上。 Samples prepared by the following method: The silica particles are dispersed in ethanol, the suspension was diluted with one drop of depositing the carbon film coated copper mesh by.

[0089] 接磁角测量。 [0089] Magnetic contact angle measurements. 在Dataphysics OCA 30仪器上,利用去离子水在室温下(〜21C ) 测量接触角和滚落角。 On Dataphysics OCA 30 instruments with deionized water at room temperature (~21 C) for measuring the contact angle and sliding angle. 所有的接触角和滚落角通过对在每个样品表面上的三个不同点测量数值进行平均来确定。 All the contact angle and sliding angle measured by three different points on the surface of each sample values were averaged to determine. 在分别添加探测液体和从液滴中抽取探测液体时记录动态前进角(advancing angle)禾口后退角(receding angle) 0 Record dynamic advancing angle (advancing angle) Hekou receding angle (receding angle) 0 were added to detect when the liquid and liquid extraction probe from the droplets

[0090] 制备经氨基官能化的次级硅石纳米微粒 [0090] prepared by the amino-functionalized secondary silica nanoparticles

[0091]首先,根据St0ber的方法(在St0ber等的 J. Coll. Interface Sci. 1968,26,第62 页等中公开)聚合TEOS来制备直径约为70nm的单分散硅石微粒。 [0091] First, according to St0ber method (as disclosed in St0ber like J. Coll. Interface Sci. 1968,26, p. 62, etc.) TEOS polymerization to prepare a diameter of about 70nm monodisperse silica particles. 简单地说,将6mL TEOS 在磁力搅拌下滴加入含有15mL氨水溶液(25%,催化剂)和200mL乙醇的烧瓶中。 Simply put, the 6mL TEOS added dropwise with magnetic stirring containing 15mL aqueous ammonia solution (25%, catalyst) 200mL flask and ethanol. 该反应在60C下进行5小时,然后添加在5mL乙醇中的0. 3mL APS。 The reaction was carried out for 5 hours at 60 C, and then add in 5mL of ethanol 0. 3mL APS. 搅拌在N2气氛、60C下持续12小时。 Stirred in N2 atmosphere, 60 C at 12 hours. 次级纳米微粒通过离心分离出来,并丢弃上层清液。 Secondary nanoparticle isolated by centrifugation, and the supernatant was discarded. 然后将微粒用乙醇洗涤三次。 Microparticles were then washed three times with ethanol. 将白色粉末在50C下真空干燥16小时。 The white powder was dried in vacuum at 50 C for 16 hours.

[0092] 通过茚三酮测试来检测次级硅石纳米微粒的周边是否存在氨基。 [0092] by ninhydrin test to detect the secondary silica nanoparticles surrounding the existence of groups. 将氨基官能化的次级硅石微粒在室温下加入5%茚三酮的水溶液中。 The amino-functionalized secondary silica particles, 5% ninhydrin aqueous solution at room temperature. 微粒的颜色在几分钟内由白色变成蓝色,这表明硅石微粒表面上成功地接枝了氨基片段。 Color particles within a few minutes from white to blue, indicating that the fragment amino successfully grafted on the silica particle surface.

[0094] 首先合成直径为700nm的裸硅石微粒。 [0094] First bare synthetic silica particles having a diameter of 700nm. 在室温下,将IOmL TEOS在磁力搅拌下滴加入含有21mL氨水溶液、75mL异丙醇和25mL甲醇的烧瓶中。 At room temperature under magnetic stirring IOmL TEOS was added dropwise a solution containing ammonia 21mL, 25mL flask 75mL isopropanol and methanol. 5小时后,将微粒通过离心分离出来,用去离子水/乙醇洗涤并在50C下真空干燥16小时。 After 5 hours, the microparticles isolated by centrifugation, washed with deionized water / ethanol, washed and dried in vacuo at 50 C for 16 hours. 然后,将1. 5g硅石微粒重新分散在40mL无水甲苯中,将在5mL无水甲苯中的0. 2g GPS滴加到剧烈搅拌的硅石悬浮液中。 Then, 1. 5g silica fine particles redispersed in 40mL of anhydrous toluene, anhydrous toluene at 0. 2g GPS dropwise added 5mL vigorously stirred suspension of silica. 将悬浮液在队气氛、50C下搅拌M小时。 The suspension was stirred in the team atmosphere, 50 C under M hours. 然后,将初级微粒通过离心分离出来,并用甲苯洗涤三次。 Then, the primary particles isolated by centrifugation, and washed three times with toluene. 将经洗涤的粉末在50C下真空干燥16小时。 The powder-washed and dried in vacuum at 50 C for 16 hours.

[0095] m^m^mtm^mm^mt (mrmm^tmrmrmm^) [0095] m ^ m ^ mtm ^ mm ^ mt (mrmm ^ tmrmrmm ^)

[0096] 分别将经氨基官能化的次级硅石纳米微粒(0. 4g)悬浮在20mL乙醇中,将0. 6g经环氧官能化的初级硅石微粒悬浮在15mL乙醇中。 [0096] respectively, by amino-functionalized secondary silica nanoparticles (0. 4g) was suspended in 20mL ethanol, 0. 6g by epoxy-functionalized primary silica particles suspended in 15mL of ethanol. 此后,在剧烈搅拌下将初级硅石微粒悬浮液滴加到次级硅石纳米微粒悬浮液中。 Thereafter, with vigorous stirring primary silica microparticle suspension was added dropwise a secondary silica nanoparticle suspension. 该悬浮液在队气氛下回流M小时。 The suspension was refluxed under an atmosphere of team M hours. 然后将微粒通过离心分离出来,并用乙醇洗涤。 Then the microparticles isolated by centrifugation, and washed with ethanol. 粉末在50C下真空干燥16小时。 Powder was dried in vacuum at 50 C for 16 hours. 图1中的TEM照片显示,结果得到覆盆子型微粒。 The TEM photograph in Fig. 1 shows the results obtained raspberry-type microparticles.

[0097] 狐肺双■耐日講氧,-i\mm [0097] fox double lung ■ resistant Sundays speak oxygen, -i \ mm

[0098] 首先,通过如下过程在铝基材上制备环氧-胺支撑层,其中环氧过量10% :将0. 44g TPTGE和0. Mg Jeffamine D-230溶解在ImL甲苯中,其中环氧/氨基摩尔比为2.2 : 1。 [0098] First, the production of ethylene by the following procedure on an aluminum substrate - amine support layer, wherein the epoxy excess of 10%: the 0. 44g TPTGE and 0. Mg Jeffamine D-230 were dissolved in toluene ImL, wherein the epoxy / amino molar ratio of 2.2: 1. 此后,利用自动涂膜器从铝板上拉下约为30μπι(湿膜厚度)的膜,然后在75C 下固化2小时。 Thereafter, the film is about the use of automatic 30μπι (wet film thickness) of the film pulled from the aluminum plate and then cured at 75 C for 2 hours. 然后,将0.05g覆盆子型氨基官能化的硅石微粒悬浮在ImL乙醇中。 Then, 0.05g raspberry amino-functionalized silica type fine particles suspended in ImL ethanol. 通过自动涂膜器使悬浮液沉积在第一环氧层上(湿膜厚度约为60 μ m),然后将其保持在75C下18小时。 It allows automatic coating suspension deposited on the first epoxy layer (wet film thickness of about 60 μ m), and then held at 75 C for 18 hours. 冷却下来后,将该膜在超声仪中用乙醇冲洗,以除去未固定的微粒,并在室温下干 After cooling down, the film was rinsed in ethanol using ultrasound to remove unfixed particles, and dried at room temperature

O O

[0099] 实施例1 [0099] Example 1

[0100] 通过将PDMS接枝到含有覆盆子型微粒的双层结构膜上得到本发明的超疏水膜。 [0100] The PDMS grafted onto the two-layer structure film containing fine particles obtained raspberry type superhydrophobic film of the present invention. 经表面粗糙化的膜首先与经胺封端的DMS-A15在80C下反应4小时,以确保环氧-胺膜或大硅石微粒上的剩余环氧基团都转化成胺端基。 The surface roughened film is first and amine-terminated DMS-A15 for 4 hours at 80 C under in order to ensure the epoxy - amine film or remaining epoxy groups on a large silica particles are converted to amine end groups. 该反应后,该膜用甲苯仔细洗涤,以除去未反应的DMS-15。 After the reaction, the membrane was washed carefully with toluene to remove unreacted DMS-15. 最后,使膜与环氧封端的DMS-E21在80C下反应4小时,然后用甲苯洗涤, 得到覆盖粗糙表面的PDMS层。 Finally, the film with an epoxy-capped DMS-E21 reacted at 80 C for 4 hours, then washed with toluene to give a layer of PDMS covering the roughened surface.

[0101] 对比例A [0101] Comparative Example A

[0102] 通过如下过程在铝基材上制备平滑的环氧-胺膜,该膜表面采用PDMS改性,但不包括任何微粒:将0. 44g TPTGE和0. 24g Jeffamine D-230溶解在ImL甲苯中,其中环氧/ 氨基摩尔比约为2.2 : 1。 [0102] was prepared by the following procedure on a smooth aluminum substrate epoxy - amine membrane, the membrane using PDMS surface modified, but does not include any particulate: The 0. 44g TPTGE and 0. 24g Jeffamine D-230 were dissolved in ImL toluene, wherein the epoxy / amino molar ratio of about 2.2: 1. 此后,利用自动涂膜器从铝板上拉下约为30μπι(湿膜厚度)的膜,然后在75C下固化2小时。 Thereafter, the film is about the use of automatic 30μπι (wet film thickness) of the film pulled from the aluminum plate and then cured at 75 C for 2 hours. 最后,将氨基-PDMS(DMS-A15)接枝到所得膜上。 Finally, the amino -PDMS (DMS-A15) grafted onto the resulting film.

[0103] 对比例B [0103] Comparative Example B

[0104] 为了比较,如下制备仅含有初级硅石微粒的膜(反应条件与上述相同)。 [0104] For comparison, was prepared as follows containing only primary silica microparticle membrane (reaction conditions are the same as above). 根据对比例A中概括的过程制备环氧-胺膜,其中胺过量10 %,接着根据上述概括的过程表面接枝表面上含有环氧基团的初级硅石微粒。 Comparative Example A according to the procedure outlined in the preparation of epoxy - amine film, wherein the amine excess of 10%, then the primary silica particles containing an epoxy group grafted on the surface of the surface according to the process outlined above. 未固定的初级微粒通过在超声仪中用乙醇进行冲洗去除。 Unfixed primary particles by using ultrasound to remove the ethanol rinse. 最后,将氨基-PDMS (DMS-A15)接枝到所得膜上。 Finally, the amino -PDMS (DMS-A15) grafted onto the resulting film.

[0105] 膜的浸润性通过水在其表面上的接触角(CA)来反映。 [0105] infiltration of the film reflected by water contact angle (CA) on its surface. 在平滑膜上(对比例A), 前进水CA为92士2 (图加),后退CA(CAhysteresis)约为40。 Smooth membrane (Comparative A), advancing water CA 92 persons 2 (Figure plus), backward CA (CAhysteresis) is approximately 40 . 对于用PDMS改性的仅含有初级微粒的膜(对比例B),前进水CA增加,达到141 士1.5 (图2b),同时后退CA显著增加至110。 For the film (Comparative Example B) contains only primary particles modified with PDMS, advancing water CA increased, reaching 141 persons 1.5 (Figure 2b), while significantly increasing backward CA to 110 . 甚至将膜颠倒放置时,水滴仍挂在膜表面上。 Even when the film is placed upside down, the water droplets still hanging on the membrane surface. 与此显著不同,对于用PDMS 表面改性的含有本发明的覆盆子性微粒的膜,前进水CA进-步增加至168士Γ (图2c), 而后退CA约为4。 And this significantly different for PDMS surface modified with the present invention comprises a film raspberry particles, advancing water CA into - further increased to 168 persons Γ (Fig. 2c), but retreat CA about 4 . 更重要的是,20 μ L水滴在表面上的滚降角为5士1。 More importantly, 20 μ L of water droplets on the surface of the roll-off angle of 5 persons 1 .

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Classifications
International ClassificationC08J3/00, C09D5/03, C08J3/14
Cooperative ClassificationC09D7/1283, C09D7/1275, C08K9/04, Y10T428/24942, B05D5/08, Y10T428/2982, C08K3/36, C08G59/50, C09D5/1618, Y10T428/2991, Y10T428/25, C09D7/1225, C09D5/031
European ClassificationC08G59/50, B05D5/08, C09D5/03B, C09D7/12D2B, C09D5/16C3E, C09D7/12N2, C09D7/12N3
Legal Events
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