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Publication numberCN1578725 A
Publication typeApplication
Application numberCN 02821676
PCT numberPCT/US2002/034033
Publication date9 Feb 2005
Filing date24 Oct 2002
Priority date29 Oct 2001
Also published asCA2464733A1, DE60234857D1, EP1448366A1, EP1448366A4, EP1448366B1, US6881445, US20050186412, WO2003037613A1
Publication number02821676.8, CN 02821676, CN 1578725 A, CN 1578725A, CN-A-1578725, CN02821676, CN02821676.8, CN1578725 A, CN1578725A, PCT/2002/34033, PCT/US/2/034033, PCT/US/2/34033, PCT/US/2002/034033, PCT/US/2002/34033, PCT/US2/034033, PCT/US2/34033, PCT/US2002/034033, PCT/US2002/34033, PCT/US2002034033, PCT/US200234033, PCT/US2034033, PCT/US234033
InventorsPK阿罗拉
Applicant创新化学技术有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Forming thin films on substrates using a porous carrier
CN 1578725 A
Abstract  translated from Chinese
本发明涉及一种含多孔载体(10)和两亲型物料的复合材料。 The present invention relates to a method comprising a porous carrier (10) and an amphiphilic material composites. 该复合材料可用于在底材上形成薄膜的方法和系统。 The composite material can be used in a method and system for forming a thin film on a substrate.
Claims(23)  translated from Chinese
1.一种在底材上形成薄膜的方法,所述方法包括:在室内提供底材;在室内插入含多孔载体和两亲型物料的复合材料;在该室内,进行将复合材料的温度设置为大约20至大约400℃和将压力设置为大约0.000001至大约760托中的至少一种操作以引发两亲型物料的汽化;和收回其上有薄膜的底材。 1. A method of forming a thin film on a substrate, the method comprising: providing a substrate in a chamber; indoors insert comprising a porous carrier material and amphiphilic composites; in the chamber, the temperature of the composite material were provided about 20 to about 400 ℃ and the pressure was set at about 0.000001 to about 760 torr at least one operation to initiate vaporization amphiphilic material; and retracting the substrate on which the film.
2.如权利要求1所述的方法,其中该底材包括玻璃、其上有抗反射涂层的玻璃、二氧化硅、氧化锗、陶瓷、瓷、玻璃纤维、金属和热固性材料和热塑性材料中的至少一种。 2. The method of claim 1, wherein the substrate comprises a glass, on which anti-reflection coated glass, silicon dioxide, germanium oxide, ceramics, porcelain, glass fiber, metal and thermoset materials and thermoplastic materials at least one.
3.如权利要求1所述的方法,其中该多孔载体具有平均孔径为大约1微米至大约1,000微米的孔。 The method according to claim, wherein the porous support has an average pore size of from about 1 micron to about hole 000 microns.
4.如权利要求1所述的方法,其中该多孔载体的孔隙率使得每立方厘米多孔载体可以吸收大约0.001克至大约5克两亲型物料。 4. The method of claim 1, wherein the porosity of the porous carrier such that each cubic centimeter of the porous support can absorb from about 0.001 g to about 5 g amphiphilic material.
5.如权利要求1所述的方法,其中该多孔载体包括氧化铝、硅酸铝、铝、黄铜、青铜、铬、铜、金、铁、镍、钯、铂、碳化硅、银、不锈钢、锡、钛、钨、锌和锆中的至少一种。 5. The method of claim 1, wherein the porous carrier comprises alumina, aluminum silicate, aluminum, brass, bronze, chromium, copper, gold, iron, nickel, palladium, platinum, silicon carbide, silver, stainless steel , tin, titanium, tungsten, zinc, and zirconium at least one.
6.如权利要求1所述的方法,将温度和压力中至少一项设定好后,将底材在该室内保持大约10秒至大约24小时。 The method as claimed in claim 1, the temperature and pressure in the at least one set, the substrate is maintained at about 10 seconds the chamber to about 24 hours.
7.如权利要求1所述的方法,其中该两亲型物料可表示为化学式I、II、V、VI、VII和RY中的至少一个:RmSiZn(I)其中每个R各自是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚、取代硅烷、或硅氧烷;每个Z各自是卤素、羟基、烷氧基和乙酸基中的一种;m是大约1至大约3,n是大约1至大约3,m+n等于4;RmSHn(II)其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚;S是硫;H是氢;m是大约1至大约2,n是大约0至1;RY,其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚,Y是下列官能团之一:-COOH、-SO3H、-PO3、-OH和-NH2;RSiNSiR (V)其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚;R(CH2CH2O)qP(O)x(OH)y(VI)其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚,q是大约1至大约10,x和y独立地是大约1至大约4;和[R(SiO)x(OH)y]n(VII)其中R是含有大约1至大约30个碳原子的烷基、芳基、氟化烷基、烷基醚或氟化烷基醚;x是大约1至大约4;y是大约1至大约4;n是大约1至大约500。 7. The method of claim 1, wherein the amphiphilic material expressed by chemical formula I, II, V, VI, VII and RY at least one of: RmSiZn (I) wherein each R is independently containing from about 1 to about 30 carbon atoms, an alkyl group, fluorinated alkyl, alkyl ether or fluorinated alkyl ether, a substituted silane, or siloxane; and each Z are each halogen, hydroxy, alkoxy, and acetoxy-in one kind; m is from about 1 to about 3, n is from about 1 to about 3, m + n is equal to 4; RmSHn (II) wherein R is an alkyl group containing from about 1 to about 30 carbon atoms, a fluorinated alkyl group, alkyl ether or a fluorinated alkyl ether; S is sulfur; H is hydrogen; m is from about 1 to about 2, n is about 0 to 1; RY, wherein R is an alkyl group containing from about 1 to about 30 carbon atoms, , fluorinated alkyl, alkyl ether or fluorinated alkyl ether, Y is one of the following functional groups: -COOH, -SO3H, -PO3, -OH and -NH2; RSiNSiR (V) wherein R is containing from about 1 to about an alkyl group of 30 carbon atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ether; R (CH2CH2O) qP (O) x (OH) y (VI) wherein R is an about 1 to about 30 carbon alkyl atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ether, q is from about 1 to about 10, x and y are independently from about 1 to about 4; and [R (SiO) x (OH) y] n (VII) wherein R is an alkyl group containing from about 1 to about 30 carbon atoms, an aryl group, fluorinated alkyl, alkyl ether or fluorinated alkyl ether; x is from about 1 to about 4; y is about 1 to about 4; n is from about 1 to about 500.
8.如权利要求1所述的方法,其中在设置温度前先设置压力。 8. The method of claim 1, wherein the first set pressure before the set temperature.
9.如权利要求1所述的方法,其中温度设置为大约40至大约350℃,压力设置为大约0.00001至大约200托。 9. The method of claim 1, wherein the temperature is set to about 40 to about 350 ℃, the pressure is set at about 0.00001 to about 200 torr.
10.如权利要求1所述的方法,其中以大约0.01nm/sec或更大且大约1nm/sec或更小的速度形成该薄膜。 10. The method of claim 1, wherein approximately 0.01nm / sec or more and about 1nm / sec or less, the film forming speed.
11.如权利要求1所述的方法,其中该薄膜的厚度为大约1nm至大约250nm。 11. The method of claim 1, wherein the film has a thickness of from about 1nm to about 250nm.
12.一个形成薄膜的系统,所述系统包括:与热源和真空系统中至少一个相连的成膜室;一种含有可安放在成膜室中的多孔载体和两亲型物料的复合材料;和一种可安放在成膜室中的在其上形成薄膜的底材。 12. A film formation, the system comprising: a heat source and a vacuum system coupled to the at least one film-forming chamber; can be placed in a deposition chamber containing the porous support and the composite amphiphilic material; and A can be placed in the deposition chamber in which the film is formed on the substrate.
13.如权利要求12所述的系统,其中该成膜室与热源和真空系统相连。 13. The system of claim 12, wherein the source is connected to the film forming chamber and the vacuum system.
14.如权利要求12所述的系统,其中该多孔载体具有平均孔径为大约5微米至大约500微米的孔。 14. The system of claim 12, wherein the porous support has an average pore diameter of the hole from about 5 microns to about 500 microns.
15.如权利要求12所述的系统,其中该复合材料在每立方厘米多孔载体中含有大约0.01克至大约2克两亲型物料。 15. The system of claim 12, wherein the composite contains from about 0.01 g to about 2 g amphiphilic material per cubic centimeter in the porous carrier.
16.如权利要求12所述的系统,其中该复合材料进一步含有非极性有机溶剂、成膜催化剂和猝灭剂中的至少一种。 16. The system of claim 12, wherein the composite material further comprises a non-polar organic solvents, film-forming catalysts and at least one quencher.
17.一种成膜复合材料,所述材料含有:具有平均孔径为大约1微米至大约1,000微米的孔的多孔载体,和一种两亲型物料,其中该多孔载体的孔隙率使得每立方厘米多孔载体可以吸收大约0.001克至大约5克两亲型物料。 17. A method of forming a composite material, said material comprising: having an average pore size of about 1 micron to about 1,000 microns pores of the porous support, and an amphiphilic material, wherein the porosity of the porous carrier such that per cubic centimeter The porous carrier can absorb about 0.001 g to about 5 g amphiphilic materials.
18.如权利要求17所述的成膜复合材料,其中该多孔载体包括氧化铝、硅酸铝、铝、黄铜、青铜、铬、铜、金、铁、镍、钯、铂、碳化硅、银、不锈钢、锡、钛、钨、锌和锆中的至少一种。 18. The composite material 17 according to claim deposition, wherein the porous carrier comprises alumina, aluminum silicate, aluminum, brass, bronze, chromium, copper, gold, iron, nickel, palladium, platinum, silicon carbide, silver, stainless steel, tin, titanium, tungsten, at least one zinc and zirconium.
19.如权利要求17所述的成膜复合材料,其中该多孔载体具有平均孔径为大约5微米至大约500微米的孔,而且该多孔载体的孔隙率使得每立方厘米多孔载体可以吸收大约0.01克至大约1克两亲型物料。 19. The composite material 17 according to the film formation as claimed in claim wherein the porous support has an average pore size of about 5 microns to about 500 microns holes and porosity of the porous carrier such that each cubic centimeter of the porous support can absorb approximately 0.01 g to about 1 g amphiphilic materials.
20.如权利要求17所述的成膜复合材料,其中该复合材料具有圆柱形、球形、椭圆形、片状、圆盘形、塞形、丸状、立方体、长方形和圆锥形中的一种形状。 20. The composite material 17 according to the film formation as claimed in claim wherein the composite has a cylindrical, spherical, oval, sheet-like, disc-shaped, plug-shaped, pellet, cube, rectangular and conical one shape.
21.一种在底材上形成薄膜的方法,所述方法包括:在室内提供底材;在该室内在底材上形成氧化涂层;在室内插入含多孔载体和POSS两亲型物料的复合材料;在该室内,进行将复合材料的温度设置为大约20至大约400℃和将压力设置为大约0.000001至大约760托中的至少一种操作以引发POSS两亲型物料的汽化;和收回其上有薄膜的底材。 21. A method for forming a thin film on a substrate, said method comprising: providing a substrate in the chamber; in the chamber to form an oxide coating on the substrate; indoors insert containing composite porous carrier and amphiphilic materials POSS material; in the chamber, the temperature in the set of composite material is about 20 to about 400 ℃ and the pressure to at least one operating about 0.000001 to about 760 torr to induce vaporization of amphiphilic POSS materials; and to recover their There are films on substrates.
22.如权利要求21所述的方法,其中该POSS两亲型物料包括至少一种选自聚(对羟基苄基倍半硅氧烷)、聚(对羟基苄基倍半硅氧烷-共-甲氧基苄基倍半硅氧烷)、聚(对羟基苄基倍半硅氧烷-共-叔丁基倍半硅氧烷)、聚(对羟基苄基倍半硅氧烷-共-环己基倍半硅氧烷)、聚(对羟基苄基倍半硅氧烷-共-苯基倍半硅氧烷)、聚(对羟基苄基倍半硅氧烷-共-二环庚基倍半硅氧烷)、聚(对羟基苯基乙基倍半硅氧烷)、聚(对羟基苯基乙基倍半硅氧烷-共-对羟基-α-甲基苄基倍半硅氧烷)、聚(对羟基苯基乙基倍半硅氧烷-共-甲氧基苄基倍半硅氧烷)、聚(对羟基苯基乙基倍半硅氧烷-共-叔丁基倍半硅氧烷)、聚(对羟基苯基乙基倍半硅氧烷-共-环己基倍半硅氧烷)、聚(对羟基苯基乙基倍半硅氧烷-共-苯基倍半硅氧烷)、聚(对羟基苯基乙基倍半硅氧烷-共-二环庚基倍半硅氧烷)、聚(对羟基-α-甲基苄基倍半硅氧烷)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-对羟基苄基倍半硅氧烷)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-甲氧基苄基倍半硅氧烷)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-叔丁基倍半硅氧烷)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-环己基倍半硅氧烷)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-苯基倍半硅氧烷)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-二环庚基倍半硅氧烷)、聚(对羟基苄基倍半硅氧烷-共-对羟基苯基乙基倍半硅氧烷)的物质。 22. The method of claim 21, wherein the POSS amphiphilic material comprises at least one member selected from poly (p-hydroxy benzyl silsesquioxane), poly (p-hydroxy benzyl silsesquioxane - Total - methoxybenzyl silsesquioxane), poly (p-hydroxy benzyl silsesquioxane - co - t-butyl silsesquioxane), poly (p-hydroxy benzyl silsesquioxane - Total - cyclohexyl silsesquioxane), poly (p-hydroxy benzyl silsesquioxane - co - phenyl silsesquioxane), poly (p-hydroxy benzyl silsesquioxane - co - dicycloheptyl silsesquioxane), poly (p-hydroxyphenyl ethyl silsesquioxane), poly (p-hydroxyphenyl ethyl silsesquioxane - co - -α- methyl p-hydroxy benzyl sesquisulfate siloxane), poly (p-hydroxyphenyl ethyl silsesquioxane - co - methoxybenzyl silsesquioxane), poly (p-hydroxyphenyl ethyl silsesquioxane - co - t butyl silsesquioxane), poly (p-hydroxyphenyl ethyl silsesquioxane - co - cyclohexyl silsesquioxane), poly (p-hydroxyphenyl ethyl silsesquioxane - co - phenyl silsesquioxane), poly (p-hydroxyphenyl ethyl silsesquioxane - co - dicycloheptyl silsesquioxane), poly (p-hydroxy-methyl benzyl times -α- half silicon siloxane), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - p-hydroxy benzyl silsesquioxane), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - methoxybenzyl silsesquioxane), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - t-butyl silsesquioxane), poly (p-hydroxy -α - methyl benzyl silsesquioxane - co - cyclohexyl silsesquioxane), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - phenyl silsesquioxane), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - dicycloheptyl silsesquioxane), poly (p-hydroxy benzyl silsesquioxane - total - on hydroxyphenylethyl silsesquioxane) of the material.
23.如权利要求21所述的方法,其中该薄膜以大约0.05nm/sec或更大且大约0.5nm/sec或更小的速度形成。 23. The method according to claim 21, wherein the film is about 0.05nm / sec or more and about 0.5nm / sec or less, the speed of formation.
Description  translated from Chinese
使用多孔载体在底材上形成薄膜 A porous film formed on a substrate support

发明领域本发明主要涉及薄膜。 Field of the Invention The present invention relates generally to film. 具体地,本发明涉及使用多孔载体在底材上形成优质薄膜。 In particular, the present invention relates to the use of a porous support formed of high-quality thin film on a substrate.

发明背景可聚合两亲型分子和水解类烷基硅烷被用于在各种表面上形成薄膜。 BACKGROUND OF THE INVENTION polymeric amphiphilic molecules and hydrolysable alkyl silane is used to form a thin film on a variety of surfaces. 薄膜具有许多不同的用途。 Film has many different uses. 例如,可以在透镜上形成抗划伤薄膜,或在金属上形成防腐薄膜。 For example, anti-scratch film may be formed on the lens, or the formation of corrosion film on the metal.

难以直接在透镜上形成两亲型分子的薄膜,因此首先在第一室的无水环境中在透镜上形成二氧化硅层。 Difficult to form a thin film of amphiphilic molecules directly on the lens, and therefore the first layer of silicon dioxide anhydrous environment in the first chamber is formed on the lens. 然后将有二氧化硅涂层的透镜转移至第二室以沉积两亲型分子薄膜。 Then the silica-coated lens transferred to a second chamber to deposit a thin film of amphiphilic molecules. 在转移过程中,有二氧化硅涂层的透镜曝露在空气中的水蒸气中,后者将该表面水解并随后使得两亲型分子和透镜之间可以坚固地粘合。 During the transfer, silica-coated lens exposed to water vapor in the air, which is the surface hydrolysis and then makes it possible to firmly bond between the amphiphilic molecules and lens. 在与二氧化硅层相同的室中形成两亲型薄膜会导致室内部的腐蚀、使其不经彻底清洗就不能重复用于这两个步骤的对室的污染,并导致室内部形成肮脏的难以清洗的薄膜。 Formed in the same chamber in the silica layer amphiphilic film can cause corrosion inside the chamber so that it can not be thoroughly cleaned without contamination of the chamber for repeat these two steps, and results in the formation chamber dirty The film is difficult to clean. 尽管如此,在某些情况下,需要两个室是不方便的。 Nevertheless, in some cases, the two chambers is inconvenient.

如果在底材上形成薄膜,成膜物通常溶解在溶剂内。 If the thin film is formed on a substrate, the film-forming material generally is dissolved in a solvent. 然后将溶剂/成膜物混合物接触底材。 Then the solvent / mixture contacting the substrate film material. 以此方法形成薄膜的一个问题在于该溶剂通常是有毒的,而且由于可燃性还是危险的。 One problem in this method of forming a thin film of the solvent that normally is toxic, and because flammable or dangerous. 换句话说,使用可以溶解成膜物的溶剂会引发严重的健康和环境问题。 In other words, the use of a solvent capable of dissolving the film-forming material can cause serious health and environmental problems. 溶剂的处理是一个重要的环境问题,特别是在油基和卤化碳溶剂的情况下。 Handling of solvents is an important environmental issue, especially in the case of oil-based and halocarbon solvent.

此外,使用这种溶剂还会生成作为副产物的氯化氢气体,这就产生了额外的严重健康危害,除非使用中和剂阱并按照EPA和OS HA规程进行适当的处理。 In addition, the use of such a solvent is also generated as a by-product of hydrogen chloride gas, which resulted in additional serious health hazard, unless neutralizer trap and appropriate treatment and OS HA in accordance with EPA regulations. 适当的使用和处理在操作环境中是非常困难的,尤其由于操作者必须监测这种使用的进程。 With proper use and handling in the operating environment it is very difficult, especially because the operator must monitor the process of such use. 因此,每一操作者和实验室就需要有有毒气体监测器或使用蒸汽面具,这对操作者而言是不舒服的。 Thus, each operator and laboratory on the need for toxic gas monitoring device or mask the use of steam, which in terms of the operator is uncomfortable.

薄膜形成领域内的最新发展是使用安瓿将成膜物输送到底材上。 The latest developments in the field of thin film formation is the use of ampoules in the end the film-forming material was transported on. 使用汽相涂装方法,将含有成膜物的安瓿与底材一起置于真空室内。 Vapor phase coating method, ampules containing the film-forming material together with the substrate in a vacuum chamber. 形成真空后,安瓿破裂,释放出汽化并继续在底材上形成薄膜的成膜物。 After the formation of a vacuum, ampoule rupture, releasing the film material vaporized and the film continues to be formed on the substrate. 安瓿是一种用来将成膜物加入该室的易于操作、方便的运载工具。 Ampoule is a film-forming material is added to the ease of operation of the chamber, a convenient means of delivery. 然而,在此方法中使用安瓿时存在几个问题。 However, there are several problems when used in this method ampoule.

首先,当安瓿破裂释放出成膜物时,碎裂的玻璃会损坏底材。 First, when a film was released ampoule broken, broken glass may damage the substrate. 由于安瓿内部与真空室之间的压力差,安瓿以不合意的很大的力量破裂,将玻璃碎片溅射得真空室内到处都是。 As the pressure inside the vacuum chamber ampoule difference between the ampoule undesirable great power broken, the shards of glass vacuum chamber of the sputtering was everywhere. 相关得问题在于除了底材,成膜物还不合意地在玻璃碎片上形成薄膜,由此减少了用于底材的成膜物的量。 In addition to the problem that was related to the substrate, the film formation was not desirably forming a thin film on the glass fragments, thereby reducing the amount of material for forming substrate.

第二,当安瓿以很大的力量破裂时,成膜物容易喷出,从而在底材上形成不均匀的薄膜。 Second, when a large force to rupture the ampoule, film was easily discharged, so uneven film is formed on the substrate. 无力控制成膜物的释放产生了检查和经常清洗涂层底材的需要。 Inability to control the release of the film-forming material to produce inspection and regular cleaning coating substrates needs.

发明概述本发明一个方面涉及含多孔载体和两亲型物料的复合材料。 SUMMARY The present invention relates to an aspect of containing porous carrier and amphiphilic composite materials. 两亲型物料用来在底材上形成薄膜。 Amphiphilic material used to form a thin film on a substrate. 因此可以将该复合材料用于在底材上形成薄膜的方法和系统。 The composite material can be used in the methods and systems of forming a thin film on a substrate. 由于使用多孔载体将两亲型物料输送到室内,因此对底材的损伤减缓,同时有利于两亲型分子蒸汽的均匀分布。 The use of the amphiphilic porous carrier material delivered to the room, and therefore slow down the damage to the substrate, while facilitating uniform distribution of amphiphilic molecules of steam. 此外,当两亲型物料汽化时,多孔载体减缓溅射。 In addition, when the amphiphilic material is vaporized porous carrier slowing sputtering.

因此,使用浸透了两亲型分子的多孔载体复合材料在底材上形成的薄膜具有连续性。 Therefore, soaked film amphiphilic molecules porous support composite is formed on a substrate having continuity. 在按照常规方法制成的薄膜中常见的针孔和其它漆膜缺陷被减至最少和/或完全消除。 In the film formed by a conventional method common in the film pinholes and other defects are minimized and / or eliminated.

本发明的另一方面涉及含多孔载体和多面体低聚倍半硅氧烷(silsesquioxane)两亲型物料的复合材料。 Another aspect of the present invention comprising a porous carrier and a polyhedral oligomeric silsesquioxane (silsesquioxane) amphiphilic composite materials. 当使用多面体低聚倍半硅氧烷两亲型物料时,在使用二氧化硅(或其它金属氧化物型涂料)涂料提高粘合性的情况下,不必使底材曝露在水蒸气中。 When using polyhedral oligomeric silsesquioxane amphiphilic material, in the case of silica (or other metal oxide coating) coating to improve the adhesion, the substrate is not necessary to exposure to water vapor. 因此,可以在一个室中形成二氧化硅和两亲型薄膜,从而简化涂布过程。 Thus, the silica can be formed and an amphiphilic film chamber, thereby simplifying the coating process.

附图简要说明图1是按照本发明的一个方面形成薄膜的复合材料的图示。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is in accordance with one aspect of the present invention illustrating the formation of a thin film of the composite material.

图2是按照本发明的另一方面形成薄膜的复合材料的图示。 2 is a diagram in accordance with another aspect of the present invention to form a film of the composite material.

图3是按照本发明的又一方面形成薄膜的复合材料的图示。 Figure 3 is a further aspect of the present invention illustrating the formation of a thin film of the composite material.

图4是按照本发明的一个方面形成薄膜的系统示意图。 Figure 4 is a schematic view of the film forming system in accordance with one aspect of the present invention.

发明详述使用含多孔载体和两亲型物料的复合材料,可以在底材上有效地形成均匀和连续的薄膜,同时不会损坏底材。 DETAILED DESCRIPTION containing porous carrier and amphiphilic composite materials, uniform and continuous film can be effectively formed on the substrate, without damaging the substrate. 在某些情况下类似于海绵状金属的多孔载体构成一种有益的媒介物,其有利于由两亲型物料制成的薄膜的蒸汽淀积。 In some cases similar to the sponge-like porous metal support constituting a useful vehicle, which is advantageous from the vapor deposited film made of amphiphilic material.

两亲型分子具有在薄膜内自组合和/或本体聚合的固有能力。 Amphiphilic molecules within the film has an inherent ability to self-assembling and / or bulk polymerization. 两亲型分子通常含有首基和尾基(尾基为非活性、非极性基团,首基为活性、极性基团)。 Amphiphilic molecules usually contain a head group and a tail group (tail group is non-reactive, non-polar groups, the first group is active, polar groups). 两亲型分子通常包括可聚合两亲型分子、水解类烷基硅烷、水解类全卤烷基硅烷、氯硅烷、聚硅氧烷、烷基硅氮烷、全氟烷基硅氮烷、二硅氮烷和倍半硅氧烷。 Amphiphilic molecules typically include polymerizable amphiphilic molecules, hydrolysable alkylsilane, perhaloalkyl hydrolysable silane, chlorosilane, polysiloxanes, alkyl silazane, perfluoroalkyl silazanes, two silazanes sesquisiloxanic.

两亲物的极性基团或部分可以是羧酸、醇、硫醇、伯胺、仲胺和叔胺、氰化物、硅烷衍生物、膦酸酯、磺酸酯及类似物。 Amphiphile polar group or moiety may be carboxylic acids, alcohols, thiols, primary amines, secondary and tertiary amines, cyanides, silane derivatives, phosphonate, sulfonate, and the like. 非极性基团或部分主要包括烷基、全氟烷基、烷基醚基团和全氟烷基醚基团。 Non-polar group or moiety include alkyl, perfluoroalkyl, alkyl ether group and a perfluoroalkyl ether group. 这些非极性基团可以包括丁二炔、乙烯基不饱和或稠合线型或支链芳环。 These non-polar groups may include diacetylene, vinyl-unsaturated or fused linear or branched aromatic ring.

在一个具体实施例中,两亲型分子可表示为化学式I:RmSiZn(I)其中每个R各自是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚、取代硅烷、或硅氧烷;每个Z各自是卤素、羟基、烷氧基和乙酸基中的一种;m是大约1至大约3,n是大约1至大约3,m+n等于4。 In one particular embodiment, the amphiphilic molecules expressed by chemical formula I: RmSiZn (I) wherein each R is independently is an alkyl group containing from about 1 to about 30 carbon atoms, fluorinated alkyl, alkyl ether or fluoro alkyl ether, a substituted silane, or siloxane; and each Z are each halogen, hydroxy, alkoxy, and acetoxy-one; m is from about 1 to about 3, n is from about 1 to about 3, m + n equals 4. 在另一具体实施例中,R是含有大约6至大约20个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚。 In another particular embodiment, R is an alkyl group containing from about 6 to about 20 carbon atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ether. 烷基可含有丁二炔、乙烯基不饱和、单芳环和稠合线型或支链芳环。 Alkyl may contain diacetylene, vinyl-unsaturated, single aromatic ring and fused linear or branched aromatic ring.

在另一具体实施例中,两亲型分子可表示为化学式II:RmSHn(II)其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚;S是硫;H是氢;m是大约1至大约2,n是大约0至1。 In another particular embodiment, the amphiphilic molecules can be expressed as the chemical formula II: RmSHn (II) wherein R is an alkyl group containing from about 1 to about 30 carbon atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ethers; S is sulfur; H is hydrogen; m is from about 1 to about 2, n is about 0-1. 在另一具体实施例中,R是含有大约6至大约20个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚。 In another particular embodiment, R is an alkyl group containing from about 6 to about 20 carbon atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ether. 该烷基链可含有丁二炔、乙烯基、单芳族化合物或稠合线型或支链芳香部分。 The alkyl chain may contain diacetylene, vinyl, single aromatics, or fused linear or branched aromatic moiety.

在又一具体实施例中,该两亲型分子表示为RY,其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚,Y是下列官能团之一:-COOH、-SO3H、-PO3、-OH和-NH2。 In another particular embodiment, the amphiphilic molecules expressed as RY, wherein R is an alkyl group containing from about 1 to about 30 carbon atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ether, Y is one of the following functional groups: -COOH, -SO3H, -PO3, -OH and -NH2. 在另一具体实施例中,R是含有大约6至大约20个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚。 In another particular embodiment, R is an alkyl group containing from about 6 to about 20 carbon atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ether. 该烷基链可含有丁二炔、乙烯基不饱和、单芳族或稠合线型或支链芳香部分。 The alkyl chain may contain diacetylene, vinyl-unsaturated, single aromatic or fused linear or branched aromatic moiety.

在又一具体实施例中,该两亲型分子可包括下列化学式(III)和(IV)中的一种或多种:CF3(CF2)7CH2CH2-Si(CH3)2Cl (III)CF3(CF2)7CH2CH2-Si(OEt)3(IV)在另一具体实施例中,该两亲型分子是由化学式V表示的二硅烷基胺:RSiNSiR (V)其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚。 In another particular embodiment, the amphiphilic molecules may comprise the following chemical formula (III) and (IV) in one or more of: CF3 (CF2) 7CH2CH2-Si (CH3) 2Cl (III) CF3 (CF2) 7CH2CH2-Si (OEt) 3 (IV) In another particular embodiment, the amphiphilic molecule is two silyl amine represented by the formula V: RSiNSiR (V) wherein R is containing from about 1 to about 30 carbon atoms, alkyl, fluorinated alkyl, alkyl ether or fluorinated alkyl ether. 在另一具体实施例中,R是含有大约6至大约20个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚。 In another particular embodiment, R is an alkyl group containing from about 6 to about 20 carbon atoms, fluorinated alkyl, alkyl ether or fluorinated alkyl ether.

在另一具体实施例中,该两亲型分子可表示为化学式(VI):R(CH2CH2O)qP(O)x(OH)y(VI)其中R是含有大约1至大约30个碳原子的烷基、氟化烷基、烷基醚或氟化烷基醚,q是大约1至大约10,x和y独立地是大约1至大约4。 In another particular embodiment, the amphiphilic molecules can be expressed as the formula (VI): R (CH2CH2O) qP (O) x (OH) y (VI) wherein R is containing from about 1 to about 30 carbon atoms, alkyl, fluorinated alkyl, alkyl ether or fluorinated alkyl ether, q is from about 1 to about 10, x and y are independently from about 1 to about 4.

在又一具体实施例中,通过聚合含硅化合物(例如原硅酸四乙酯(TEOS)、四甲氧基硅烷和/或四乙氧基硅烷)形成两亲型分子。 In another particular embodiment, (e.g., tetraethyl orthosilicate (TEOS), tetramethoxysilane and / or tetraethoxysilane) is formed by polymerizing silicon-containing compound of amphiphilic molecules.

美国专利6,238,781、6,206,191、6,183,872、6,171,652、6,166,855(罩面层)、5,897,918、5,851,674、5,882,170、5,800,918、5,776,603、5,766,698、5,759,618、5,645,939、5,552,476和5,081,192、Hoffmann等人,和“Vapor Phase Self-Assembly of Fluorinated Monlayers on Siliconand German Oxide”,Langmuir,13,1877-1880,1997中描述了两亲型分子(和在某些情况下的含两亲型分子的组合物),由于两亲型物料的教导,以上文献在此引入作为参考。 U.S. Patent 6,238,781,6,206,191,6,183,872,6,171,652,6,166,855 (overcoat), 5,897,918,5,851,674,5,882,170,5,800,918,5,776,603,5,766,698,5,759,618,5,645,939,5,552,476 and 5,081,192, Hoffmann et al., And "Vapor Phase Self-Assembly of Fluorinated Monlayers on Siliconand German Oxide ", Langmuir, 13,1877-1880,1997 described amphiphilic molecules (and compositions containing amphiphilic molecules in some cases), due to the teachings of amphiphilic material, more hereby incorporated by reference.

可水解成两亲型物料的两亲型分子和化合物的具体例子包括十八烷基三氯硅烷、辛基三氯硅烷、产自Shin Etsu的商品名为KA-7803的十七烷基氟-1,1,2,2-四氢化癸基三氯硅烷、产自Degussa商品名为Dynasylan 9116的十六烷基三甲氧基硅烷、产自Degussa商品名为Dynasylan F8261的十三烷基氟化辛基三乙氧基硅烷、产自Degussa商品名为Dynasylan MTMS的甲基三甲氧基硅烷、产自Degussa商品名为Dynasylan MTES的甲基三乙氧基硅烷、产自Degussa商品名为Dynasylan PTMO的丙基三甲氧基硅烷、产自Degussa商品名为Dynasylan PTEO的丙基三乙氧基硅烷、产自Degussa商品名为Dynasylan IBTMO的丁基三甲氧基硅烷、产自Degussa商品名为Dynasylan BTEO的丁基三乙氧基硅烷、产自Degussa商品名为Dynasylan OCTEO的辛基三乙氧基硅烷、产自Degussa商品名为Dynasylan 8262的在乙醇中的氟烷基硅烷、产自Degussa商品名为Dynasylan F8263的在异丙醇中的氟烷基硅烷配方物、产自Degussa商品名为DynasylanF 8800的改性氟烷基硅氧烷、产自Degussa商品名为Dynasylan F8810的水基改性氟烷基硅氧烷。 Specific examples of amphiphilic molecules and compounds can be hydrolyzed to the amphiphilic material comprises octadecyl trichlorosilane, octyl trichlorosilane, produced from Shin Etsu under the tradename KA-7803 of heptadecyl-fluoro - 1,1,2,2-tetrahydronaphthalene-decyl trichlorosilane manufactured by Degussa under the trade name Dynasylan 9116 of hexadecyl trimethoxy silane, produced from Degussa under the trade name Dynasylan F8261 oct-fluorinated alkyl group of thirteen triethoxysilane, Degussa produced goods name Dynasylan MTMS methyl trimethoxysilane, manufactured by Degussa commodity name Dynasylan MTES methyl triethoxysilane, manufactured by Degussa under the trade name Dynasylan PTMO propylene trimethoxysilane, Degussa under the trade name Dynasylan PTEO yield of propyl triethoxy silane, Degussa produced goods name Dynasylan IBTMO butyl trimethoxysilane, produced from Degussa under the trade name Dynasylan BTEO self-butyl triethoxysilane, produced by Degussa octyl triethoxysilane commodity name Dynasylan OCTEO and produced from Degussa under the trade name Dynasylan in ethanol fluoroalkylsilane 8262, and produced the Degussa under the trade name Dynasylan F8263 in isopropanol fluoroalkyl silane formulation was manufactured by Degussa under the trade name DynasylanF 8800 fluoroalkyl modified silicone, manufactured by Degussa Dynasylan F8810 commodity aqueous fluoroalkyl-modified silicone named alumoxane. 可水解成两亲型物料的两亲型分子和化合物的其它例子包括产自Daikin Industries,Ltd.商品名为Optool DSX的碳氟化合物及其水解产物;产自Shin Etsu的商品名为KA-1003(乙烯基三氯硅烷)、商品名为KBM-1003(乙烯基三甲氧基硅烷)、商品名为KBE-1003(乙烯基三乙氧基硅烷)、商品名为KBM-703(氯代丙基三甲氧基硅烷)、X-12-817H、X-71-101、X-24-7890、KP801M、KA-12(甲基二氯硅烷)、KA-13(甲基三氯硅烷)、KA-22(二甲基二氯硅烷)、KA-31(三甲基氯硅烷)、KA-103(苯基三氯硅烷)、KA-202(二苯基二氯硅烷)、KA-7103(三氟丙基三氯硅烷)、KBM-13(甲基三甲氧基硅烷)、KBM-22(二甲基二甲氧基硅烷)、KBM-103(苯基三甲氧基硅烷)、KBM-202SS(二苯基二甲氧基硅烷)、KBE-13(甲基三乙氧基硅烷)、KBE-22(二甲基二乙氧基硅烷)、KBE-103(苯基三乙氧基硅烷)、KBE-202(二苯基二乙氧基硅烷)、KBM-3063(己基三甲氧基硅烷)、KBE-3063(己基三乙氧基硅烷)、KBM-3103(癸基三甲氧基硅烷)、KBM-7103(三氟丙基三甲氧基硅烷)、KBM-7803(十七烷基氟-1,1,2,2-四氢癸基三甲氧基硅烷)和KBE-7803(十七烷基氟-1,1,2,2-四氢癸基三乙氧基硅烷)的硅烷。 Can be hydrolyzed to the amphiphilic material in another example of amphiphilic molecules include compounds produced and Daikin Industries, Ltd fluorocarbon tradename Optool DSX their hydrolysates;. Produced from Shin Etsu under the tradename KA-1003 (vinyl trichlorosilane), the trade name of KBM-1003 (vinyltrimethoxysilane), trade name KBE-1003 (vinyltriethoxysilane), trade name KBM-703 (chloropropyl trimethoxysilane), X-12-817H, X-71-101, X-24-7890, KP801M, KA-12 (methyldichlorosilane), KA-13 (methyltrichlorosilane), KA- 22 (dimethyldichlorosilane), KA-31 (trimethylchlorosilane), KA-103 (phenyl trichlorosilane), KA-202 (diphenyl dichlorosilane), KA-7103 (trifluoro propyl trichlorosilane), KBM-13 (methyltrimethoxysilane), KBM-22 (dimethyl dimethoxysilane), KBM-103 (phenyltrimethoxysilane), KBM-202SS (two phenyl dimethoxy silane), KBE-13 (methyl triethoxysilane), KBE-22 (dimethyl ethoxy silane), KBE-103 (phenyltriethoxysilane), KBE -202 (diphenyl diethoxy silane), KBM-3063 (hexyl trimethoxy silane), KBE-3063 (hexyl triethoxysilane), KBM-3103 (decyl trimethoxysilane), KBM- 7103 (trifluoropropyl trimethoxysilane), KBM-7803 (heptadecyl-1,1,2,2-tetrahydro-decyl trimethoxysilane) and KBE-7803 (heptadecyl fluoro - 1,1,2,2-tetrahydro-decyl triethoxysilane) silane.

两亲型物料的其它具体例子包括C9F19C2H4Si(OCH3)3、(CH3O)3SiC2H4C6F12C2H4Si(OCH3)3、C9F19C2H4Si(NCO)3、(OCN)3SiC2H4Si(NCO)3、Si(NCO)4、Si(OCH3)4、CH3Si(OCH3)3、CH3Si(NCO)3、C8H17Si(NCO)3、(CH3)2Si(NCO)2、C8F17CH2CH2Si(NCO)3、(OCN)3SiC2H4C6F12C2H4Si(NCO)3、(CH3)3SiO--[Si(CH3)2--O--]n--Si(CH3)3(粘度为50厘沲)、(CH3O)2(CH3)SiC2H4C6F12C2H4Si(CH3)(OCH3)2、C8F17CH2CH2Si(OCH3)3、粘度为50厘沲的聚二甲基硅氧烷(KF96,ShinEtsu制造)、粘度为42厘沲而且在两个末端都含有羟基的改性聚二甲基硅氧烷(KF6001,Shin Etsu制造)、粘度为50厘沲且含有羧基的改性聚二甲基硅氧烷(X-22-3710,Shin Etsu制造)。 Other specific examples of amphiphilic materials comprising C9F19C2H4Si (OCH3) 3, (CH3O) 3SiC2H4C6F12C2H4Si (OCH3) 3, C9F19C2H4Si (NCO) 3, (OCN) 3SiC2H4Si (NCO) 3, Si (NCO) 4, Si (OCH3) 4 , CH3Si (OCH3) 3, CH3Si (NCO) 3, C8H17Si (NCO) 3, (CH3) 2Si (NCO) 2, C8F17CH2CH2Si (NCO) 3, (OCN) 3SiC2H4C6F12C2H4Si (NCO) 3, (CH3) 3SiO - [ Si (CH3) 2 - O -] n - Si (CH3) 3 (having a viscosity of 50 centistokes), (CH3O) 2 (CH3) SiC2H4C6F12C2H4Si (CH3) (OCH3) 2, C8F17CH2CH2Si (OCH3) 3, a viscosity 50 centistokes polydimethylsiloxane (KF96, manufactured ShinEtsu), and a viscosity of 42 centistokes at both ends are modified polydimethylsiloxane containing hydroxyl group (KF6001, Shin Etsu, Ltd.), viscosity of 50 centistokes and a carboxyl group-containing modified polydimethylsiloxane (X-22-3710, manufactured Shin Etsu).

在另一具体实施例中,两亲型物料含有加入至含氟聚合物中的聚硅氧烷重复单元。 In another particular embodiment, the amphiphilic material is added to the fluoropolymer containing polysiloxane repeat units. 通过含氟单体与聚硅氧烷(含有作为端基的反应基)的聚合反应可以获得含有聚硅氧烷重复单元的含氟聚合物。 By a fluorine-containing monomer and polysiloxane (containing end groups as reactive groups) polymerization of fluorine-containing polymer can be obtained polysiloxane repeating unit. 将烯键式不饱和单体(例如丙烯酸、其酯、甲基丙烯酸、其酯、乙烯基醚、苯乙烯、其衍生物)化学键合至聚硅氧烷末端,由此形成反应基。 The ethylenically unsaturated monomer (e.g., acrylic acid, its ester, methacrylic acid, their esters, vinyl ethers, styrene, derivatives thereof) chemically bonded to the end of the polysiloxane, thereby forming a reactive group.

通过含有氟原子的烯键式不饱和单体(含氟单体)的聚合反应制得含氟聚合物。 By containing a fluorine atom ethylenically unsaturated monomer (fluorine-containing monomer) polymerization reaction of fluorine-containing polymers. 含氟单体的例子包括氟代烯烃(例如氟乙烯、1,1-二氟乙烯、四氟乙烯、六氟丙烯、全氟-2,2-二甲基-1,3-二醇)、丙烯酸或甲基丙烯酸的氟烷基酯和氟乙烯基醚。 Examples of fluorine-containing monomer include fluoroolefins (e.g., fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-diol), acrylic or methacrylic acid ester and a fluoroalkyl fluorovinyl ether. 可以使用两个或多个含氟单体形成共聚物。 You can use two or more fluorine-containing monomers to form a copolymer.

也可以使用一种含氟单体与其它单体的共聚物作为两亲型物料。 You can also use a fluorine-containing monomer with other comonomers as amphiphilic materials. 其它单体的例子包括烯烃(例如乙烯、丙烯、异戊二烯、氯乙烯、1,1-二氯乙烯)、丙烯酸酯(例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸-2-乙基己酯)、甲基丙烯酸酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、二甲基丙烯酸乙二醇酯)、苯乙烯类(例如苯乙烯、乙烯基甲苯、α-甲基苯乙烯)、乙烯基醚(例如甲基乙烯醚)、乙烯基酯(例如乙酸乙烯酯、丙酸乙烯酯、肉桂酸乙烯酯)、丙烯酰胺(例如N-叔丁基丙烯酰胺、N-环己基丙烯酰胺)、甲基丙烯酰胺和丙烯腈。 Examples of other monomers include olefins (e.g. ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylates (e.g. methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate ), methacrylates (e.g. methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrenes (e.g., styrene, vinyl toluene, α- methyl styrene), vinyl ethers (e.g. methyl vinyl ether), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamides (e.g., N- tert-butylacrylamide, N - cyclohexyl acrylamide), methacrylamides and acrylonitrile.

两亲型分子进一步包括任何上述化合物的水解产物。 Amphiphilic molecules further comprises hydrolysis products of any of the above compounds. 特别地,用酸或碱处理任何上述化合物产生理想地适于在底材上形成薄膜的两亲型物料。 Particularly suitable for forming a thin film of amphiphilic material on a substrate with an acid or alkali treatment to produce any of the above compounds ideal.

两亲型分子具体包括多面体低聚倍半硅氧烷(POSS),美国专利6,340,734、6,284,908、6,057,042、5,691,396、5,589,562、5,422,223、5,412,053、J.Am.Chem.Soc.1992,114,6701-6710、J.Am.Chem.Soc.1990,112,1931-1936、Chem.Rev.1995,95,1409-1430和Langmuir,1994,10,4367中描述了这类化合物,这些文献在此引入作为参考。 Amphiphilic molecules specifically include polyhedral oligomeric silsesquioxane (POSS), U.S. Patent 6,340,734,6,284,908,6,057,042,5,691,396,5,589,562,5,422,223,5,412,053, J.Am.Chem.Soc.1992,114,6701-6710, J.Am.Chem.Soc.1990,112,1931-1936, Chem.Rev.1995,95,1409-1430 and Langmuir, 1994,10,4367 Such compounds are described, which is hereby incorporated by reference. POSS低聚物/聚合物含有活性羟基基团。 POSS oligomers / polymers containing reactive hydroxyl groups. 此外,POSS聚合物/低聚物具有相对刚性、热稳定的硅氧结构,其氧硅比率为大约1.5。 Furthermore, POSS polymer / oligomer having a relatively rigid, thermally stable silicon-oxygen structure, which silicon oxide ratio of about 1.5. 这些化合物被特有地认为是硅氧烷和二氧化硅之间的中间体。 These compounds are characteristically considered intermediate between silicone and silica. 该无机结构反过来被使这些系统能够增溶和衍生的烃/碳氟化合物外层覆盖,这以与烷基三氯氢烷相似的方式使底材表面具有疏水/疏油性。 The inorganic structure in turn is enabling these systems to solubilization and derived hydrocarbon / fluorocarbon outer covering, which alkyl with the alkyl trichlorosilane manner similar to the substrate surface hydrophobic / oleophobic.

在一个具体实施例中,该POSS聚合物含有化学式(VII)代表的化合物:[R(SiO)x(OH)y]n(VII)其中R是含有大约1至大约30个碳原子的烷基、芳基、氟化烷基、烷基醚或氟化烷基醚;x是大约1至大约4;y是大约1至大约4;n是大约1至大约500。 Compound In one specific embodiment, the POSS-containing polymer of formula (VII) represented by: [R (SiO) x (OH) y] n (VII) wherein R is an alkyl group containing from about 1 to about 30 carbon atoms, , aryl, fluorinated alkyl, alkyl ether or fluorinated alkyl ether; x is from about 1 to about 4; y is from about 1 to about 4; n is from about 1 to about 500. 在另一具体实施例中,R是含有大约6至大约20个碳原子的烷基、芳基、氟化烷基、烷基醚或氟化烷基醚;x是大约1至大约3;y是大约1至大约3。 In another particular embodiment, R is an alkyl group containing from about 6 to about 20 carbon atoms, an aryl group, a fluorinated alkyl, alkyl ether or fluorinated alkyl ether; x is from about 1 to about 3; y from about 1 to about 3. 可以通过在水中搅拌RSiX3(例如烷基三卤硅烷)并使其水解,使用酸或碱(分别如HCL或氢氧化铵)以进一步水解第一水解产物,由此制得这种化合物。 It can be stirred in water RSiX3 (e.g., alkyl trihalosilane) and allowed hydrolysis using an acid or a base (e.g., respectively HCL or ammonium hydroxide) to further the hydrolysis products of the first hydrolysis, thereby obtaining such compounds.

POSS聚合物的例子包括聚(对羟基苄基倍半硅氧烷)(PHBS)、聚(对羟基苄基倍半硅氧烷-共-甲氧基苄基倍半硅氧烷)(PHB/MBS)、聚(对羟基苄基倍半硅氧烷-共-叔丁基倍半硅氧烷)(PHB/BS)、聚(对羟基苄基倍半硅氧烷-共-环己基倍半硅氧烷)(PHB/CHS)、聚(对羟基苄基倍半硅氧烷-共-苯基倍半硅氧烷)(PHB/PS)、聚(对羟基苄基倍半硅氧烷-共-二环庚基倍半硅氧烷)(PHB/BHS)、聚(对羟基苯基乙基倍半硅氧烷)(PHPES)、聚(对羟基苯基乙基倍半硅氧烷-共-对羟基-α-甲基苄基倍半硅氧烷)(PHPE/HMBS)、聚(对羟基苯基乙基倍半硅氧烷-共-甲氧基苄基倍半硅氧烷)(PHPE/MBS)、聚(对羟基苯基乙基倍半硅氧烷-共-叔丁基倍半硅氧烷)(PHPE/BS)、聚(对羟基苯基乙基倍半硅氧烷-共-环己基倍半硅氧烷)(PHPE/CHS)、聚(对羟基苯基乙基倍半硅氧烷-共-苯基倍半硅氧烷)(PHPE/PS)、聚(对羟基苯基乙基倍半硅氧烷-共-二环庚基倍半硅氧烷)(PHPE/BHS)、聚(对羟基-α-甲基苄基倍半硅氧烷)(PHMBS)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-对羟基苄基倍半硅氧烷)(PHMB/HBS)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-甲氧基苄基倍半硅氧烷)(PHMB/MBS)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-叔丁基倍半硅氧烷)(PHMB/BS)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-环己基倍半硅氧烷)(PHMB/CHS)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-苯基倍半硅氧烷)(PHMB/PS)、聚(对羟基-α-甲基苄基倍半硅氧烷-共-二环庚基倍半硅氧烷)(PHMB/BHS)、聚(对羟基苄基倍半硅氧烷-共-对羟基苯基乙基倍半硅氧烷)(PHB/HPES)。 Examples of POSS polymers include poly (p-hydroxy benzyl silsesquioxane) (PHBS), poly (p-hydroxy benzyl silsesquioxane - co - methoxybenzyl silsesquioxane) (PHB / MBS), poly (p-hydroxy benzyl silsesquioxane - co - t-butyl silsesquioxane) (PHB / BS), poly (p-hydroxy benzyl silsesquioxane - co - cyclohexyl sesquisulfate siloxane) (PHB / CHS), poly (p-hydroxy benzyl silsesquioxane - co - phenyl silsesquioxane) (PHB / PS), poly (p-hydroxy benzyl silsesquioxane - Total - dicycloheptyl silsesquioxane) (PHB / BHS), poly (p-hydroxyphenyl ethyl silsesquioxane) (PHPES), poly (p-hydroxyphenyl ethyl silsesquioxane - Total - -α- methyl p-hydroxy benzyl silsesquioxane) (PHPE / HMBS), poly (p-hydroxyphenyl ethyl silsesquioxane - co - methoxybenzyl silsesquioxane) (PHPE / MBS), poly (p-hydroxyphenyl ethyl silsesquioxane - co - t-butyl silsesquioxane) (PHPE / BS), poly (p-hydroxyphenyl ethyl silsesquioxane - co - cyclohexyl silsesquioxane) (PHPE / CHS), poly (p-hydroxyphenyl ethyl silsesquioxane - co - phenyl silsesquioxane) (PHPE / PS), poly (p- hydroxyphenylethyl silsesquioxane - co - dicycloheptyl silsesquioxane) (PHPE / BHS), poly (p-hydroxy -α- methyl benzyl silsesquioxane) (PHMBS), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - p-hydroxy benzyl silsesquioxane) (PHMB / HBS), poly (p-hydroxy-methyl benzyl times -α- half silicone alkyl - co - methoxybenzyl silsesquioxane) (PHMB / MBS), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - t-butyl silsesquioxane) ( PHMB / BS), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - cyclohexyl silsesquioxane) (PHMB / CHS), poly (p-hydroxy-methyl benzyl times -α- silsesquioxane - co - phenyl silsesquioxane) (PHMB / PS), poly (p-hydroxy -α- methyl benzyl silsesquioxane - co - dicycloheptyl silsesquioxane) (PHMB / BHS), poly (p-hydroxy benzyl silsesquioxane - co - p-hydroxyphenyl ethyl silsesquioxane) (PHB / HPES).

将两亲型分子加在多孔载体上和/或加入多孔载体中以形成有利于薄膜形成过程的复合材料。 The amphiphilic molecules applied to the porous support and / or added to a porous support to form a thin film formation process in favor of a composite material. 该复合材料可以储存在气密的或以其它方式密闭的容器内。 The composite material can be stored in or otherwise closed in an airtight container. 该多孔载体可以起到类似海绵的作用和/或看上去像海绵。 The porous support may play a similar role sponge and / or look like a sponge.

为了利于将两亲型分子加入多孔载体,该两亲型分子可以非必要地与溶剂结合。 In order to facilitate the amphiphilic molecules added to a porous support, the amphiphilic molecule may optionally be combined with a solvent. 然后将溶剂和两亲型分子的混合物或两亲型分子(不含溶剂)与多孔载体接触充足的时间以使该混合物/两亲型分子渗入孔隙。 Then the mixture of solvent and amphiphilic molecules or amphiphilic molecules (solvent-free) and porous support into contact sufficient time to make the mixture / amphiphilic molecules penetrate pores. 在该结合过程中,多孔载体可以浸在该混合物/两亲型分子中,或将该混合物/两亲型分子喷或倒在多孔载体上。 In this bonding process, the porous carrier may be immersed in the mixture / amphiphilic molecules, or the mixture / amphiphilic molecules sprayed or poured on a porous support. 或者,也可以将该两亲型分子熔化并与多孔载体接触,该两亲型分子可以与溶剂结合,然后接触多孔载体,或者使用注射器将该两亲型分子注入多孔载体中。 Alternatively, you can melt the amphiphilic molecules in contact with the porous support, the amphiphilic molecules can be combined with a solvent, and then contacted the porous support, or the use of a syringe injecting amphiphilic molecules porous carrier. 无论两亲型分子是怎样加入多孔载体中的,理想的是两亲型分子在整个多孔载体中基本均匀地分布。 No matter how amphiphilic molecules added to the porous carrier, preferably amphiphilic molecules throughout the porous carrier substantially uniformly distributed.

可以与两亲型分子结合的溶剂通常是非极性有机溶剂。 Amphiphilic molecules may be bound to a non-solvent is generally a polar organic solvent. 这样的溶剂通常包括醇类(例如异丙醇)、烷(例如环己烷和甲基环己烷)、芳族化合物(例如甲苯、三氟甲苯)、烷基卤代硅烷、烷基或氟烷基取代的环己烷、醚、全氟化液体(例如全氟己烷)和其它含烃液体。 Such solvents generally include alcohols (e.g. isopropanol), an alkoxy (e.g., cyclohexane and methylcyclohexane), aromatic compounds (e.g. toluene, trifluoro toluene), a halogenated alkyl silanes, alkyl or fluoroalkyl alkyl-substituted cyclohexane, ethers, perfluorinated liquids (e.g. perfluorohexane), and other hydrocarbonaceous liquid. 全氟化液体的例子包括那些产自3M商品名为FluorinertTM和NovecTM的物质。 Examples of perfluorinated liquids include those manufactured by 3M under the trade name FluorinertTM and NovecTM substances. 当两亲型分子与一种或多种溶剂结合时,可以非必要地使用热能促进均匀混合物的形成。 When amphipathic molecules with one or more solvents in combination, may optionally be used to promote the formation of a homogeneous mixture of thermal energy.

一种成膜催化剂和/或猝灭剂可以与两亲型物料或两亲型物料和溶剂的混合物结合使用以促进成膜过程。 A film-forming catalyst and / or quencher may be used in combination with a mixture of amphiphilic material or amphiphilic material and solvent in order to promote film formation process. 成膜催化剂包括金属氯化物(例如氯化锌和氯化铝)、无机酸,猝灭剂包括锌粉和胺。 Forming catalysts include metal chlorides (e.g., aluminum chloride and zinc chloride), inorganic acid, and an amine quenchers include zinc powder. 每种物质在两亲型物料或两亲型物料与溶剂的混合物中的含量为大约0.01wt%至大约0.1wt%。 The content of each substance in the mixture amphiphilic material or amphiphilic material and solvent is about 0.01wt% to about 0.1wt%.

通过任何适当的方法对浸透了两亲型物料与溶剂的混合物的多孔载体进行处理以除去溶剂或基本除去所有溶剂。 A mixture of saturated amphiphilic porous carrier material and the solvent are processed by any suitable method to remove the solvent, or substantially all of the solvent was removed. 例如,可以使用蒸发或真空蒸馏。 For example, evaporation or vacuum distillation. 去除溶剂后,或在多孔溶剂浸透了不使用溶剂的两亲型物料的情况下,进行加热直至达到恒重。 After removing the solvent, or in a case where the porous solvent impregnated amphiphilic material without using a solvent, heating is conducted until constant weight is reached. 在这种情况下,在大约40至大约100℃下加热是有效的。 In this case, at about 40 to about 100 ℃ heating is effective. 在大多数情况下,两亲型物料固化,变成半固体或变成低粘度液体并保留在多孔载体的孔隙中。 In most cases, the amphiphilic material solidified into semi-solid or liquid into a low viscosity and remains in the pores of the porous carrier.

多孔载体可以由任何对两亲型分子是惰性的材料制成,例如金属、金属氧化物和陶瓷。 The porous carrier may be made of any material which is inert amphiphilic molecules, such as metals, metal oxides and ceramics. 如果使用金属作为多孔载体材料,该多孔载体可以是海绵状金属。 If using a metal as the porous carrier material, the porous carrier may be spongelike metal. 可以形成多孔载体的材料的例子包括氧化铝、硅酸铝、铝、黄铜、青铜、铬、铜、金、铁、镁、镍、钯、铂、碳化硅、银、不锈钢、锡、钛、钨、锌、锆、Hastelloy、Kovar、Invar、Monel、Inconel和各种其它合金中的一种或多种。 Examples of the porous support may be formed of materials include alumina, aluminum silicate, aluminum, brass, bronze, chromium, copper, gold, iron, magnesium, nickel, palladium, platinum, silicon carbide, silver, stainless steel, tin, titanium, tungsten, zinc, zirconium, Hastelloy, Kovar, Invar, Monel, Inconel and various other alloys of one or more.

将粉末、颗粒和/或纤维形式的这类材料压缩制成多孔载体,或压缩并烧结。 The powders, granules and / or fibers in the form of a porous support made of such materials compressed, or compressed and sintered. 任何制成的形状都可以使用。 Made any shape can be used. 压缩多孔载体材料的形状包括圆柱形、球形、椭圆形、片状、圆盘、塞形、丸状、立方体、长方形、圆锥形,它们可以是任何与某种具体应用相适应的大小。 Compressing the porous carrier material comprising a cylindrical shape, spherical, elliptical, flake, disc shaped plug, pellets, cubes, rectangular, conical, they may be of any size and adapted to a specific application. 参看图1至3,揭示了多孔载体的多种形状/大小。 Referring to Figures 1-3, discloses a variety of shapes / sizes of the porous support. 在每一个图中,多孔材料10含有保存两亲型分子的孔12。 In each figure, the porous material 10 containing stored amphiphilic molecules hole 12.

在一个具体实施例中,该多孔载体具有平均孔径为大约1微米至大约1,000微米的孔。 In one particular embodiment, the porous support has an average pore size of from about 1 micron to about hole 000 microns. 在另一具体实施例中,该多孔载体具有平均孔径为大约5微米至大约500微米的孔。 In another particular embodiment, the porous support has an average pore diameter of the hole from about 5 microns to about 500 microns. 在又一具体实施例中,该多孔载体具有平均孔径为大约10微米至大约200微米的孔。 In another particular embodiment, the porous support has an average pore size of from about 10 microns to about hole 200 microns. 在再一具体实施例中,该多孔载体具有平均孔径为大约20微米至大约100微米的孔。 In another particular embodiment, the porous support has an average pore size of from about 20 microns to about hole 100 microns. 可以调整最初被压缩在一起的颗粒的大小,由此控制孔径。 You can adjust the initial size of the particles are compressed together, thereby controlling the aperture.

多孔载体的例子包括那些产自Mott Corporation商品名为MottPorous Metal的材料、那些产自Filtros Ltd.商品名为Kellundite的材料和那些产自Provair Advanced Materials Inc.商品名为Metal Foam、Porous Metal Media和Sinterflo的材料。 Examples of the porous carrier include those produced from Mott Corporation Product name MottPorous Metal material, and those produced Filtros Ltd. under the trade name Kellundite materials and those produced Provair Advanced Materials Inc. under the trade name Metal Foam, Porous Metal Media and Sinterflo  material.

在一个具体实施例中,该多孔载体的孔隙率使得每立方厘米多孔载体能够吸收大约0.001g至大约5g两亲型物料。 In one particular embodiment, the porosity of the porous carrier such that each cubic centimeter of the porous support can absorb from about 0.001g to about 5g amphiphilic material. 在另一具体实施例中,该多孔载体的孔隙率使得每立方厘米多孔载体能够吸收大约0.01g至大约2g两亲型物料。 In another particular embodiment, the porosity of the porous carrier such that each cubic centimeter of the porous support can absorb from about 0.01g to about 2g amphiphilic material. 在又一具体实施例中,该多孔载体的孔隙率使得每立方厘米多孔载体能够吸收大约0.05g至大约1g两亲型物料。 In another particular embodiment, the porosity of the porous carrier such that each cubic centimeter of the porous support can absorb from about 0.05g to about 1g amphiphilic material. 在一个孔隙率如上的具体实施例中,两亲型物料包括两亲型分子和溶剂。 In a particular embodiment of a porosity above, the amphiphilic material comprises an amphiphilic molecules and solvents. 在另一个孔隙率如上的具体实施例中,两亲型物料包括两亲型分子,不含溶剂。 In another particular embodiment, the porosity of the above, the amphiphilic material comprises amphiphilic molecules, solvent-free.

本发明的方法和复合材料有利于在底材上形成薄膜。 The method of the present invention and the composite material in favor of forming a thin film on a substrate. 底材包括那些具有多孔和无孔表面的底材,例如玻璃、有抗反射涂层(例如氟化镁)的玻璃、二氧化硅(其它金属氧化物)、氧化锗、陶瓷、瓷、玻璃纤维、金属和有机材料,包括热固性材料(例如聚碳酸酯)和热塑性材料。 Substrates include those substrates having a porous and non-porous surfaces, such as glass, antireflection coating (e.g., magnesium fluoride) glass, silica (other metal oxides), germanium oxide, ceramics, porcelain, glass fiber , metal and organic materials, including thermoset materials (such as polycarbonate), and thermoplastic material. 其它有机材料包括聚苯乙烯及其混合聚合物、聚烯烃(特别是聚乙烯和聚丙烯)、聚丙烯酸化合物、聚乙烯基化合物(例如聚氯乙烯和聚乙酸乙烯酯)、聚酯和橡胶,还有由粘胶丝制成的丝和纤维素醚、纤维素酯、聚酰胺、聚氨酯、聚酯(例如聚对苯二酸乙二醇酯)和聚丙烯腈。 Other organic materials include polystyrene and its mixed polymers, polyolefins (especially polyethylene and polypropylene), polyacrylic acid compounds, polyvinyl compounds (such as polyvinyl chloride and polyvinyl acetate), polyester and rubber, also made by the viscose rayon filaments and cellulose ethers, cellulose esters, polyamides, polyurethanes, polyesters (such as poly ethylene terephthalate) and polyacrylonitrile.

玻璃具体包括透镜,例如眼镜、载物玻璃、双目透镜、显微镜透镜、望远镜透镜、暗箱物镜、录像透镜、电视屏幕、电脑屏幕、LCDs、镜子、棱镜,及类似物。 Specifically including glass lenses, such as glasses, loading glass, binocular lenses, microscope lenses, telescope lenses, camera obscura lens, video lenses, television screens, computer screens, LCDs, mirrors, prisms, and the like. 底材可以含有一种材料的底层,用来提高底材表面与两亲型分子之间的粘合性。 The substrate may comprise a layer of material, to improve the adhesion between the substrate surface and the amphiphilic molecules.

采用本发明的多孔载体,使用任何适当的薄膜形成技术将两亲型分子作为薄膜涂敷到底材表面上。 The porous carrier according to the present invention, using any suitable film-forming technique as a thin film of amphiphilic molecules on the surface of the coating material in the end. 多孔载体用来将两亲型分子有效地输送至底材表面,同时将对底材的损伤减至最低或完全消除并将两亲型分子的浪费减至最低。 The porous carrier used to amphiphilic molecules effectively delivered to the substrate surface while the substrate will minimize or completely eliminate damage and waste of amphiphilic molecules is minimized.

成膜技术包括:在具有减压、升温、光照和动力(power)中至少一种条件的室内或封闭环境中,将底材曝露于加在多孔载体上的两亲型分子中。 Film formation techniques include: having a reduced pressure, heating, lighting and power (power) of at least one condition of the indoor or closed environment, will be exposed to the substrate is applied to the porous support amphiphilic molecules. 优选地,使用减压和/或升温。 Preferably, pressure and / or temperature. 强加的减压、升温、光照和/或动力条件引起两亲型分子的汽化或升华,由此进入室气氛中,并随后在底材表面以均匀和连续的形式自组合和/或本体聚合,由此形成薄膜。 Imposed pressure, temperature, light and / or dynamic conditions that cause amphiphilic molecules vaporized or sublimated, thereby entering the room atmosphere, and then the substrate surface to form a uniform and continuous self-assembling and / or bulk polymerization, thereby forming a thin film.

在一个具体实施例中,该底材在大约0.000001至大约760托的压力下曝露在两亲型分子中。 In one particular embodiment, the substrate at about 0.000001 to about 760 torr pressure exposed amphiphilic molecules. 在另一具体实施例中,该底材在大约0.00001至大约200托的压力下曝露在两亲型分子中。 In another particular embodiment, the substrate at about 0.00001 to about 200 Torr exposed amphiphilic molecules. 在又一具体实施例中,该底材在大约0.0001至大约100托的压力下曝露在两亲型分子中。 In another particular embodiment, the substrate at about 0.0001 to about 100 Torr exposed amphiphilic molecules.

在一个具体实施例中,将该复合材料/多孔载体加热至大约20至大约400℃。 In one particular embodiment, the composite / porous carrier was heated to about 20 to about 400 ℃. 在另一具体实施例中,将该复合材料/多孔载体加热至大约40至大约350℃。 In another particular embodiment, the composite / porous carrier was heated to about 40 to about 350 ℃. 在又一具体实施例中,将该复合材料/多孔载体加热至大约50至大约300℃。 In another particular embodiment, the composite / porous carrier was heated to about 50 to about 300 ℃. 只有该复合材料/多孔载体需要在上述温度下引发成膜作用。 Only the composite / porous support required in the film-forming initiators at said temperature. 在该室中,该底材的温度与该复合材料/多孔载体大致相同或不同。 In this chamber, the substrate temperature and the composite / porous support substantially the same or different. 该复合材料/多孔载体的温度与室气氛大致相同或不同。 The composite / porous support with the chamber atmosphere temperature is substantially the same or different. 该底材的温度与室气氛大致相同或不同。 The substrate temperature and the chamber atmosphere substantially the same or different. 在一个具体实施例中,底材、复合材料和气氛中每一项都在大约20至大约400℃。 In one particular embodiment, the substrate, each of the composite material, and an atmosphere in about 20 to about 400 ℃.

在一个具体实施例中,两亲型物料的用量为室容积的大约110-3mmole/ft3至大约10mmole/ft3。 In one particular embodiment, the amount of amphiphilic material chamber volume is approximately 1 10-3mmole / ft3 to about 10mmole / ft3. 在另一具体实施例中,两亲型物料的用量为室容积的大约110-2mmole/ft3至大约1mmole/ft3。 In another particular embodiment, the amount of amphiphilic material chamber volume is approximately 1 10-2mmole / ft3 to about 1mmole / ft3.

在一个具体实施例中,底材和两亲型物料保持接触大约10秒钟至大约24小时(在特定的温度和压力下)。 In one particular embodiment, the substrate and amphiphilic material is kept in contact for about 10 seconds to about 24 hours (at a given temperature and pressure). 在另一具体实施例中,底材和两亲型物料保持接触大约30秒钟至大约1小时。 In another particular embodiment, the substrate and the amphiphilic material to remain in contact for about 30 seconds to about 1 hour. 或者,可以忽略时间限度,只要监测厚度,这样可以在得到所需厚度后终止该过程。 Alternatively, you can omit the time limit, as long as the monitor thickness, so that the process can be terminated after the desired thickness.

成膜率主要取决于两亲型物料的同一性、多孔载体的同一性、成膜条件(温度、压力及类似情况)中的一项或多项。 Deposition rate depends on the identity of amphiphilic materials, porous carrier identity, the film formation conditions (temperature, pressure and the like) of one or more. 在一个具体实施例中,成膜率为大约0.01nm/sec或更大且大约1nm/sec或更小(nm是膜厚度)。 In one particular embodiment, the film forming rate is about 0.01nm / sec or more and about 1nm / sec or less (nm a film thickness). 在另一具体实施例中,成膜率为大约0.05nm/sec或更大且大约0.5nm/sec或更小。 In another particular embodiment, the film forming rate is about 0.05nm / sec or more and about 0.5nm / sec or less.

成膜技术的常用例子包括真空淀积、真空涂敷、箱式涂装、溅射涂装、汽相淀积或化学气相淀积(CVD)(例如低压化学气相淀积(LPCVD)、等离子体增效化学气相淀积(PECVD)、高温化学气相淀积(HTCVD))、和喷镀。 Examples of conventional deposition techniques include vacuum deposition, vacuum coating, box-type coating, sputter coating, vapor deposition or chemical vapor deposition (CVD) (e.g., low pressure chemical vapor deposition (LPCVD), plasma Efficiency chemical vapor deposition (PECVD), high-temperature chemical vapor deposition (HTCVD)), and spraying. 这些技术是该技术领域内已知的,为了本文的简短,这里不作描述。 These techniques are known within the art, for brevity of this article, are not described here.

汽相淀积/化学气相淀积技术和方法已经在文献中广泛地作过说明,例如:Thin Solid Films,1994,252,32-37;Ruth A.的Vacuumtechnology第三版,Elsevier Publication,1990,311-319;Appl.Phys.Lett.1992,60,1866-1868;Polymer Preprints,1993,34,427-428;美国专利6,265,026、6,171,652、6,051,321、5,372,851和5,084,302,由于它们关于在底材上形成薄膜或沉积有机化合物的理论,以上文献在此引入作为参考。 Vapor deposition / chemical vapor deposition techniques and methods have been extensively described in the literature as, for example: Thin Solid Films, 1994,252,32-37; Ruth A. The Vacuumtechnology third edition, Elsevier Publication, 1990, 311-319; Appl.Phys.Lett.1992,60,1866-1868; Polymer Preprints, 1993,34,427-428; 6,265,026,6,171,652,6,051,321,5,372,851 and US Patent 5,084,302, since they form a thin film on a substrate on or theory, the deposition of organic compounds in the above document is incorporated herein by reference.

参看图4,描述了一种形成薄膜的方法和系统。 Referring to Figure 4, describes a method and system for forming a film. 总的来说,在本发明中使用室20(例如真空室)。 In general, the use of chamber 20 (e.g., a vacuum chamber) in the present invention. 该室可以是一个带门的隔热长方形金属盒,该门关闭时用垫圈密封并允许插入和去除物品。 The chamber may be an insulated rectangular metal boxes with doors, sealing gasket when the door is closed and allows the insertion and removal of items. 该盒子可以有一个内室,其非必要地与一个能够吸得例如0.0001托真空的高度真空泵22相连。 The box may have an inner chamber, which can unnecessarily sucked for example with a 0.0001 Torr vacuum pump 22 is connected to the height. 该室的例子包括产自Satis Vacuum AG商品名为Satis,诸如MC LAB 260、MC LAB 360、900DLS、1200TLS和150的室;产自Leybold Vacuum商品名为Univex,诸如300、350和400的室;产自Denton Vacuum商品名为Integrity36、39、44和50的室;和产自Balzers商品名为Balinit的室。 Examples include the chamber produced Satis Vacuum AG tradename Satis,, 1200TLS room such as MC LAB 260, MC LAB 360,900DLS and 150; produced from Leybold Vacuum tradename Univex, such as 300, 350 and 400 of the chamber; produced from Denton Vacuum tradename room Integrity36,39,44 and 50; and a labor room called Balinit from Balzers merchandise.

该室可以配有分离的加热装置以将室24加热和/或将两亲型物料26加热/汽化和/或将底材28加热。 Heating means the chamber can be equipped with a separate chamber 24 to heat and / or amphiphilic material 26 heating / vaporization and / or heating the substrate 28. 可以使用许多不同的装置(例如电阻电极、电阻加热器、感应圈或电子或激光束)以便将两亲型物料迅速加热至汽化所需的高温。 Many different devices can be used (e.g. resistive electrode, resistance heater, an induction loop or an electron or laser beam) so as amphiphilic material is rapidly heated to a high temperature vaporization required. 可以使用电热器实现此目的。 You can use an electric heater for this purpose. 该加热器可以加热放有复合材料32的坩锅30。 The heater can be heated crucible placed 30 of the composite 32.

要涂布本发明的疏水性薄膜的底材34被置于该室内的任何适当的位置。 To a hydrophobic film coating of the present invention the substrate 34 is placed in any suitable position of the chamber. 将多孔载体和两亲型物料的复合材料32也置于室内并与加热装置26接触,将门关闭。 The porous carrier and amphiphilic composite material 32 may also be placed indoors and in contact with the heating device 26, the door is closed. 尽管显示的是圆锥形排列方式,但多孔载体和两亲型物料的复合材料32和底材34可以以任何方式安置。 Although the arrangement shown is conical, but the porous carrier material and amphiphilic composites 32 and substrate 34 may be arranged in any manner. 非必要地对室20施加大约210+2至大约510-4托的范围内的强真空。 Optionally applying a strong vacuum within the range of about 2 10 + 2 to about 5 10-4 Torr of chamber 20. 将连接泵22与室20的阀36关闭以保持室20处于恒定高真空下。 Connect the pump 22 and valve chamber 20 36 is closed to keep the chamber 20 is at a constant high vacuum. 将两亲型分子迅速加热从而将该物料汽化。 The amphiphilic molecules thereby rapidly heating the material vaporized. 气相两亲型分子均匀而且非常迅速地在整个室20内扩散。 Gas amphiphilic molecules evenly and very quickly spread throughout the room 20. 当两亲型分子汽化时,室内真空略微上升,但仍保持在大约210+2至大约510-4托。 When the amphiphilic molecules vaporizing, indoor vacuum rose slightly, but remained at about 2 10 + 2 to about 5 10-4 Torr. 将室20在该条件下保持大约10秒至大约60分钟,或通过可以安置在该室内的石英晶体监测厚度(以获得所需的厚度)。 The chamber 20 is maintained for about 10 seconds to about 60 minutes in this condition, or may be placed in the chamber by quartz crystal thickness monitor (to obtain the desired thickness). 在此时间内,两亲型分子自组合并使其自身粘附到底材34表面并形成连续均匀的薄膜。 During this time, the amphiphilic molecules self-assembled and allowed to adhere to itself in the end surface of the timber 34 and form a continuous uniform film. 底材34可以旋转以促进两亲型物料在底材34上的均匀涂布。 Substrate 34 may be rotated to facilitate uniform coating of amphiphilic material on a substrate (34).

在选定的时间后,将真空泵阀36打开以抽空室20内过量的气相两亲型物料。 After the selected time, the vacuum valve 36 is opened to evacuated chamber 20. Gas excess amphiphilic material. 可以非必要地在室和泵之间使用冷阱或冷凝器以冷凝或捕获过量的两亲型物料蒸气,使其不会漏到大气中。 It may optionally between the chamber and the pump using a cold trap or condenser to condense or capture excess amphiphilic material vapor, so it does not leak into the atmosphere. 通过另一个阀38让清洁的空气进入室20,由此将其提高至大气压,而且将室20打开移出已涂布的底材34。 Through another valve 38 so that the clean air into the chamber 20, whereby it increased to atmospheric pressure, and the chamber 20 to open 34 out of the coated substrate.

可以通过FTIR和/或NMR使用该技术领域内已知的方法对成膜组合物进行表征。 Film-forming composition can be characterized using the methods known in the art by FTIR and / or NMR. 可以通过该技术领域内已知的方法(例如美国专利4,745,169)确定其它化学性质(例如羟基百分比)。 It may be (e.g., U.S. Patent No. 4,745,169) determining other chemical properties (e.g., hydroxy percentage) by the methods known in the art. 其它物理特性和光谱表征法也可以使用,而且它们在该技术领域是已知的。 Other physical properties and spectroscopic characterization methods can be used, and they are known in the art of.

两亲型物料和/或由其形成的薄膜含有活性羟基基团,它参与了与底材的化学键合(氢和/或共价)。 Amphiphilic material and / or by forming a thin film containing a reactive hydroxyl groups, it is involved with the chemical bonding (hydrogen and / or covalent) of the substrate. 当底材表面与湿气(空中浮游的水分子)反应时,与层的自组合相类似,使得共价键连接到表面上,由此提供永久透明的均匀薄膜,其可以抵抗许多剧烈条件,即,保持其优异的疏水性/疏油性。 When the surface of the substrate with moisture (airborne water molecules) reacting the layer of self-assembly is similar, such that a covalent bond to the surface, thereby providing a permanent transparent uniform film, which is resistant to a number of severe conditions, i.e., to maintain its excellent hydrophobic / oleophobic.

该薄膜在表面上提供了一些优点,包括抗划伤性、眼镜上抗反光涂料的保护、保护表面免受腐蚀、防潮层、减少摩擦、抗静电、耐污染性、fringerprint resistance等等。 The film on the surface provides several advantages, including scratch resistance, anti-reflective coating on glasses protection, protecting the surface from corrosion, moisture-proof layer, reduce friction, antistatic, stain resistance, fringerprint resistance and so on. 该薄膜通常在性质上是疏水的。 The films are typically hydrophobic in nature.

在底材上使用浸透了两亲型分子的多孔载体的复合材料形成的薄膜在底材上具有均匀的厚度。 A thin film on a substrate using a porous carrier impregnated amphiphilic molecules form a composite material having a uniform thickness on a substrate. 在一个具体实施例中,制成薄膜的厚度为大约1nm至大约250nm。 In one particular embodiment, a film made of a thickness of about 1nm to about 250nm. 在另一具体实施例中,制成薄膜的厚度为大约2nm至大约200nm。 In another particular embodiment, the thickness of the film formed from about 2nm to about 200nm. 在又一具体实施例中,制成薄膜的厚度为大约5nm至大约100nm。 In another particular embodiment the thickness of the film formed from about 5nm to about 100nm. 在再一个具体实施例中,制成薄膜的厚度为大约8nm至大约20nm。 In a further particular embodiment the thickness of the film formed from about 8nm to about 20nm. 可以通过调整淀积参数控制薄膜的厚度,例如在减压、升温、光照和/或power中至少一个条件下,底材和复合材料在室内保留的时间。 The deposition parameters can be controlled by adjusting the thickness of the film, for example under reduced pressure, heating, lighting, and / or at least one of the power conditions, the substrate and the composite material retention time in the room.

在一个具体实施例中,薄膜相对均匀,在于假定底材具有平坦的表面,在底材平坦部分的表面上,薄膜的厚度差别不会大于大约25nm。 In one particular embodiment, the film is relatively uniform, assuming that the substrate has a flat surface, the flat portion of the upper surface of the substrate, the film thickness difference is not greater than about 25nm. 在另一具体实施例中,薄膜相对均匀,在于假定底材具有平坦的表面,在底材平坦部分的表面上,薄膜的厚度差别不会大于大约15nm。 In another particular embodiment, the film is relatively uniform, assuming that the substrate has a flat surface, the flat portion of the upper surface of the substrate, the film thickness difference is not greater than about 15nm.

在底材上使用浸透了两亲型分子的多孔载体的复合材料形成的薄膜在性质上是连续的。 A thin film on a substrate using a porous carrier impregnated amphiphilic molecules form a composite material in nature is continuous. 换句话说,按照本发明制得的薄膜中的针孔和其它漆膜缺陷被减至最低和/或完全消除。 In other words, according to the present invention, the films obtained in the pinholes and other film defects are minimized and / or eliminated.

在一个具体实施方案中,使用POSS聚合物作为两亲型物料和玻璃作为底材时,二氧化硅(或其它金属氧化物)层和两亲型物料薄膜的形成可以只在一个室中进行。 In one particular embodiment, the polymer used as the substrate POSS, silica (or other metal oxide) layer and a thin film forming amphiphilic material may be used as only one chamber amphiphilic material and glass. 这是因为在其上形成POSS聚合物两亲型物料层时,不需要将二氧化硅层曝露在水蒸气下。 This is because POSS polymer amphiphilic material layer formed thereon, the silicon dioxide layer need not be exposed to water vapor. 此外,在室内部形成任何POSS聚合物两亲型物料层都不是有害的,而且不会妨碍该室随后重复用于前述两步法。 In addition, the chamber any POSS polymer amphiphilic material layer is not harmful and does not prevent the chamber is then repeated for the preceding two-step process.

下列实施例举例说明了本发明。 The following examples illustrate the present invention. 除非下列实施例以及说明书和权利要求书中其他地方另行指明,所有的份和百分比都是基于重量的,所有的温度都是摄氏度,而且压力是在大气压下或在大气压附近。 The book elsewhere unless the following examples and the specification and claims otherwise indicated, all parts and percentages are by weight, all temperatures are in degrees Celsius, and pressure is at atmospheric or near atmospheric pressure.

实施例1在一个5升烧杯中加入三升蒸馏水。 Example 1 was added three liters of distilled water in a 5 liter beaker. 然后将该烧杯冷却至5℃,并通过冷凝器循环保持该温度,然而,也可以使用该技术领域内任何已知的保持温度的方法,例如加冰。 The beaker was then cooled to 5 ℃, circulating through the condenser and maintained at that temperature, however, also possible to use any known method of maintaining the temperature within the art, such as ice. 逐滴加入十八烷基三氯硅烷(300克),同时搅拌并保持该温度。 Was added dropwise octadecyl trichlorosilane (300 g), while stirring and maintaining the temperature. 然后将溶液水解,产生精细的晶体物质。 The solution is then hydrolyzed to produce a fine crystalline material. 将反应混合物进一步搅拌大约30分钟,继续保持温度。 The reaction mixture was further stirred for about 30 minutes, maintaining the temperature. 然后让该反应混合物恢复室温,同时搅拌。 The reaction mixture was then allowed to resume room temperature while stirring. 回到室温后,将该反应混合物搅拌大约10小时。 After returned to room temperature, the reaction mixture was stirred for about 10 hours. 然后将该反应混合物过滤并用水清洗去除所有的酸,然后干燥。 Then the reaction mixture was filtered and washed with water to remove all acid, and then dried. 将该混合物风干,然后在95℃烘干2小时,或者也可以使用该技术领域内已知的其它干燥法。 The mixture was dried, and then dried for 2 hours at 95 ℃, or may be provided with other known in the art drying method. 将混合物干燥后,得到熔点为70-72℃的白色粉末。 The mixture was dried to give a white powder having a melting point of 70-72 ℃.

实施例2重复实施例1的程序,只是使用十七烷基氟-1,1,2,2-四氢癸基三氯硅烷代替十八烷基三氯硅烷。 Example 2 The procedure of Example 1 was repeated, except that 1,1,2,2-tetrahydro-heptadecyl decyl trichlorosilane in place of octadecyltrichlorosilane. 将混合物干燥后,得到熔点为67℃的白色粉末。 The mixture was dried to give a white powder having a melting point of 67 ℃.

实施例3重复实施例1的程序,只是使用辛基三氯硅烷代替十八烷基三氯硅烷。 Example 3 The procedure of Example 1 was repeated, except that instead of octadecyl trichlorosilane octyl trichlorosilane. 将混合物干燥后,得到非常粘稠的澄清油。 The mixture is dried, to give a very viscous clear oil.

实施例4在一个250毫升的烧瓶中搅拌十六烷基三甲氧基硅烷(25克)、15毫升蒸馏水、40毫升2-丙醇和2毫升浓盐酸。 Example 4 was stirred hexadecyl trimethoxy silane (25 g) in a 250 ml flask, 15 ml of distilled water, 40 ml of 2-propanol and 2 ml of concentrated hydrochloric acid. 该混合物在几分钟内变成白色粘稠沉淀物并变得难以搅拌。 The mixture became a thick white precipitate in a few minutes and stirring becomes difficult. 再加入100毫升50∶50水-2-丙醇混合物,将该反应混合物在室温下搅拌10小时,然后加热至70℃达2小时以完全水解,产生微细粉末。 100 ml of water was added a 50:50 mixture of 2-propanol, the reaction mixture was stirred at room temperature for 10 hours, then heated to 70 ℃ for 2 hours to complete the hydrolysis, to produce a fine powder. 按照实施例1进行分离和过滤。 Separation and filtration in Example 1. 然后将反应混合物在98℃的烘箱中干燥2小时。 The reaction mixture was then dried in an oven at 98 ℃ for 2 hours. 该混合物变成油状,而且在室温中固化,产生熔点为65℃的白色、蜡状固体。 The mixture became oily, and cured at room temperature, a melting point of 65 ℃ produce a white, waxy solid.

实施例5重复实施例4的程序,只是使用1∶1摩尔比的十三烷基氟代辛基三乙氧基硅烷和十六烷基三甲氧基硅烷代替十六烷基三甲氧基硅烷。 Example 5 The procedure of Example 4 was repeated, but using 1 molar tridecyl fluoro octyltriethoxysilane and hexadecyl trimethoxysilane ratio instead of hexadecyl trimethoxysilane. 得到半固体。 To give a semi-solid.

实施例6将重量百分比不定的十三烷基氟代辛基三乙氧基硅烷和十六烷基三甲氧基硅烷混合在一起。 6 weight percent indefinite tridecyl fluoro octyltriethoxysilane and hexadecyl trimethoxysilane mixed examples. 此外,加入四乙氧基硅烷以占混合物总重量的大约5%至大约10%。 In addition, tetraethoxysilane is added to account for about 5% of the total weight of the mixture to about 10%. 然后将该混合物在实施例4和5的实验条件下水解,然而,在水解的四乙氧基硅烷中加入2-乙基己酸锌(辛酸锌)作为交联剂的催化剂以增加反应活性部位的数量。 The mixture is then hydrolyzed under the experimental conditions of Examples 4 and 5, however, was added 2-ethylhexanoate, zinc (zinc octoate) in the hydrolyzed tetraethoxysilane as a catalyst to increase the cross-linking agent reactive sites number. 使用rotavap在减压下清除醇和水。 Use rotavap remove alcohol and water under reduced pressure. 该混合物产生一种白色糊状半固体。 This mixture produces a white semi-solid paste.

尽管已经通过某些具体实施例解释了本发明,但应该理解的是,对于那些本领域的技术人员而言,在阅读本说明书时,对本发明的各种修改都是显而易见的。 Although the present invention has been explained by certain specific embodiments, it should be understood that those skilled in the art, in reading this description of various modifications of the invention are apparent. 因此,应该理解的是,这里公开的本发明意在涵盖这样的落入所附权利要求书范围内的修改。 Therefore, it should be understood that the invention disclosed herein is intended to cover such modifications as fall within the appended claims and the scope of.

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Classifications
International ClassificationG02B1/10, C03C17/00, C09D1/00, C09D7/12, B05D3/12, C23C14/12, B05D7/24, C03C25/22, B05D3/02, C23C14/24, C09D183/16, C09D183/04
Cooperative ClassificationC23C14/243, C03C17/001, C23C14/12, B05D1/60, C03C25/22, Y10T428/24997
European ClassificationB05D1/60, C03C17/00B, C23C14/24A, C03C25/22, C23C14/12
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