Search Images Maps Play Gmail Drive Calendar Translate More »
Sign in

Patents

  1. Advanced Patent Search
Publication numberCN105765014 A
Publication typeApplication
Application numberCN 201480055028
PCT numberPCT/US2014/058715
Publication date13 Jul 2016
Filing date2 Oct 2014
Priority date4 Oct 2013
Also published asCA2926194A1, EP3055371A1, EP3055371A4, US20160237283, WO2015051053A1
Publication number201480055028.3, CN 105765014 A, CN 105765014A, CN 201480055028, CN-A-105765014, CN105765014 A, CN105765014A, CN201480055028, CN201480055028.3, PCT/2014/58715, PCT/US/14/058715, PCT/US/14/58715, PCT/US/2014/058715, PCT/US/2014/58715, PCT/US14/058715, PCT/US14/58715, PCT/US14058715, PCT/US1458715, PCT/US2014/058715, PCT/US2014/58715, PCT/US2014058715, PCT/US201458715
Inventors布赖恩·科恩, 百德瑞斯·麦苏里亚, 塔米·麦特洛克, 阿莱娜·麦格雷戈
Applicant月神创新公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Transparent hydrophobic coating materials with improved durability and methods of making same
CN 105765014 A
Abstract
Durable, transparent, inorganic-organic hybrid hydrophobic coating materials for glass, metal or plastic substrates are provided. The coating materials are generally an acid catalyzed condensation reaction product comprised of an organic polymeric silane (e.g., a polyol functionalized with a silane through a urethane linkage or a polyamine functionalized with a silane through a urea linkage, such as isocyanatopropyltrimethoxysilane or isocyanatopropyltriethoxysilane), an inorganic metal alkoxide (e.g., silicon alkoxides such as tetraethoxysilane or tetramethoxysilane) and a fluorinated silane (e.g., (3,3,3-trifluoropropyl)trimethoxysilane or nonafluorohexyltrimethoxysilane).
Claims(33)  translated from Chinese
1. 一种疏水性涂覆材料,包括由下列物质组成的酸催化的缩合反应产物: 有机聚硅烷; 无机金属醇盐;以及氟硅烷。 A hydrophobic coating material consisting comprises acid catalyzed condensation reaction product of: an organic polysilane; inorganic metal alkoxide; and a fluorosilane.
2. 根据权利要求1所述的疏水性涂覆材料,其中所述有机聚硅烷是硅烷官能化的多元醇或多胺。 The hydrophobic coating material of claim 1, wherein the organopolysiloxane is a silane functionalized polyols or polyamines.
3. 根据权利要求1所述的疏水性涂覆材料,其中所述有机聚硅烷是与异氰酸酯封端的硅烷反应的含有两个到四个羟基的聚己酸内酯多元醇。 According to claim 1, wherein the hydrophobic coating material, wherein the organopolysiloxane is polycaprolactone polyols containing two to four hydroxyl groups with the isocyanate-terminated silane reactions.
4. 根据权利要求1所述的疏水性涂覆材料,其中所述官能化的聚己酸内酯多元醇分子量为50 ~10000g/mol。 Polycaprolactone polyols according to the molecular weight of the hydrophobic coating material of claim 1, wherein the functionalized to 50 ~ 10000g / mol.
5. 根据权利要求1所述的疏水性涂覆材料,其中所述有机聚硅烷是聚脲硅烷。 According to claim 1 wherein the hydrophobic coating material, wherein the organopolysiloxane is a polyurea silane.
6. 根据权利要求5所述的疏水性涂覆材料,其中聚脲硅烷是含有至少两个一级或者二级胺基团的胺与异氰酸酯封端的硅烷的反应产物。 According to claim 5, wherein the hydrophobic coating material, wherein the polyurea reaction product of a silane containing at least two primary or secondary amine groups of the amine with an isocyanate-terminated silane.
7. 根据权利要求6所述的疏水性涂覆材料,其中所述聚脲硅烷是二亚乙烯三胺和异氰酸酯封端的硅烷的反应产物。 According to claim 6, wherein the hydrophobic coating material, wherein the polyurea silane is a reaction product of ethylene triamine and isocyanate-terminated silane.
8. 根据权利要求7所述的疏水性涂覆材料,其中所述金属醇盐包括至少一种每分子具有至少一个硅烷基的可水解的化合物,所述硅烷基用通式Si(Rl)x(R2)4_x表示,其中Rl表示Ci-C8烷基、环氧基团、乙烯基、丙稀酸基;R2表不可水解的烷氧基或者卤素基团;X为0、1、2或者3。 8. The hydrophobic coating material as claimed in claim 7, wherein the metal alkoxide comprises at least one compound having per molecule at least one hydrolyzable silyl group, the silyl group represented by the formula Si (Rl) x (R2) 4_x represented, wherein Rl represents Ci-C8 alkyl group, an epoxy group, vinyl group, acrylic group; R2 form non-hydrolyzable alkoxy or halogen groups; X is 1, 2 or 3 .
9. 根据权利要求8所述的疏水性涂覆材料,其中所述氟硅烷是通式为Rf^SKRqxU2)^ 的化合物,其中,Rf 1表示全部或者部分全氟化的片段;R1表示烷基;R2表示可水解的烷氧基或者卤素基团;X为〇、1或者2。 9. A compound according to claim 8 wherein the hydrophobic coating material, wherein the fluoro silane of the general formula Rf ^ SKRqxU2) ^, wherein, Rf 1 represents a fragment of the whole or part of the perfluorinated; Rl represents alkyl ; R2 represents a hydrolyzable alkoxy or halogen groups; X is square, 1 or 2.
10. 根据权利要求1所述的疏水性涂覆材料,其中所述氟硅烷是双硅烷封端的全氟聚醚或者氟封端的硅烷。 According to claim 1 wherein the hydrophobic coating material, wherein the fluoro silane is bis-silane-terminated perfluoropolyether or a fluorine silane terminated.
11. 根据权利要求1所述的疏水性涂覆材料,其中所述氟硅烷是(3,3,3_三氟丙基)三甲氧基硅烷或者九氟己基三甲氧基硅烷。 11. The hydrophobic coating material of claim 1, wherein said fluorosilane is (3,3,3_ trifluoropropyl) trimethoxysilane or nonafluorohexyl trimethoxysilane.
12. 根据权利要求1所述的疏水性涂覆材料,其中所述有机聚硅烷和无机金属醇盐以重量比为1:10~10:1存在。 According to claim 1 wherein the hydrophobic coating material, wherein said organopolysiloxane and an inorganic metal alkoxide in a weight ratio of 1:10 to 10: 1 is present.
13. 根据权利要求12所述的疏水性涂覆材料,其中所述氟硅烷以含量为0.0001~ lwt. %存在。 According to claim 12 wherein the hydrophobic coating material, wherein said fluoro silane in an amount of 0.0001 ~ lwt.% Exists.
14. 一种涂覆的基材,其包括基材和在基材上的涂层,其中所述涂层由权利要求1所述的疏水性涂覆材料组成。 14. A coated substrate comprising a substrate and a coating on the substrate, wherein said coating is made of a hydrophobic coating material of claim 1 wherein the components.
15. 根据权利要求13所述的涂覆的基材,其中所述基材是玻璃基材、聚合物基材或者金属基材。 15. A substrate according to claim 13 wherein the coating, wherein the substrate is a glass substrate, a polymer substrate or a metal substrate.
16. 根据权利要求13所述的涂覆的基材,其中所述涂层是在高温下固化的。 16. A substrate according to claim 13 wherein the coating, wherein the coating is cured at elevated temperature.
17. -种制备疏水性涂覆材料的方法,所述方法包括在酸催化的水解缩合反应条件下反应包括下列物质的反应混合物: 有机聚硅烷; 无机金属醇盐;以及氟硅烷。 17. - Preparation of a hydrophobic coating material, said method comprising species in acid-catalyzed hydrolysis condensation reaction conditions include reaction mixtures following materials: organic polysilane; inorganic metal alkoxides; and a fluorosilane.
18. 根据权利要求17所述的方法,其中所述有机聚硅烷是硅烷官能化的多元醇或者多胺。 18. The method according to claim 17, wherein said organopolysiloxane is a silane functionalized polyol or polyamine.
19. 根据权利要求17所述的方法,其中所述有机聚硅烷是含有2~4个羟基的聚己酸内酯多元醇与异氰酸酯封端的硅烷的反应产物。 The reaction product of polycaprolactone polyol and isocyanate 19. The method of claim 17, wherein the organopolysiloxane containing 2 to 4 hydroxyl-terminated silane.
20. 根据权利要求17所述的方法,其中所述官能化的聚己酸内酯多元醇的分子量为50 ~10000g/mol〇 20. The method according to claim 17, wherein the functionalized polycaprolactone polyol having a molecular weight of 50 ~ 10000g / mol〇
21. 根据权利要求17所述的方法,其中所述有机聚硅烷是聚脲硅烷。 21. The method according to claim 17, wherein said organopolysiloxane polyurea silane.
22. 根据权利要求21所述的方法,其中所述聚脲硅烷是含有至少2个一级或者二级胺基团的胺与异氰酸酯封端的硅烷的反应产物。 22. The method according to claim 21, wherein the polyurea reaction product of a silane containing at least two primary or secondary amine groups of the amine with an isocyanate-terminated silane.
23. 根据权利要求22所述的方法,其中所述聚脲硅烷是二亚乙基三胺与异氰酸酯封端的硅烷的反应产物。 23. The method according to claim 22, wherein said silane is a polyurea reaction product of diethylenetriamine with the isocyanate-terminated silanes.
24. 根据权利要求23所述的方法,其中所述金属醇盐包括至少一种含有至少一个硅烷基团的可水解的化合物,用通式每分子表示,其中R 1表示Q-Cs烷基,环氧基团,乙烯基,丙稀酸基;其中R2表不可水解的烷氧基或者卤素基团;X为〇、1、2或者3。 24. The method according to claim 23, wherein the metal alkoxide comprises at least one compound of at least one hydrolyzable silane group-containing, per molecule represented by the general formula, wherein R 1 represents a Q-Cs alkyl, an epoxy group, vinyl group, acrylic group; wherein R2 table nonhydrolyzable alkoxy or halogen groups; X is square, 1, 2 or 3.
25. 根据权利要求24所述的方法,其中所述氟硅烷是通式为的化合物,其中Rf1表示全部或者部分全氟化的片段,R1表示烷基、可水解的烷氧基或者卤素基团,X 为0、1或者2。 25. The method according to claim 24, wherein said fluoro silane compound of the general formula, wherein Rf1 is a perfluorinated fragments all or part of the, Rl represents an alkyl group, an alkoxy group or a hydrolyzable halogen groups , X is 0, 1 or 2.
26. 根据权利要求17所述的方法,其中所述氟硅烷是双硅烷封端的全氟聚醚或者氟封端的硅烷。 26. The method according to claim 17, wherein said fluoro silane is bis-silane-terminated perfluoropolyether or a fluorine silane terminated.
27. 根据权利要求17所述的方法,其中所述氟硅烷是(3,3,3_三氟丙基)三甲氧基硅烷或者九氟己基三甲氧基硅烷。 27. The method according to claim 17, wherein said fluorosilane is (3,3,3_ trifluoropropyl) trimethoxysilane or nonafluorohexyl trimethoxysilane.
28. 根据权利要求17所述的方法,其中所述有机聚硅烷和无机金属醇盐以重量比为1: 10~10:1存在。 28. The method of claim 17, wherein said organopolysiloxane and an inorganic metal alkoxide in a weight ratio of 1:10 to 10: 1 is present.
29. 根据权利要求28所述的方法,其中所述氟硅烷以含量为0.0001~lwt. %存在。 29. The method according to claim 28, wherein said fluoro silane in an amount of 0.0001 ~ lwt.% Exists.
30. 根据权利要求17所述的方法,包括在水性酸催化剂存在下进行所述反应,所述酸催化剂的含量足以使反应混合物的pH在5以下。 30. The method of claim 17, comprising performing the reaction in the presence of an aqueous acid catalyst, the content of the acid catalyst is sufficient to make the pH of the reaction mixture at 5 or less.
31. 根据权利要求30所述的方法,其中所述反应混合物的pH为2~4。 31. The method according to claim 30, wherein the pH of the reaction mixture is from 2 to 4.
32. 根据权利要求30所述的方法,其中所述酸催化剂是无机酸或者有机酸。 32. The method according to claim 30, wherein said acid catalyst is an inorganic acid or an organic acid.
33. 根据权利要求32所述的方法,其中所述酸催化剂选自由盐酸、硫酸、硝酸和醋酸构成的组。 33. The method according to claim 32, wherein the acid catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and acetic acid formed.
Description  translated from Chinese
具有改良的耐久性的透明疏水性涂覆材料及其制备方法 Durability transparent hydrophobic coating material and method with improved

[0001 ] 政府权益 [0001] government interests

[0002] 本发明是在由美国海军空战中心授予的合约号为NOS.N68335-10-C-0523 (2765.01)和呢8335-12-〇0117(2675.02)的政府支助下进行的。 [0002] The present invention is under contract number by the US Naval Air Warfare Center awarded the NOS.N68335-10-C-0523 (2765.01) and it 8335-12- 〇0117 (2675.02) is conducted by government support. 政府享有本发明的某些权益。 The Government has certain rights in the invention.

技术领域 TECHNICAL FIELD

[0003] 本文公开的实施例通常涉及涂覆材料,尤其涉及透明和疏水性的涂覆材料。 [0003] Example embodiments disclosed herein relates generally to the coating material, and more particularly to a transparent hydrophobic coating material. 根据本文公开的实施例,所述涂覆材料展现出改良的对磨损和侵蚀环境的耐久性。 According to the embodiments disclosed herein, the coating material exhibits improved wear and erosion environment durability.

背景技术 Background technique

[0004] 在诸如汽车或飞机挡风玻璃表面上的甩水性(watershedding)会影响司机或飞行员在恶劣条件下在操作过程中的视野。 [0004] On the surface, such as a car or airplane windshield thrown aqueous (watershedding) will affect the driver or pilot Perspective under harsh conditions during operation. 增强表面甩水能力的常用方法是进行降低挡风玻璃表面能的疏水性表面处理,从而引导水在挡风玻璃表面上形成水珠(bead up)和滚落。 Common method for surface water thrown capacity enhancement is to be reduced surface of the windshield of a hydrophobic surface treatment can, in order to guide the water drops formed on the surface of the windshield (bead up) and tumble. 各种类型的表面处理,例如,蜡、疏水有机硅聚合物(如RAIN-X®防水剂)或具有非常高的接触角(contact angles)和极低的滚离角(roll off angles)的超级疏水涂层,已被开发出以改善玻璃、金属或聚合物表面的疏水性。 Various types of surface treatment, for example, waxes, hydrophobic silicone polymer (such as RAIN-X® water repellent) or have very high contact angles (contact angles) and low roll-off angle (roll off angles) super hydrophobic coatings have been developed to improve the hydrophobicity of glass, metal or polymer surfaces. 然而,这些已知的表面处理均不耐用。 However, these known surface treatments are not durable.

[0005] Kanagasabapathy等人1的美国专利No · 8,338,351公开了一种在具有大于165度的接触角的表面上产生透明、近乎透明和半透明的超级疏水性涂层的涂覆组合物和工艺,该组合物包含疏水性的倍半氧硅烷纳米颗粒,所述纳米颗粒包含附着力促进剂基团和低表面能基团。 [0005] Kanagasabapathy et al 1 of U.S. Patent No · 8,338,351 discloses a method of generating a transparent coating composition on a surface having a contact angle greater than 165 degrees, nearly transparent and translucent super hydrophobic coating material and process, the composition comprises a hydrophobic half times silanes nanoparticles, the nanoparticles comprise an adhesion promoter group and a low surface energy group.

[0006] Van Benthem等人的美国专利No . 8,187,707公开了一种超级疏水性涂层,该涂层展现出大于140度的接触角,其包括覆盆子形状的颗粒,所述颗粒包括一级颗粒和粘附在所述一级颗粒表面的二级颗粒。 [0006] Van Benthem et al., U.S. Patent No. 8,187,707 discloses a super-hydrophobic coating that exhibits a contact angle greater than 140 degrees, including a raspberry-shaped particles, the particles including primary particles and secondary particles adhered to the surface of the primary particles.

[0007] Azzopardi等人的美国专利No. 6,340,502公开了一种用于疏水性/疏油性涂层的组合物,该组合物含有烷氧基硅烷和卤代硅烷,烷氧基硅烷和卤代硅烷每一个均至少在其一个分子末端具有全氟化的基团,还公开了将该涂层施加到透明基质上的方法。 [0007] Azzopardi et al., U.S. Patent No. 6,340,502 discloses a composition for the hydrophobic / oleophobic coating, the composition contains an alkoxysilane and halosilane, alkoxysilane halosilane having at least each one of a perfluorinated group in a molecular end thereof, also discloses a method the coating applied to the transparent substrate.

[0008] 已知的可以赋予疏水性/疏油性的试剂的例子有,如EP0492417,EP0492545和EP0672779中所述的烷基硅烷。 [0008] The known way of imparting hydrophobicity / oleophobic agents exemplified, such as EP0492417, EP0492545 and EP0672779 in said alkyl silane. 根据这些出版物,这种疏水层可以从含有氟化的有机硅烷(烷基-trilaho-或者三烷氧基硅烷,其烷基至少包含一个末端全氟化的基团)的溶液获得, 以无水的有机溶剂被施加到基材的表面。 According to these publications, this layer may be hydrophobic (-trilaho- or alkyl trialkoxysilanes, alkyl comprising at least a perfluorinated end groups) from a fluorinated organosilane solution obtained, with no water, an organic solvent is applied to the surface of the substrate. 与这些涂层有关的问题之一是这些涂层的耐用度和抗腐蚀性,可以通过这些涂层的逐步脱落得以证明,尤其是通过汽车挡风玻璃雨刷的性能得以证明,这使得必须再次使用疏水涂层。 One of these coatings and related problem is that these coatings durability and corrosion resistance, can be proved by the gradual loss of these coatings, in particular, it is proved by the windscreen wipers performance, which makes it necessary to use it again hydrophobic coating.

[0009] Wilkes等人的美国专利No. 6072018描述了耐磨性无机/有机杂化材料的形成,这种材料由至少一种金属醇盐和低分子量的硅烷官能化的有机物(例如,二级胺或三级胺,月旨肪族二元醇,芳香族二元醇或三醇)的溶胶-凝胶(sol-gel)缩合反应而形成。 [0009] Wilkes et al., U.S. Patent No. 6072018 describes a wear resistance inorganic / organic hybrid material is formed, which material is composed of at least one metal alkoxide and a low molecular weight silane functional organic (e.g., two amine or tertiary amine, aimed month aliphatic diol, an aromatic diol or triol) sol - gel (sol-gel) formed by the condensation reaction. 该出版物中公开的材料使得具有异氰酸酯官能化的硅烷的低分子量的化合物功能化,这种材料是耐磨性的,但不是疏水性的。 The publication discloses a material such functionalized compound having a low molecular weight isocyanate-functional silane, this material is wear resistance, but not hydrophobic.

[0010] 在本领域对于透明的疏水涂层仍有需要,以提高玻璃基材、聚合基材和金属基材的甩水能力,这种涂层在磨损或者恶劣的环境中(例如,在接触酸、碱或者有机溶剂、雨或者紫外线后)是耐用的。 [0010] in the art for a transparent hydrophobic coating still needs to raise a glass substrate, polymeric substrate and the metal substrate slinger ability of this coating is worn or harsh environments (for example, the contact after the acid, base or an organic solvent, rain or UV) is durable. 这种所需的涂层在大量的应用中是有用的,这些应用包括作为挡风玻璃、太阳能板、涂料、电子元件等等的透明防护涂层。 This required a large number of applications in the coatings are useful in applications such as windshields, solar panels, coatings, electronic components, etc. The transparent protective coating. 本文中公开的实施例意在提高这样所需的涂层。 Embodiments disclosed herein are intended to raise such desired coating.

发明内容 SUMMARY

[0011] 通常,本文中所公开的涂覆材料显示出改善的耐用性,耐磨性,耐溶剂性(例如水、 油、碳氢化合物、喷气燃料、溶剂、稀酸、稀碱),防雨性能,耐盐水性,抗紫外线性能,柔韧性, 对多种基材(包括金属、玻璃、塑料和涂料表面)的附着力。 [0011] Typically, the coating material disclosed herein shows improved durability, abrasion resistance, solvent resistance (e.g. water, oils, hydrocarbons, jet fuel, solvent, acid, alkali), anti - rain resistance, salt water resistance, UV resistance, flexibility, a variety of substrates (including metal, glass, plastic and painted surfaces) adhesion. 因此,本文中所公开的实施例中的这种新颖的透明疏水性涂覆材料显示出了改善的在磨损或者恶劣的环境中的耐用性,环境抗性和耐化学药品性,这增加了玻璃基材、聚合物基材和金属基材上的甩水性。 Thus, for example, in the novel transparent hydrophobic coating material herein disclosed embodiment shows wear or harsh environmental improvement in durability, environmental resistance and chemical resistance, which increases the glass substrate, a polymer substrate and thrown aqueous metal substrate.

[0012] 根据本文所描述的实施例,用于玻璃基材、金属基材或者塑料基材的耐用的、透明的、无机-有机杂化疏水性涂覆材料通常是酸催化的缩合反应产物,该产物由有机聚硅烷、 无机金属醇盐和氟硅烷组成。 [0012] According to embodiments described herein case for glass substrates, metal substrates or plastic substrates durable, transparent, inorganic - organic hybrid materials are generally hydrophobic coating acid catalyzed condensation reaction product, the product was purified by organopolysiloxane, an inorganic metal alkoxide and silane fluoride composition.

[0013] 某些实施例会使用硅烷官能化的多元醇或者多胺(例如聚氨酯硅烷或聚脲硅烷) 作为有机聚硅烷。 [0013] Certain embodiments Regular use of silane functional polyol or polyamine (such as silane or polyurethane polyurea silane) as an organic polysilane. 这些硅烷官能化的多元醇可以是,例如,与异氰酸酯封端的硅烷反应的具有2~4个羟基的聚己酸内酯多元醇,或者具有至少两个一级胺基团或者二级胺基团的多胺(例如二亚乙基三胺)。 These silane functionalized polyols may be, for example, with an isocyanate-terminated silane having a polycaprolactone polyol having 2 to 4 hydroxyl groups, or having at least two primary amino groups or secondary amino group polyamines (e.g. diethylene triamine). 优选地,这些有机聚硅烷平均分子量为50~10000g/mol。 Preferably, the organopolysiloxane of average molecular weight 50 ~ 10000g / mol.

[0014] 根据一些实施例,金属醇盐包括至少一种每分子具有至少一个硅烷基的可水解的化合物,硅烷基用通式Si (R1 )X(R2 )4-x表示,其中,R1表示C1-C8烷基、环氧基团、乙烯基、丙烯酸基;R 2表示可水解的烷氧基或者卤素基团;X为〇,1,2或者3。 [0014] Some of the compounds according to the embodiment, comprises at least one metal alkoxide having per molecule at least one hydrolyzable silane group of embodiments, a silyl group represented by the formula Si (R1) X (R2) 4-x, where, Rl represents C1-C8 alkyl group, an epoxy group, a vinyl group, an acrylic group; R 2 represents a hydrolyzable alkoxy or halogen groups; X is square, 1, 2 or 3. 优选为四甲氧基硅烷和四乙氧基硅烷。 Preferably tetramethoxysilane and tetraethoxysilane.

[0015] 氟硅烷可以是通式为Rf1Si(R1)x(R2) 3-X的化合物,其中,Rf1表示全部全氟化或者部分全氟化的片段;R1表示烷基,可水解的烷氧基或者卤素基团;X为〇,1或者2。 [0015] fluorosilane may be of the general formula Rf1Si (R1) x (R2) 3-X compound, wherein, all fragments of the Rf1 represents a perfluorinated or partially perfluorinated; Rl represents an alkyl group, an alkoxy hydrolyzable group, or a halogen group; X is square, 1 or 2. 氟硅烷可以是双硅烷封端的全氟聚醚或者氟封端的硅烷,例如。 Fluoro silane can be a fluorine or a perfluoropolyether silane terminated bis silane terminated, for example. (3,3,3-三氟丙基)三甲基硅烷或者九氟己基三甲氧基硅烷。 (3,3,3-trifluoropropyl) trimethylsilane or nonafluorohexyl trimethoxysilane.

[0016] 某些实施例中的有机聚硅烷和无机金属醇盐以重量比为约1:10到约10:1存在。 1 exists: [0016] Certain embodiments of the organopolysiloxane and an inorganic metal alkoxide in a weight ratio of from about 1:10 to about 10. 氟硅烷的含量约为0 · 0001-lwt · %。 Silane fluorine content of about 0 · 0001-lwt ·%.

[0017] 可选择性地,涂覆材料也可以含有金属氧化物纳米粒子(以增加耐磨性),和/或紫外线稳定剂(以增加抗紫外线能力),缓蚀剂(以增加抗腐蚀性)。 [0017] optionally, the coating material may contain metal oxide nanoparticles (to increase the wear resistance), and / or ultraviolet stabilizers (to increase the UV resistance), corrosion inhibitors (to increase corrosion resistance ).

[0018] 涂覆材料可作为涂到基材(例如,玻璃、聚合物或金属)上的涂料,并固化以在基材上形成光学透明的疏水性固化涂层。 [0018] The coating material may be applied as a coating to a substrate (e.g., glass, polymer or metal) on a substrate and cured to form the optical transparency in a hydrophobic cured coating.

[0019] 涂覆材料可以通过在酸催化的水解缩合反应条件下反应含有有机聚硅烷、无机金属醇盐和氟硅烷的反应混合物而制得。 [0019] coating material can be prepared by acid-catalyzed hydrolysis condensation reaction conditions containing organopolysiloxane, the reaction mixtures of inorganic metal alkoxide and FAS system. 水性酸催化剂通常以其含量足以使反应混合物的PH 在5以下(例如,约2~4之间)存在。 The aqueous acid catalyst is typically sufficient for its content of the reaction mixture at PH 5 or less (e.g., between about 2 to 4) exists. 酸催化剂可以是无机酸或有机酸,例如,盐酸、硫酸、硝酸和醋酸。 The acid catalyst may be an inorganic or organic acid, such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid.

[0020] 在对下列目前优选的示例性实施例的详细说明进行仔细考虑后,本发明的这些方面和其它方面将更为清楚。 [0020] In the following detailed description of currently preferred exemplary embodiment of careful consideration, these and other aspects of the present invention will become more apparent.

具体实施方式 detailed description

[0021]正如上面所提到的那样,根据本文中所述的实施例,用于玻璃基材、金属基材或者塑料基材的耐用的、透明的、无机-有机杂化疏水性涂覆材料通常是由有机聚硅烷、无机金属醇盐和氟化硅组成的酸催化的缩合反应产物。 [0021] As mentioned above, according to the embodiments described herein, for the glass substrates, metal substrates or plastic substrates durable, transparent, inorganic - organic hybrid hydrophobic coating material typically acid catalyzed condensation of an organic polysilane, inorganic metal alkoxide and silicon fluoride composition of reaction products.

[0022] A ·有机聚硅烷 [0022] A · organopolysiloxane

[0023] 所述涂覆材料的有机聚硅烷组分必须包括多元醇或多胺,所述多元醇(包含但不限于二元醇、三元醇、四元醇、五元醇等等)是通过聚氨酯键(urethane linkage)用金属醇盐官能化的硅烷(例如,异氰酸酯封端的硅烷),所述多胺是通过脲键用金属醇盐官能化的硅烷。 [0023] The organopolysiloxane component of the coating material must include a polyamine or a polyol, the polyol (including but not limited to, diols, triols, tetrols, pentahydric alcohols, etc.) is by urethane linkage (urethane linkage) with a metal alcohol salt functional silane (for example, isocyanate-terminated silane), the polyamine is a urea bond by metal alcohol salt functional silane. 多元醇和异氰酸酯封端的硅烷之间的反应可以用诸如二月桂酸二丁基锡之类的锡催化剂催化。 The reaction polyol and isocyanate-terminated silane can be used between the tin catalyzed such as dibutyl tin dilaurate or the like. 也可以使用其它的来源于,例如,聚酯、聚醚、聚碳酸酯等的多元醇。 You can also use the other derived from, for example, polyester, polyether and polycarbonate polyols.

[0024] 在优选的实施例中,多元醇或多胺分别是通过聚氨酯键或脲键用异氰酸酯基丙基三甲氧基硅烷(isocyanatopropyltrimethoxysi lane)或异氰酸酯基丙基三乙氧基硅烷(isocyanatopropy Itri ethoxy si lane)官能化的石圭烧。 [0024] In a preferred embodiment, the polyol or polyamine, respectively, by a polyurethane bond or urea bond with an isocyanate propyl trimethoxysilane (isocyanatopropyltrimethoxysi lane) or isocyanate propyl triethoxysilane (isocyanatopropy Itri ethoxy si lane) functionalized stone Kyu burn.

[0025] 聚氨酯硅烷可以由多种分子的、低聚的或多聚的基于多元醇(所述多元醇拥有至少2个羟基,优选地为3或者4个羟基)的聚醚或者聚酯制成。 [0025] The silane can be from a variety of polyurethane molecules, oligomeric or polymeric based polyol (said polyol has at least two hydroxyl groups, preferably 3 or 4 hydroxyl groups) of polyether or polyester . 可以使用分子量为50-10000g/ mo 1,优选地,1000-2000g/mo 1的多元醇。 You can use the molecular weight of 50-10000g / mo 1, preferably, the polyol 1000-2000g / mo 1's. 例如,可以使用商品化的商标名为CAPA™的聚醚多元醇(购自Perstorp公司),或商品化的商标名为ARCOL K基于多元醇的聚醚(购自Bayer Material Science)。 For example, commercially available under the trade name CAPA ™ polyether polyols (available from Perstorp company), or commercially available under the trade name ARCOL K based on polyether polyols (available from Bayer Material Science).

[0026] 典型的聚酯和聚醚多元醇包括重均分子量在上述范围内的聚己酸内酯二元醇或三元醇,聚氧乙烯二元醇或三元醇,聚丙烯二元醇和三元醇。 [0026] A typical polyester and polyether polyols include weight average molecular weight within the above range polycaprolactone diol or triol, polyoxyethylene diol or triol, diol and polypropylene triol. 优选为具有以下结构的聚己酸内酯: L0028J 其中,m+n+p = 7~16可以米用。 Polycaprolactone preferably has the following structure: L0028J wherein, m + n + p = 7 ~ 16 m can be used.

Figure CN105765014AD00061

[0029]可选择地,可以采用以相同的方式与异氰酸酯封端的硅烷通过脲键反应的多胺。 [0029] Alternatively, the polyamine can be employed in the same manner with the isocyanate-terminated silane by the reaction of urea bond. 聚脲硅烷可以从多种分子的、低聚的或者聚合的多胺(所述每个多胺分子拥有至少2个一级胺基团或者二级胺基团,优选地,3或者4个胺基团)制得。 Polyurea silanes (per polyamine molecule has the at least two primary amino groups or secondary amino groups from the oligomeric or polymeric polyamines more molecules, preferably, 3 or 4-amine group) was obtained. 可以使用分子量为50-10000g/ mol,优选地,lOO-lOOOg/mol的多胺。 Can be used as a molecular weight 50-10000g / mol, preferably, lOO-lOOOg / mol polyamines. 可以满意地使用,例如,二亚乙烯三胺或商品化的JEFFAMINE®胺(购自Huntsman Petrochemical Corporation),例如JEFFAMINE®T-403聚醚胺 It can be satisfactorily used, for example, diethylenetriamine or ethylene triamine commercially available JEFFAMINE® amine (available from Huntsman Petrochemical Corporation), e.g. JEFFAMINE®T-403 polyetheramine

[0030]在本文中使用的术语"多胺",指任何含有两个或更多个一级胺或二级胺官能团的脂肪族或者芳香族化合物。 [0030] As used herein, the term "polyamine" refers to any aliphatic or aromatic compound containing two or more primary amine or secondary amine functional groups. 多胺化合物可以含有任何合适的骨架链结构,包括饱和的或者不饱和的,以及直链的、支链的或环状的结构。 Polyamine compound may contain any suitable backbone chain structure, including saturated or unsaturated, and linear, branched or cyclic structure. 代表性的多胺包括聚醚胺,例如具有以下结构的二元胺: Representative polyamines include polyether amines, e.g., diamines having the following structure:

Figure CN105765014AD00071

[0032] 其中x = 2~70,优选地,X为2~7。 [0032] where x = 2 ~ 70, preferably, X is 2 to 7.

[0033]可选择地,聚醚胺是具有如下结构的三胺: [0033] Alternatively, the polyether amine is a triamine having the following structure:

Figure CN105765014AD00072

Ι_υυ;^」 具中η = 0~5;x+y+z为3~100。1 尤选地,n = l,x+y+z = 5~6。 Ι_υυ; ^ 'with the η = 0 ~ 5; x + y + z is 3 to 100.1 optionally particular, n = l, x + y + z = 5 ~ 6.

[0036] B ·无机金属醇盐 [0036] B · inorganic metal alkoxide

[0037] 涂覆材料的无机金属醇盐组分包括至少一种金属醇盐,例如,基于Si,Al,Ti,Zr等等的金属醇盐。 [0037] The inorganic metal alkoxide component of the coating material comprises at least one metal alkoxide, e.g., based on Si, Al, Ti, Zr and the like metal alkoxides. 优选的是硅醇盐。 Preferred is a silicon alkoxide. 硅醇盐也可包括单官能化的有机基团,例如,环氧化物、烷基、苯基、乙烯基、巯基、甲基丙烯酸盐等等,或者可包括双硅烷封端的化合物,例如,二(三甲氧基)硅乙烷。 The silicon alkoxide may also comprise monofunctional organic group, e.g., epoxides, alkyl, phenyl, vinyl, mercapto, methacrylate, etc., or a double-silane terminated compound may include, for example, two (trimethoxy) ethane silicon.

[0038] 优选的金属醇盐包括至少一种每分子至少含有一个硅基Si (R1)x(R2)4-X的可水解的化合物;其中R1表示烷基(例如,C1-C8,可聚合基团(例如,环氧化物、乙烯基、丙烯酸),或者其它末端含有另外的有机基团(羟基、异氰酸盐、氨基、硫醇等)的烷基)的烷基;R 2表示可水解的基团(例如,烷氧基或者卤素基团,优选地,甲氧基、乙氧基或氯基);X为〇,1,2,3。 [0038] Preferred metal alkoxide comprises at least one compound of a silicon-Si (R1) x (R2) 4-X hydrolyzable per molecule contains at least; wherein R1 represents an alkyl group (e.g., C1-C8, polymerizable group (for example, epoxy, vinyl, acrylic acid), or other end of the other organic group (a hydroxyl group, an isocyanate, an amino group, a thiol, etc.) alkyl) alkyl; R 2 represents hydrolyzable groups (e.g., alkoxy or halogen groups, preferably methoxy, ethoxy or chloro); X-is square, 1,2,3. 优选地,金属醇盐是四乙氧基硅烷或者四甲氧基硅烷。 Preferably, the metal alkoxide is tetraethoxysilane or tetramethoxysilane.

[0039] C.氟硅烷 [0039] C. fluorosilane

[0040]代表性的氟硅烷化合物的例子包括通式为Rf 1S i (R1) X (R2) 3-x的化合物,其中,Rf1 表示全部或部分全氟化的片段(例如,3,3,3-三氟丙基,(全氟丁基)乙基,(全氟己基)乙基, (全氟辛基)乙基,全氟十二烷基,全氟十四烷基,十七氟-I,1,2,2-四氢辛基,九氟己基或十三氟-I,1,2,2-四氢辛基);R 1表示烷基(例如,C1-C8,优选地,C1-C4一级烷基或者二级烷基); R2表示可水解的基团(例如,烷氧基或者卤素基团,优选为甲氧基、乙氧基或氯基);X为〇,1 或者2。 [0040] Representative examples of the silane compound include fluorine formula Rf 1S i (R1) X (R2) 3-x compound, where, all or part of the Rf1 represents a perfluorinated fragments (e.g., 3,3, 3- trifluoropropyl, (perfluorobutyl) ethyl, (perfluorohexyl) ethyl, (perfluorooctyl) ethyl, perfluoro dodecyl, tetradecyl perfluoro, heptadecafluoro -I, 1,2,2- tetrahydro-octyl, nonafluorohexyl or tridecylfluorooctyl -I, 1,2,2- tetrahydro-octyl); R 1 represents an alkyl group (e.g., C1-C8, preferably , C1-C4 alkyl group or a secondary alkyl); R2 represents a hydrolyzable group (e.g., alkoxy or halogen groups, preferably methoxy, ethoxy or chloro); X-is square , 1 or 2.

[00411优选地,使用通式为Rf2LQ-C(R)2-Si(R1) x(R2)3-丄的氟化硅化合物,其中Rf2表示多价聚(全氟烷基)或聚(全氟氧化烯烃)片段;Q表示有机二价连接基团(例子包括酰胺、醚、 酯或聚氨酯连接基团);R1表示烷基(例如,C1-C8,优选为C 1-C4一级烷基或者二级烷基);R2表示可水解的基团;X为0,1或者2;R表示氢或者1-4个碳的烷基,R基团可以是相同或者不同的。 [00411 Preferably, the formula Rf2LQ-C (R) 2-Si (R1) x (R2) 3- Shang silicon fluoride compound, wherein Rf2 represents a polyvalent poly (perfluoroalkyl) or poly (full fluoro olefin oxide) segment; the Q represents an organic divalent linking group (examples include amide, ether, ester or urethane connecting groups); Rl represents alkyl (e.g., C1-C8, preferably a C 1-C4 alkyl or two alkyl groups); R2 represents a hydrolyzable group; X is 0, 1 or 2; R represents hydrogen or a 1-4 carbon alkyl radical, R groups may be the same or different. 优选地,R是氢。 Preferably, R is hydrogen.

[0042] 可水解的基团R2可以是相同或者不同的,并且通常在适当的条件下(例如,在酸性水溶液条件下)可以水解,以便氟化的硅烷化合物随后可以发生缩合反应。 [0042] The hydrolysable groups R2 may be the same or different, and typically under appropriate conditions (e.g., under acidic aqueous conditions) may be hydrolyzed to the compound may then be fluorinated silane condensation reaction. 优选地,可水解的基团在水解条件下产生能够发生缩合反应的基团,例如硅烷醇基。 Preferably, the hydrolyzable group capable of condensation reaction to produce a group under hydrolysis conditions, such as silanol groups.

[0043] 某些实施例采用了包括双硅烷封端的全氟聚醚或者氟封端的硅烷的氟化硅组分, 例如,(3,3,3_三氟丙基)三甲氧基硅烷,九氟己基三甲氧基硅烷等等。 [0043] Certain embodiments include using a bis-silane-terminated perfluoropolyether or a fluorinated silicon component silane terminated fluorine, e.g., (3,3,3_ trifluoropropyl) trimethoxysilane, nine fluorine-hexyl trimethoxy silane and the like.

[0044] D.金属氧化物颗粒 [0044] D. metal oxide particles

[0045] 选择性地,在涂料制剂中可以使用金属氧化物颗粒以赋予所需性质,例如耐磨性、 电学性能或者光学性能。 [0045] Alternatively, the formulation may be used in the coating of metal oxide particles to impart desired properties such as wear resistance, electrical properties or optical properties. 例如,可以使用二氧化硅、二氧化钛、氧化锆和/或氧化铝的金属氧化物颗粒。 For example, silica, titania, zirconia and / or alumina particles of metal oxide. 优选为二氧化娃(Si〇2)。 Preferably dioxide baby (Si〇2). 针对光学透明度,优选地,颗粒不超过IOOnm,例如,在约Inm-1 OOnm之间。 For optical clarity, Preferably, the particles not exceeding IOOnm, e.g., between about Inm-1 OOnm. 优选的颗粒尺寸为直径I -1 Onm的球形纳米颗粒。 The preferred particle size diameter of I -1 Onm spherical nanoparticles. 如果存在颗粒,制剂中所包含的颗粒可达约50wt. %,优选为在约20wt. %-30wt. %之间,均基于总的制剂重量。 If there granules, granular formulations contain up to about 50wt.%, Preferably between about 20wt.% -30wt.%, All based on the total weight of the formulation. [0046] D.组分及性质 [0046] D. Composition and properties

[0047] 制剂的组分可改变,这取决于所需要的最终属性,例如,柔韧性、硬度、耐磨性、透明度或其它所需要的物理性质。 [0047] The components of the formulation may be varied, depending on the final properties desired, e.g., flexibility, hardness, wear resistance, transparency, or other desired physical properties. 通常,在制剂中,聚硅烷与金属醇盐或者有机官能化的金属醇盐的重量比可以约为1:10-10:1,优选为约3:1。 Typically, in the formulation, with the metal alkoxide polysilane or organofunctional metal alkoxides weight can range from about 1: 10-10: 1, preferably from about 3: 1. 在制剂中,使用的氟硅烷的重量百分比为约0·0001-lwt. %,优选为约0.0005-0.OOlwt. %。 In preparation, the weight percentage of fluorine silanes used is from about 0 · 0001-lwt.%, Preferably about 0.0005-0.OOlwt.%.

[0048] 涂覆材料可以通过将无机和有机组分与水和水性酸催化剂在合适的溶剂(例如, 异丙醇)中混合而制得。 [0048] The coating material may be inorganic and organic components with water and an aqueous acid catalyst in a suitable solvent (e.g., isopropanol) were mixed and prepared. 加入水性酸催化剂以引发可水解的硅烷基的水解反应。 Added to the aqueous acid catalyst to initiate hydrolysis reaction hydrolyzable silane groups. 优选的酸催化剂包括无机酸(例如,盐酸、硫酸和硝酸)或有机酸(例如,醋酸)。 Preferred acid catalysts include inorganic acids (e.g., hydrochloric acid, sulfuric acid and nitric acid) or organic acids (e.g., acetic acid). 加入足够的酸催化剂,以将反应混合物的pH降低到5以下,优选为pH为2~4。 Sufficient acid catalyst was added to the reaction mixture the pH is lowered to 5 or less, preferably a pH of 2-4.

[0049] 氟化硅组分可以随后被直接加入到无机和有机组分的溶液中。 [0049] fluorinated silicon component may then be added directly to the solution of the inorganic and organic components. 可选择地,氟组分可以在适当的溶剂中用酸化水进行预水解,该过程可以有或者没有氟官能化的表面活性剂的协助。 Alternatively, the fluorine component may be pre-hydrolyzed in a suitable solvent with acidified water, the process may assist with or without surfactant fluorine functionalized. 涂层制剂是通过有机、无机和氟硅烷组分的水解和缩合反应而制备的,产生通过S i -OS i键连接的氟官能化的有机-无机网状结构。 Coating formulations are prepared by hydrolysis of organic, inorganic and fluorosilane component prepared by a condensation reaction and to produce fluorine-connected by S i -OS i bond functionalized organic - inorganic network structures.

[0050] 因此,所获得的涂料制剂可以在溶剂中混合,或者选择性地,不需要溶剂而混合。 [0050] Thus, the coating formulation obtained may be mixed in a solvent, or alternatively, mixed solvent is not necessary. 如果使用溶剂,溶剂可以是醇类(甲醇、乙醇、丙醇、异丙醇、丁醇等等)或者其它水溶性溶剂(例如:丙酮)。 If a solvent is used, the solvent may be alcohols (methanol, ethanol, propanol, isopropanol, butanol, etc.) or other water-soluble solvent (for example: acetone). 在该制剂中,固体的浓度取决于最终的应用所需要的厚度或者应用方法。 In this formulation, the concentration of solids depends on the thickness of the final application or application methods require. 但是,代表性地,制剂可含5wt. %-100wt· %的固体,优选的固体浓度为15wt. %_25wt. %。 However, typically, the formulation may contain 5wt.% -100wt ·% Solids, the solids concentration of preferably 15wt.% _25wt.%.

[0051] 涂覆材料的溶液可以通过使用任何方便的涂膜方法施用于基材,包括浸、刷、浇涂、喷等,涂层的固化可以在大的温度范围内完成,这取决于所需要的属性,例如,耐磨性、 柔韧性等,或者取决于涂覆基材的热限制。 [0051] The solution of the coating material by using any convenient method of coating applied to the substrate, including immersion, brushing, flow coating, spraying, etc., curing of the coating can be completed in a wide temperature range, depending on the required attributes, for example, abrasion resistance, flexibility, etc., depending on the coated substrate or thermal limitations. 涂层可以在约25°C-150°C的温度范围内固化,优选为约75°C。 The coating may range from about 25 ° C-150 ° C curing temperature range, preferably from about 75 ° C. 固化温度可以根据与基材的兼容性进行调整。 Curing temperature can be adjusted and the compatibility of the substrate.

[0052]固化涂层的厚度可以在约0.5微米-20微米的范围内,优选为约1微米-5微米。 [0052] The thickness of the cured coating may be within the range of about 0.5 microns 20 microns, preferably from about 1 [mu] m -5 [mu] m.

[0053] 在本文中所描述的固化疏水性涂层显示出视觉透明度。 [0053] The hydrophobic coating cured as described herein exhibit visual transparency. 更确切地说,这种固化疏水性涂层对可见光显示出至少约99.5%的透明度,优选为至少约100%的透明度。 More specifically, such a curable hydrophobic coating to visible light exhibits a transparency of at least about 99.5%, preferably at least about 100% transparency. 这种固化疏水性涂层在雾中对可见光的透明度改变不超过1 %,优选为不超过0.1 %。 Such curing hydrophobic coating to visible light transparency in the mist never exceeded 1%, preferably not more than 0.1%.

[0054] 在本文中所描述的疏水性涂层适用于多种基材涂层,以诶基材提供增加的耐化学药品性、防油性、防水性、液体/气体阻隔性、耐磨性、抗腐蚀性和甩水能力。 [0054] The hydrophobic coating described herein is suitable for coating a variety of substrates, eh substrate to provide increased resistance to chemicals, oil repellency, water repellency, the liquid / gas barrier properties, abrasion resistance, corrosion resistance and rejection of water capacity. 合适的基材包括但不限于玻璃、金属(例如,铝和钢铁)、塑料(例如,聚碳酸酯和丙烯酸的)、硬化水泥、混泥土或者水泥浆、木材和涂漆表面。 Suitable substrates include, but are not limited to, glass, metals (such as aluminum and steel), plastics (such as polycarbonate and acrylic), hardened cement, concrete or grout, wood and painted surfaces.

[0055] 通过参考下列本发明的非限制性实施例将进一步理解本发明。 [0055] The present invention by reference to the following non-limiting examples will further understanding of the present invention.

[0056] 实施例1 [0056] Example 1

[0057] 包含下列制剂的涂覆材料可以以约1-5微米厚度的涂层施用于3/16英寸厚的聚碳酸酯基材上。 [0057] The following formulation containing the coating material may be a coating of about 1-5 microns in thickness applied onto a polycarbonate substrate 3/16 inch thick. 涂层在约90°C的温度下固化。 Coating is cured at a temperature of about 90 ° C. 然后对涂覆的基材进行测试,测试了接触角、甩水角(watershed angle)和视觉外观(包含透明度、雾度和清晰度特性),并将该涂覆基材与未涂覆的聚碳酸酯基材进行了对比。 Then the coated substrate test, the test of the contact angle, swing angle of water (watershed angle) and visual appearance (including transparency, haze and clarity characteristics), and the coated substrate and uncoated poly carbonate substrate were compared.

[0058] 涂覆材料制剂 [0058] The coating material formulation

[0059] 合成硅烷官能化的多元醇: [0059] Synthesis of silane functional polyol:

[0060] 在干净的、完全干燥的玻璃器皿中称量聚己酸内酯多元醇。 [0060] weighed polycaprolactone polyol in a clean, completely dry glassware. 在另一个干净的并彻底干燥的玻璃器皿中,称量正确的摩尔比的异氰酸酯硅烷(例如,聚己酸内酯二元醇需要两倍于己酸内酯的摩尔当量的异氰酸酯)。 In another clean and thoroughly dried glassware, weighing correct isocyanate silane molar ratio (for example, polycaprolactone diol polycaprolactone need twice the molar equivalents of isocyanate). 装异氰酸酯的玻璃器皿用氮气层覆盖并用橡胶隔片密封。 Loading isocyanate glassware covered and sealed with a rubber septum with a nitrogen blanket. 在聚己酸内酯多元醇中称量催化剂(例如,二月桂酸二丁基锡)。 Weighing catalyst polycaprolactone polyol (for example, dibutyl tin). 相对于异氰酸酯和聚己酸内酸多元醇的共同重量,催化剂的重量为0.1%。 By weight with respect to the common isocyanate and polycaprolactone acid polyol weight of the catalyst was 0.1%. 随后,也用氮气层覆盖这个瓶子,并用橡胶隔片密封。 Subsequently, also covered with a layer of nitrogen bottle and sealed with a rubber septum.

[0061] 聚己酸内酯多元醇和催化剂被设置为在冰浴中搅拌。 [0061] polycaprolactone polyol and the catalyst is set to stirring in an ice bath. 异氰酸酯被缓慢地滴加入搅拌的己酸内酯-催化剂混合物中,使用正氮气流来控制滴加速率。 Isocyanate was slowly added dropwise with stirring polycaprolactone - catalyst mixture, using a positive nitrogen stream to control the addition rate. 在滴加过程中应当保持冰浴;该反应放热而冰浴降低了副反应发生的概率。 During the addition, the ice bath was maintained shall; The reaction was exothermic and ice-bath reduces the probability of side reactions. 一旦将异氰酸酯全部加入,随着冰浴融化,允许该反应升至室温。 Once all of the isocyanate was added, as the ice bath melted and the reaction allowed to warm to room temperature. 该反应在室温下要搅拌至少六个小时。 The reaction was stirred at room temperature to be at least six hours. 通过红外光谱(FTIR)可以检测到异氰酸酯峰(~2270CHT 1)的下降。 By infrared spectroscopy (FTIR) can detect isocyanate peak (~ 2270CHT 1) decreases. 一旦异氰酸酯完全反应并且其峰消失,将聚氨酯硅烷装瓶,并将其用氮气覆盖。 Once complete reaction of isocyanate and its peaks disappear, polyurethane silane bottling, and blanketed with nitrogen. 瓶子应当是琥珀色玻璃或者其它深色玻璃,从而减小曝光,因为这可能导致剩余的催化剂变色。 Amber glass bottle should be of glass or other dark-colored, so as to reduce exposure, as this may cause discoloration of the remainder of the catalyst.

[0062]标准涂料合成: [0062] Standard synthetic paint:

[0063] 首先混合硅烷。 [0063] first mixed silane. 0.4摩尔的有机硅烷和0.6摩尔的无机硅烷的摩尔比是典型的。 0.4 moles of organic silane and a molar ratio of 0.6 moles of inorganic silane is typical. 加入少量的氟硅烷,不超过总涂料制剂的〇. 5%。 Amount of fluorine is added to the silane, does not exceed the square of the total coating formulation. 5%. 向该混合物中加入与氟硅烷含量相当的含氟表面活性剂。 To this mixture was added with fluorosilane levels of these fluorinated surfactant. 在基于溶剂的体系中,这可以更好地混合氟硅烷。 In a solvent-based system, which can better mix fluorosilane.

[0064]接着,向硅烷混合物中加入溶剂。 [0064] Subsequently, the silane mixture was added to the solvent. 溶剂的体积应当约为总涂料溶液的50-80%,可达90%,取决于所需要的涂层厚度。 Volume of solvent should be about 50-80% of the total coating solution, up to 90%, depending on the desired coating thickness. 代表性的溶剂包括异丙醇、乙醇或1-丙醇。 Representative solvents include isopropanol, ethanol or 1-propanol.

[0065]在硅烷完全分散到溶剂中后,加入酸化水。 [0065] After the silane is fully dispersed in a solvent, acidified water. 水应当酸化至0.05-0.1 M的摩尔浓度, 取决于所需要的水解速率。 Water should be acidified to a molar concentration of 0.05-0.1 M, depending on the desired rate of hydrolysis. 盐酸或者硝酸可以用于减小水溶液的pH。 Hydrochloric acid or nitric acid can be used to reduce the pH of the aqueous solution. 加入摩尔比足以水解硅烷上烷氧基的酸化水。 Join molar ratio sufficient to hydrolyze the alkoxy silane acidified water.

[0066]将涂层溶液混合1-2小时,取决于水解的完成度。 [0066] The coating solution was mixed for 1-2 hours, depending on the degree of completion of the hydrolysis. 一旦硅烷被水解,在涂覆前,通过Ιμπι的过滤器过滤涂料。 Once the silane is hydrolyzed before coating, the paint was filtered through a filter Ιμπι. 可以使用流涂、刷涂、喷涂或者浸涂的方法进行涂料应用,以获得最好的结果。 You can use flow coating, brushing, spraying or dip coating application methods to get the best results. 一旦涂覆,允许多余的涂料在固化前从基材上滚落。 Once coated, allowing excess coating before curing rolled from the substrate. 在室温下,涂层表干(tack free)约15分钟。 At room temperature, the coating is dry (tack free) for about 15 minutes. 可选择地,涂料可以在75-90°C下固化30-60分钟,以增加硬度和韧性。 Alternatively, the coating can be cured for 30-60 minutes at 75-90 ° C below, to increase the hardness and toughness. [0067]表1:具体的涂料制剂 [0067] Table 1: The specific coating formulations

Figure CN105765014AD00101

[0069] 表2显示了对于所选择的涂覆基材,其增加的水接触角和减小的甩水角。 [0069] Table 2 shows the coated substrate chosen, which increases the rejection of water contact angle and the angle of water decreased.

[0070] 表2:对于涂覆和未涂覆的基材,其水接触角和甩水角 [0070] Table 2: For coated and uncoated substrates, the water contact angle and swing angle of water

Figure CN105765014AD00102

[0072]表3显示了涂覆的基材的优异的光学属性,没有损失透明度、雾度(haze)或清晰度。 [0072] Table 3 shows the excellent optical properties of coated substrates, there is no loss of transparency, the haze (haze) or clarity.

[0073]表3:涂覆和未涂覆的基材的光学属性 [0073] Table 3: coated and uncoated substrate optical properties

Figure CN105765014AD00103

[0075]表4显示了涂层给经过处理的基材提供了改善的耐磨性,其通过更低的雾度值衡量。 [0075] Table 4 shows the coating to the substrate after processing provides improved wear resistance through its lower haze value measured.

[0076] 表4:对于涂覆和未涂覆的基材,Taber磨损对透光性能的影响(ASTMD4060-500g/ 500次;CSlOF 旋转(wheels)) [0076] Table 4: for coated and uncoated substrates, Taber abrasion on light transmission properties (ASTMD4060-500g / 500 times; CSlOF rotation (wheels))

Figure CN105765014AD00111

[0078] 加入硅胶(Nissan Chemical Snowtex IPA-ST)可以改善如表5所示的耐磨性 [0078] added silica (Nissan Chemical Snowtex IPA-ST) can improve the abrasion resistance as shown in Table 5

[0079] 表5:加入硅胶后的磨损效果:涂层A对比涂层B [0079] Table 5: worn-silica gel was added after: A Comparative Coating B Coating

Figure CN105765014AD00112

[0081 ] 实施例2 [0081] Example 2

[0082]合成硅烷官能化的多胺: [0082] Synthesis of silane functionalized polyamine:

[0083]在干净的、完全干燥的玻璃器皿中称量多胺(例如,二亚乙基三胺)。 [0083] Weighing polyamine (e.g., diethylene triamine) in a clean, fully-dried glassware. 在另一个干净的且完全干燥的玻璃器皿中称量正确摩尔比的异氰酸酯硅烷(例如,二亚乙基三胺需要三倍于异氰酸酯的摩尔当量)。 Weighing the right molar ratio of isocyanate silane in another clean and completely dry glassware (for example, diethylene triamine need three times the molar equivalent of isocyanate). 装异氰酸酯的玻璃器皿用氮气层覆盖,并用橡胶隔片密封。 Loading isocyanate glassware with nitrogen blanket covered and sealed with a rubber septum.

[0084] 多胺被设置为在冰浴中搅拌。 [0084] is set to polyamine stirred in an ice bath. 将异氰酸酯缓慢滴加到搅拌中的胺混合物中,使用正氮气流控制滴加速率。 The isocyanate was slowly added dropwise to the stirred mixture of amines, flow control using a positive nitrogen addition rate. 在滴加过程中保持冰浴,因为该反应放热并且冰浴可以减少副反应的发生。 The ice bath was maintained in the course of the dropwise addition, since the reaction is exothermic and an ice bath to reduce side reactions. 一旦加入所有的异氰酸酯,因为冰浴融化,允许反应升到室温。 Once all of the isocyanate, because melting ice bath, the reaction was allowed to rise to room temperature. 在室温下该反应至少搅拌六小时。 The reaction was stirred at room temperature for at least six hours. 通过红外光谱(FTIR)测定异氰酸酯峰(~2270cm-l)的下降。 Determination decline isocyanate peak (~ 2270cm-l) by infrared spectroscopy (FTIR). 一旦异氰酸酯完全反应并且峰消失,瓶装聚脲硅烷并用氮气覆盖。 Once complete reaction of the isocyanate and the peak disappears, polyurea bottled silane and blanketed with nitrogen.

[0085] 氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺氺 [0085] Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui Shui

[0086] 虽然本发明结合目前认为最实用和优选的实施例进行了说明,但是应当 [0086] While the combination of the present invention is presently considered to be the most practical and preferred embodiment has been described, it should be

[0087] 理解的是本发明不限于所公开的实施例,恰恰相反,本发明意欲涵盖包 [0087] understood that the present invention is not limited to the disclosed embodiments, on the contrary, the present invention is intended to cover package

[0088] 含在本发明的精髓和范围内的各种改进和等效设定。 [0088] included within the spirit and scope of the invention various modifications and equivalent settings.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US20090198000 *30 Jan 20096 Aug 2009Evonik Degussa GmbhLiquid fluorine-containing and two-component compositions for the surface treatment of mineral and non-mineral substrates
Classifications
International ClassificationC09D5/00, C09D183/00, C09D7/12
Cooperative ClassificationC09D7/1225, C08G18/325, C08G18/246, C08K3/36, C09D5/00, C09D175/06, C09D167/04, C08G18/718, C08G63/6952, C08G18/4277, C08G63/912
Legal Events
DateCodeEventDescription
13 Jul 2016C06Publication
9 Nov 2016C10Entry into substantive examination
6 Oct 2017REGReference to a national code
Ref country code: HK
Ref legal event code: DE
Ref document number: 1226764
Country of ref document: HK