TW201502221A - Production of defined nanoscale coatings - Google Patents

Production of defined nanoscale coatings Download PDF

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Publication number
TW201502221A
TW201502221A TW103106782A TW103106782A TW201502221A TW 201502221 A TW201502221 A TW 201502221A TW 103106782 A TW103106782 A TW 103106782A TW 103106782 A TW103106782 A TW 103106782A TW 201502221 A TW201502221 A TW 201502221A
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Taiwan
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coating
acid
method step
formula
compound
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TW103106782A
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Chinese (zh)
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Sabine Leick
Holger Pfeifer
Dieter Adam
Markus Hallack
Stephan Wieber
Juri Tschernjaew
Manfred Dannehl
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Evonik Industries Ag
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • B05D5/086—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers having an anchoring layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B05D2601/22—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention relates to a method for producing defined nanoscale coatings by tailoring the rheological flow properties of a primer solution for processing, and optimizing the amphiphobic surface properties by means of subsequent energy input. In this way it is possible to produce coatings having amphiphobic properties, and at the same time to tailor the film thickness of the coatings. This method of the invention encompasses four operating steps. First the surface is coated by sol-gel methods with a solution comprising SiO2 nanoparticles. In the second method step, this coating is dried and crosslinked, and in the third method step, the coating is treated with energetic radiation. Finally a second, fluorinated coating is applied.

Description

製造清晰之奈米級塗層之方法 Method of making a clear nanoscale coating

本發明係關於一種藉由調節供加工之底漆溶液(primer solution)之流變流動性質且利用隨後之能量輸入使兩疏(amphiphobic)表面性質最佳化以製造清晰之奈米級塗層的方法。以此方式，可製造具有兩疏性質之塗層，同時調節該塗層之膜厚度。本發明之方法包含四個操作步驟。首先，藉由溶膠-凝膠(sol-gel)方法以包含SiO2奈米粒子之溶液塗覆表面。在第二方法步驟中，此塗層被乾燥且交聯，且在第三方法步驟中該塗層以帶能輻射處理。最後，施加第二的氟化塗層。 The present invention relates to a method for producing a clear nano-scale coating by adjusting the rheological flow properties of a primer solution for processing and utilizing subsequent energy input to optimize the properties of the amphiphobic surface. method. In this way, a coating having two properties can be produced while adjusting the film thickness of the coating. The method of the invention comprises four operational steps. First, the surface was coated with a solution containing SiO 2 nanoparticles by a sol-gel method. In a second method step, the coating is dried and crosslinked, and in a third method step the coating is treated with band energy radiation. Finally, a second fluorinated coating is applied.

依照先前技藝，迄今確實已甚可能藉由施加氟矽烷或長鏈烷基矽烷至平滑或結構化之表面而獲得疏水性。然而現今還不可能產生不僅具有超疏水性也具有令人滿意之疏油性的有效兩疏表面。 According to the prior art, it has heretofore been possible to obtain hydrophobicity by applying fluorodecane or long-chain alkyl decane to a smooth or structured surface. However, it has not been possible today to produce an effective two-skin surface which not only has superhydrophobicity but also has satisfactory oleophobicity.

為解決此問題，已有很多解決方法，但還不理想。例如，Hikita等人(Seimitsu Kobunshi no Kiso to JitsuyokaGijutsu, 2008,349-355)描述一種藉由溶膠-凝膠方法所施加且由Si(OEt)4、水性氫氯酸、膠態SiO2及全氟辛基三乙氧基矽烷所構成之塗層。利用此類塗層，確實可能在以水及以癸烷之測量中達成極良好之接觸角。然而，技術人員容易明瞭：此類塗層尤其在玻璃上會僅具有極差之黏合性及耐磨性。 There are many solutions to solve this problem, but it is not ideal. For example, Hikita et al. (Seimitsu Kobunshi no Kiso to Jitsuyoka Gijutsu, 2008, 349-355) describe a method applied by a sol-gel method and consisting of Si(OEt) 4 , aqueous hydrochloric acid, colloidal SiO 2 and perfluoro A coating composed of octyltriethoxydecane. With such coatings, it is indeed possible to achieve very good contact angles in the measurement of water and in decane. However, it will be readily apparent to the skilled person that such coatings will only have very poor adhesion and abrasion resistance, especially on glass.

Hong等人(Thin Solid Films,1999,351(1,2),pp.274-278)描述一種在安全玻璃上之具有約800Å膜厚度的經交聯矽石塗層，及藉由噴佈塗覆所施加之氟碳層。第一層之二階段交聯造成特別的粗糙度。然而，Hong等人也教示在紫外光、水及摩擦力之結合影響下因此種塗覆所致之疏水性的喪失。 Hong et al. (Thin Solid Films, 1999, 351(1, 2), pp. 274-278) describe a crosslinked vermiculite coating having a film thickness of about 800 Å on a safety glass, and by spraying Cover the applied fluorocarbon layer. The two-stage cross-linking of the first layer results in a special roughness. However, Hong et al. also teach the loss of hydrophobicity due to the combination of ultraviolet light, water and friction.

Liu等人(Thin Solid Film,2011,519(19),pp 6224-6229)描述在玻璃表面上之包含SiO2粒子之第一層和施加覆蓋該第一層之包含聚二甲基矽氧烷的第二層。彼之調查集中於藉由不同之物理及化學方法施加含SiO2的層。此層之疏水性主要是基於物理蓮花效應(lotus effect)。技術人員容易明瞭：此類之層將僅具有受限形式之疏水性。 Liu et al. (Thin Solid Film, 2011, 519(19), pp 6224-6229) describe a first layer comprising SiO 2 particles on a glass surface and a polydimethyl methoxy oxane covering the first layer The second layer. His investigation focused on the application of layers containing SiO 2 by different physical and chemical methods. The hydrophobicity of this layer is primarily based on the physical lotus effect. It will be readily apparent to the skilled person that such layers will only have a limited form of hydrophobicity.

目的 purpose

因此，鑒於所述之先前技術，本發明基礎所在之目的是要提供一種用於塗覆基材之方法，該基材係諸如玻璃，例如具有兩疏性質，亦即同時具疏水及疏油性。此方法也 是要容易實施的且是要獲得良好黏合個別基材並長時間維持其性質之塗層。 Accordingly, in view of the prior art described, the basis of the present invention is to provide a method for coating a substrate, such as glass, for example having a sparse nature, i.e., both hydrophobic and oleophobic. This method is also It is easy to implement and is to obtain a coating that adheres well to individual substrates and maintains their properties for a long time.

本發明之目的更特別是要提供一種不僅可用於塗覆玻璃表面也可塗覆其他表面(例如金屬或聚合物)之此類的方法。 It is a further object of the invention to provide a process which is not only useful for coating glass surfaces but also for coating other surfaces such as metals or polymers.

另外，本發明之特別目的是要發展一種方法，藉由此方法提供一種塗層，其膜厚度可被調節且其具有兩疏性質，同時顯現出光澤表面外觀且實質上不引起擴散光散射。 In addition, a particular object of the present invention is to develop a method by which a coating is provided which has a film thickness which is adjustable and which has two sparse properties while exhibiting a glossy surface appearance without substantially causing diffused light scattering.

達成 Reach

藉由包含以下方法步驟之創新方法處理表面達成各項目的： The surface is achieved by an innovative approach that includes the following method steps:

a)施加具有在1至10mPas之間的溶液黏度的組成物。此組成物包含0.01至10重量%之TEOS(四乙氧基矽烷)及/或MTES(甲基三乙氧基矽烷)、0.01至10重量%之具有在20至250奈米之間的粒子尺寸的SiO2粒子、酸(尤其是無機酸之水溶液)及10至90重量%之醇。此醇較佳是甲醇、乙醇、異丙醇、正丙醇、異丁醇、正丁醇或第三丁醇。塗覆較佳藉由旋轉、浸漬或狹縫模具式塗覆或洩塗(flooding)進行。 a) Applying a composition having a solution viscosity of between 1 and 10 mPas. The composition comprises 0.01 to 10% by weight of TEOS (tetraethoxydecane) and/or MTES (methyltriethoxydecane), 0.01 to 10% by weight of particles having a particle size of between 20 and 250 nm. SiO 2 particles, an acid (especially an aqueous solution of a mineral acid) and 10 to 90% by weight of an alcohol. The alcohol is preferably methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol or tert-butanol. The coating is preferably carried out by spin coating, dipping or slot die coating or flooding.

b)在100至350℃之溫度下乾燥且交聯該組成物，該塗層隨後具有在20至250奈米之間的膜厚度。 b) drying and crosslinking the composition at a temperature of from 100 to 350 ° C, the coating subsequently having a film thickness of between 20 and 250 nm.

c)以紫外光或以電漿照射該表面。 c) irradiating the surface with ultraviolet light or with plasma.

d)以包含氟烷基矽烷(fluoroalkylsilane)之混合物及/或以氟醇(fluoroalcohol)與異氰酸丙基三甲氧基矽烷(isocyanatopropyltrimethoxysilane)及/或異氰酸丙基三乙氧基矽烷(isocyanatopropyltriethoxysilane)之反應產物塗覆該表面。此組成物較佳也包含酸，更佳是無機酸之水溶液。塗覆係在方法步驟d)中較佳藉由旋轉、浸漬或狹縫模具式塗覆、洩塗、化學氣相沉積(CVD)或物理氣相沉積(PVD)進行。 d) consisting of a mixture comprising fluoroalkylsilane and/or fluoroalcohol and isocyanatopropyltrimethoxysilane and/or isocyanatopropyltriethoxysilane The reaction product of the coating coats the surface. The composition preferably also contains an acid, more preferably an aqueous solution of a mineral acid. The coating is preferably carried out in method step d) by spin, dipping or slot die coating, bleed coating, chemical vapor deposition (CVD) or physical vapor deposition (PVD).

待塗覆之表面更特別地包含未經塗覆、經有機預塗覆或無機預塗覆之玻璃、金屬或聚合物表面。玻璃表面更特別地可以是安全玻璃。關於該聚合物，透明塑膠諸如PMMA、聚碳酸酯或PET尤其是適合的。 The surface to be coated more particularly comprises an uncoated, organic pre-coated or inorganic pre-coated glass, metal or polymer surface. The glass surface may more particularly be a safety glass. Transparent plastics such as PMMA, polycarbonate or PET are especially suitable for this polymer.

在依照本發明之方法中，該表面在方法步驟a)之前被預先處理是全然可能的，但非強制的。此種預先處理可包含例如以酸及/或以鹼處理。這可在多個單獨之步驟中進行。因此在某些情況中，以可變的順序連續地以酸及鹼清洗或噴佈該表面是合宜的。或者是或另外地，該表面也可在進行方法步驟a)之前以紫外光或以電漿照射。 In the method according to the invention, it is entirely possible, but not mandatory, that the surface be pre-processed prior to method step a). Such pretreatment can include, for example, treatment with an acid and/or a base. This can be done in a number of separate steps. Therefore, in some cases, it may be convenient to continuously or spray the surface with an acid and an alkali in a variable order. Alternatively or additionally, the surface can also be irradiated with ultraviolet light or with a plasma before carrying out method step a).

此照射及在方法步驟c)中之照射可在類似條件下進行，且在特定情況中不需同樣地進行。 This irradiation and the irradiation in method step c) can be carried out under similar conditions and in the specific case without the need to carry out the same.

預先處理之需求及此等預先處理之特定的實施整體是取決於待塗覆之表面而定。一方面，因此，這些預先處理可用於清潔，諸如用以移除例如在該材料表面上之處理劑。另一方面，彼也可活化該表面以改良對於依照本發明 所要施加之塗層的黏合性。該表面之確切的本質可藉由技術人員以就其材料功能之相關等方面來決定，無需花費及勞力。 The requirements for pre-treatment and the particular implementation of such pre-treatments depend on the surface to be coated. In one aspect, therefore, these pre-treatments can be used for cleaning, such as to remove a treatment agent, for example, on the surface of the material. On the other hand, he can also activate the surface to improve the The adhesion of the coating to be applied. The exact nature of the surface can be determined by the skilled person in terms of the function of the material, without spending or labor.

在方法步驟c)中及在隨意之預先處理中的照射條件為，在使用紫外光之情況中是使用具有在150至380奈米之間的波長及1至1000瓦/平方公尺(W/m2)輻射功率的紫外光。 The irradiation conditions in method step c) and in the random pretreatment are such that in the case of ultraviolet light, a wavelength between 150 and 380 nm and 1 to 1000 watts per square meter (W/) are used. m 2 ) ultraviolet light of radiant power.

電漿照射更特別地是以具有大於8kV且小於30kV之電壓及小於30kHz之頻率的大氣壓電漿(在該電漿源與該表面之距離為50微米至50毫米(較佳為0.5至10毫米)之間)，以0.1至1000毫米/秒之處理速率進行。 The plasma irradiation is more particularly an atmospheric piezoelectric slurry having a voltage of more than 8 kV and less than 30 kV and a frequency of less than 30 kHz (the distance between the plasma source and the surface is 50 to 50 mm (preferably 0.5 to 10 mm). Between )), at a processing rate of 0.1 to 1000 mm/sec.

在方法步驟a)及d)中及該表面之隨意的預先處理中所用之酸包含多種無機酸或二或多種無機酸之混合物，其更特別地以水溶液形式被添加。在此文中特別適合的是氫氯酸及/或硝酸。方法步驟a)之塗層組成物較佳具有0.01至1.0莫耳濃度。在方法步驟d)中所隨意添加之酸係以同樣濃度被使用。對於該預先處理而言，此類濃度也已證實對水性酸或水性鹼是合宜的。 The acid used in process steps a) and d) and in the random pretreatment of the surface comprises a plurality of mineral acids or a mixture of two or more mineral acids, more particularly in the form of an aqueous solution. Particularly suitable for this purpose are hydrochloric acid and/or nitric acid. The coating composition of process step a) preferably has a concentration of from 0.01 to 1.0 moles. The acid which is optionally added in process step d) is used in the same concentration. For this pretreatment, such concentrations have also proven to be suitable for aqueous or aqueous bases.

本發明之一重要特徵是該SiO2粒子，其在方法步驟a)中藉由溶膠-凝膠方法被導入該塗層中。在此方面，本發明特別有二個較佳具體例。該SiO2粒子不僅對該兩疏表面性質有貢獻，同時令人驚訝地也作為流變改良劑，使廣範圍之塗層厚度能被製造。令人驚訝地，已發現：在方法步驟b)中之化學交聯使該膜有不均勻之收縮，在所製造之 底漆塗層中產生表面形貌。以此方式，不僅該等粒子本身引起粗糙表面，上述收縮也引起粗糙表面，此轉而對該塗層之兩疏性質有決定性貢獻。同樣令人驚訝的是：發生此收縮，卻無任何預期之巨觀的裂痕。此種裂痕轉而不僅會導致該表面之不利的外觀；反而，在該表面上該塗層之完全或至少部分喪失黏合性會變得更可能。 An important feature of the invention is the SiO 2 particles which are introduced into the coating by a sol-gel process in process step a). In this regard, the invention has two preferred embodiments. The SiO 2 particles not only contribute to the properties of the two sparse surfaces, but also surprisingly also serve as rheology modifiers, enabling a wide range of coating thicknesses to be produced. Surprisingly, it has been found that the chemical cross-linking in process step b) causes uneven shrinkage of the film, resulting in a surface topography in the resulting primer coating. In this way, not only do the particles themselves cause a rough surface, but the above-mentioned shrinkage also causes a rough surface, which in turn makes a decisive contribution to the two properties of the coating. Equally surprising is the occurrence of this contraction without any expected macroscopic cracks. Such cracking may in turn not only result in an unfavorable appearance of the surface; rather, it may become more likely that the coating will completely or at least partially lose adhesion on the surface.

在該第一具體例中，該SiO2粒子是粒子尺寸在80至250奈米之間的煙矽石(fumed silica)，其可已藉由利用例如甲基丙烯基矽烷、聚二甲基矽氧烷、辛基矽烷、聚矽氧流體(silicone fluid)、六甲基二矽氧烷、十六烷基矽烷或胺基矽烷之後處理步驟而經親水或疏水表面改質。 In the first embodiment, the SiO 2 particles are fumed silica having a particle size of between 80 and 250 nm, which may have been utilized by utilizing, for example, methacryl decane, polydimethyl hydrazine. The oxane, octyl decane, silicone fluid, hexamethyldioxane, cetyldecane or aminodecane is post-treated to be modified by a hydrophilic or hydrophobic surface.

在第二之同樣較佳具體例中，該SiO2粒子是非結晶型之沉澱矽石或沉澱矽酸鈣或矽酸鋁，彼等具有在20至200奈米之間的粒子尺寸。 In a second preferred embodiment, the SiO 2 particles are amorphous amorphous precipitated vermiculite or precipitated calcium niobate or aluminum niobate having a particle size of between 20 and 200 nm.

依照本發明之粒子尺寸是指一次粒子尺寸(primary particle size)。該等粒子也可極佳地採取相對小之凝集結構型。然而，若可能，這些結構不應超過500奈米之整體尺寸。在此情況中較佳是凝集的結構，其本身與該單獨於具體例地具有在80至250奈米之間的粒子尺寸。 The particle size in accordance with the present invention refers to the primary particle size. These particles can also advantageously take a relatively small agglomerated structure. However, if possible, these structures should not exceed the overall size of 500 nm. In this case, it is preferred that the agglomerated structure itself has a particle size of between 80 and 250 nm, which is specific to the specific example.

也可能結合二個較佳具體例，亦即不僅添加煙矽石也添加經表面改質之沉澱矽石(在其個別所指之尺寸範圍內)至該溶膠-凝膠混合物。 It is also possible to combine two preferred embodiments, i.e., not only the addition of soot or the surface modified precipitated vermiculite (within its individually indicated size range) to the sol-gel mixture.

在方法步驟b)中乾燥且同時交聯來自方法步驟a)之塗層較佳是在具有紅外線(IR)燈之爐中或藉由熱板進行1至 120分鐘之時間。 Drying in process step b) and simultaneously crosslinking the coating from method step a) is preferably carried out in an oven with an infrared (IR) lamp or by means of a hot plate 1 to 120 minutes.

在方法步驟d)中，如以上所陳述的，該塗覆之進行是以氟烷基矽烷及/或以氟醇與異氰酸丙基三甲氧基矽烷及/或異氰酸丙基三乙氧基矽烷之反應產物的溶膠-凝膠塗覆。在此二個具體例(彼等也可互相結合)中，在每一情況中也有變化型。關於在方法步驟d)中之氟烷基矽烷，該變化型是如下：在第一變化形中，該氟烷基矽烷是式CF3-(CF2)m-(CF2)n-Si-(R)3之化合物，其中m=0-6且n=1-18。基團R更特別可以是氯、烷基(更特別是甲基或乙基)、或烷氧基(-O-烷基)諸如甲氧基或乙氧基。 In process step d), as stated above, the coating is carried out as a fluoroalkyl decane and/or as a fluoroalcohol with isocyanate propyl trimethoxy decane and/or isocyanatopropyltriethyl Sol-gel coating of the reaction product of oxoxane. In these two specific examples (which may also be combined with each other), there are also variations in each case. With regard to the fluoroalkylnonane in process step d), the variant is as follows: in the first variant, the fluoroalkylnonane is of the formula CF 3 -(CF 2 ) m -(CF 2 ) n -Si- (R) 3 of the compounds wherein m=0-6 and n=1-18. The group R more particularly may be chloro, alkyl (more particularly methyl or ethyl), or alkoxy (-O-alkyl) such as methoxy or ethoxy.

在第二變化型中，該氟烷基矽烷是式CF3-(CF2)n-Si-R3之化合物，其中n是1至12之間的數目且其中R是氯、烷基(更特別是甲基或乙基)、或烷氧基諸如甲氧基或乙氧基。此種化合物之實例是全氟辛基乙基三乙氧基矽烷或全氟烷基三氯矽烷。 In a second variant, the fluoroalkylnonane is a compound of the formula CF 3 -(CF 2 ) n -Si-R 3 wherein n is a number between 1 and 12 and wherein R is chloro, alkyl (more In particular methyl or ethyl), or an alkoxy group such as methoxy or ethoxy. Examples of such compounds are perfluorooctylethyltriethoxydecane or perfluoroalkyltrichlorodecane.

在第三變化型中，所討論之化合物是全氟聚醚(perfluoropolyether)或式F3C-(OC3F6)n-O-(CF2)2-(CH2)2-O-CH2-Si(OCH3)3之至少部分氟化的聚醚，其中n是2至30之間的數目。 In a third variant, the compound in question is a perfluoropolyether or a formula F 3 C-(OC 3 F 6 ) n -O-(CF 2 ) 2 -(CH 2 ) 2 -O-CH An at least partially fluorinated polyether of 2- Si(OCH 3 ) 3 wherein n is a number between 2 and 30.

關於以氟醇與異氰酸丙基三甲氧基矽烷及/或異氰酸丙基三乙氧基矽烷之反應產物的塗覆，所討論之氟醇較佳是式F(CF2)nCH2CH2OH之化合物，其中n是偶數，或是式F-(CF2CF2)q-CH2CH2-OH之化合物，其中q是2至10之間的數目。 With respect to the coating of the reaction product of fluoroalcohol with isocyanatopropyltrimethoxydecane and/or isocyanatopropyltriethoxydecane, the fluoroalcohol discussed is preferably of the formula F(CF 2 ) n CH A compound of 2 CH 2 OH, wherein n is an even number, or a compound of the formula F-(CF 2 CF 2 ) q -CH 2 CH 2 -OH, wherein q is a number between 2 and 10.

再者，本發明之大的優點是：在方法步驟b)中之聚合基質的熱燒結及化學交聯之後，將另外能量送入所製造之表面中。令人驚訝地，在方法步驟d)中該底漆之隨後的疏水化的情況中，這導致明顯更高之水接觸角。與預期相反地，此步驟同樣地導致油接觸角之明顯增加。 Furthermore, a great advantage of the invention is that after thermal sintering and chemical crosslinking of the polymeric matrix in process step b), additional energy is fed into the surface being produced. Surprisingly, in the case of the subsequent hydrophobization of the primer in process step d), this results in a significantly higher water contact angle. Contrary to expectations, this step likewise resulted in a significant increase in the oil contact angle.

再者，令人驚訝地獲得依照本發明所處理之表面的優點，就是一方面彼在人眼中顯出光澤且另一方面彼顯現有超疏水表面功能及同時有強的疏油表面功能。在此方法之前，依照先前技藝，藉由表面結構化結合習知之表面(全)氟化確實已成功地產生超疏水表面，但卻沒有同時獲得光澤性及無擴散之散射性等性質。利用本發明之方法，令人驚訝地，經由使用本發明之SiO2粒子(其同時作為流變輔助劑)與方法步驟a)及b)，成功地產生光澤奈米級表面結構而製造所要之表面外觀。在方法步驟c)及d)中，兩疏表面功能化特別藉由本發明之活化步驟c)而強化，藉此提供所要之超疏水及強疏油的功能，同時維持所要之表面外觀。 Furthermore, the advantage of obtaining a surface treated in accordance with the present invention is surprisingly that on the one hand it exhibits luster in the human eye and on the other hand it exhibits a superhydrophobic surface function and at the same time a strong oleophobic surface function. Prior to this method, in accordance with the prior art, super-hydrophobic surfaces have been successfully produced by surface structuring in combination with conventional surface (per) fluoridation, but without the properties of both gloss and diffusion-free scattering. By means of the process according to the invention, surprisingly, by using the SiO 2 particles of the invention, which simultaneously serve as rheology aids, and process steps a) and b), a glossy nano-scale surface structure is successfully produced to produce the desired Surface appearance. In process steps c) and d), the two sparse surface functionalizations are in particular enhanced by the activation step c) of the invention, thereby providing the desired superhydrophobic and strong oleophobic function while maintaining the desired surface appearance.

本發明之部分，與本發明之方法並列地，是已藉由本發明之方法處理其表面之至少部分的物件。此等物件可被使用以作為玻璃材料(glazing)，例如在該基材是玻璃或透明聚合物時。此等物件可應用在廣泛的範圍中。實例包括機動車輛構造、家具製作、廣告表面、公用物件、顯示器、電器外殼或功能物件。 Part of the invention, alongside the method of the invention, is an article that has been treated for at least a portion of its surface by the method of the invention. Such articles can be used as glazing, for example when the substrate is a glass or a transparent polymer. These objects can be used in a wide range of applications. Examples include motor vehicle construction, furniture making, advertising surfaces, utility items, displays, electrical enclosures, or functional items.

依照本發明之塗層係藉由以下方法步驟製造，而藉由所述之流變輔助劑併入該塗層基質調節膜厚度。 The coating according to the invention is produced by the following method steps, and the coating matrix is incorporated by the rheology aid to adjust the film thickness.

首先使用酸及鹼清潔5×5公分之玻璃表面。 First clean the 5 x 5 cm glass surface with acid and alkali.

然後，包含MTES之塗層底漆藉由方法步驟a)經由在1000-6000rpm下之旋轉塗覆30秒而施加。然後採取二種方式-(a)作為比較用實例及(b)作為本發明之實例。 The coated primer comprising MTES is then applied by method step a) by spin coating at 1000-6000 rpm for 30 seconds. Then, two methods are employed - (a) as a comparative example and (b) as an example of the present invention.

(a)在不導入粒子之情況下，純的基質具有在20-70奈米之間的厚度的層。 (a) A pure substrate having a thickness of between 20 and 70 nm without introducing particles.

(b)在導入SiO2粒子(Nanopol®，直徑：40奈米)之情況下，依照粒子形態、粒子類型及粒子尺寸形成具有在20-250奈米之間之厚度的多層。 (b) In the case of introducing SiO 2 particles (Nanopol ® , diameter: 40 nm), a multilayer having a thickness of between 20 and 250 nm is formed in accordance with particle morphology, particle type and particle size.

若經清潔且活化之玻璃表面與包含SiO2粒子之塗層底漆被熱固化且隨後依照c)藉由235奈米紫外光活化20分鐘且最後依照d)被疏水化，則： If the cleaned and activated glass surface is thermally cured with a coating primer comprising SiO 2 particles and subsequently activated by 235 nm UV light for 20 minutes according to c) and finally hydrophobized according to d):

(a)(比較用實例)，在無此UV活化步驟之情況下，測量到對水之最大接觸角為至高140°及對油之最大接觸角為至高60°。 (a) (Comparative Example), in the absence of this UV activation step, the maximum contact angle to water was measured to be as high as 140° and the maximum contact angle to oil was as high as 60°.

(b)(本發明)在依照c)利用UV活化步驟之情況下，測量到對水之接觸角為遠高於150°及對油之接觸角為遠高於125°。 (b) (Invention) In the case of using the UV activation step according to c), the contact angle to water was measured to be much higher than 150° and the contact angle to oil was much higher than 125°.

Claims (15)

一種處理表面之方法，其特徵在於對表面進行下列方法步驟：a. 施加具有在1至10mPas之間的溶液黏度，包含0.01至10重量%之TEOS(四乙氧基矽烷)及/或MTES(甲基三乙氧基矽烷)、0.01至10重量%之具有在20至250奈米之間的粒子尺寸的SiO2粒子、酸及10至90重量%之醇的組成物，b. 在100至350℃之溫度下乾燥且交聯該組成物，該塗層隨後具有在20至250奈米之間的膜厚度，c. 以紫外光或以電漿照射該表面，及d. 以包含氟烷基矽烷之混合物及/或以氟醇與異氰酸丙基三甲氧基矽烷(isocyanatopropyltrimethoxysilane)及/或異氰酸丙基三乙氧基矽烷(isocyanatopropyltriethoxysilane)之反應產物塗覆該表面。 A method of treating a surface, characterized in that the surface is subjected to the following method steps: a. applying a solution viscosity of between 1 and 10 mPas, comprising 0.01 to 10% by weight of TEOS (tetraethoxynonane) and/or MTES ( Methyltriethoxydecane), 0.01 to 10% by weight of a composition having a particle size of between 20 and 250 nm, SiO 2 particles, an acid and a composition of 10 to 90% by weight of an alcohol, b. at 100 to Drying and crosslinking the composition at a temperature of 350 ° C, the coating then having a film thickness between 20 and 250 nm, c. irradiating the surface with ultraviolet light or with plasma, and d. containing halothane The surface is coated with a mixture of decane and/or with a reaction product of fluoroalcohol and isocyanatopropyltrimethoxysilane and/or isocyanatopropyltriethoxysilane. 如申請專利範圍第1項之方法，其中所述之表面是未經塗覆、經有機塗覆或經無機塗覆之玻璃、金屬或聚合物表面。 The method of claim 1, wherein the surface is an uncoated, organically coated or inorganically coated glass, metal or polymer surface. 如申請專利範圍第1項之方法，其中在方法步驟a之前該表面以酸、以鹼或彼此分開地以酸及以鹼預先處理及/或以紫外光或以電漿照射。 The method of claim 1, wherein the surface is pretreated with an acid, with a base or with a base and/or with ultraviolet light or with a plasma before the method step a. 如申請專利範圍第1項之方法，其中在方法步驟c中之照射係以具有1至1000瓦/平方公尺輻射功率而波長在150至380奈米之間的紫外光進行。 The method of claim 1, wherein the illuminating in method step c is carried out with ultraviolet light having a radiant power of 1 to 1000 watts per square meter and a wavelength of between 150 and 380 nm. 如申請專利範圍第1項之方法，其中在方法步驟c中之照射係以具有大於8kV及小於30kV之電壓及小於30kHz之頻率的大氣壓電漿，在該電漿源與該表面之距離為50微米至50毫米之間，以0.1至1000毫米/秒之處理速率進行。 The method of claim 1, wherein the illumination in the method step c is an atmospheric piezoelectric slurry having a voltage greater than 8 kV and less than 30 kV and a frequency less than 30 kHz, and the distance between the plasma source and the surface is 50. Between microns and 50 mm, at a processing rate of 0.1 to 1000 mm/sec. 如申請專利範圍第1項之方法，其中在方法步驟a中之酸包含一或多種無機酸，更特別是0.01至1.0莫耳濃度之氫氯酸或硝酸。 The method of claim 1, wherein the acid in process step a comprises one or more mineral acids, more particularly from 0.01 to 1.0 moles of hydrochloric acid or nitric acid. 如申請專利範圍第1項之方法，其中該SiO2粒子是粒子尺寸在80至250奈米之間的煙矽石(fumed silica)或是粒子尺寸在20至200奈米之間的經表面改質的沉澱矽石。 The method of claim 1, wherein the SiO 2 particles are fumed silica having a particle size between 80 and 250 nm or a surface modification having a particle size between 20 and 200 nm. A quality precipitated vermiculite. 如申請專利範圍第1項之方法，其中在方法步驟b中之乾燥係在爐中以紅外線燈或利用熱板進行1至120分鐘。 The method of claim 1, wherein the drying in method step b is carried out in an oven using an infrared lamp or using a hot plate for 1 to 120 minutes. 如申請專利範圍第5項之方法，其中該電漿源與該表面之距離在0.5至10毫米之間。 The method of claim 5, wherein the plasma source is between 0.5 and 10 mm from the surface. 如申請專利範圍第1項之方法，其中在方法步驟d中之氟烷基矽烷(fluoroalkylsilane)是式CF3-(CF2)m-(CH2)n-Si-(R)3之化合物，其中m=0-6且n=1-18且R=Cl或O-烷基，或者包含式CF3-(CF2)n-Si-R3之化合物，其中n是1至12間之數目且R是-O-烷基或Cl，或者包含式F3C-(OC3F6)n-O-(CF2)2-(CH2)2-O-CH2-Si(OCH3)3之氟化聚醚，其中n是2至30間之數目，或者包含全氟聚 醚。 The method of claim 1, wherein the fluoroalkylsilane in the method step d is a compound of the formula CF 3 -(CF 2 ) m -(CH 2 ) n -Si-(R) 3 , wherein m = 0-6 and n = 1-18 and R = Cl or O- alkyl, or comprises formula CF 3 - n -Si-R compound (CF 2) 3 of, where n is the number of from 1 to 12 And R is -O-alkyl or Cl, or comprises Formula F 3 C-(OC 3 F 6 ) n -O-(CF 2 ) 2 -(CH 2 ) 2 -O-CH 2 -Si(OCH 3 ) A fluorinated polyether of 3 , wherein n is a number between 2 and 30, or comprises a perfluoropolyether. 如申請專利範圍第1項之方法，其中該氟醇(fluoroalcohol)是式F(CF2)nCH2CH2OH之化合物，其中n是偶數，或者式F-(CF2CF2)q-CH2CH2-OH之化合物，其中q是2至10間之數目。 The method of claim 1, wherein the fluoroalcohol is a compound of the formula F(CF 2 ) n CH 2 CH 2 OH, wherein n is an even number, or the formula F-(CF 2 CF 2 ) q - A compound of CH 2 CH 2 -OH wherein q is a number between 2 and 10. 如申請專利範圍第1項之方法，其中在方法步驟a中之醇是甲醇、乙醇、異丙醇、正-丙醇、異丁醇、正-丁醇或第三-丁醇。 The method of claim 1, wherein the alcohol in process step a is methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol or tert-butanol. 如申請專利範圍第1項之方法，其中在方法步驟a中之塗覆係利用旋轉、浸漬、狹縫或模具式塗覆，或洩塗(flooding)進行。 The method of claim 1, wherein the coating in method step a is performed by spin, dipping, slit or die coating, or flooding. 如申請專利範圍第1至13項中任一項之方法，其中在方法步驟d中之塗覆係利用旋轉、浸漬、狹縫或模具式塗覆，洩塗，CVD或PVD進行。 The method of any one of claims 1 to 13, wherein the coating in method step d is performed by spin, dipping, slit or die coating, bleed, CVD or PVD. 一種物件，其特徵在於此物件之至少部分表面已利用如申請專利範圍第1至14項中至少一項之方法處理。 An article characterized in that at least a portion of the surface of the article has been treated by the method of at least one of claims 1 to 14.
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