WO2004037936A1 - Process and composition for coating - Google Patents

Process and composition for coating Download PDF

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Publication number
WO2004037936A1
WO2004037936A1 PCT/EP2003/011911 EP0311911W WO2004037936A1 WO 2004037936 A1 WO2004037936 A1 WO 2004037936A1 EP 0311911 W EP0311911 W EP 0311911W WO 2004037936 A1 WO2004037936 A1 WO 2004037936A1
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atoms
silane
substrate
coating
process according
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PCT/EP2003/011911
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French (fr)
Inventor
Gerhard Jonschker
Joachim Krakehl
Oliver Zindel
Heiko Sievers
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Nanogate Coating Systems Gmbh
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Application filed by Nanogate Coating Systems Gmbh filed Critical Nanogate Coating Systems Gmbh
Priority to EP03779813A priority Critical patent/EP1556452B1/en
Priority to DE60321943T priority patent/DE60321943D1/de
Priority to AU2003287967A priority patent/AU2003287967A1/en
Publication of WO2004037936A1 publication Critical patent/WO2004037936A1/en

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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to a process and composition for coating of substrates with a hydrophobic and/or oleophobic surface.
  • Such coatings are known that add hydrophobic and/or oleophobic properties to substrates. Such coatings should preferably be abrasion resistant, longterm stable, and easy to apply.
  • the stability is typically accomplished by heavily cross-linking the substrate and the molecules of the coating material. According to current knowledge, such cross-linking aids in the stability of the films, even when such films are comparatively thin.
  • the process step of the coating process should allow for easy handling.
  • the coating material is brought into contact with the substrate for example by polishing, wiping, spraying or rinsing. After application excess material has to be removed.
  • the task of the present invention is the provision of a cost effective process for coating and the required composition.
  • the problem is solved by a process for the generation of an oleophobic and/or hydrophobic coating on a substrate by spraying on a coating material, characterized in that a solution of a coating material containing less than 10 % by weight of at least a silane in a carrier with a droplet size of smaller than 100 ⁇ m diameter in average when leaving the spray nozzle is sprayed on.
  • the term casualsilane ⁇ used according to the present invention does not encompass a single silane only, but furthermore relates to mixtures of silanes also.
  • the term drawncarrier relates to a liquid, having a defined viscosity at ambient temperature and pressure.
  • the viscosity is measured with a rotational viscosimeter (Brookfield rheometer according to DIN 53018 part 1 and 2, DIN 53019-1) coaxial cylinder system.
  • the vapor pressure of the carrier at ambient temperature and pressure preferably should be at least the one of water (2.3 kPa) or higher.
  • the evaporation number of the carrier preferably should be less than that of water (80) in comparison to that of diethylether (1).
  • the distance between nozzle and article is adjusted that at least 30%, particularly at least 50%, of the solvent of the droplets evaporates before the droplets impinge on the article.
  • the silane For good adhesion performance, it is best for the silane to contain at least one reactive group for linking it with the substrate, in particular mineral substrate, particularly a ceramic and/or a siliceous substrate, preferably with siliceous glasses, sanitary ware, tiles, where said reactive group of the silane is not directly connected to an atom that is fluorinated.
  • the silane preferably is an alkylsilane conforming to the general formula (I)
  • R 1 , R 2 , R 3 , R 4 each contains organic residues containing from 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 0 to 6 oxygen atoms, 0 to 33 fluorine atoms, 0 to 33 chlorine atoms, 0 to 5 nitrogen atoms, and that is present in a concentration of up to 10 % by weight.
  • Such silanes are in particular disclosed in EP 0587667 Bl, which is fully incorporated by reference.
  • Silanes as described in this invention include non-fluorinated silanes, such as
  • CH 2 CHSi(OOCCH 3 ) 3
  • CH 2 CHSiCI 3
  • CH 2 CHSi(OCH 3 ) 3
  • CH 2 CHSi(OC 2 H 5 ) 3
  • CH 2 CHSi(OC 2 H 4 OCH 3 ) 3
  • CH 2 CHCH 2 Si(OCH 3 ) 3
  • CH 2 C(CH 3 )COOC 3 H 7 Si(OCH 3 ) 3
  • CH 2 C(CH 3 )COOC 3 H 7 Si(OC 2 H 5 ) 3
  • Said silanes may be prepared according to known methods; cf. W. Noll
  • Silanes as described in this invention can also be fluorinated, such as
  • micellar structure is destroyed on the surface, whereby a cross-linking can occur shortly due to the concentration during the flight of the droplet.
  • the very fine application favors a formation of a uniform coating.
  • the concentration of the droplet during the flight provides a fast formation of the actual coating with the additives. Since there is no carrier in large excess that would have to evaporate from the surface, practically no veil formation or similar artifacts can be observed.
  • the micellar structured silanes remain at least partially connected or structured upon impinging on the substrate.
  • said carrier preferably has a viscosity in the range from 0.2 to 15 mPa, such that a spray of the coating material contains droplets smaller than or up to 100 ⁇ m average droplet-size, particularly up to 75 ⁇ m, preferably up to 50 ⁇ m average droplet-size.
  • the droplet size being in particular dependent on the viscosity and other physical properties of the composition sprayed on the article, is therefore dependent on the spray nozzle. Commonly available nozzles are known providing such desired droplet sizes.
  • the article is preferably sprayed in a first track covering a part of the substrate only, then drying said track, followed by spraying a further track of the substrate after a significant amount, in particular at least 70 % of the carrier remaining on the surface of the first track has evaporated. Because of the high market potential and the size of the market for metals, tiles, siliceous glass, ceramic, and/or polymer surfaces, it is advantageously to use said process for these applications.
  • the coating composition is coated in tracks where the beginning of each track always is on the same edge of the article to achieve optimal uniformity of the coating.
  • a composition for providing substrates with a hydrophobic and/or oleophobic surface characterized in that it contains less than 10 % by weight of at least a silane in a liquid carrier having a viscosity in the range from 0.2 to 15 mPa.
  • a liquid carrier having a viscosity in the range from 0.2 to 15 mPa.
  • said composition is characterized by containing an alkylsilane conforming to the general formula (I)
  • R 1 , R 2 , R 3 , R 4 each contains organic residues containing 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 0 to 6 oxygen atoms, 0 to 33 fluorine atoms, 0 to 33 chlorine atoms and 0 to 5 nitrogen atoms.
  • the silane according to the present invention is of particular advantage, if it is conforming to the general formula I being a fluorinated alkylsilane, particularly a perfluorinated alkylsilane, where R 1 is a linear or branched alkyl group containing from 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 3 to 33 fluorine atoms, 0 to 6 oxygen atoms, and 0 to 5 nitrogen atoms and where R 2 ,R 3 ,R 4 each are selected from the group containing chlorine or linear or branched alkyl groups each containing 1 to 4 carbon atoms or linear or branched alkoxy groups each containing 1 to 4 carbon atoms.
  • the fluorinated or perfluorinated residue preferably e. g. should contain a spacer group, e.g. ⁇ (CH 2 ) 2 - in connection to the Si-group.
  • the invention is particularly suitable, if the coating composition comprises silanes, which in combination with a carrier lead to autophobic behavior.
  • autophobic means the effect that liquids agglomerate on surfaces to form droplets by themselves. This effect particularly leads to good results, when the droplets impinge on the article, after they have been concentrated during their flight.
  • Particularly suitable as carrier is a solvent or a mixture of solvents for said silanes or a dilution of dissolved silanes such like water and/or alcohols, particularly lower molecular weight alcohols such as methanoi, ethanol, and propanol; particularly isopropanol is suitable.
  • solvents particularly lower molecular weight alcohols such as methanoi, ethanol, and propanol; particularly isopropanol is suitable.
  • the advantage of said solvents is that on the one hand they exhibit a low viscosity and on the other hand they possess sufficiently high vapor pressure at room temperature or slightly elevated temperatures. Additionally, the aforementioned substances are readily used in technical processes without compromising the environment.
  • Said composition may contain additional additives, namely metal salts, metal organic compositions, nano particles, surfactants, silicones, colorants, catalysts, conserving agents, perfumes and/or salts of organic bases.
  • additional additives namely metal salts, metal organic compositions, nano particles, surfactants, silicones, colorants, catalysts, conserving agents, perfumes and/or salts of organic bases.
  • a surfactant is added to the coating composition for reducing the surface tension of the carrier.
  • catalysts can be added, which can affect a cross-linking of the silanes with each other in the carrier and/or provide a linking of the silanes with the substrate.
  • a catalyst is added to the coating composition and initiated after application of the coating material. This way it can be insured that the silanes comprised in the coating composition react only, after the coating was applied by said process.
  • the catalysts can be used in an amount such that a sufficiently long storage of the coating material is possible, particularly storage of at least one week. Typical storage times might be several months as well. Usage -of low amounts of catalysts is possible, because the amount of catalyst is concentrated in the coating material during flight of droplets.
  • Catalysts encompass in particular non-volatile acids, as they are known, and in particular UV activated catalysts as described in EP 0 587 667 Bl.
  • the vapor pressure of the carrier is selected such that during spray of the coating material the fine droplets are concentrated.
  • the extend of the concentration is such that directly after impinging of the droplets on the surface, the cross-linking is catalyzable and/or the catalytic cross-linking starts by itself.
  • the concentration of the silanes can be lower than the previously mentioned 10 % by weight in the preferred embodiment. It was found that even with low concentration of silanes of below 5 % by weight, even below 2 % by weight, satisfactory coatings can be obtained. It should be noted that the concentration of the droplets to achieve the necessary concentration of the silanes in the composition is dependent on how small the droplets actually can be produced and can be adjusted by the distance from the nozzle to the article, the temperature, preferably room temperature, and the atmospheric pressure. It . should be understood that this description does not preclude chemical interactions among the components listed, but instead describes the components of a composition according to the invention in the form in which they are generally used as ingredients to prepare such a composition.
  • Visual appearance was determined by the human eye. Key criteria include detection of artifacts (e.g. veil formation, blooming, ...), transparency, and clarity. Hydrophobicity was evaluated by contact angle measurement in ° against demineralized water in air. Unless otherwise stated, said contact angle is determined by dynamic advancing contact angle measurements using a Kr ⁇ ss ® instrument.

Abstract

The present invention realtes to a process and composition for coating of substrates with a hydrophobic and/or olephobic surface. The invention in particular relates to a process for the generation of an oleophobic and/or hydrophobic coating on a substrate by spraying on a coating material, characterized in that said coating material containing less than 10 % by weight of at least a silane in a liquid carrier with a droplet size of up to 100 µm diameter in average when leaving the spray nozzle is sprayed on.

Description

Process and composition for coating
The present invention relates to a process and composition for coating of substrates with a hydrophobic and/or oleophobic surface.
Various coatings are known that add hydrophobic and/or oleophobic properties to substrates. Such coatings should preferably be abrasion resistant, longterm stable, and easy to apply.
The stability is typically accomplished by heavily cross-linking the substrate and the molecules of the coating material. According to current knowledge, such cross-linking aids in the stability of the films, even when such films are comparatively thin.
To accomplish cost effective coating processes, the process step of the coating process should allow for easy handling. Typically, the coating material is brought into contact with the substrate for example by polishing, wiping, spraying or rinsing. After application excess material has to be removed.
Therefore, the task of the present invention is the provision of a cost effective process for coating and the required composition. In a first embodiment of the present invention, the problem is solved by a process for the generation of an oleophobic and/or hydrophobic coating on a substrate by spraying on a coating material, characterized in that a solution of a coating material containing less than 10 % by weight of at least a silane in a carrier with a droplet size of smaller than 100 μm diameter in average when leaving the spray nozzle is sprayed on.
The term „silaneλ used according to the present invention does not encompass a single silane only, but furthermore relates to mixtures of silanes also.
The term „carrier" according to the present invention relates to a liquid, having a defined viscosity at ambient temperature and pressure. The viscosity is measured with a rotational viscosimeter (Brookfield rheometer according to DIN 53018 part 1 and 2, DIN 53019-1) coaxial cylinder system. The vapor pressure of the carrier at ambient temperature and pressure preferably should be at least the one of water (2.3 kPa) or higher. The evaporation number of the carrier preferably should be less than that of water (80) in comparison to that of diethylether (1).
Preferably, the distance between nozzle and article is adjusted that at least 30%, particularly at least 50%, of the solvent of the droplets evaporates before the droplets impinge on the article.
For good adhesion performance, it is best for the silane to contain at least one reactive group for linking it with the substrate, in particular mineral substrate, particularly a ceramic and/or a siliceous substrate, preferably with siliceous glasses, sanitary ware, tiles, where said reactive group of the silane is not directly connected to an atom that is fluorinated. For the coating resulting from said process to exhibit good hydrophobicity, the silane preferably is an alkylsilane conforming to the general formula (I)
Figure imgf000004_0001
wherein R1, R2, R3, R4 each contains organic residues containing from 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 0 to 6 oxygen atoms, 0 to 33 fluorine atoms, 0 to 33 chlorine atoms, 0 to 5 nitrogen atoms, and that is present in a concentration of up to 10 % by weight. Such silanes are in particular disclosed in EP 0587667 Bl, which is fully incorporated by reference.
Silanes as described in this invention include non-fluorinated silanes, such as
Si(OCH3) 4, Si(OC2H5.4, Si(0-n- or i-C3H7)4, Si(OC4H9)4, SICI4, HSiCI3,
Si(OOCCH3)4, CH3SiCI3, CH3Si(OC2H5)3, C2H5SiCI3, C2H5Si(OC2H5)3,
CH7Si(OCH3)3, C6H5Si(OCH3)3, C6H5Si(OC2H5)3, (CH3O)3SiC3H6CI, (CH3)2SiCI2, (CH3)2Si(OCH3)2, (CH3)2Si(OC2H5)2/
(CH3)2Si(OH)2, (C6H5)2SiCI2, (C6Η5)2Si(OCH3)2,
(C6H5)2Si(OC2H5)2, (i-C3H7)3SiOH,
CH2=CHSi(OOCCH3)3, CH2=CHSiCI3, CH2=CHSi(OCH3)3,
CH2=CHSi(OC2H5)3, CH2=CHSi(OC2H4OCH3)3, CH2=CHCH2Si(OCH3)3, CH2=CHCH2Si(OC2H5)3/ CH2=CHCH2Si(OOCCH3)3,
CH2=C(CH3)COOC3H7Si(OCH3)3, CH2=C(CH3)COOC3H7Si(OC2H5)3,
(C2H5O)3SiC6H4NH2, CH3(C2H5O)2Si(CH2)4NH2,
(C2H5O)3SiC3H6NH2, (CH3)2(C2H5O)SiCH2NH2,
(C2H5O)3SiC3H6CN, (CH3O)3SiC4H8SH, (CH30)3SiC6Hi2SH, (CH30)3SiC3H5SH, (C2H50)3SiC3H5SH, (CH30)3SiC3H6NHC2H4NH2, (CH30)3SiC3H6NHC2H4NHC2H4NH2,
Figure imgf000005_0001
Figure imgf000005_0002
Said silanes may be prepared according to known methods; cf. W. Noll
"Chemie und Technologie der Silicone", Verlag Chemie GmbH,
Weinheim/Bergstrasse (1968). Silanes as described in this invention can also be fluorinated, such as
CF3CH2CH2SiY3
C2F5CH2CH2SiY3
C4FgCH2CH2SiY3 n-C6F13CH2CH2SiY3 n-C8Fι7CH2CH2SiY3 n-Cι0F2ιCH2CH2SiY3
(Y = OCH3, OC2H5 or Cl)
CF3CH2CH2SiCI2(CH3)
CF3CH2CH2SiCI(CH3)2 CF3CH2CH2Si(CH3)(OCH3)2 i-C3F70(CH2)3SiCI2(CH3) n-C6F13CH2CH2SiCI2(CH3) n-C6Fι3CH2CH2SiCI(CH3)2
Essential is the cognition that particularly good coatings can be obtained, if silanes, in particular alkylsilanes, are used in the coating in low concentration, but with a sufficiently low viscosity that allows for a very fine spray. It was found that despite the low concentration of silanes, nevertheless very stable, i.e. abrasion resistant, coatings can be obtained. The reasons for this are not completely understood yet, but the following mechanism might be responsible: in the very fine droplets of the spray, the silanes appear to be organized like micelles during the flight of the droplet from the nozzle to the article. At the same time, the carrier can evaporate efficiently due to the small size of the droplets. Despite of the high dilution of the composition when leaving the nozzle, a comparatively concentrated droplet is impinging on the surface.
It is assumed that said micellar structure is destroyed on the surface, whereby a cross-linking can occur shortly due to the concentration during the flight of the droplet. The very fine application favors a formation of a uniform coating. The concentration of the droplet during the flight provides a fast formation of the actual coating with the additives. Since there is no carrier in large excess that would have to evaporate from the surface, practically no veil formation or similar artifacts can be observed. In fact, it can be assumed that the micellar structured silanes remain at least partially connected or structured upon impinging on the substrate.
In order to achieve the aforementioned concentration of the carrier including the silane during the flight of the droplet from leaving the nozzle to impinging on the surface, said carrier preferably has a viscosity in the range from 0.2 to 15 mPa, such that a spray of the coating material contains droplets smaller than or up to 100 μm average droplet-size, particularly up to 75 μm, preferably up to 50 μm average droplet-size. The droplet size, being in particular dependent on the viscosity and other physical properties of the composition sprayed on the article, is therefore dependent on the spray nozzle. Commonly available nozzles are known providing such desired droplet sizes.
To achieve the best visual appearance of the film and possibly even to make a cleaning step after coating redundant , the article is preferably sprayed in a first track covering a part of the substrate only, then drying said track, followed by spraying a further track of the substrate after a significant amount, in particular at least 70 % of the carrier remaining on the surface of the first track has evaporated. Because of the high market potential and the size of the market for metals, tiles, siliceous glass, ceramic, and/or polymer surfaces, it is advantageously to use said process for these applications.
Preferably, the coating composition is coated in tracks where the beginning of each track always is on the same edge of the article to achieve optimal uniformity of the coating.
In a second embodiment of the present invention, the problem is solved by a composition for providing substrates with a hydrophobic and/or oleophobic surface, characterized in that it contains less than 10 % by weight of at least a silane in a liquid carrier having a viscosity in the range from 0.2 to 15 mPa. Preferably said composition is characterized by containing an alkylsilane conforming to the general formula (I)
SiR^^R4 (I)
wherein R1, R2, R3, R4 each contains organic residues containing 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 0 to 6 oxygen atoms, 0 to 33 fluorine atoms, 0 to 33 chlorine atoms and 0 to 5 nitrogen atoms.
To achieve sufficient hydrophobicity, the silane according to the present invention is of particular advantage, if it is conforming to the general formula I being a fluorinated alkylsilane, particularly a perfluorinated alkylsilane, where R1 is a linear or branched alkyl group containing from 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 3 to 33 fluorine atoms, 0 to 6 oxygen atoms, and 0 to 5 nitrogen atoms and where R2,R3,R4 each are selected from the group containing chlorine or linear or branched alkyl groups each containing 1 to 4 carbon atoms or linear or branched alkoxy groups each containing 1 to 4 carbon atoms. The fluorinated or perfluorinated residue preferably e. g. should contain a spacer group, e.g. ~(CH2)2- in connection to the Si-group.
The invention is particularly suitable, if the coating composition comprises silanes, which in combination with a carrier lead to autophobic behavior. In this text „autophobic" means the effect that liquids agglomerate on surfaces to form droplets by themselves. This effect particularly leads to good results, when the droplets impinge on the article, after they have been concentrated during their flight.
Particularly suitable as carrier is a solvent or a mixture of solvents for said silanes or a dilution of dissolved silanes such like water and/or alcohols, particularly lower molecular weight alcohols such as methanoi, ethanol, and propanol; particularly isopropanol is suitable. The advantage of said solvents is that on the one hand they exhibit a low viscosity and on the other hand they possess sufficiently high vapor pressure at room temperature or slightly elevated temperatures. Additionally, the aforementioned substances are readily used in technical processes without compromising the environment.
Said composition may contain additional additives, namely metal salts, metal organic compositions, nano particles, surfactants, silicones, colorants, catalysts, conserving agents, perfumes and/or salts of organic bases.
Preferably, a surfactant is added to the coating composition for reducing the surface tension of the carrier. Also, catalysts can be added, which can affect a cross-linking of the silanes with each other in the carrier and/or provide a linking of the silanes with the substrate. Furthermore, it is advantageous that a catalyst is added to the coating composition and initiated after application of the coating material. This way it can be insured that the silanes comprised in the coating composition react only, after the coating was applied by said process.
The catalysts can be used in an amount such that a sufficiently long storage of the coating material is possible, particularly storage of at least one week. Typical storage times might be several months as well. Usage -of low amounts of catalysts is possible, because the amount of catalyst is concentrated in the coating material during flight of droplets. Catalysts encompass in particular non-volatile acids, as they are known, and in particular UV activated catalysts as described in EP 0 587 667 Bl.
Typically, the vapor pressure of the carrier is selected such that during spray of the coating material the fine droplets are concentrated. The extend of the concentration is such that directly after impinging of the droplets on the surface, the cross-linking is catalyzable and/or the catalytic cross-linking starts by itself.
The concentration of the silanes can be lower than the previously mentioned 10 % by weight in the preferred embodiment. It was found that even with low concentration of silanes of below 5 % by weight, even below 2 % by weight, satisfactory coatings can be obtained. It should be noted that the concentration of the droplets to achieve the necessary concentration of the silanes in the composition is dependent on how small the droplets actually can be produced and can be adjusted by the distance from the nozzle to the article, the temperature, preferably room temperature, and the atmospheric pressure. It. should be understood that this description does not preclude chemical interactions among the components listed, but instead describes the components of a composition according to the invention in the form in which they are generally used as ingredients to prepare such a composition.
The invention is described by the following examples:
Examples:
Example 1 :
60 g isopropanol, 4 g isopropoxyethanol, 2 g Dynasilan®F8261 (Degussa), 3 g octyltriethoxysilane and 1 g dimethyldiethoxysilane were added to a reaction vessel and stirred briefly. The mixture was stirred for 15 min. 0.1 g of sulfuric acid, which was dissolved in 29.9 g demineralized water, was then the slowly added and the reaction mixture was stirred for 30 min.
Example 2:
59.97 g isopropanol, 5.5 g isopropoxyethanol, 1.5 g Dynasilan®F8261 (Degussa), 2 g octyltrimethoxysilane and 1 g dimethoxysilane were added to a reaction vessel and stirred briefly. After addition of 0.03 g fatty alcohol (C8 to Cι0) glycoside (Sapetin®-N) (surfactant) the mixture was stirred for 15 min. 0.1 g of sulfuric acid, dissolved in 29.9 g water, were then slowly added and the reaction mixture was stirred for 30 min. Example 3 :
64 g isopropanol, 2.78 g isopropoxyethanol and 1 g heptadecafluoro- decyltrimethoxysilane (Shin Etsu) were added to a reaction vessel and stirred briefly. The mixture was stirred for 15 min. 0.2 g sulfuric acid was slowly added to the mixture.
Example 4:
10 x 10 cm glass substrates were cleaned using a commercially available scouring milk and isopropanol before coating. At room temperature, said glass substrates were coated 4 times using spray coating with parameters including 2.5 bar pressure and 40 cm distance from nozzle to substrate. The coating was performed on the fireside of the substrates. The equipment for spray coating was a SATAJET® 90RP nozzle MSB.
The results obtained are given in the following table:
Table:
Figure imgf000012_0001
Visual appearance was determined by the human eye. Key criteria include detection of artifacts (e.g. veil formation, blooming, ...), transparency, and clarity. Hydrophobicity was evaluated by contact angle measurement in ° against demineralized water in air. Unless otherwise stated, said contact angle is determined by dynamic advancing contact angle measurements using a Krϋss® instrument.

Claims

Claims:
1. A process for the generation of an oleophobic and/or hydrophobic coating on a substrate by spraying on a coating material, characterized in that said coating material containing less than 10 % by weight of at least a silane in a liquid carrier with a droplet size of up to 100 μm diameter in average when leaving the spray nozzle is sprayed on.
2. A process according to claim 1, characterized in that said silane contains at least one reactive group for linking it with a mineral substrate, particularly a ceramic and/or a siliceous substrate, particularly with siliceous glasses, sanitary ware, tiles, where said reactive group of the silane is not directly connected to an atom that is fluorinated.
3. A process according to any of the claims 1 or 2, characterized in that said silane is an alkylsilane conforming to the general formula (I)
SiR1R2R3R4 (I)
wherein R1, R2, R3, R4 each contains organic residues containing 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 0 to 6 oxygen atoms, 0 to 33 fluorine atoms, 0 to 33 chlorine atoms and 0 to 5 nitrogen atoms.
4. The process according to any of the claims 1 to 3, characterized by using a liquid carrier being a solvent and/or dilution of solvent, in particular having a viscosity in the range from 0.2 to 15 mPa.
5. The process according to any of the claims 1 to 4, characterized by using a spray nozzle providing a droplet size up to 75 μm average droplet size, particularly up to 50 μm, in particular up to 15 μm.
6. The process according to any of the claims 1 to 5, characterized in that the substrate is sprayed in a first track covering a part of the substrate only, then drying said track, followed by spraying a further track of the substrate after at least 70 % of said carrier of the first track has evaporated.
7. The process according to one of claims 1 to 6, characterized in that metals, tiles, siliceous glass, ceramic, and/or polymer surfaces are coated.
8. The process according to one of claims 1 to 7, characterized in that the coating material is coated in tracks and that the beginning of each track always is on the same edge of the article.
9. The process according to one of claims 1 to 8, characterized in that a catalyst is added and is initiated after application of the coating material.
10. A composition for providing substrates with a hydrophobic and/or oleophobic surface, characterized in that it contains less than 10 % by weight of at least a silane in a liquid carrier having a viscosity in the range from 0.2 to 15 mPa.
11. The composition according to claim 10, characterized in that said silane is an alkylsilane conforming to the general formula (I) SiR1R2R3R4 (I)
wherein R1, R2, R3, R4 each contains organic residues containing 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 0 to 6 oxygen atoms, 0 to 33 fluorine atoms, 0 to 33 chlorine atoms and 0 to 5 nitrogen atoms.
12. The coating composition according to claim 11, wherein said alkylsilane is a fluorinated alkylsilane, particularly a perfluorinated alkylsilane, where R1 is a linear or branched alkyl group each containing 1 to 18 carbon atoms, 3 to 37 hydrogen atoms, 3 to 33 fluorine atoms, 0 to 6 oxygen atoms and 0 to 5 nitrogen atoms, and where R2,R3,R4 are each selected from the group containing chlorine or linear or branched alkyl groups each containing 1 to 4 carbon atoms or linear or branched alkoxy groups each containing 1 to 4 carbon atoms.
13. The coating composition according to claim 10 to 12, characterized in that said silane contains at least one reactive group for linking it with a mineral substrate, particularly a ceramic and/or a siliceous substrate, particularly with siliceous glasses, sanitary ware, tiles, wherein said reactive group of the silane is not directly connected to an atom being fluorinated.
14. The coating composition according to one of claims 10 to 13, characterized in that said carrier is a solvent and/or solvent dilution, in particular comprising water and/or an alcohol, particularly a linear or branched alcohol containing up to 5 carbon atoms, very particularly methanol, ethanol, or propanol, especially particularly isopropanol.
15. The coating composition according to one of claims 10 to 14, characterized by containing additives, in particular a surfactant and/or a catalyst.
16. The coating composition according to claim 15, characterized in that said catalyst catalyses the cross-linking of the silanes with each other or with the substrate.
17. The coating composition according to one of claims 10 to 16, characterized in that the concentration of the silane is up to 5 %, particularly up to 2 % by weight.
PCT/EP2003/011911 2002-10-28 2003-10-27 Process and composition for coating WO2004037936A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP03779813A EP1556452B1 (en) 2002-10-28 2003-10-27 Process and composition for coating
DE60321943T DE60321943D1 (en) 2002-10-28 2003-10-27
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GB2430395A (en) * 2005-09-21 2007-03-28 Ford Global Tech Llc High-velocity impact polymer reaction coating at ambient air pressure
US7744984B2 (en) 2006-06-28 2010-06-29 Ford Global Technologies, Llc Method of treating substrates for bonding
CN102199395A (en) * 2010-03-23 2011-09-28 上海沪正纳米科技有限公司 Colorless transparent self-cleaning paint and preparation method thereof
US8586149B2 (en) 2003-06-18 2013-11-19 Ford Global Technologies, Llc Environmentally friendly reactive fixture to allow localized surface engineering for improved adhesion to coated and non-coated substrates
CN113754472A (en) * 2021-08-10 2021-12-07 浙江零零零环境科技有限公司 Hydrophobic and oleophobic treatment method for silicon carbide ceramic membrane

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DE102006025243A1 (en) 2006-05-29 2007-12-06 Rheinmetall Waffe Munition Gmbh Protective layer for parts, in particular a weapon, a gun carriage, a tower or the like, in particular as a corrosion protection of these parts
CN110938373B (en) * 2019-12-12 2020-11-24 吉林大学 Fluorine-free oleophobic coating and application thereof

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Publication number Priority date Publication date Assignee Title
US8586149B2 (en) 2003-06-18 2013-11-19 Ford Global Technologies, Llc Environmentally friendly reactive fixture to allow localized surface engineering for improved adhesion to coated and non-coated substrates
GB2430395A (en) * 2005-09-21 2007-03-28 Ford Global Tech Llc High-velocity impact polymer reaction coating at ambient air pressure
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US7744984B2 (en) 2006-06-28 2010-06-29 Ford Global Technologies, Llc Method of treating substrates for bonding
CN102199395A (en) * 2010-03-23 2011-09-28 上海沪正纳米科技有限公司 Colorless transparent self-cleaning paint and preparation method thereof
CN113754472A (en) * 2021-08-10 2021-12-07 浙江零零零环境科技有限公司 Hydrophobic and oleophobic treatment method for silicon carbide ceramic membrane

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AU2003292950A1 (en) 2004-05-25
AU2003292950A8 (en) 2004-05-25
DE10394025D2 (en) 2005-09-22
DE60321943D1 (en) 2008-08-14
AU2003287967A1 (en) 2004-05-13
EP1556452A1 (en) 2005-07-27
WO2004039896A2 (en) 2004-05-13
EP1556452B1 (en) 2008-07-02

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