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WO2018125842A1 - Procédé de préparation d'une composition de revêtement durable et facile à nettoyer, antimicrobienne - Google Patents

Procédé de préparation d'une composition de revêtement durable et facile à nettoyer, antimicrobienne Download PDF

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Publication number
WO2018125842A1
WO2018125842A1 PCT/US2017/068332 US2017068332W WO2018125842A1 WO 2018125842 A1 WO2018125842 A1 WO 2018125842A1 US 2017068332 W US2017068332 W US 2017068332W WO 2018125842 A1 WO2018125842 A1 WO 2018125842A1
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Prior art keywords
preparation
coating composition
group
oxidation state
coating
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PCT/US2017/068332
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English (en)
Inventor
Long Yin
Tao Song
Yu Li
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3M Innovative Properties Co
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3M Innovative Properties Co
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Classifications

    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/24—Organic compounds containing halogen
    • C11D3/245—Organic compounds containing halogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present disclosure relates to a preparation method of a coating composition having a durable easy -cleaning effect and a durable antimicrobial function.
  • CN105482536 discloses a transparent and antimicrobial hydrophilic paint comprising the following components: at least one of silicate salt or sol, nanometer oxide dispersions, alkali metal phosphates, inorganic antimicrobial agents, inhibitors, humectants, and solvents.
  • the antimicrobial effect was achieved by adding nano-copper or nano-silver into the paint; yet, the antimicrobial durability was not tested.
  • US2012204762 discloses an aqueous silane system for bare corrosion protection and corrosion protection of metals.
  • bare corrosion protection of metal substrates is greatly improved by adding a metal salt into a silane and sol-gel system.
  • its easy-cleaning feature and antimicrobial performances of the coating were not mentioned, and were not tested either.
  • the present disclosure is intended to provide a preparation method of a durable easy-cleaning and antimicrobial coating composition to allow coated articles prepared by the method to have an easy- cleaning effect and an antimicrobial function that are both relatively enduring.
  • the present disclosure provides a preparation method of a durable easy-cleaning and antimicrobial coating composition, comprising steps of:
  • reaction mixture i 1) adding an acid into an alcohol -water solution comprising at least one orthosilicate and at least one fluorinated polyether silane compound to perform hydrolysis and co-condensation at a temperature of 20 to 80°C, so as to form a reaction mixture i;
  • reaction mixture ii 1) placing the reaction mixture i at room temperature to perform aging for 12 to 72 h, so as to form a reaction mixture ii;
  • the high-valence metal salt is one or more selected from the group consisting of aluminum salts (in an oxidation state of 3+), chromium salts (in an oxidation state of 3+), cerium salts (in an oxidation state of 3+ or 4+), zirconium salts (in an oxidation state of 4+), and vanadium salts (in an oxidation state of 5+); and
  • the inorganic antimicrobial agent is one or more selected from the group consisting of silver salts (in an oxidation state of 1+), copper salts (in an oxidation state of 2+), and zinc salts (in an oxidation state of 2+).
  • the present disclosure provides a coated article prepared according to the preparation method of the coating composition, comprising a substrate and a dry coating applied on the substrate, wherein the dry coating comprises a coating obtained by drying the coating composition obtained by the preparation method applied onto the substrate surface.
  • the present disclosure provides a preparation method of the coated article, comprising steps of: applying the coating composition obtained according to the preparation method onto at least part of a surface of the substrate to form a liquid film layer of the wet coating composition on the at least part of the surface of the substrate, and drying the liquid film of the wet coating composition to obtain a dry coating attached to the surface of the substrate.
  • the preparation method of a durable easy-cleaning and antimicrobial coating composition as provided herein includes steps of:
  • reaction mixture i 1) adding an acid into an alcohol -water solution comprising at least one orthosilicate and at least one fluorinated polyether silane compound to perform hydrolysis and co-condensation at a temperature of 20 to 80°C, so as to form a reaction mixture i;
  • reaction mixture ii 1) placing the reaction mixture i at room temperature to perform aging for 12 to 72 h, so as to form a reaction mixture ii;
  • the high-valence metal salt is one or more selected from the group consisting of aluminum salts (in an oxidation state of 3+), chromium salts (in an oxidation state of 3+), cerium salts (in an oxidation state of 3+ or 4+), zirconium salts (in an oxidation state of 4+), and vanadium salts (in an oxidation state of 5+); and 4) adding at least one inorganic antimicrobial agent into the reaction mixture iii to form a coating composition, wherein the inorganic antimicrobial agent is one or more selected from the group consisting of silver salts (in an oxidation state of 1+), copper salts (in an oxidation state of 2+), and zinc salts (in an oxidationation
  • the orthosilicate content is 1-10 wt% based on the total weight of the coating composition as 100 wt%. If the orthosilicate content is lower than 1 wt%, it may not be easy to form a coating of a desired thickness on the substrate, and the coated article obtained thereby may have poor abrasion resistance, salt-fog resistance, or high-temperature and high-humidity resistance; and if the orthosilicate content is higher than 10 wt%, the coated article obtained thereby may have evident defects in the appearance.
  • the orthosilicate can be represented by a general formula I:
  • R represents a hydrogen atom or CI -4 alkyl
  • R which may be identical or different, is one or more selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, and t-butyl.
  • the content of the fluorinated polyether silane compound is 0.05-5 wt% based on the total weight of the coating composition as 100 wt%. If the content of the fluorinated polyether silane compound is lower than 0.05 wt%, the coated article obtained thereby may have poor easy-cleaning performance; and if the content of the fluorinated polyether silane compound is higher than 5 wt%, the coated article obtained thereby may have evident defects in the appearance.
  • the fluorinated polyether silane compound can be represented by a general formula II:
  • the polyfluoropolyether chain segment includes a perfluorinated repeating unit, being one or more selected from the group consisting of: -(C n F2 n O)-, -(CF(Z)O)-, -(CF(Z)C n F2nO)-, -(C n F2nCF(Z)0)-, and -
  • n is an integer and 1 ⁇ n ⁇ 12; and Z represents perfluoroalkyl, oxygen- substituted perfluoroalkyl, perfluoroalkoxy, or oxygen-substituted perfluoroalkoxy having a linear, branched or cyclic structure and comprising 1 to 9 carbon atoms and 0 to 4 oxygen atoms.
  • a ratio by weight of the orthosilicate to the fluorinated polyether silane compound is from 2: 1 to 25 : 1.
  • the ratio by weight of the orthosilicate to the fluorinated polyether silane compound is lower than 2: 1, the coated article obtained thereby may have evident defects in the appearance; and when the ratio by weight of the orthosilicate to the fluorinated polyether silane compound is higher than 25 : 1, the coated article obtained thereby may have poor easy-cleaning performance.
  • the acid is an inorganic acid or an organic acid, where the inorganic acid is one or more selected from the group consisting of hydrochloric acid, nitric acid and phosphoric acid; and the organic acid is one or more selected from the group consisting of formic acid and acetic acid.
  • the content of the high-valence metal salt is 0.2-5 wt% based on the total weight of the coating composition as 100 wt%.
  • the coated article obtained thereby may have poor abrasion resistance, salt-fog resistance or high- temperature, and high-humidity resistance; and when the content of the high-valence metal salt is higher than 5 wt%, a problem may arise that the high-valence metal salt is dissolved incompletely or the concentration thereof is too high.
  • the high-valence metal salt is at least one metal salt selected from the group consisting of nitrate or acetate, and the high-valence metal salt is one or more selected from the group consisting of aluminum nitrate, chromium nitrate, cerium nitrate, zirconium nitrate, vanadium nitrate, aluminum acetate, chromium acetate, cerium acetate and zirconium acetate.
  • the content of the inorganic antimicrobial agent is 0.05-5 wt% based on the total weight of the coating composition as 100 wt%.
  • the content of the inorganic antimicrobial agent is lower than 0.05 wt%, the coated article obtained thereby may have poor antimicrobial performance; and when the content of the inorganic antimicrobial agent is higher than 5 wt%, the problem of the inorganic antimicrobial agent not being able to dissolve completely or the concentration thereof is too high may arise.
  • the inorganic antimicrobial agent is at least one metal salt selected from the group consisting of nitrate or sulphate, and the inorganic antimicrobial agent is one or more selected from the group consisting of silver nitrate, copper nitrate, zinc nitrate, copper sulfate, and zinc sulfate.
  • the coating composition has a pH value less than or equal to 4. When the coating composition has a pH value higher than 4, the coated article obtained thereby may have poor abrasion resistance, salt-fog resistance, or poor high-temperature and high-humidity resistance.
  • the coating composition of the present disclosure may also further comprise additives.
  • the additives includes one or more of detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, flavors, dyes, pigments, and organic polymer binders.
  • the surfactant is a non-ionic surfactant that can improve wettability of the coating composition on a substrate surface.
  • the non-ionic surfactant may be one or more selected from the group consisting of polyoxyethylene non-ionic surfactants, polyhydric alcohol non-ionic surfactants, alkylolamide non-ionic surfactants, fluorocarbon non-ionic surfactants, organosilicon non-ionic surfactants, and modified organosilicon non-ionic surfactants.
  • the content of the non-ionic surfactant is 0.01-2 wt%, preferably 0.01-1 wt%, and particularly preferably 0.05-0.5 wt% based on the total weight of the coating composition as 100 wt%. If the content of the non-ionic surfactant is higher than 2 wt%, the coated article obtained thereby may have poor appearance, abrasion resistance, salt-fog resistance or poor high-temperature and high-humidity resistance.
  • the coating composition provided herein is a coating composition obtained according to the preparation method of the coating composition.
  • the coated article provided here includes a substrate and a dry coating applied on the substrate, wherein the dry coating includes a coating obtained by drying the coating composition applied onto the substrate surface.
  • the substrate is one or more selected from the group consisting of ceramic tile substrates, glass substrates, stone substrates and metal substrates.
  • the "ceramic tiles" as described here or in the claims are applicable to porcelain materials prepared from fire-resistant clays, tile materials, concrete, ceramics, marbles, limestones, and other stone materials or slate.
  • the ceramic tile substrate is one or more selected from the group consisting of vitrified tiles, glazed tiles, rustic tiles, microlites, polished tiles, granite-simulating tiles, and marble-simulating tiles.
  • the stone substrate is one or more selected from the group consisting of marble, granite, and artificial stone.
  • the metal substrate is one or more selected from the group consisting of stainless steel, cold rolled steel, galvanized steel, chromized steel, phosphated steel, iron, aluminum, titanium, magnesium, copper, zinc, and alloys
  • the dry coating may have any appropriate thickness as required, and the thickness of the dry coating may be from 50 nm to 10 um, or from 100 nm to 5 um, or from 200 nm to 1 um.
  • the preparation method of a coated article provided herein includes steps of: applying the coating composition provided in the present disclosure onto at least part of a surface of the substrate to form a liquid film layer of the wet coating composition on the at least part of the surface of the substrate, and drying the liquid film of the wet coating composition to obtain a dry coating attached to the surface of the substrate.
  • the coating composition can be applied onto the substrate surface by methods known in the prior art; and the methods are preferably one or more of blade coating, wipe coating, brush coating, dip coating, and spray coating.
  • the antiskid liquid can be dried by an appropriate drying method known in the prior art.
  • the drying process can be performed in a room temperature or higher temperature condition.
  • the temperature may be from 40 to 200°C, or from 60 to 180°C, or from 80 to 150°C.
  • Preferred embodiment 1 is a preparation method of a durable, easy-cleaning and antimicrobial coating composition, including steps of:
  • reaction mixture i 1) adding an acid into an alcohol-water solution comprising at least one orthosilicate and at least one fluorinated polyether silane compound to perform hydrolysis and co-condensation at a temperature of 20 to 80°C, so as to form a reaction mixture i;
  • reaction mixture ii 1) placing the reaction mixture i at room temperature to perform aging for 12 to 72 h, so as to form a reaction mixture ii;
  • the high-valence metal salt is one or more selected from the group consisting of aluminum salts (in an oxidation state of 3+), chromium salts (in an oxidation state of 3+), cerium salts (in an oxidation state of 3+ or 4+), zirconium salts (in an oxidation state of 4+), and vanadium salts (in an oxidation state of 5+); and
  • the inorganic antimicrobial agent is one or more selected from the group consisting of silver salts (in an oxidation state of 1+), copper salts (in an oxidation state of 2+), and zinc salts (in an oxidation state of 2+).
  • Preferred embodiment 2 is the preparation method of preferred embodiment 1, wherein the orthosilicate content is 1- 10 wt% based on the total weight of the coating composition as 100 wt%.
  • Preferred embodiment 3 is the preparation method of preferred embodiment 1, wherein the orthosilicate can be represented by a general formula I:
  • R represents a hydrogen atom or C I -4 alkyl
  • R which may be identical or different, is one or more selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, and t-butyl.
  • Preferred embodiment 4 is the preparation method of preferred embodiment 1, wherein the content of the fluorinated polyether silane compound is 0.05-5 wt% based on the total weight of the coating composition as 100 wt%.
  • Preferred embodiment 5 is the preparation method of preferred embodiment 1, wherein the fluorinated polyether silane compound can be represented by a general formula II:
  • a is an integer and 0 ⁇ a ⁇ l; b is an integer and 2 ⁇ b ⁇ 4; Rf represents a multivalent polyfluoropolyether chain segment; Q represents an organic bivalent linking group; R 1 represents CI -8 alkyl; R represents a hydrogen atom or CI -4 alkyl, and R, which may be identical or different, is one or more selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, and t-butyl.
  • Preferred embodiment 6 is the preparation method of preferred embodiment 5, wherein the polyfluoropolyether chain segment includes a perfluorinated repeating unit, being one or more selected from the group consisting of: -(C n F 2n O)-, -(CF(Z)O)-, -(CF(Z)C n F 2n O)-, -(C n F 2n CF(Z)0)-, and - (CF2CF(Z)0)-, where n is an integer and 1 ⁇ n ⁇ 12; and Z represents perfluoroalkyl, oxygen-substituted perfluoroalkyl, perfluoroalkoxy, or oxygen-substituted perfluoroalkoxy having a linear, branched, or cyclic structure and comprising 1 to 9 carbon atoms and 0 to 4 oxygen atoms.
  • the polyfluoropolyether chain segment includes a perfluorinated repeating unit, being one or more selected from the group consisting
  • Preferred embodiment 7 is the preparation method of preferred embodiment 1, wherein a ratio by weight of the orthosilicate to the fluorinated polyether silane compound is from 2: 1 to 25: 1.
  • Preferred embodiment 8 is the preparation method of preferred embodiment 1, wherein the acid is an inorganic acid or an organic acid, wherein the inorganic acid is one or more selected from the group consisting of hydrochloric acid, nitric acid, and phosphoric acid; and the organic acid is one or more selected from the group consisting of formic acid and acetic acid.
  • Preferred embodiment 9 is the preparation method of preferred embodiment 1, wherein the content of the high- valence metal salt is 0.2-5 wt% based on the total weight of the coating composition as 100 wt%.
  • Preferred embodiment 10 is the preparation method of preferred embodiment 1, wherein the high- valence metal salt is at least one metal salt selected from the group consisting of nitrate or acetate; and the high- valence metal salt is one or more selected from the group consisting of aluminum nitrate, chromium nitrate, cerium nitrate, zirconium nitrate, vanadium nitrate, aluminum acetate, chromium acetate, cerium acetate, and zirconium acetate.
  • Preferred embodiment 11 is the preparation method of preferred embodiment 1, wherein the content of the inorganic antimicrobial agent is 0.05-5 wt% based on the total weight of the coating composition as 100 wt%.
  • Preferred embodiment 12 is the preparation method of preferred embodiment 1, wherein the inorganic antimicrobial agent is at least one metal salt selected from the group consisting of nitrate or sulphate; and the inorganic antimicrobial agent is one or more selected from the group consisting of silver nitrate, copper nitrate, zinc nitrate, copper sulfate, and zinc sulfate.
  • the inorganic antimicrobial agent is at least one metal salt selected from the group consisting of nitrate or sulphate
  • the inorganic antimicrobial agent is one or more selected from the group consisting of silver nitrate, copper nitrate, zinc nitrate, copper sulfate, and zinc sulfate.
  • Preferred embodiment 13 is the preparation method of preferred embodiment 1, wherein the coating composition has a pH value less than or equal to 4.
  • Preferred embodiment 14 is the preparation method of preferred embodiment 1, wherein the coating composition further comprises 0.01-2 wt% additives based on the total weight of the coating composition as 100 wt%; and the additives includes one or more of detergents, surfactants, leveling agents, colorants, brighteners, light stabilizers, flavors, dyes, pigments, and organic polymer binders.
  • Preferred embodiment 15 is a coated article, including a substrate and a dry coating applied on the substrate, wherein the dry coating includes a coating obtained by drying the coating composition obtained by the preparation method according to the preferred embodiments 1 to 14 applied onto the substrate surface.
  • Preferred embodiment 16 is the coated article of preferred embodiment 15, wherein the substrate is one or more selected from the group consisting of ceramic tile substrates, glass substrates, stone substrates, and metal substrates.
  • Preferred embodiment 17 is the coated article of preferred embodiment 16, wherein the ceramic tile substrate is one or more selected from the group consisting of vitrified tiles, glazed tiles, rustic tiles, microlites, polished tiles, granite -simulating tiles, and marble-simulating tiles.
  • Preferred embodiment 18 is the coated article of preferred embodiment 16, wherein the stone substrate is one or more selected from the group consisting of marble, granite, and artificial stone.
  • Preferred embodiment 19 is the coated article of preferred embodiment 16, wherein the metal substrate is one or more selected from the group consisting of stainless steel, cold rolled steel, galvanized steel, chromized steel, phosphated steel, iron, aluminum, titanium, magnesium, copper, zinc, and alloys comprising the above metals.
  • Preferred embodiment 20 is a preparation method of a coated article, including steps of: applying the coating composition obtained by the preparation method according to the preferred embodiments 1 to 14 onto at least part of a surface of the substrate to form a liquid film layer of the wet coating composition on the at least part of the surface of the substrate; and drying the liquid film of the wet coating composition to obtain a dry coating attached to the surface of the substrate.
  • Preferred embodiment 21 is the preparation method of preferred embodiment 20, wherein the coating composition is applied onto the surface of the substrate by the following methods: blade coating, wipe coating, brush coating, dip coating, and spray coating.
  • Chromium nitrate nonahydrate Cr(N0 3 ) 3 9H 2 0, purity > 99.0 wt% Shanghai Zhanyun Chemical
  • Cerium nitrate hexahydrate Ce(N0 3 ) 3 6H 2 0, purity > 99.0 wt% Co., Ltd.
  • Vanadium nitrate V0 2 N0 3 , purity 50-52 wt%
  • Zinc nitrate hexahydrate Zn(N0 3 ) 2 6H 2 0, purity > 99.0 wt%
  • Zinc sulfate heptahydrate ZnS0 4 7H 2 0, purity > 99.0 wt%
  • Deionized water Deionized water (DI H 2 0) Home-made in 3M
  • Alkyl polyglucoside surfactant TRITONTM Dow Chemical Co.
  • Comparative examples are evaluated through the contact angle tests; and the antimicrobial performance of coated articles provided in Examples and Comparative examples are evaluated through tests of the antimicrobial ratio. On this basis, in the present disclosure, abrasion resistance of coated articles provided in
  • Examples and Comparative examples are evaluated through the observed changes in the contact angle and in the antimicrobial ratio before and after the wet grinding test; salt-fog resistance of coated articles provided in Examples and Comparative examples are evaluated through the observed changes in the contact angle and in the antimicrobial ratio before and after the salt-fog test; and high-temperature and high- humidity resistance of coated articles provided in Examples and Comparative examples are evaluated through the observed changes in the contact angle and in the antimicrobial ratio before and after the high- temperature and high-humidity test.
  • the instrument for performing the contact angle tests is a Kruss DSA100 automatic contact angle tester commercially available from Kruss Corporation.
  • hexadecane drop is quantitatively injected onto a surface of the coated article, and the hexadecane drop is tested for the contact angle after its shape no longer changes. Five different regions are selected randomly on the surface of the coated article; and the above experiment is repeated to obtain five numerical values of the hexadecane contact angle which are then averaged.
  • the averaged hexadecane contact angle is less than 60°, it indicates that the surface of the coated article has an oleophilic effect, and a lower numerical value indicates better oleophilicity of the surface; and if the averaged hexadecane contact angle is greater than or equal to 60°, it indicates that the surface of the coated article has an oleophobic effect, and a higher numerical value indicates better oleophobicity of the surface. If the averaged water contact angle measured on the surface of the coated article is greater than or equal to 110°, and at the same time the averaged hexadecane contact angle is greater than or equal to 60°, it indicates that the coated article has good easy-cleaning performance.
  • the antimicrobial performance of the coated articles herein is shown through tests of the antimicrobial ratio.
  • Test organisms for testing the antimicrobial ratio are Escherichia coli (a gram-negative bacterium) and Staphylococcus aureus (a gram -positive bacterium).
  • Tests of the antimicrobial ratio are performed according to JIS Z 2801-2010. Control products (not including the substrate of the same material as the coating composition) and coated articles are respectively clipped into a size with an area of about 50 mm ⁇ 50 mm (three samples each), and sterilization is performed thereon. Several milliliters of bacterium liquid are added dropwise onto each sample surface to maintain the viable count on each sample surface at about 10 5 . The sample surface with the bacterium liquid added dropwise thereon is covered with a plastic film; and then all samples are placed into a sterile plate, which is placed into a constant-temperature incubator at 36 ⁇ 1°C to culture the samples for 24 h. The viable count is obtained beside the flame within the sterile chamber; and the antimicrobial ratio of each sample is calculated according to the following formula:
  • antimicrobial ratio [(A-B)/A] * 100%
  • A represents the average viable count on each sample surface of the control products after 24 h; and B represents the average viable count on each sample surface of the coated articles after 24 h.
  • Antimicrobial ratios of three samples each of the control products and the coated articles are averaged respectively.
  • the averaged antimicrobial ratio measured on the surface of the coated article is greater than or equal to 99%, it indicates that the coated article has good antimicrobial performance.
  • the abrasion resistance of the coated articles herein is shown through changes in the contact angle and in the antimicrobial ratio before and after the wet grinding test.
  • the instrument for performing the wet grinding tests is Sheen Wet Abrasion Scrub Tester REF 903 commercially available from Sheen Corporation.
  • the water contact angle and the hexadecane contact angle obtained by measurement on the surface of the coated article after the wet grinding test are compared with those before the wet grinding test respectively. If the losses in the water contact angle and in the hexadecane contact angle are both less than or equal to 10%, it indicates that, with regard to the easy-cleaning performance, the coated article has good abrasion resistance and is labelled as V; and if the loss in either contact angle is greater than 10%, it indicates that, with regard to the easy-cleaning performance, the coated article does not have good abrasion resistance and is labelled as x.
  • the antimicrobial ratio obtained by measurement on the surface of the coated article after the wet grinding test is still greater than or equal to 90%, it indicates that, with regard to the antimicrobial performance, the coated article has good abrasion resistance and is labelled as V; and if the antimicrobial ratio is less than 90%, it indicates that, with regard to the antimicrobial performance, the coated article does not have good abrasion resistance and is labelled as x.
  • the salt-fog resistance of coated articles herein is shown through changes in the contact angle and in the antimicrobial ratio before and after the salt-fog test.
  • the instrument for performing the salt-fog tests is Q-Fog SF-1 600L commercially available from Q-Lab Corporation.
  • the salt-fog test is performed according to ASTM B 117-07.
  • the coated article is placed into a salt- fog chamber with a temperature in the exposed zone thereof being constant within a range of 35 ⁇ 2°C.
  • a 5 ⁇ 1 wt% sodium chloride solution is sprayed, and drips have a pH value maintained within a range of 6.5-7.2.
  • the test is stopped.
  • the coated article is taken out, cleaned with deionized water, and then measured for the water contact angle, the hexadecane contact angle, and the antimicrobial ratio on the surface thereof.
  • the water contact angle and the hexadecane contact angle obtained by measurement on the surface of the coated article after the salt-fog test are compared with those before the salt-fog test respectively. If the losses in the water contact angle and in the hexadecane contact angle are both less than or equal to 10%, it indicates that, with regard to the easy-cleaning performance, the coated article has good salt-fog resistance and is labelled as V; and if the loss in either contact angle is greater than 10%, it indicates that, with regard to the easy-cleaning performance, the coated article does not have good salt-fog resistance and is labelled as x.
  • the antimicrobial ratio obtained by measurement on the surface of the coated article after the salt- fog test is still greater than or equal to 90%, it indicates that, with regard to the antimicrobial
  • the coated article has good salt-fog resistance and is labelled as V; and if the antimicrobial ratio is less than 90%, it indicates that, with regard to the antimicrobial performance, the coated article does not have good salt-fog resistance and is labelled as x.
  • the high-temperature and high-humidity resistance of coated articles herein is shown through changes in the contact angle and in the antimicrobial ratio before and after the high-temperature and high- humidity test.
  • the instrument for performing the high-temperature and high-humidity test is C7-340 commercially available from Votsch Industrietechnik Corporation.
  • the high-temperature and high-humidity test is performed according to GB/T 2423.3-2006.
  • the coated article is placed into a test chamber at a temperature constant within a range of 85 ⁇ 2°C and a relative humidity constant within a range of 85 ⁇ 3 RH%.
  • the test is stopped.
  • the coated article is taken out, cleaned with deionized water, and then measured for the water contact angle, the hexadecane contact angle, and the antimicrobial ratio on the surface thereof.
  • the water contact angle and the hexadecane contact angle obtained by measurement on the surface of the coated article after the high-temperature and high-humidity test are compared with those before the high-temperature and high-humidity test respectively. If the losses in the water contact angle and in the hexadecane contact angle are both less than or equal to 10%, it indicates that, with regard to the easy- cleaning performance, the coated article has good high-temperature and high-humidity resistance and is labelled as V; and if the loss in either contact angle is greater than 10%, it indicates that, with regard to the easy -cleaning performance, the coated article does not have good high-temperature and high-humidity resistance and is labelled as x.
  • the antimicrobial ratio obtained by measurement on the surface of the coated article after the high- temperature and high-humidity test is still greater than or equal to 90%, it indicates that, with regard to the antimicrobial performance, the coated article has good high-temperature and high-humidity resistance and is labelled as V; and if the antimicrobial ratio is less than 90%, it indicates that, with regard to the antimicrobial performance, the coated article does not have good high-temperature and high-humidity resistance and is labelled as x.
  • the resulting mixture was heated up to 80°C, stirred for 2 h under a condensation reflux condition, then cooled to room temperature and stopped from stirring, and aged for 12 h at room temperature;
  • Coating compositions of Examples 2 to 6 were prepared by the same method as Example 1 ; types and contents of ingredients included in the coating compositions are listed in Table 2.
  • the resulting mixture was heated up to 40°C, further stirred for 2 h, then cooled to room temperature and stopped from stirring, and aged for 24 h at room temperature;
  • this mixture was stirred for 1 h at room temperature, and 0.50 g of solid silver nitrate was added therein; and stirring was further performed for 30 min at room temperature to obtain a colorless clear transparent coating composition.
  • a product NovecTM 1720 commercially available from 3M was used as a coating composition and denoted as Comparative example 4.
  • Example 4 a ratio by weight of tetraethyl orthosilicate to tetramethyl orthosilicate is 6:4.
  • a coated article was prepared by a blade coating method, including steps as follows:
  • a vitrified tile 200 mm 200 mm 10 mm was used as a substrate of the coated article.
  • a surface of the vitrified tile was first cleaned with a cleanser essence (brand White Cat, commercially available from Shanghai Hutchison White Cat Co., Ltd.), subsequently rinsed with deionized water, and then blown dry with compressed air;
  • a cleanser essence brand White Cat, commercially available from Shanghai Hutchison White Cat Co., Ltd.
  • a coil bar of an automatic blade coater (K303 Multicoater, commercially available from RK Print Coat Instruments Corporation) was placed on one end of the vitrified tile, and 5 g of the coating composition filtered off was dropped uniformly with a dropper into a gap between the coil bar and the vitrified tile; at room temperature, the coating composition was blade coated with the automatic blade coater on the surface of the vitrified tile;
  • the wet-film thickness of the coating composition was about 12 ⁇ , which was denoted as T-12, as shown in Table 3;
  • a coated article was prepared by the same method as Example 7; the substrate type of the coated article, blade coating conditions and thermal treatment conditions are listed in Table 3. As shown in Table 3, if the wet-film thickness in the blade coating process is 1.5 um, it is denoted as T- 1.5; if the wet-film thickness of the coating composition in the blade coating process is 3 um, it is denoted as T-3; if the wet-film thickness of the coating composition in the blade coating process is 6 um, it is denoted as T-6; and if the wet-film thickness of the coating composition in the blade coating process is 12 um, it is denoted as T-12.
  • a coated article was prepared by a dip coating method, including steps as follows:
  • an automatic dip coater (SKVDX2S-500, commercially available from KSV NIMA Corporation) subjected the glass to dip coating in the coating composition;
  • the dip speed was 300 mm/min
  • the dip time was 1 min
  • the pull speed was 300 mm/min, with details listed in Table 3;
  • Coated articles were prepared by the same method as Example 9; the substrate types of the coated articles, blade coating conditions and thermal treatment conditions are listed in Table 3.
  • a coated article was prepared by wipe coating, including steps as follows:
  • 439 stainless steel (100 mm 50 mm 1 mm) was used as a substrate of the coated article.
  • a surface of the 439 stainless steel was first cleaned with a cleanser essence (brand White Cat, commercially available from Shanghai Hutchison White Cat Co., Ltd.), subsequently rinsed with deionized water, and then blown dry with compressed air;
  • a cleanser essence brand White Cat, commercially available from Shanghai Hutchison White Cat Co., Ltd.
  • a spunbonded polypropylene nonwoven cloth commercially available from 3M Corporation was clipped into 50 mm ⁇ 20 mm strips. 6 g of the coating composition obtained from Example 6 was drawn by a dropper, 3 g of which was then dropped onto one end of the 439 stainless steel and the other 3 g was dropped onto the middle of the 304 stainless steel. The nonwoven cloth was pressed by hand to perform uniform coating from one end with the coating composition to the other end without the coating composition on the 439 stainless steel; and
  • Coated articles were prepared by the same method as Example 9 to serve as Comparative examples 5 to 8; the substrate types of the coated articles, dip coating conditions and thermal treatment conditions are listed in Table 3.
  • the averaged water contact angles obtained by measurement on the surfaces of the coated articles provided according to Examples 7 to 12 are all greater than 110°; and at the same time the averaged hexadecane contact angles are all greater than 60°; these coated articles therefore had good easy-cleaning performance.
  • the averaged antimicrobial ratios obtained by measurement on the surfaces of the coated articles provided according to Examples 7 to 12 are all greater than 99%, and thus these coated articles had good antimicrobial performance.

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Abstract

L'invention concerne un procédé de préparation d'une composition de revêtement durable et facile à nettoyer, antimicrobienne, le procédé comprenant les étapes consistant à : 1) ajouter un acide dans une solution d'alcool-eau comprenant au moins un orthosilicate et un composé de type polyéthersilane fluoré pour effectuer une hydrolyse et une cocondensation à 20 jusqu'à 80°, de manière à former un mélange réactionnel i ; 2) placer le mélange réactionnel i à température ambiante pour effectuer un vieillissement pendant 12 à 72 h, de manière à former un mélange réactionnel ii ; 3) ajouter un acide dans une solution aqueuse comprenant au moins un sel métallique à valence élevée pour ajuster le pH de la solution à 1-4, puis mélanger la solution avec le mélange réactionnel ii, de manière à former un mélange réactionnel iii, le sel métallique à valence élevée étant un ou plusieurs sels choisis dans le groupe constitué par les sels d'aluminium (dans un étage d'oxydation de 3+), les sels de chrome (dans un étage d'oxydation de 3+), les sels de cérium (dans un étage d'oxydation de 3+ ou 4+), les sels de zirconium (dans un étage d'oxydation de 4+) et les sels de vanadium (dans un étage d'oxydation de 5+) ; et 4) ajouter au moins un agent antimicrobien inorganique dans le mélange réactionnel iii pour former une composition de revêtement, l'agent antimicrobien inorganique étant un sel d'argent (dans un étage d'oxydation de 1+), un sel de cuivre (dans un étage d'oxydation de 2+) ou un sel de zinc (dans un étage d'oxydation de 2+).
PCT/US2017/068332 2016-12-26 2017-12-22 Procédé de préparation d'une composition de revêtement durable et facile à nettoyer, antimicrobienne Ceased WO2018125842A1 (fr)

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