WO2014209832A1 - Article portant un revêtement à base de silanol et son procédé de fabrication - Google Patents

Article portant un revêtement à base de silanol et son procédé de fabrication Download PDF

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Publication number
WO2014209832A1
WO2014209832A1 PCT/US2014/043566 US2014043566W WO2014209832A1 WO 2014209832 A1 WO2014209832 A1 WO 2014209832A1 US 2014043566 W US2014043566 W US 2014043566W WO 2014209832 A1 WO2014209832 A1 WO 2014209832A1
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Prior art keywords
coating
substrate
silanol
group
article
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PCT/US2014/043566
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English (en)
Inventor
Jitendra S. Rathore
Suresh S. Iyer
Chetan P. Jariwala
Vijay Rajamani
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3M Innovative Properties Company
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Publication of WO2014209832A1 publication Critical patent/WO2014209832A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09D5/008—Temporary coatings

Definitions

  • Anti-fog coatings are used in high humidity areas where water vapors easily condense, for example, on eye glasses, bathroom mirrors, inside surfaces of car windshields, etc.
  • One common method to prevent fogging is the use of polymer mirrors or heated elements installed behind conventional glass mirrors. Physically heating the glass electronically can make the glass defog quickly. Air conditioning can also make the glass defog, for instance, as commonly employed to defog automobile glass. Such physical methods show excellent anti-fog results, yet
  • the articles include a substrate and a silanol coating disposed on a major surface of the substrate.
  • the silanol coatings adhere to the surface of the substrate but are not covalently bonded to the substrate. That is, the silanol coatings adhere without curing and can be removed by dissolution in water, if desired.
  • the silanol coatings provide anti-fogging characteristics to the articles.
  • an article in a first aspect, includes (a) a substrate and (b) a silanol coating attached to a major surface of the substrate.
  • the silanol coating is not covalently bonded to the substrate.
  • the silanol coating contains an aminosilanol polymer that is a reaction product of water and an aminosilane of Formula (I).
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl.
  • the group R 2 is a divalent group comprising an alkylene, arylene, -N(R 5 )-, or a combination thereof.
  • the group R 3 is a hydrolyzable group and the group R 4 is a non-hydrolyzable group.
  • the group R 5 is hydrogen or alkyl.
  • the variable x is equal to 2 or 3.
  • a method of making an article includes providing a substrate and applying a coatable composition to a major surface of the substrate.
  • the coatable composition contains an aminosilanol polymer that is a reaction product of water and an aminosilane of Formula (I).
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl.
  • the group R 2 is a divalent group comprising an alkylene, arylene, -N(R 5 )-, or a combination thereof.
  • the group R 3 is a hydrolyzable group and the group R 4 is a non-hydrolyzable group.
  • the group R 5 is hydrogen or alkyl.
  • the variable x is equal to 2 or 3.
  • the method further includes forming a silanol coating, wherein the silanol coating is not covalently bonded to the substrate.
  • Figure 1 is an exemplary schematic of an article including a substrate and a silanol coating.
  • the articles include a substrate and a silanol coating disposed on a major surface of the substrate.
  • the silanol coating adheres to but is not covalently bonded to the substrate.
  • the silanol coating includes an aminosilanol polymer that is a reaction product of water and an aminosilane. The silanol coating tends to improve the resistance of the resulting article to fogging.
  • any numerical range by endpoints is meant to include the endpoints of the range, all numbers within the range, and any narrower range within the stated range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).
  • all numbers expressing quantities or ingredients, measurement of properties and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term "about.”
  • the numerical parameters set forth in the foregoing specification and attached listing of embodiments can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claimed embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
  • a and/or B means A, B, or a combination of A and B.
  • coatable composition refers to a solution or dispersion including components (e.g., an aminosilane, an aminosilanol polymer, surfactant, water, water-miscible organic solvents, fillers, additives, and the like) that are suitable for applying onto a major surface of a substrate as a coating.
  • components e.g., an aminosilane, an aminosilanol polymer, surfactant, water, water-miscible organic solvents, fillers, additives, and the like
  • fluid layer refers to a coatable composition that has been applied onto a surface, for example onto a major surface of a substrate, prior to being subjected to a drying process.
  • sianol coating refers to the components remaining after application of a coatable composition onto a major surface of a substrate and drying (e.g., removing at least the majority of water, water-miscible organic solvent, or both) the coatable composition.
  • aminosilane refers to a molecule having an amino group (i.e., a primary amino group, secondary amino group, or tertiary amino group) and a silyl group that is hydrolyzable.
  • aminosilanol polymer refers to the reaction product of three or more aminosilane compounds with water.
  • the aminosilanol polymer has multiple -O-Si-0- linkages. The number of linkages can be at least 2, at least 3, at least 10, at least 20, at least 50, at least 100, or even more.
  • the aminosilanol polymer is typically soluble in water, in a water-miscible organic solvent, or both.
  • adjacent in reference to a coating (e.g., the silanol coating) being adjacent to a substrate, means that the coating can contact a surface of the substrate or can be separated from a surface of the substrate by one or more other coatings.
  • silanol coating in reference to a silanol coating being attached to a substrate, means that the silanol coating can be attached to (e.g., adhere to) the substrate by any forces (e.g., electrostatic interaction, hydrogen bonding, van der Waals forces, etc.) except by formation of a covalent bonds between molecule on the substrate surface and the silanol coating.
  • forces e.g., electrostatic interaction, hydrogen bonding, van der Waals forces, etc.
  • alkyl refers to a monovalent group that is a radical of an alkane.
  • the alkyl group can have 1 to 20 carbon atoms and can be linear, branched, cyclic, or a combination thereof. When the alkyl is linear, it can have 1 to 20 carbon atoms. When the alkyl is branched or cyclic, it can have 3 to 20 carbon atoms.
  • alkylene refers to a divalent group that is a radical of an alkane.
  • the alkylene group can have 1 to 20 carbon atoms and can be linear, branched, cyclic, or a combination thereof. When the alkylene is linear, it can have 1 to 20 carbon atoms. When the alkylene is branched or cyclic, it can have 3 to 20 carbon atoms.
  • alkoxy refers to refers to a monovalent group having an oxy group bonded directly to an alkyl group.
  • aryl refers to a monovalent group that is a radical of an aromatic carbocyclic compound.
  • the aryl group has at least one aromatic carbocyclic ring and can have 1 to 5 optional rings that are connected to or fused to the aromatic carbocyclic ring.
  • the additional rings can be aromatic, aliphatic, or a combination thereof.
  • the aryl group usually has 5 to 20 carbon atoms.
  • arylene refers to a divalent group that is a radical of an aromatic carbocyclic compound.
  • the arylene group has at least one aromatic carbocyclic ring and can have 1 to 5 optional rings that are connected to or fused to the aromatic carbocyclic ring.
  • the additional rings can be aromatic, aliphatic, or a combination thereof.
  • the arylene group usually has 5 to 20 carbon atoms.
  • alkaryl refers to an aryl group substituted with at least one alkyl group.
  • the alkaryl group contains 6 to 40 carbon atoms.
  • the alkaryl group often contains an aryl group having 5 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.
  • aralkyl refers to an alkyl group substituted with at least one aryl group.
  • the aralkyl group contains 6 to 40 carbon atoms.
  • the aralkyl group often contains an alkyl group having 1 to 20 carbon atoms and an aryl group having 5 to 20 carbon atoms.
  • aralkylene refers to a divalent group that is an alkylene group substituted with an aryl group or an alkylene group attached to an arylene group.
  • Aralkylene groups often have an alkylene portion with 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms and an aryl or arylene portion with 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • aryloxy refers to a monovalent group having an oxy group bonded directly to an aryl group.
  • aralkyloxy refers to a monovalent group having an oxy group bonded directly to an aralkyl group. Equivalently, it can be considered to be an alkoxy group substituted with an aryl group.
  • acyloxy refers to a monovalent group of formula -0(CO)R b where R b is alkyl, aryl, or aralkyl.
  • Suitable alkyl R b groups often have 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • Suitable aryl R b groups often have 6 to 12 carbon atoms such as, for example, phenyl.
  • Suitable aralkyl R b groups often have an alkyl group with 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms that is substituted with an aryl having 6 to 12 carbon atoms such as, for example, phenyl.
  • halo refers to a halogen atom such as fluoro, bromo, iodo, or chloro. When part of a reactive silyl, the halo group is often chloro
  • silyl refers to a monovalent group of formula -Si(R 3 ) x (R 4 ) 3 _ x having at least two hydro lyzable groups R 3 and up to 1 hydro lyzable group R 4 .
  • the variable x is equal to 2 or 3.
  • the silyl group is of formula -Si(R 3 ) 2 (R 4 ) or -Si(R 3 ) 3 .
  • hydrolyzable group refers to a group that can react with water having a pH of
  • Typical hydrolyzable groups include, but are not limited to, alkoxy, aryloxy, aralkyloxy, acyloxy, or halo.
  • the term is often used in reference to one of more groups bonded to a silicon atom in a silyl group.
  • non-hydrolyzable group refers to a group that cannot react with water having a pH of 1 to 10 under conditions of atmospheric pressure.
  • Typical non-hydrolyzable groups include, but are not limited to alkyl, aryl, alkaryl, and aralkyl. As used herein, the term is often used in reference to one of more groups bonded to a silicon atom in a silyl group.
  • an article in a first aspect, includes (a) a substrate and (b) a silanol coating attached to a major surface of the substrate.
  • the silanol coating is not covalently bonded to the substrate.
  • the silanol coating contains an aminosilanol polymer that is a reaction product of water and an aminosilane of Formula (I).
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl.
  • the group R 2 is a divalent group comprising an alkylene, arylene, -N(R 5 )-, or a combination thereof.
  • the group R 3 is a hydrolyzable group and the group R 4 is a non-hydrolyzable group.
  • the group R 5 is hydrogen or alkyl.
  • the variable x is equal to 2 or 3.
  • the aminosilane can have a primary amino group (i.e., both R 1 groups in Formula (I) are hydrogen), a secondary amino group (i.e., one R 1 group is hydrogen ant the other R 1 group is alkyl, aryl, alkaryl, or aralkyl), or a tertiary amino group (i.e., both of the R 1 groups in Formula (I) are alkyl or aryl).
  • the group R 2 is often an alkylene or two or more alkylene groups connected to a -N (Regroup. Suitable alkylene groups often have 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 3 carbon atoms.
  • the group R 5 is often hydrogen.
  • Suitable silyl groups have either two or three hydrolyzable R 3 groups.
  • Suitable hydrolyzable groups include alkoxy, aryloxy, aralkyloxy, acyloxy, or halo groups.
  • the hydrolyzable group is an alkoxy or halo group.
  • Some example alkoxy groups have 1 to 6 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms (i.e., methoxy and ethoxy).
  • the halo group is often chloro. If there are two hydrolyzable groups, then there is a single non- hydrolyzable group R 4 .
  • Suitable non-hydrolyzable groups include alkyl, aryl, alkaryl, and aralkyl groups.
  • the hydrolyzable R 3 groups When mixed with water, the hydrolyzable R 3 groups are typically converted to hydroxyl groups.
  • the non-hydrolyzable group is an alkyl such as an alkyl having 1 to 6 carbon atoms, 1 to 3 carbon atoms, or 1 or two carbon atoms (i.e., methyl or ethyl).
  • Some aminosilanes of Formula (I) are of Formula (la).
  • Group -(R 6 -NH) p -CH 2 CH 2 - in Formula (la) is equal to group -R 2 - in Formula (I).
  • groups R 1 , R 3 , and R 4 are defined as in Formula (I).
  • Group R is an alkylene, arylene, aralkylene, -N(R 5 )-, or a combination thereof.
  • the aminosilane can have two or more amino groups.
  • the amino group N(R ! ) 2 - is a primary or secondary amino group.
  • R 1 , R 6 , R 3 , and R 4 are the same as defined above for Formula (la).
  • Some more specific examples include compounds of Formula (lb) where R 6 is an alkylene having 1 to 6 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms.
  • some exemplary silyl groups include trimethoxysilyl, triethoxysilyl,
  • Some even more specific example compounds of Formula (lb) include, but are not limited to, aminoethylaminopropyltrimethoxysilane,
  • aminoethylaminopropyltriethoxysilane N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and benzylaminoethylaminopropyltrimethoxysilane.
  • the aminosilane has a single amino group.
  • the amino group N(R ! ) 2 - is often a primary or secondary amino group.
  • the amino group is separated from the silyl group by three carbon atoms.
  • Some exemplary compounds of Formula (Ic) have a silyl group such as trimethoxysilyl, triethoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl.
  • Some example compounds of Formula (Ic) include, but are not limited to, aminopropyltrimethoxysilane and aminopropyltriethoxysilane.
  • the hydrolyzable R 3 group typically is converted to a hydroxyl group.
  • the aminosilanes of Formula (I) become aminosilanol compounds of Formula (II).
  • Formula (II) the groups R 1 , R 2 , R 4 and the variable x are the same as defined for Formula (I).
  • Some aminosilanol compounds are of Formula (Ila), Formula (lib), or Formula (lie) corresponding to those formed from the aminosilanes of Formula (la), Formula (lb), or Formula (Ic) respectively.
  • aminosilanols can undergo hydrogen bonding between the amino group and the silanol group as shown below in Formula (lie- 1 ) for the aminosilanols of Formula (He) with the resulting formation of a ring-like structure.
  • group R 7 is equal to -OH when x is equal to 3 and is equal to R 4 when x is equal to 2.
  • the hydrogen on the amino group -NHR can hydrogen bond with the silanol group -Si(OH) 2 R 7 .
  • the aminosilanols can react, however, in water to form an aminosilanol polymer by a condensation reaction. This reaction is usually exothermic. The condensation reaction results in the formation of multiple -O-Si-0- linkages.
  • the aminosilanol polymer has at least 2 -O-Si-0- linkages but often has at least 5, at least 10 linkages, at least 20 linkages, at least 50 linkages, at least 100 linkages, or at least 200 linkages.
  • the aminosilanol polymer resulting from the reaction of multiple aminosilanols of Formula (II) can be of Formula (III).
  • the variable q is equal to at least 1 but is often equal to at least 2, at least 3, at least 5, at least 10, at least 20, at least 50, at least 100, at least 200, or even greater.
  • group R 7 is equal to hydroxyl when x is equal to 3 and is equal to R 4 when x is equal to 2.
  • the aminosilanol units can undergo hydrogen bonding between the -SiOH group and the amino group of formula -IS ⁇ R 1 ) ⁇
  • the -SiOH group can form a crosslink with another polymeric unit of Formula (III).
  • the amount of aminosilane of Formula (I) added to water to form the aminosilanol polymer of Formula (III) is typically at least 0.1 weight percent based on a total weight of the coatable composition (e.g., the mixture of water and aminosilane).
  • the amount of aminosilane is at least 0.5 weight percent, at least 1 weight percent, at least 2 weight percent, at least 3 weight percent, at least 5 weight percent, or at least 10 weight percent.
  • the amount of the aminosilane can be up to 50 weight percent or higher depending on the solubility of the aminosilane in the water and the viscosity of the resulting mixture. In some embodiments, the amount of aminosilane is up to 40 weight percent, up to 30 weight percent, up to 25 weight percent, or up to 20 weight percent.
  • the amount of aminosilane is in a range of 0.1 to 50 weight percent, in a range of 1 to 50 weight percent, in a range of 1 to 40 weight percent, in a range of 1 to 30 weight percent, or in a range of 1 to 20 weight percent.
  • the aminosilanol polymer of Formula (III) is typically soluble in water.
  • the coatable composition used to apply the aminosilanol polymer to a surface of the substrate can include the aminosilanol polymer and water. In some embodiments, no other components are added to the coatable composition. In other embodiments, however, other components such as a non-ionic surfactant, a water-miscible organic solvent (i.e., a co-solvent), a filler, tetraethylorthosilicate (TEOS), or the like can be added to the coatable composition.
  • a non-ionic surfactant i.e., a water-miscible organic solvent (i.e., a co-solvent)
  • TEOS tetraethylorthosilicate
  • the coatable composition used to form a silanol coating contains a non-ionic surfactant, or more than one non-ionic surfactant.
  • a non-ionic surfactant typically improves wetting of a substrate (e.g., a hydrophobic substrate) when the coatable composition is applied to a major surface of a substrate.
  • non- ionic surfactant any suitable non- ionic surfactant can be used.
  • Example non- ionic surfactants include, but are not limited to, an alkyl ethoxylate, an ethylene oxide/propylene oxide block copolymer, an alkyl polyglycoside, a linear secondary alcohol ethoxylate, a branched secondary alcohol ethoxylate, an alkylphenol ethylene oxide condensate, an ethyleneoxide-propyleneoxide-ethylene oxide triblock based copolymer, an alkyl polyglucoside, or a combination thereof.
  • Suitable non- ionic surfactants are available under the trade designation TERGOTOL TMN- 10 surfactant (i.e., a branched secondary alcohol ethoxylate), and TRITON X- 100 surfactant (i.e., an octylphenol ethoxylate) commercially available from The Dow Chemical Company (Midland, MI).
  • TERGOTOL TMN- 10 surfactant i.e., a branched secondary alcohol ethoxylate
  • TRITON X- 100 surfactant i.e., an octylphenol ethoxylate
  • the non-ionic surfactant is often used in an amount in a range of 0.01 to 10 weight percent based on the total weight of the coatable composition. In some embodiments, the amount of non- ionic surfactant is present in an amount equal to at least 0.05 weight percent, at least 0.1 weight percent, or at least 1 weight percent. The amount of the non-ionic surfactant can be up to 8 weight percent, at least 0.01 to 7 weight percent, or 0.01 to 4 weight percent, 0.1 to 7 weight percent, or 0.1 to 4 weight percent of the total coatable composition.
  • the coatable composition contains a polar co-solvent (i.e., a water-miscible organic solvent), or more than one polar co-solvent, in addition to water.
  • Suitable co-solvents include for example and without limitation, alcohols such as ethanol, isopropyl alcohol, n-butanol, n-propanol, and iso-butyl alcohol; ethers such as a glycol ether (e.g., diethylene glycol dimethyl ether), 1 ,4-dioxane, and tert-butyl methyl ether; ketones such as diethyl ketone, methyl ethyl ketone, acetone, and methyl iso-butyl ketone; esters such as ethyl acetate, propylene carbonate, and 2-methoxyethyl acetate; and halogenated solvents such as chloroform.
  • any desired amount of the co-solvent can be included in the coatable composition.
  • the water in the reaction mixture used to form the aminosilanol polymer is at least partially replaced in the coatable composition by a water-miscible organic solvent that may dry at a lower temperature.
  • the coatable composition can include 1 to 90 weight percent water-miscible organic solvent based on a total weight of the coatable composition. The amount of water- miscible organic solvent is often in a range of 1 to 70 weight percent, 1 to 50 weight percent, 1 to 20 weight percent, or 1 to 10 weight percent, or 30 to 70 weight percent, or 50 to 90 weight percent of the total coatable composition.
  • the coatable composition optionally includes additional components such as
  • TEOS tetraethylorthosilicate
  • the TEOS can be present in an amount of 0 to 10 weight percent. If present, the amount of TEOS can be in a range of 0.01 to 10 weight percent, in a range of 0.01 to 5 weight percent, in a range of 0.01 to 1 weight percent, in a range of 1 to 10 weight percent, or in a range of 1 to 5 weight percent based on the total weight of the coatable composition.
  • the coatable composition optionally can further include at least one filler such as silica particles, alumina particles, zirconia particles, or combinations thereof.
  • the coatable composition can contain up to 20 weight percent, up to 15 weight percent, up to 10 weight percent, or up to 5 weight percent filler based on the total weight of solids in the coatable composition. In some embodiments, the coatable compositions contain 1 to 20 weight percent, 1 to 10 weight percent, or 1 to 5 weight percent filler.
  • the coatable composition is applied to a substrate to prepare articles having a silanol coating.
  • Suitable substrates comprise glass, ceramic material, polymeric material such as polyethylene terephthalate (PET) or polycarbonate, metals such as aluminum, chromium, iron, nickel, titanium, or the like, or a combination thereof.
  • PET polyethylene terephthalate
  • the substrate may be flat, curved or shaped.
  • the substrate can be flexible or rigid, transparent or opaque, and colored or clear.
  • the substrate is in the form of a film, sheet, panel or pane of material, or molded material, and may be a part of an article such as motor vehicle window and windshield, mirror, eye glasses, helmet visor, face shield, building window or door, solar panel, architectural glazing, and decorative glass frame.
  • the silanol coatings may, if desired, cover only a portion of the substrate.
  • the substrate is transparent.
  • transparent means transmitting at least 85 percent of incident light in the visible spectrum (about 400-700 nm wavelength).
  • Transparent substrates may be colored or colorless.
  • an article that includes (a) a substrate and (b) a silanol coating attached or adhered to a major surface of the substrate.
  • the silanol coating is not covalently bonded to the substrate. Accordingly, the silanol coating can be attached to the substrate by any forces (e.g., electrostatic interaction, hydrogen bonding, van der Waals forces, etc.) except by covalent bonds between molecules on the substrate surface and molecules in the silanol coating.
  • forces e.g., electrostatic interaction, hydrogen bonding, van der Waals forces, etc.
  • This is in contrast to the use of aminosilane molecules in primer layers, in which the aminosilane molecules form covalent bonds with molecules on the substrate surface, thereby enhancing adhesion between the substrate and any additional coatings disposed on the primer layer.
  • the formation of the dried silanol coating does not require any curing catalyst or radiation.
  • the strength of adhesion of the silanol coating to a substrate can be evaluated, for example, using the Tape Peel Test described in the Examples.
  • the silanol coating attached to a major surface of the substrate is dry. That is, the majority of the water or water-miscible organic solvent in the coatable composition has been removed.
  • dry silanol coating or references to the silanol coating being dry means that the silanol coating contains no greater than 5 weight percent, no greater than 2 weight percent, no greater than 1 weight percent water, or no greater than 0.5 weight percent water based on the weight of the silanol coating.
  • the dry silanol coating is formed by removing water, the water miscible solvent, or a combination thereof from the fluid layer of the coatable composition that is applied to the substrate.
  • the dry silanol coating typically can be redissolved in water, a water-miscible organic solvent, or a mixture thereof at room temperature (e.g., 20°C to 25°C) or near room temperature. That is, the dried silanol coating is either not crosslinked or is so lightly crosslinked so that it can be removed by dissolution. In many embodiments, the silanol coating is soluble in water at room temperature or near room temperature. This easy removal process may be desirable if the silanol coating needs to be replaced.
  • the silanol coatings typically impart anti-fog properties to substrates coated therewith.
  • Coatings are considered anti-fogging if a coated substrate resists the formation of small, condensed water droplets in sufficient density to significantly reduce the transparency of the coated substrate such that it cannot be adequately viewed through by the human eye after exposure to repeated human breath directly on the article and/or after holding the article above a source of steam.
  • a coating may still be regarded as anti-fogging even though a uniform water film or a small number of large water droplets forms on the coated substrate so long as the transparency of the coated substrate is not significantly reduced such that it cannot be readily seen through. In many instances, a film of water that does not significantly reduce the transparency of the substrate will remain after the substrate has been exposed to a steam source.
  • optically clear articles there are numerous instances where the value of optically clear articles would be enhanced if the tendency of the articles to cause light scattering or glare or to be obscured by the formation of a fog on a surface of the article could be reduced.
  • motor vehicle windows and windshields, architectural glazings, eyeglasses, face shields, building windows, and decorative glass frames may all scatter light in a manner that causes an annoying and disruptive glare.
  • Use of such articles may also be
  • the coated articles of this invention have exceptional anti-fog properties while also separately having greater than 90 percent transmission of 550 nm light.
  • the (dried) silanol coating can remain adhered (e.g., the article passes the Tape Peel Test) to the substrate even upon exposure to water vapor. More specifically, the coating can be subjected to air comprising 100 percent humidity at 20°C for 24 hours without any detectable decrease in the tape peel adhesion value of the silanol coating to the substrate, as compared to tape peel adhesion value immediately prior the subjection to the air comprising 100% humidity at 20°C.
  • the coating can be subjected to air comprising 100% humidity at 20°C for 48 hours, or 72 hours, or 96 hours without any detectable decrease in the tape peel adhesion value of the silanol coating to the substrate, as compared to tape peel adhesion value immediately prior the subjection to the air comprising 100% humidity at 20°C.
  • Figure 1 provides an exemplary schematic of an article 10 according to certain
  • the article 10 includes a substrate 12 and a silanol coating 14 attached to a major surface of the substrate 12.
  • the optimal average thickness of the silanol coating is usually dependent upon the particular coatable composition used.
  • the thickness can be varied by varying the thickness of the fluid layer of the coatable composition applied to the substrate.
  • average thickness of the (dry) silanol coating is in the range of 100 to 10,000 angstroms (A), in the range of 500 to 2500 A, in the range of 750 to 2000 A, or in the range of 1000 to 1500 A.
  • the thickness can be measured using an ellipsometer such as a Gaertner Scientific Corp. Model No. LI 15C.
  • the dry silanol coating often contains at least 50 weight percent of the aminosilanol polymer.
  • the silanol coating can contain at least 60 weight percent, at least 70 weight percent, at least 80 weight percent, or at least 90 weight percent aminosilane polymer.
  • the amount of the aminosilanol polymer in the silanol coating can be up to 99.5 weight percent, up to 95 weight percent, up to 90 weight percent, up to 80 weight percent, or up to 60 weight percent.
  • the silanol coating contains the aminosilanol polymer in an amount in a range of 50 to 99.5 weight percent, in a range of 50 to 85 weight percent, in a range of 50 to 75 weight percent, in a range of 50 to 60 weight percent, in a range of 75 to 99.5 weight percent, or in a range of 60 to 80 weight percent.
  • the weight percents are based on the total weight of the dry silanol coating.
  • the dry silanol coating often contains 0 to 20 weight percent, 0.01 to 20 weight percent, 0.05 to 20 weight percent, 0.1 to 20 weight percent, 0.5 to 20 weight percent, 0.1 to 10 weight percent, or 0.1 to 5 weight percent non-ionic surfactant based on the total weight of the silanol coating.
  • the dry silanol coating often contains 0 to 10 weight percent, 0.1 to 10 weight percent, 0.1 to 5 weight percent, 0.1 to 3 weight percent, 0.1 to 2 weight percent, or 0.1 to 1 weight percent TEOS based on the total weight of the silanol coating.
  • the dry silanol coating often contains 0 to 20 weight percent, 0.5 to 15 weight percent, 1 to 10 weight percent, or 1 to 5 weight percent filler based on the total weight of the silanol coating.
  • a method of making an article includes providing a substrate and applying a coatable composition to a major surface of the substrate.
  • the coatable composition contains an aminosilanol polymer that is a reaction product of water and an aminosilane of Formula (I).
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl.
  • the group R 2 is a divalent group comprising an alkylene, arylene, -N(R 5 )-, or a combination thereof.
  • the group R 3 is a hydrolyzable group and the group R 4 is a non-hydrolyzable group.
  • the group R 5 is hydrogen or alkyl.
  • the variable x is equal to 2 or 3.
  • the method further includes forming a silanol coating, wherein the silanol coating is not covalently bonded to the substrate.
  • the coatable composition is applied to the substrate as a fluid layer using conventional techniques, for example and without limitation, wipe coating, bar coating, roll coating, curtain coating, rotogravure coating, knife coating, spray coating, spin coating, or dip coating, of the composition on the major surface of the substrate.
  • the wet thickness of the fluid layer i.e., coatable composition applied to the substrate
  • the actual fluid layer thickness can vary considerably from one particular point to another, it is often desirable to apply the coatable composition uniformly over the surface of the substrate. For example, to minimize visible interference color variations in the final coating, it may be desirable to control the average coating thickness of the fluid layer within 200 A, within 150 A, or within 100 A across the substrate.
  • a silanol coating is formed from the fluid layer by drying. Drying can be accomplished via one or more various routes. Typically, the drying method includes allowing the composition applied to the substrate (e.g., fluid layer) to dry under ambient conditions, thereby forming a silanol coating as the water (and optional water-miscible organic solvent) evaporates. In certain embodiments the drying method comprises wiping the fluid layer applied to the substrate (e.g., wiping with a cloth), thereby removing liquid within the fluid layer. To speed the drying process, in certain embodiments the fluid layer is dried at a temperature of 25°C to 100°C, thereby forming the silanol coating. An oven with circulating air or inert gas such as nitrogen is often used for such heated drying purposes.
  • the silanol coating resulting from drying the fluid layer on the substrate according to methods of the invention typically can be removed by dissolution in water, a water-miscible organic solvent, or a mixture thereof.
  • the method further includes washing the silanol coating off the major surface of the substrate with water.
  • such a method preferably further includes applying at least a second portion of the coatable composition as a fluid layer to the major surface of the substrate, following removal of the coating. Due to the ease of application and removal of the coating, a substrate can be coated with a portion of the composition once, twice, three times, four times, or any number of times.
  • an advantage of embodiments of the present disclosure is that although the silanol coating has anti-fog properties and significant adhesion to a substrate, the silanol coating is easily washed off of the substrate and optionally replaced with a new coating, if needed or desired.
  • the simplicity of the method of preparing the article which does not require specialized equipment, allows a consumer or other user to conveniently apply a coatable composition onto a substrate and form a coating, as well as to remove and replace the coating with a new coating in the event a fresh coating is desired.
  • coatable compositions, fluid layers, silanol coatings, and substrate materials described above are suitable for use in the method of preparing the article.
  • Item 1 is an article including (a) a substrate; and (b) a silanol coating attached to a major surface of the substrate.
  • the silanol coating is not covalently bonded to the substrate.
  • the silanol coating includes an aminosilanol polymer that is a reaction product of water and an aminosilane of Formula (I)
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 2 is a divalent group comprising an alkylene, arylene, -N(R 5 )-, or a combination thereof;
  • R 3 is a hydrolyzable group
  • R 4 is a non-hydrolyzable group
  • R 5 is hydrogen or alkyl
  • x is equal to 2 or 3.
  • Item 2 is an article of item 1 , wherein the silanol coating further includes a non- ionic surfactant.
  • Item 3 is an article of item 1 or item 2, wherein the aminosilane is of Formula (la)
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 6 is a divalent group comprising an alkylene, arylene, aralkylene, -N(R 5 )- , or a combination thereof;
  • R 3 is a hydrolyzable group
  • R 4 is a non-hydrolyzable group
  • R 5 is hydrogen or alkyl
  • p is equal to 0 or 1 ;
  • x 2 or 3.
  • Item 4 is an article of item 3, wherein p is equal to 0 and each R 1 is hydrogen or alkyl.
  • Item 5 is an article of item 3, wherein p is equal to 1, each R 1 is hydrogen or alkyl, and R 6 is alkylene.
  • Item 6 is an article of item 1 or item 2, wherein the aminosilane is of Formula (lb)
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 6 is a divalent group comprising an alkylene, arylene, aralkylene, -N(R 5 )- , or a combination thereof;
  • R 3 is a hydrolyzable group
  • R 4 is a non-hydrolyzable group
  • x is equal to 2 or 3.
  • Item 7 is an article of item 6, wherein the aminosilane includes
  • aminoethylaminopropyltrimethoxysilane aminoethylaminopropyltriethoxysilane, N-(2- aminoethyl)-3-aminopropylmethyldimethoxysilane, or
  • Item 8 is an article of item 1 or item 2, wherein the aminosilane is of Formula (Ic)
  • R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 3 is a hydrolyzable group
  • R 4 is a non-hydrolyzable group
  • x is equal to 2 or 3.
  • Item 9 is an article of item 8, wherein the aminosilane includes
  • aminopropyltrimethoxysilane or aminopropyltriethoxysilane are aminopropyltrimethoxysilane or aminopropyltriethoxysilane.
  • Item 10 is an article of any one of items 1 to 9, wherein the silanol coating includes at least 50 weight percent aminosilanol polymer based on a total weight of the silanol coating.
  • Item 1 1 is an article of any one of items 1 to 10, wherein the silanol coating further includes at least one filler comprising silica particles, alumina particles, zirconia particles, or combinations thereof.
  • Item 12 is an article of any one of items 1 to 1 1, wherein the silanol coating further includes tetraethylorthosilicate (TEOS).
  • TEOS tetraethylorthosilicate
  • Item 13 is an article of any one of items 1 to 12, wherein the silanol coating can be removed by dissolution in water.
  • Item 14 is an article of any one of items 1 to 13, wherein the silanol coating can be subjected to air comprising 100% humidity at 20°C for 24 hours without any detectable decrease in the tape peel adhesion value of the coating to the substrate, as compared to tape peel adhesion value immediately prior the subjection to the air comprising 100% humidity at 20°C.
  • Item 15 is an article of item 2, wherein the surfactant includes an alkyl ethoxylate, an ethylene oxide/propylene oxide block copolymer, an alkyl polyglycoside, a linear secondary alcohol ethoxylate, a branched secondary alcohol ethoxylate, an alkylphenol ethylene oxide condensate, or a combination thereof.
  • the surfactant includes an alkyl ethoxylate, an ethylene oxide/propylene oxide block copolymer, an alkyl polyglycoside, a linear secondary alcohol ethoxylate, a branched secondary alcohol ethoxylate, an alkylphenol ethylene oxide condensate, or a combination thereof.
  • Item 16 is an article of any one of items 1 to 15, wherein the substrate includes glass, a polymeric material, a metal, or a combination thereof.
  • Item 17 is an article of any one of items 1 to 16, wherein the aminosilanol polymer includes at least five -O-Si-0- linkages.
  • Item 18 is a method for coating an article, the method including (a) providing a substrate; (b) applying a coatable composition to a major surface of the substrate, the coatable composition containing an aminosilanol polymer that is a reaction product of water and an aminosilane of Formula (I)
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 2 is a divalent group comprising an alkylene, arylene, -N(R 5 )-, or a combination thereof;
  • R 3 is a hydrolyzable group
  • R 4 is a non-hydrolyzable group
  • R 5 is hydrogen or alkyl
  • x is 2 or 3;
  • Item 19 is a method of item 18, wherein the aminosilane is of Formula (la)
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 6 is a divalent group comprising an alkylene, arylene, aralkylene, -N(R 5 )- , or a combination thereof;
  • R 3 is a hydrolyzable group
  • R 4 is a non-hydrolyzable group
  • R 5 is hydrogen or alkyl
  • p is equal to 0 or 1 ;
  • x 2 or 3.
  • Item 20 is a method of item 19, wherein p is equal to 0 and each R 1 is hydrogen or alkyl.
  • Item 21 is a method of item 20, wherein p is equal to 1 , each R 1 is hydrogen or alkyl, and R 6 is alkylene.
  • Item 22 is a method of item 18, wherein the aminosilane is of Formula (lb)
  • each R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 6 is a divalent group comprising an alkylene, arylene, aralkylene, -N(R 5 )- , or a combination thereof;
  • R 3 is a hydro lyzable group
  • R 4 is a non-hydrolyzable group
  • x is equal to 2 or 3.
  • Item 23 is a method of item 22, wherein the aminosilane includes
  • aminoethylaminopropyltrimethoxysilane aminoethylaminopropyltriethoxysilane, N-(2- aminoethyl)-3-aminopropylmethyldimethoxysilane, or
  • Item 24 is a method of item 18, wherein the aminosilane is of Formula (Ic)
  • R 1 is hydrogen, alkyl, aryl, alkaryl, or aralkyl
  • R 3 is a hydrolyzable group
  • R 4 is a non-hydrolyzable group
  • x is equal to 2 or 3.
  • Item 25 is a method of item 24, wherein the aminosilane includes
  • aminopropyltrimethoxysilane or aminopropyltriethoxysilane are aminopropyltrimethoxysilane or aminopropyltriethoxysilane.
  • Item 26 is a method of any one of items 18 to 25, wherein the silanol coating includes at least 50 weight percent aminosilanol polymer based on a total weight of the silanol coating.
  • Item 27 is a method of any one of items 18 to 26, wherein the aminosilanol polymer includes at least five -O-Si-0- linkages.
  • Item 28 is a method of any one of items 18 to 27, wherein the method further includes drying the coatable composition at a temperature of 25°C to 100°C after applying the coatable composition to the substrate.
  • Item 29 is a method of any one of items 18 to 28, wherein the method further includes wiping the coatable composition after applying the coatable composition to the substrate.
  • Item 30 is a method of any one of items 18 to 29, wherein applying the coatable composition to the substrate includes wipe coating, bar coating, roll coating, curtain coating, rotogravure coating, knife coating, spray coating, spin coating, or dip coating the coatable composition on the major surface of the substrate.
  • Item 31 is a method of any one of items 18 to 30, wherein the coatable composition further includes a non-ionic surfactant.
  • Item 32 is a method of any one of items 18 to 31 , wherein the silanol coating further includes tetraethylorthosilicate (TEOS).
  • TEOS tetraethylorthosilicate
  • Item 33 is a method of any one of items 18 to 32, wherein the silanol coating further includes at least one filler comprising silica particles, alumina particles, zirconia particles, or combinations thereof.
  • Item 34 is a method of any one of items 18 to 33, wherein the silanol coating can be subjected to air comprising 100% humidity at 20°C for 24 hours without any detectable decrease in the tape peel adhesion value of the coating to the substrate, as compared to tape peel adhesion value immediately prior the subjection to the air comprising 100% humidity at 20°C.
  • Item 35 is a method of item 31, wherein the surfactant includes an alkyl ethoxylate, an ethylene oxide/propylene oxide block copolymer, an alkyl polyglycoside, a linear secondary alcohol ethoxylate, a branched secondary alcohol ethoxylate, an alkylphenol ethylene oxide condensate, or a combination thereof.
  • the surfactant includes an alkyl ethoxylate, an ethylene oxide/propylene oxide block copolymer, an alkyl polyglycoside, a linear secondary alcohol ethoxylate, a branched secondary alcohol ethoxylate, an alkylphenol ethylene oxide condensate, or a combination thereof.
  • Item 36 is a method of any one of items 18 to 35, wherein the silanol coating can be removed by dissolution in water.
  • Item 37 is a method of any one of items 18 to 36, wherein the substrate includes glass, a polymeric material, a metal, or a combination thereof.
  • Item 38 is a method of any one of items 18 to 37, wherein the coatable composition further contains a co-solvent including ethanol, isopropyl alcohol, n-butanol, n-propanol, iso-butyl alcohol, diethylene glycol dimethyl ether, 1 ,4-dioxane, tert-butyl methyl ether, diethyl ketone, methyl ethyl ketone, acetone, methyl iso-butyl ketone, ethyl acetate, propylene carbonate, 2- methoxyethyl acetate, or chloroform.
  • a co-solvent including ethanol, isopropyl alcohol, n-butanol, n-propanol, iso-butyl alcohol, diethylene glycol dimethyl ether, 1 ,4-dioxane, tert-butyl methyl ether, diethyl ketone, methyl eth
  • Comparative Examples were determined by subjecting them to water vapors by breathing out air directly onto the coated substrate and then visually examining the surfaces. Based on the visual examination, the anti-fog performance of each sample was determined and the samples were assigned an anti-fog performance rating. The criteria used for determining the anti-fog performance and anti-fog performance rating for the samples is described in Table 1 , below.
  • EX1 anti-fog coating formulation 5 g of AS- 1 was added dropwise to 95 g of distilled water while constantly stirring during the addition.
  • the addition of aforementioned aminosilane i.e., AS- 1 resulted in exothermic hydrolization of alkoxy groups into silanol groups, thus forming oligomers.
  • 0.25 g of SURF- l was added to the solution as a surfactant.
  • CE-A was prepared in the same manner as EX1, except that 5 g of AS-6 was used instead of AS- 1.
  • EX2-EX18 were prepared in the same manner as EX1 by except that the type and amount of the aminosilane, water and the surfactant were varied as summarized in Table 2, below.
  • Table 2 Coatable Compositions
  • the anti-fog coating solution of EX1 prepared above was applied onto a 5 cm X 5 cm (2- inch X 2-inch) glass substrate using a paper towel soaked in the coating solution (coatable composition). Thereafter, the excess solution was wiped off and dried with a clean paper towel. A thin layer of solid adherent coating (silanol coating) was formed upon evaporation of the solvent.
  • the same coating method was used for coating a variety of different substrates (e.g., polyethylene terephthalate (PET), polycarbonate, and aluminum) for each of EX1-EX18.
  • the tape peel test and anti-fog performances were determined using the methods described above. Table 3 summarizes the data for each sample.

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Abstract

L'invention porte sur des articles portant des revêtements à base de silanol et sur des procédés de fabrication des articles. Plus précisément, les articles selon l'invention comprennent un substrat et un revêtement attaché à une surface principale du substrat. Le revêtement à base de silanol comprend un polymère d'aminosilanol qui est un produit réactionnel d'eau et d'un aminosilane. Le revêtement à base de silanol adhère au substrat mais n'y est pas lié de façon covalente. Si on le souhaite, le revêtement à base de silanol peut être enlevé de l'article par dissolution dans de l'eau. Le revêtement à base de silanol peut être disposé sur un grand nombre de substrats et a tendance à assurer une résistance améliorée à la formation de buée.
PCT/US2014/043566 2013-06-28 2014-06-23 Article portant un revêtement à base de silanol et son procédé de fabrication WO2014209832A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105086556A (zh) * 2015-08-11 2015-11-25 陈曦 一种防腐涂料用纳米颗粒的制备方法
WO2020079530A1 (fr) * 2018-10-18 2020-04-23 3M Innovative Properties Company Compositions de silanol et procédés d'utilisation
CN112437789A (zh) * 2018-07-19 2021-03-02 3M创新有限公司 磺酸根官能涂料组合物、其制备方法以及由其制得的制品

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Publication number Priority date Publication date Assignee Title
FR2664282A1 (fr) * 1990-07-09 1992-01-10 Solvay Procede pour rendre hydrophile la surface d'articles en resines a base de chlorure de vinyle.
EP1197538A2 (fr) * 2000-10-13 2002-04-17 Shin-Etsu Chemical Co., Ltd. Compostion aqueuse de revêtement
US20080280050A1 (en) * 2006-01-11 2008-11-13 Evonik Degussa Gmbh Ceramic Wall Cladding Composites with Electromagnetic Shielding Properties
US20120312192A1 (en) * 2011-06-09 2012-12-13 Michael Ray Detty Anti-Fouling Coating Compositions and Methods For Preventing the Fouling of Surfaces
US20130149544A1 (en) * 2011-12-07 2013-06-13 Samsung Electronics Co., Ltd. Methods of material hydrophilization by siloxanes containing nitrilopoly (methylenephosphonic acid) or derivatives thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2664282A1 (fr) * 1990-07-09 1992-01-10 Solvay Procede pour rendre hydrophile la surface d'articles en resines a base de chlorure de vinyle.
EP1197538A2 (fr) * 2000-10-13 2002-04-17 Shin-Etsu Chemical Co., Ltd. Compostion aqueuse de revêtement
US20080280050A1 (en) * 2006-01-11 2008-11-13 Evonik Degussa Gmbh Ceramic Wall Cladding Composites with Electromagnetic Shielding Properties
US20120312192A1 (en) * 2011-06-09 2012-12-13 Michael Ray Detty Anti-Fouling Coating Compositions and Methods For Preventing the Fouling of Surfaces
US20130149544A1 (en) * 2011-12-07 2013-06-13 Samsung Electronics Co., Ltd. Methods of material hydrophilization by siloxanes containing nitrilopoly (methylenephosphonic acid) or derivatives thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105086556A (zh) * 2015-08-11 2015-11-25 陈曦 一种防腐涂料用纳米颗粒的制备方法
CN112437789A (zh) * 2018-07-19 2021-03-02 3M创新有限公司 磺酸根官能涂料组合物、其制备方法以及由其制得的制品
CN112437789B (zh) * 2018-07-19 2022-12-20 3M创新有限公司 磺酸根官能涂料组合物、其制备方法以及由其制得的制品
WO2020079530A1 (fr) * 2018-10-18 2020-04-23 3M Innovative Properties Company Compositions de silanol et procédés d'utilisation

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