WO2016176388A1 - Particule d'oxyde inorganique fluoré réticulable pour revêtements architecturaux - Google Patents

Particule d'oxyde inorganique fluoré réticulable pour revêtements architecturaux Download PDF

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WO2016176388A1
WO2016176388A1 PCT/US2016/029663 US2016029663W WO2016176388A1 WO 2016176388 A1 WO2016176388 A1 WO 2016176388A1 US 2016029663 W US2016029663 W US 2016029663W WO 2016176388 A1 WO2016176388 A1 WO 2016176388A1
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coating
inorganic oxide
group
surface modified
oxide particles
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PCT/US2016/029663
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English (en)
Inventor
Anilkumar Raghavanpillai
Hau-Nan LEE
Jelena LASIO
Brad M. Rosen
Stephanie A. BERNARD
James J. Hughes
Vincent FRANCO
John Russell Crompton Jr.
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The Chemours Company Tt, Llc
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Publication of WO2016176388A1 publication Critical patent/WO2016176388A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)

Definitions

  • This invention relates to an ethylenically crosslinkable fluorinated inorganic oxide particle compound and its use as an additive in
  • architectural coating compositions such as water-based latex paints, to provide durable surface effects.
  • the coating compositions of interest in the present invention include alkyd coating compositions, urethane coating compositions, water- dispersible coating compositions, and unsaturated polyester coating compositions, typically a paint, clear coating, or stain. All of the above- listed coating compositions after drying or curing often show low
  • hexadecane contact angles are readily wetted by oil, and are susceptible to soiling.
  • the coating compositions are described in Outlines of Paint Technology (Halstead Press, New York, NY, Third edition, 1990) and Surface Coatings Vol. I, Raw Materials and Their Usage (Chapman and Hall, New York, NY, Second Edition, 1984).
  • Inorganic particles hydrophobized with fluorosilanes have been used to impart hydrophobic as well as oleophobic properties as
  • Water-based latex coating bases such as those employed as paint coatings, have a tendency to have low oil repellency and poor cleanability ratings.
  • small molecule additives including fluorosurfactants, have been used. Due to their small molecular size, however, the additives do not provide long-term performance and durability in exterior paint, which is subjected to more extreme environmental conditions. The additives can wash away from the coating surface within a few days.
  • the present invention addresses the issues described above by introducing crosslinkable fluorinated inorganic oxide particles into a coating composition. Due to the crosslinkable nature of the fluoroadditive, the compositions of the present invention provide performance as well as durability to the water-based latex coatings. Additionally, the low surface energy of the fluorinated groups allows the particles to migrate to the coating surface before crosslinking to form a durable additive at the coating surface. The particles of the invention impart unexpectedly desirable surface effects such as: increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating films.
  • the present invention comprises surface modified inorganic oxide particles comprising an oxide of X wherein X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; at least one of said particles having a surface covalently bonded to
  • a 1 is (CH 2 ) k — N(R 9 -R f i )-R 9 , (CH 2 )k— NH-C(O)-NH, (CH 2 )k— NH-C(S)-NH, (CH 2 )k— NH-C(O)O, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)- NH-SO 2 , (CH 2 )k— NH-C(S)-NH-SO 2 , (CH 2 )k—
  • m is 1 to 4;
  • k, n, o, p, and r are each independently 1 to 20;
  • E is a C2 to C20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C6 to C10 aryl group;
  • Rn is chosen from a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more -0-, -CH 2 -, -CFH-, or combinations thereof;
  • Q 2 is (CH 2 )k, (CH 2 )kOC(0), or (CH 2 )kC(0)0;
  • R 8 is H or a straight or branched alkyl chain of 2 to 30 carbons having 0 to 15 olefinic
  • the present invention further comprises a method of forming a coated substrate with durable dirt pickup resistance comprising contacting a coating base with surface modified inorganic oxide particles to form a coating, contacting a substrate with the coating to form a coating film, allowing the surface modified inorganic oxide particles to migrate to the coating film surface, and crosslinking the ethylenically unsaturated groups of surface modified inorganic oxide particles of the coating film with each other, wherein the surface modified inorganic oxide particles comprise an oxide of X, where X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and at least one of said particles has a surface covalently bonded to
  • a 1 is (CH 2 )k— N(R 9 -R f i)-R 9 , (CH 2 )k— NH-C(O)-NH, (CH 2 )k— NH-C(S)-NH, (CH 2 )k— NH-C(O)O, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)- NH-SO 2 , (CH 2 )k— NH-C(S)-NH-SO 2 , (CH 2 )k— NH-C
  • FIG. 1 depicts a Transmission Electron Microscope (TEM) image of particles from Example 1 .
  • TEM Transmission Electron Microscope
  • FIG. 2 depicts a TEM image of particles from Example 2.
  • FIG. 3 depicts a TEM image of particles from Example 3.
  • (meth)acrylic or “(meth)acrylate” indicate, respectively, methacrylic and/or acrylic, and methacrylate and/or acrylate; and the term (meth)acrylamide indicates methacrylamide and/or acrylamide.
  • alkyd coating as used hereinafter is meant a conventional liquid coating based on alkyd resins, typically a paint, clear coating, or stain.
  • alkyd resins are complex branched and cross-linked polyesters containing unsaturated aliphatic acid residues.
  • urethane coating as used hereinafter is meant a conventional liquid coating based on Type I urethane resins, typically a paint, clear coating, or stain.
  • Urethane coatings typically contain the reaction product of a polyisocyanate, usually toluene diisocyanate, and a polyhydric alcohol ester of drying oil acids. Urethane coatings are classified by ASTM D16 into five categories. Type I urethane coatings contain a minimum of 10% by weight of a pre-reacted autoxidizable binder, characterized by the absence of significant amounts of free isocyanate grous.
  • Type I urethane coatings are the largest volume category of polyurethane coatings and include paints, clear coatings, or stains.
  • the cured coating for a Type I urethane coating is formed by air oxidation and polymerization of the unsaturated drying oil residue in the binder.
  • unsaturated polyester coating as used hereinafter is meant a conventional liquid coating based on unsaturated polyester resins, dissolved in monomers and containing initiators and catalysts as needed, typically as a paint, clear coating, stain, or gel coat formulation.
  • water-dispersed coatings as used herein is meant surface coatings intended for the decoration or protection of a substrate, comprising essentially an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous phase, and optionally containing surfactants, protective colloids and thickeners, pigments and extender pigments, preservatives, fungicides, freeze-thaw stabilizers, antifoam agents, agents to control pH, coalescing aids, and other ingredients.
  • surfactants protective colloids and thickeners
  • pigments and extender pigments preservatives
  • fungicides fungicides
  • freeze-thaw stabilizers freeze-thaw stabilizers
  • antifoam agents agents to control pH, coalescing aids, and other ingredients.
  • Water-dispersed coatings are exemplified by, but not limited to, pigmented coatings such as latex paints, unpigmented coatings such as wood sealers, stains, and finishes, coatings for masonry and cement, and water- based asphalt emulsions.
  • pigmented coatings such as latex paints
  • unpigmented coatings such as wood sealers, stains, and finishes
  • coatings for masonry and cement and water- based asphalt emulsions.
  • the film forming material is a latex polymer of acrylate acrylic, styrene acrylic, vinyl-acrylic, vinyl, or a mixture thereof.
  • Such water-dispersed coating compositions are described by C. R. Martens in "Emulsion and Water-Soluble Paints and Coatings" (Reinhold Publishing Corporation, New York, NY, 1965).
  • coating base a liquid formulation of a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating, which is later applied to a substrate for the purpose of creating a lasting film on said surface.
  • the coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating.
  • the coating base formulation may include a polymer resin and pigment dispersed in water, where the polymer resin is an acrylic polymer latex, vinyl-acrylic polymer, vinyl polymer, Type I urethane polymer, alkyd polymer, epoxy polymer, or unsaturated polyester polymer, or mixtures thereof.
  • coating base a liquid formulation of a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating, which is later applied to a substrate for the purpose of creating a lasting film on said surface.
  • the coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating.
  • the coating base formulation may include a polymer resin and pigment dispersed in water, where the polymer resin is an acrylic polymer latex, vinyl-acrylic polymer, vinyl polymer, Type I urethane polymer, alkyd polymer, epoxy polymer, or unsaturated polyester polymer, or mixtures thereof.
  • the present invention comprises surface modified inorganic oxide particles comprising an oxide of X wherein X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; at least one of said particles having a surface covalently bonded to
  • each L 1 represents an oxygen covalently bonded to an X
  • each L 2 is independently selected from the group consisting of H, a C1-C2 alkyl, OCH3, OCH2CH3, and OH
  • a 1 is (CH 2 )k— N(R 9 -R f i)-R 9 , (CH 2 )k— NH-C(O)-NH, (CH 2 )k— NH-C(S)-NH, (CH 2 )k— NH-C(O)O, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)- NH-SO 2 , (CH 2 )k— NH-C(S)-NH-SO 2 , (CH 2 )k— NH-C
  • the crosslinkable surface modified inorganic oxide particles of the present invention can be made by covalently grafting fluorosilanes and olefinic silanes to an inorganic oxide surface in order to impart to them both hydrophobic and crosslinkable properties.
  • the silanes used in the present invention have a divalent organic linking group which connects the silicon atom to either a fluorine rich group, such as a perfluoroalkyi group, or an olefinic group.
  • Silanes useful for the invention have at least one hydrolysable group which reacts with the surface of an inorganic particle thereby creating a covalent bond between the silane and the inorganic particle.
  • Fluorosilanes that are useful in the present invention are also known as fluoroalkyl silanes which are further described in U.S. Patent 8,058,463. These include isocyanate-derived urea or thiourea
  • fluorosilanes where A 1 is ( ⁇ 2 ) ⁇ NH-C(O)-NH or ( ⁇ 2 ) ⁇ NH-C(S)-NH; isocyanate-derived carbamate fluorosilanes, where A 1 is (CH2)k— NH- C(0)0 or 0-C(0)-NH; isocyanate-derived thiolcarbamate fluorosilanes, where A 1 is (CH 2 )k— NH-C(0)S, 0-C(S)-NH, S-C(S)-NH, or S-C(0)-NH; isocyanate-derived N-sulfone urea fluorosilanes, where A 1 is (CH2)k— NH- C(0)-NH-S0 2 or (CH 2 )k— NH-C(S)-NH-S0 2 ; isocyanate-derived N-formyl ureas, where A 1 is (CH2)k— NH-C(0)-N[C(0)H]; thioether succina
  • the urea or thiourea fluorosilane is one wherein Q 1 is chosen from the group consisting of a C 2 -Ci 2 hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of -S- -S(O)-, -S(0) 2 - and -0-C(0)-NH -.
  • a carbamate fluorosilane is one wherein Q 1 is chosen from the group consisting of a C 2 -Ci 2 hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of -S-, -S(O)-, -S(0) 2 - and -0-C(0)-NH -.
  • a thiolcarbamate fluorosilane is one wherein Q 1 is chosen from the group consisting of a C 2 -Ci 2 hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of -S- -S(O)-, -S(0) 2 - and -0-C(0)-NH -.
  • Olefinic silanes may be any silane compounds containing at least one ethylenically unsaturated group that will covalently graft to an inorganic oxide surface.
  • Specific olefinic silanes include, but are not limited to, allyl monoalkoxydialkylsilanes, allyl dialkoxyalkylsilanes, allyltrialkoxysilanes, monoalkoxydialkylvinylsilanes,
  • dialkoxyalkylvinylsilanes trialkoxyvinylsilanes, (meth)acryloxyalkyl dialkoxysilanes, (meth)acryloxyalkyl monoalkoxysilanes, or
  • (meth)acryloxyalkyl trialkoxysilanes include (meth)acryloxyethyl trimethoxysilane, acryloxypropyl trimethoxysilane, (meth)acryloxybutyl trimethoxysilane, (meth)acryloxy-pentyl trimethoxysilane,
  • trimethoxysilane allyltrimethoxysilane, allyltriethoxysilane,
  • Q 2 is (CH2)k where k is 1 to 12; in another embodiment, k is 1 to 8; and in a third embodiment, k is 1 to 6.
  • Inorganic oxide particles useful to the invention include any inorganic oxide particles that have reactive groups on the surface thereof wherein such groups are capable of reacting with the hydrolysable groups of the silanes (or precursors thereof) of the invention thereby creating a covalent bond between the inorganic particle and the silane (or precursor thereof).
  • Particularly useful inorganic particles are oxides, such as oxides of silicon, titanium, zinc, zirconium, manganese, and aluminum.
  • the surface modified inorganic oxide particles may have particle sizes of 10 nm to 15 microns, inclusive. In another embodiment, the particle size falls within 12 nm to 13 microns, and in a third embodiment, the particle size falls within 12 nm to 10 microns.
  • the surface modified inorganic oxide particles contain grafted fluorinated groups, such that they exhibit a % Fluorine of 0.5% to 45%, based on the weight of the particles. In one embodiment, the particles have a % Fluorine of about 1 % to about 15%, and in a third embodiment, the particles have a % Fluorine of about 1 % to about 10%.
  • the particle surface is modified with the fluorinated groups and olefinic groups.
  • the surface modified inorganic oxide particles contain fluorosilane groups of Formula (I) in the amount of 1 to 99%, and having ethylenically unsaturated groups of Formula (II) in the amount of 1 to 99%, based on the sum total weight of groups of Formula (I) and groups of Formula (II).
  • the surface modified inorganic oxide particles contain fluorosilane groups of Formula (I) in the amount of 1 to 75%, and having ethylenically unsaturated groups of Formula (II) in the amount of 25 to 99%, based on the sum total weight of groups of Formula (I) and groups of Formula (II).
  • the surface modified inorganic oxide particles contain fluorosilane groups of Formula (I) in the amount of 25 to 99%, and having ethylenically unsaturated groups of Formula (II) in the amount of 1 to 75%, based on the sum total weight of groups of Formula (I) and groups of Formula (II).
  • the crosslinkable surface modified inorganic oxide particles of the present invention can be made by dispersing inorganic particles in a non- polar solvent (e.g. toluene) and adding to this dispersion the desired fluorosilane. The dispersion is then heated to an elevated temperature (e.g. 80-100 °C) for about 8-10 hours. The dispersion is then allowed to cool to ambient temperature (about 20 °C).
  • the dispersion is then placed in a centrifuge, the solvent is decanted, and the resulting inorganic particles are washed with fresh solvent. Washing is preferably done at least twice.
  • the washed inorganic particles are then dried in an oven at elevated temperature (about 100-1 10 °C).
  • the resulting dried inorganic particles are the final product of the invention.
  • the resulting dried inorganic particles can be re-dispersed in a non-polar solvent (e.g. toluene) and additional fluorosilane can be added to this dispersion by repeating the entire procedure described in this paragraph.
  • a non-polar solvent e.g. toluene
  • “divergent” approach wherein “functionalized inorganic particles” are made by reacting untreated inorganic particles with a first precursor wherein the first precursor comprises a silicon atom bonded to at least one terminal hydrolysable group which reacts with the surface of the inorganic particle thereby creating a covalent bond between the first precursor and the inorganic particle.
  • the first precursor further comprises a terminal reactive group (e.g. an amine or an isocyante derived from an amine or an isothiocyanate derived an amine) thereby creating functionalized inorganic particles having "anchors" which comprise the terminal reactive group.
  • These functionalized inorganic particles are then reacted with a second precursor wherein the second precursor comprises a corresponding reactive group (e.g.
  • the second precursor is also known herein by the term "capping agent.”
  • An example of a useful first precursor and second precursor combination is wherein the first precursor comprises a terminal amine group and the second precursor comprises a terminal isocyante, isothiocyanate, vinyl, sulfonyl chloride, or sulfonamide.
  • the invention further relates to a coating composition
  • a coating composition comprising a coating base and the surface modified inorganic oxide particles defined above, where the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating.
  • the coating composition comprises the coating base in an amount of from about 95 to 99.98% and the surface modified inorganic oxide particles in an amount of from about 0.02 to 5% by weight, based on the total weight of the coating base and the surface modified inorganic oxide particles.
  • the coating composition comprises the coating base in an amount of from about 97 to 99.98% and the surface modified inorganic oxide particles in an amount of from about 0.02 to 3% by weight, based on the total weight of the coating base and the surface modified inorganic oxide particles.
  • the surface modified inorganic oxide partifcles composition produced as described above may be used directly in a coating
  • the fluoropolymer composition is useful as a coating additive, wherein the fluoropolymer composition can be added to a coating base, which is applied to a substrate. When the coating is applied to a substrate, the additive compound is allowed to first migrate to the surface and
  • the present invention provides a method of forming a coated substrate with durable dirt pickup resistance comprising contacting a coating base with surface modified inorganic oxide particles to form a coating, contacting a substrate with the coating to form a coating film, allowing the surface modified inorganic oxide particles to migrate to the coating film surface, and crosslinking the ethylenically unsaturated groups of surface modified inorganic oxide particles of the coating film with each other, wherein the surface modified inorganic oxide particles comprise an oxide of X, where X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and at least one of said particles has a surface covalently bonded to
  • a 1 is (CH 2 ) k — N(R 9 -R f i )-R 9 , (CH 2 )k— NH-C(O)-NH, (CH 2 )k— NH-C(S)-NH, (CH 2 )k— NH-C(O)O, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)S, (CH 2 ) k — NH-C(O)- NH-SO 2 , (CH 2 )k— NH-C(S)-NH-SO 2 , (CH 2 )k—
  • the coating base is a liquid formulation of a water- dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating, which is later applied to a substrate for the purpose of creating a lasting film on said surface.
  • the coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating.
  • the coating base may include a resin compound from 10 to 60% by weight, from 0.1 to 80% by weight of functional additives including pigments, fillers, and other additives, and the balance of the coating base
  • composition is water or solvent.
  • the resin compound is in an amount of about 30 to 60% by weight
  • functional additives including pigments, extenders, fillers, and other additives are in an amount of 0.1 to 60% by weight, with the balance being water or solvent.
  • the coating composition further comprises an additional fluoroadditive, such as a fluorinated polymer additive or fluorinated crosshnkable polymer compound.
  • additional fluoroadditive such as a fluorinated polymer additive or fluorinated crosshnkable polymer compound.
  • crosshnkable polymers include but are not limited to (meth)acrylic copolymers having
  • the composition comprises the coating base in an amount of from about 90 to 99.96%, the surface modified inorganic oxide particles in an amount of from about 0.02 to 5% by weight, and the crosshnkable compound in an amount of from about 0.02 to 5% by weight, based on the total weight of the coating base, the surface modified inorganic oxide particles, and the crosshnkable compound.
  • the coating composition comprises the coating base in an amount of from about 96 to 99.9%, the surface modified inorganic oxide particles in an amount of from about 0.05 to 2%, and the crosshnkable compound in an amount of from about 0.05 to 2% by weight, based on the total weight of the coating base, the surface modified inorganic oxide particles, and the crosshnkable polymer.
  • the coating composition further comprises a fluorocopolymer comprising repeat Unit A and at least one of repeat Units B, C, D, or E, in any order:
  • R ⁇ is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0- , -CH 2 -, -CFH-, or combinations thereof;
  • a 2 is 0, S, or N(R'), wherein R' is H or an alkyl of from 1 to about 4 carbon atoms;
  • Q 3 is a straight chain, branched chain or cyclic structure of alkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups;
  • v is 0 or 1 ;
  • R 1 is H or Chh;
  • R 2 is independently selected from H or an alkyl of 1 to about 4 carbon atoms;
  • Z is a hydrophilic group selected from a hydroxyl- terminated straight or branched al
  • the fluorocopolymer may comprise at least one of Units A and C, or at least one of Units A, B, and C.
  • the fluorocopolymer comprises at least one of Units A and D in order to form a crosslinkable compound.
  • the (meth)acrylate copolymers comprise two or more repeating units derived from monomers from each of five groups.
  • Monomers forming Unit A are fluorinated monomers such as perfluoroalkylalkyl
  • monomers forming Unit B are hydrophilic monomers such as hydroxyalkyi (meth)acrylates or alkoxylated (meth)acrylates
  • monomers forming Unit C are acidic monomers such as (meth)acrylic acid which are optionally neutralized to form a salt
  • monomers forming Unit D are olefin- group-containing monomers such as fatty acid (meth)
  • monomers forming Unit E are hydrophobic monomers such as alkyl (meth)acrylates.
  • the repeating units can occur in any random sequence in the proportions described above.
  • Unit A is present in an amount from about 10 to about 60 mol%; in another embodiment, Unit A is present in an amount from about 25 to about 55 mol %; and in a third embodiment, Unit A is present in an amount from about 30 to about 50 mol %. In one
  • Unit D is present in an amount from about 0.1 to about 90 mol%; in another embodiment, Unit D is present in an amount from about 2 to 40 mol%; and in a third embodiment, Unit D is present in an amount from about 2 to about 15 mol%.
  • Unit C is present in an amount of about 0.1 to 90 mol %; in another embodiment, Unit C is present in an amount from about 1 to about 60 mol %; and in a third embodiment Unit C is present in an amount from about 20 mol % to about 60 mol%.
  • Unit B is present in an amount of about 0.1 mol to 90 mol%; in another embodiment, Unit B is present in an amount of from about 0.1 to about 60 mol %; and in a third embodiment, Unit B is present in an amount of from about 10 to about 30 mol %.
  • Unit E is present in an amount of about 0.1 mol to 90 mol%; in another embodiment, Unit E is present in an amount of from about 0.1 to about 60 mol %; and in a third embodiment, Unit E is present in an amount of from about 10 to about 30 mol %.
  • Units A, B, C, D, or E are present; in a further embodiment, four of Units A, B, C, D, or E are present; and in yet a further embodiment, all five of Units A, B, C, D, and E are present.
  • the fluorocopolymer compound must have a molecular weight high enough to provide cleanability and durability but low enough to allow the polymer molecules to migrate through the coating medium.
  • the number average molecular weight M n is about 1500 to about 50,000 Daltons; in a second embodiment, the number average molecular weight M n is about 5000 to about 40,000 Daltons; and in a third embodiment, the number average molecular weight M n is about 8000 to about 35,000 Daltons.
  • the weight average molecular weight M w is about 5000 to about 50,000 Daltons; in a second
  • the weight average molecular weight M w is about 8000 to about 30,000 Daltons; and in a third embodiment, the weight average molecular weight M w is about 10,000 to about 20,000 Daltons.
  • the polydispersity index (PDI) may be about 1 .0 to about 3.0; in another embodiment, about 1 .1 to about 2.0, and in a third embodiment, about 1 .2 to about 1 .9.
  • the fluorocopolymer is a
  • the Mw can be up to 300,000, and PDI may be up to 6.0.
  • Fluorinated (meth)acrylate monomers useful for forming Unit A are synthesized from the corresponding alcohols. These fluorinated
  • (meth)acrylate compounds are prepared by either esterification of the corresponding alcohol with (meth)acrylic acid or by transesterification with methyl (meth)acrylate. Such preparations are well-known in the art.
  • Unit A is a straight or branched-chain
  • perfluoroalkyl group predominately containing from 2 to 6 carbon atoms, optionally interrupted by one or more -CH 2 - or -CFH- groups. More particularly, in Formula (III) is a straight chain perfluoroalkyl group of 2 to 6 carbon atoms, and in another embodiment, 4 to about 6 carbon atoms.
  • One preferred embodiment of the monomer forming Unit A is a perfluoroalkylethyl (meth)acrylate having the formula:
  • F(CF 2 CF 2 ) s C 2 H 4 OC(O)-C(R) CH 2 wherein s is 1 to about 3 or a mixture thereof, and preferably
  • R is H or methyl
  • linking groups Q 3 in Unit A include straight chain, branched chain or cyclic structures of alkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, and combinations of such linking groups such as
  • Q 3 is a straight chain alkylene of 1 to about 15 carbon atoms or -CONR'(CnH2n)-, the (C n H 2n ) group is linear or branched, and preferably is linear. In this case, n is 1 to 14.
  • Q 3 is a straight or branched alkylene of 1 to 4 carbon atoms
  • Q 3 is a straight or branched alkylene of 2 to 4 carbon atoms.
  • the alkyl in R' is linear or branched. Mixtures of fluorinated monomers may also be used.
  • Suitable fluorinated alcohols capable of forming the fluorinated (meth)acrylate monomers include but are not limited to
  • Examples of monomers used for form Unit B include
  • Suitable examples include, but are not limited to, one or more hydroxyalkyl (meth)acrylates, alkyloxy
  • Suitable hydroxyalkyl (meth)acrylates have alkyl chain lengths of 2 to 4 carbon atoms, and include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate.
  • R 2 is H or alkyl radical of 1 to 2 carbon atoms.
  • suitable monomers may contain between 1 and 40 oxyalkylene units per molecule. In another embodiment, monomers contain from 2 to 20 oxyalkylene units per molecule, and in a third embodiment, from 4 to 12 oxyalkylene units per molecule. Such monomers include but are not limited to ethyltriethyleneglycol
  • (meth)acrylates poly(ethylene glycol) methyl ether (meth)acrylates, propoxylated (meth)acrylates, poly(propylene glycol) (meth)acrylates, or poly(propylene glycol) methyl ether (meth)acrylates.
  • Thiol-terminated or amine-terminated monomers of similar types can also be used, and are synthesized according to conventional methods.
  • Z in Unit B is -0-
  • r in Unit B is 2 or 3.
  • R 3 and R 4 are preferably alkyls of 1 , 2, or 3 carbon atoms. Examples of preferred monomers for forming Unit B are diethylaminoethyl acrylate, and/or dimethylaminoethyl methacrylate.
  • the monomers used to form Unit C are acrylic acid or methacrylic acid; and M is H, HN(R 5 )3, Na, Li, Cs, K, or mixtures thereof. In one embodiment, M is NH 4 or Na, or a mixture thereof.
  • Repeat units of Unit C can be formed by neutralizing the copolymer with a base, including but not limited to alkali metal hydroxides, alkali metal carbonates, ammonia, alkyl amines, or alkanolamines.
  • the monomers used to form Unit D are at least one vinylic or (meth)acrylic monomer having a straight or branched alkyl chain of 2 to 30 carbons and having 1 to 15 olefinic units.
  • the alkyl chain contains 2 to 22 carbons, and in a third embodiment, the alkyl chain contains 3 to 18 carbons.
  • the alkyl chains may contain 1 to 15 olefinic units but in another embodiment may contain 1 to 6 olefinic units, and in a third embodiment may contain 1 to 3 olefinic units.
  • Such monomers may be formed from the reaction of hydroxyl- terminal (meth)acrylates or allylic compounds with fatty acids.
  • Fatty acids may include but are not limited to oleic acid, linoleic acid, ricinoleic acid, erucic acid, palmitoleic acid, vaccenic acid, eicosenoic acid, eladic acid, eurucicic acid, nervonic acid, pinolenic acid, arachidonic acid,
  • Unit D eicosapentaenoic acid, docosahexanoic acid, eicosadienoic acid, docosatetranoic acid, and mixtures thereof.
  • monomers used to form Unit D include but are not limited to oleic
  • Unit E may be formed from (meth)acrylic monomers having pendant straight chain, branched chain, or cyclic structure alkyl groups of 1 to 30 carbons.
  • the alkyl groups contain 1 to 22 carbons, and in a third embodiment, the alkyl groups contain 6 to 22 carbons.
  • Such monomers include but are not limited to stearyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, 2- ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, palmitic (meth)acrylate, caprylic (meth)acrylate, captric (meth)acrylate, mysteric (meth)acrylate, arachidic (meth)acrylate, behenic (meth)acrylate, lignoceric (meth)acrylate, or cetyl (meth)acrylate.
  • the fluorocopolymer may or may not further comprise additional repeat units outside of the units, resulting from the use of additional monomers.
  • Suitable monomers are ethylenically-unsaturated monomers, including but not limited to, amine monomers such as diethylaminoethyl acrylate and/or dimethylaminoethyl methacrylate, glycidyl (meth)acrylates, aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamides, or n-methylol (meth)acrylamide.
  • amine monomers such as diethylaminoethyl acrylate and/or dimethylaminoethyl methacrylate, glycidyl (meth)acrylates, aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamides, or n-methylol (meth)acrylamide.
  • the fluorocopolymers in the present invention are prepared by polymerization of the fluorinated and non-fluorinated monomers.
  • the polymerization process comprises contacting the fluorinated and non- fluorinated (meth)acrylate monomers as defined hereinabove in an organic solvent in the presence of a free radical initiator, chain transfer agent, and optionally other monomers in an inert atmosphere.
  • the monomers can be mixed in a suitable reaction vessel equipped with an agitation device. A heating source and a cooling source are provided as necessary.
  • the fluorinated and non-fluorinated monomers are combined in the reaction vessel with the solvent and chain transfer agent to provide a reaction mixture, and the reaction mixture is heated to an appropriate temperature, e.g.
  • the monomers may be fed one at a time, or in a mixture, to an existing solution in a reaction vessel at a selected feed rate.
  • the existing solution in the reaction vessel may contain the solvent; the solvent and chain transfer agent; or the solvent, chain transfer agent, and one or more monomers.
  • the chain transfer agent may be fed alone, or in a mixture with one or more monomers, to an existing solution in a reaction vessel at a selected feed rate.
  • the existing solution in the reaction vessel may contain the solvent; the solvent and one or more monomers; or the solvent, one or more monomers, and the initiator.
  • the initiator may be included in the existing solution or may be fed into the reactor at a later time.
  • Suitable free radical initiators include organic peroxides and azo compounds.
  • organic peroxides are benzoyl peroxide, f-butyl peroxide, acetyl peroxide, and lauryl peroxide.
  • particularly useful azo compounds include 2,2'-azobis(2- amidinopropane dihydrochloride, 2,2'-azobis(isobutyramidine)
  • Azo initiators are commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE, under the name of "VAZO".
  • Suitable redox initiators include potassium or ammonium
  • peroxydisulfate combinations of peroxides such as hydrogen peroxide with Fe 2+ , Cr 2+ , V 2+ , Ti 3+ , Co 2+ , Cu + ; combinations of HSOs " , SOs 2" , S2O3 2 -, or S2O5 2" with Ag + , Cu 2+ , Fe 3+ ' CIO 3" , or H2O2; combinations of organic alcohols with Ce 4+ , V 5+ , Cr 6+ , or Mn 3+ ; and combinations of
  • peroxydiphosphate compounds with Ag + , V 5+ , or Co 2+ .
  • Such systems may be used when low temperature or rapid activation is desirable.
  • the fluorocopolymer compounds may further comprise residue from a chain transfer agent, also known as a polymerization regulator.
  • a chain transfer agent also known as a polymerization regulator.
  • the term "residue” is herein defined as the portion of the chain transfer agent structure that is covalently bonded to the polymer molecule.
  • the total polymer reaction mixture may also include some polymer molecules that do not contain the chain transfer agent residue.
  • the chain transfer agent can be used in amounts to limit or control the molecular weight of the fluoropolymer, typically in amounts of about 1 to 25 mol%, preferably about 2 to 20 mol%, more preferably about 3 to 15 mol%, and most preferably 5 to 10 mol%, based on the total amount of chain transfer agent and monomers employed.
  • hydrophilic chain transfer agents with the formula (III):
  • the chain transfer agents are disulfide compounds of the formula D-G-S-S-G-D.
  • Suitable chain transfer agents include but are not limited to dodecanethiol, thioglycerol, mercaptoethanol, thioglycolic acid, dithioerythritol, 2-mercaptopropionic acid, and 3-mercaptopropionic acid, or mixtures thereof.
  • Suitable solvents are alkanes, alcohols and ketones having boiling points of less than 130°C.
  • Suitable organic solvents useful in the preparation of the fluoropolymer include methyl isobutyl ketone, butyl acetate, tetrahydrofuran, acetone, isopropanol, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, cyclohexane, hexane, dioxane, hexafluoroisopropanol, and mixtures of two or more thereof.
  • Cyclohexane, isopropanol, methyl isobutyl ketone, or mixtures thereof are preferred.
  • Blends of isopropanol and methyl isobutyl ketone are particularly preferred, since both solvents form azeotropes with water boiling below 100°C, facilitating their removal from the final aqueous dispersion.
  • Blends of organic solvents with other types of co-solvents, including water, may also be used.
  • the fluorocopolymer as described above used in the method of the present invention is preferably in the form of an aqueous dispersion.
  • the acidic polymer solution can be neutralized using a basic water solution to form an aqueous dipserion.
  • the amount of base necessary is calculated by assuming complete salt formation of all acid functionalities.
  • 0 - 5% mole percent excess of base is added to ensure conversion of all acid to salt.
  • the final pH of the emulsion is between about 6 and about 9, and preferably is between 6 and 8.
  • neutralization are alkali metal hydroxides, alkali metal carbonates, ammonia, alkyl amines, or alkanolamines. Ammonia solution is preferred. Following neutralization, the organic solvents may be removed by distillation to form a completely aqueous system.
  • the coating compositions may further comprise additional components to provide surface effects to the resulting coating. These additional components may include additional fluorinated additives to provide additional cleanability, dirt pickup resistance, or blocking properties to the coating. Cure additives may also be included.
  • the composition may further comprise a non-polymeric ethylenically unsaturated crosslinkable compound to provide additional crosslinking sites.
  • this non-polymeric crosslinkable compound is a fatty acid compound in an amount of about 0.001 to 1 % by weight, based on the total weight of the coating composition. Any fatty acid, including those listed above for use in forming the monomer of Unit D, may be employed. In one embodiment, the fatty acid is the same fatty acid used to form the monomer of Unit D.
  • the coating compositions may also include a pigment.
  • a pigment may be part of the coating base formulation, or may be added subsequently. Any pigment can be used with the present invention.
  • the term "pigment” as used herein means opacifying and non-opacifying ingredients which are particulate and substantially non-volatile in use. Pigment as used herein includes ingredients labeled as pigments, but also ingredients typically labeled in the coating trade as inerts, extenders, fillers, and similar substances.
  • Pigment Red 104 Toluidine Red YW (C. I. Pigment 3)- process aggregated crystals, Phthalo Blue (C. I. Pigment Blue 15)- cellulose acetate dispersion, Toluidine Red (C. I. Pigment Red 3),
  • Watchung Red BW (C.I. Pigment Red 48), Toluidine Yellow GW (C. I.
  • MONASTRAL Green BW C. I. Pigment Green 7
  • Pigment Scarlet C. I. Pigment Red 60
  • Auric Brown C. I. Pigment Brown 6
  • MONASTRAL Green G C.I. Pigment Green 7
  • MONASTRAL Maroon B MONASTRAL Orange
  • Phthalo Green GW Phthalo Green GW 951.
  • Titanium dioxide is the preferred pigment to use with the present invention. Titanium dioxide pigment, useful in the present invention, can be in the rutile or anatase crystalline form. It is commonly made by either a chloride process or a sulfate process. In the chloride process, TiCU is oxidized to T1O2 particles. In the sulfate process, sulfuric acid and ore containing titanium are dissolved, and the resulting solution goes through a series of steps to yield T1O2. Both the sulfate and chloride processes are described in greater detail in "The Pigment Handbook", Vol. 1 , 2nd Ed. , John Wiley & Sons, NY (1988), the teachings of which are incorporated herein by reference.
  • the surface modified inorganic oxide particles, crosslinkable polymer compound, and additives are effectively introduced to the coating base by thoroughly contacting, e.g., by mixing the additives with the coating base at ambient temperature. More elaborate contacting or mixing methods can be employed such as using a mechanical shaker or providing heat. Such methods are generally not necessary and generally do not substantially improve the final coating composition.
  • the crosslinkable polymer When used as an additive to a coating base, the crosslinkable polymer is generally added at about 0.02 weight % to about 5 weight % on a dry weight basis of the fluoropolymer to the weight of the wet paint. In one embodiment, from about 0.02 weight % to about 0.5 weight % is used, and in a third embodiment, from about 0.05 weight % to about 0.25 weight % of the crosslinkable polymer compound is added to the paint.
  • the coating compositions of the present invention are useful for providing a protective and/or decorative coating to a wide variety of substrates.
  • substrates include primarily construction materials and hard surfaces.
  • the substrate is preferably selected from the group consisting of wood, metal, wallboard, masonry, concrete, fiberboard, and paper. Other materials may also be used as the substrate.
  • the coatings of the present invention may be used to treat a substrate by contacting the substrate with a coating composition
  • any method of contacting a coating composition with a substrate can be used. Such methods are well known to a person skilled in the art, such as by brush, spray, roller, doctor blade, wipe, dip, foam, liquid injection, immersion or casting.
  • the polymer compound is polymerized using any conventional means, including allowing the additive to crosslink in air by oxidative curing. Radiation curing, including UV curing, may also be employed. Cure initiators and additives may be combined with the coating compositions to improve cure efficiency.
  • compositions of the present invention provide performance as well as durability to coatings. They impart unexpectedly desirable surface effects such as: increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating films. For these reasons, the compounds of the present invention are particularly suitable for use as additives to exterior coating and paints.
  • Exclusion Chromatography (SEC) system [Alliance 2695TM, Waters Corporation (Milford, MA)] equipped with with a differential refractive index detector, multi-angle light scattering photometer and a differential capillary viscometer ViscoStarTM.
  • Aqueous dispersions of fluorinated silica were added to select commercially available exterior latex paints at various percents by weight, calculated by weight of the fluorinated silica solids; the paints were free of fluoroadditives. Where fluoroacrylic copolymers were also used, they were added at 350 ppm fluorine levels to selected commercially available interior and exterior latex paints that were, prior to dosing, free of fluoroadditives. The samples were mixed using an overhead Cowles Blade stirrer at 600 rpm for 10 minutes. The mixture was then transferred to a glass bottle, sealed and placed on a roll mill overnight to allow uniform mixing of the fluoropolymer.
  • Oil contact angle measurements were used to test for the migration of fluoroadditive to the surface of the paint film. Oil contact angle testing was performed by goniometer on 1 inch strips of Leneta panel coated with dried paint film.
  • a Rame-Hart Standard Automated Goniometer Model 200 employing DROP image standard software and equipped with an automated dispensing system, 250 ⁇ syringe, and illuminated specimen stage assembly was used.
  • the goniometer camera was connected through an interface to a computer, allowing the droplet to be visualized on a computer screen.
  • the horizontal axis line and the cross line could both be independently adjusted on the computer screen using the software.
  • the sample Prior to contact angle measurement, the sample was placed on the sample stage and the vertical vernier was adjusted to align the horizontal line (axis) of the eye piece coincident to the horizontal plane of the sample.
  • the horizontal position of the stage relative to the eye piece was positioned so as to view one side of the test fluid droplet interface region at the sample interface.
  • test fluid approximately one drop of test fluid was dispensed onto the sample using a 30 ⁇ _ pipette tip and an automated dispensing system to displace a calibrated amount of the test fluid.
  • hexadecane was suitably employed.
  • Horizontal and cross lines were adjusted via the software in case of the Model 200 after leveling the sample via stage adjustment, and the computer calculated the contact angle based upon modeling the drop appearance.
  • the initial contact angle is the angle determined immediately after dispensing the test fluid to the sample surface. Initial contact angles above 30 degrees are indicators of effective oil repellency.
  • DPR testing was used to evaluate the ability of the painted panels to prevent dirt accummulation.
  • An artificial dry dirt comprised of silica gel (38.7%), aluminum oxide powder (38.7%), black iron oxide powder (19.35%) and lamp black powder (3.22%) was used for this test.
  • the dust components were mixed and placed on a roller for 48 hours for thorough mixing and stored in a decicator.
  • Exterior paint samples were drawn down to Aluminium Q-panels cut to a size of 1 .5" x 2", and four replicates of these samples were taped onto a 4" x 6" metal panel.
  • the initial whiteness (L * initial) of each Q-panel was measured using a Hunter Lab colorimeter.
  • the 4" x 6" metal panel was then inserted into a 45 degree angle slot cut in a wooden block.
  • the dust applicator containing metal mesh dispensed the dust on the panels until the panels were completely covered with dust. The excess dust was then removed by lightly tapping the mounted panels 5 times on the wooden block inside the shallow tray.
  • the 4" x 6" panel which held the dusted panels was then clamped onto a Vortex-Genie 2 for 60 seconds to remove any remaining dust.
  • the panel was then removed and tapped 10 times to dislodge any remaining dust.
  • Accelerated weathering of coated Q-panels was performed in an ATLAS Ci5000 Xenon Lamp Weather-o-Meter.
  • the Xenon lamp was equipped with Type S Boro Inner and Outer Filters.
  • Weathering cycles were performed according to D6695, cycle 2.
  • the panels were subjected to repeated 2-hour programs, which included 18 minutes of light and water spray followed by 102 minutes of light only.
  • panels were held at 63 °C and during the UV only segment relative humidity was held at 50%.
  • a 250 ml_ three-necked round bottom flask was equipped with a reflux condenser, a nitrogen sparge line, a TEFLON-coated magnetic stir bar, and a dip-tube for measurement of the internal temperature via a thermocouple was charged with MIBK (1 1 ml_) and IPA (25 ml_). The solution was subjected to sub-surface sparging with nitrogen using a needle for 1 hour at room temperature.
  • VAZO 67 (0.395 g, 2.05 mmol) was prepared using sparged MIBK/IPA (19 ml_) from the first reaction flask. VAZO 67 solution and monomer solution were loaded into two separate 20 ml syringes equipped with a 22 gauge needle.
  • the polymer solution in MIBK/IPA was heated back to 70 °C.
  • a neutralization solution consisting of NH 4 OH (2.85 g, 47.0 mmol) in H2O (58.3 ml_) was prepared and heated to 45 °C.
  • the ammonia solution was added dropwise to the polymer solution via addition funnel over 20 minutes to achieve a cloudy solution.
  • the solution was stirred at 70 °C for an additional 1 hour, and the MIBK/IPA was removed under vacuum to produce 102.5 g of a hazy yellow dispersion of polymer in water with a pH 8.0.
  • the dispersion was determined to be 22.9 weight % solids.
  • Polymer 1 semi-batch polymerization was performed using 1 H, 1 H,2H,2H- perfluorooctyl methacrylate (14.58 g, 33.8 mmol)), hydroxyethyl methacrylate (1 .46 g, 1 1 .22 mmol), Monomer A (6.25 g, 9.66 mmol) and methacrylic acid, (3.16 g, 36.74 mmol), VAZO 67 (0.395 g, 2.05 mmol), and 1 -thioglycerol (0.988 g, 9.13 mmol) chain transfer agent to provide a polymer solution with >98 % monomer conversion ( 1 H NMR).
  • DESMODUR N3300 (6.68 g) was added to a round-bottomed flask with magnetic stir bar kept under N2 atmosphere.
  • Methyl isobutyl ketone (MIBK) (10.9 g), 1 H, 1 H,2H,2H-perfluorooctanol (4.16 g, 1 1 .44 mmol), glycolic acid (0.74 g, 9.7 mmol), poly(ethyleneglycol)monomethacrylate (MW 526, 3.1 g, 5.89 mmol), trimethylolpropane diallylether (1 .40 g, 5.89 mmol) and IRGACURE 2959 (0.39g, 1.73 mmol) were added.
  • MIBK Methyl isobutyl ketone
  • the reaction mixture was heated to 60 °C and charged with catalytic dibutyltin dilaurate (0.02 g) in MIBK (0.7 g). The reaction mixture was then heated to 90 °C for 12 hours. The reaction mixture turned to a thick yellow liquid. The mixture was then cooled to 50 °C. A neutralizing solution of NH 4 OH (0.59 g, 9.7 mmol Nhta) in H2O (38 ml_) was then added. A white slurry formed at pH ⁇ 10 and the contents then stirred with heating at 50 °C for for 30 minutes. A sample was taken for weight percent solids analysis and was determined to be 14.6 % by weight. A calculated amount of this dispersion (350 ppm of F) was added to samples of exterior test paint and the drawdown panels evaluated as per the test methods described.
  • Lysine was first prepared. After raising the temperature to 90 °C, a mixture containing 10.0 g tetraethyl orthosilicate, 5.0 g of 1 H, 1 H,2 - ,2H- pefluorooctyltriethoxysilane, 5.0 g of allyltrimethoxysilane, and 17.69 g of ethanol was added. The formation of the particle was achieved by stirring the solution at 90 °C for 2 days followed by allowing the solution to cure at 100 °C for one additional 1 to complete the sol-gel reaction. Finally, the particle dispersion was filtered and rinsed with water to remove ethanol, and then re-dispersed into water. The structure of the resulting particles was analyzed using transmission electron microscopy and is shown in Figure 1. The resulting fluorinated silica was added to exterior test paint at various loading levels as described in Table 1 and evaluated by the test methods above.
  • aqueous solution containing 534.0 g of water and 0.56 g of L- Lysine was first prepared. After raising the temperature to 90 °C, a mixture containing 20.0 g tetraethyl orthosilicate, 2.5 g of 1 H, 1 H,2 - ,2H- pefluorooctyltriethoxysilane, 10.0 g of allyltnmethoxysilane, and 35.38 g of ethanol was added. The formation of the particle was achieved by stirring the solution at 90 °C for 2 days followed by allowing the solution to cure at 100 °C for one additional day to complete the sol-gel reaction.
  • the particle dispersion was filtered and rinsed with water to remove ethanol, and then re-dispersed into water.
  • the structure of the resulting particles was analyzed using transmission electron microscopy and is shown in Figure 3.
  • the resulting fluorinated silica was added to exterior test paint at various loading levels as described in Table 1 and evaluated by the test methods above.
  • Polymer 1 semi-batch polymerization was performed using 1 H, 1 H,2H,2H- perfluorooctyl methacrylate (14.58 g, 33.8 mmol), hydroxyethyl
  • Polymers 1 or 2 were applied to drawdown panels and evaluated as per the test methods described.

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Abstract

La présente invention comprend une particule d'oxyde inorganique modifiée en surface réticulable, sur laquelle sont greffés à la fois des groupes pendants fluorés et éthyléniquement insaturés. Ces particules sont utiles en tant qu'additifs pour revêtements de sorte que, lorsque le revêtement est appliqué sur un substrat, le composé additif puisse d'abord migrer vers la surface puis réticuler de manière à former une surface durable résistante à l'huile, à la saleté et à l'eau.
PCT/US2016/029663 2015-04-30 2016-04-28 Particule d'oxyde inorganique fluoré réticulable pour revêtements architecturaux WO2016176388A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109762373A (zh) * 2019-01-21 2019-05-17 济南大学 一种含氟聚合物包覆型球形铝粉及其制备工艺与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060222815A1 (en) 2003-05-15 2006-10-05 Degussa Ag Use of particles hydrophobized by fluorosilanes for the production of self-cleaning surfaces having lipophobic, oleophobic, lactophobic and hydrophobic properties
US20090176097A1 (en) * 2007-12-05 2009-07-09 E. I. Du Pont De Nemours And Company Surface modified inorganic particles
US8058463B2 (en) 2007-12-04 2011-11-15 E. I. Du Pont De Nemours And Compnay Fluorosilanes
US20140309343A1 (en) * 2011-11-11 2014-10-16 United Protective Technologies Multifunctional superhydrophobic diatomaceous earth for chemical adhesion and color change

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060222815A1 (en) 2003-05-15 2006-10-05 Degussa Ag Use of particles hydrophobized by fluorosilanes for the production of self-cleaning surfaces having lipophobic, oleophobic, lactophobic and hydrophobic properties
US8058463B2 (en) 2007-12-04 2011-11-15 E. I. Du Pont De Nemours And Compnay Fluorosilanes
US20090176097A1 (en) * 2007-12-05 2009-07-09 E. I. Du Pont De Nemours And Company Surface modified inorganic particles
US20140309343A1 (en) * 2011-11-11 2014-10-16 United Protective Technologies Multifunctional superhydrophobic diatomaceous earth for chemical adhesion and color change

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Outlines of Paint Technology, Third edition,", 1990, HALSTEAD PRESS
"Surface Coatings Vol. I, Raw Materials and Their Usage, Second Edition,", 1984, CHAPMAN AND HALL
"The Pigment Handbook, 2nd Ed.,", vol. 1, 1988, JOHN WILEY & SONS

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109762373A (zh) * 2019-01-21 2019-05-17 济南大学 一种含氟聚合物包覆型球形铝粉及其制备工艺与应用

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