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WO2015138117A1 - Compositions de revêtement comprenant des particules de silice creuses ayant une faible porosité - Google Patents

Compositions de revêtement comprenant des particules de silice creuses ayant une faible porosité Download PDF

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Publication number
WO2015138117A1
WO2015138117A1 PCT/US2015/017323 US2015017323W WO2015138117A1 WO 2015138117 A1 WO2015138117 A1 WO 2015138117A1 US 2015017323 W US2015017323 W US 2015017323W WO 2015138117 A1 WO2015138117 A1 WO 2015138117A1
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WIPO (PCT)
Prior art keywords
particle
typically
coating composition
silica
hollow
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Ceased
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PCT/US2015/017323
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English (en)
Inventor
Nathaniel A Barney
John A CROWTHER JR
Brad M Rosen
Jelena LASIO
Hau-Nan LEE
Andrew Jay Duncan
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of WO2015138117A1 publication Critical patent/WO2015138117A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
    • 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
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
    • 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
    • C09C1/3045—Treatment with inorganic 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic 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
    • C09C1/36—Compounds of titanium
    • 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
    • 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
    • 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
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • 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
    • C01P2006/14—Pore volume
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1212—Zeolites, glasses
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1233—Organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic

Definitions

  • the present disclosure relates to coating compositions comprising hollow particles. More particularly, the disclosure relates to coating compositions comprising hollow particles, more typically functionalized silica particles.
  • the coating compositions of interest in the present disclosure are water- dispersible coating compositions such as latex coating compositions, e.g. acrylic, styrene acrylic, etc.; and solvent based such as alkyd coating compositions; urethane coating compositions; and unsaturated polyester coating compositions, typically a paint, clear coating, or stain. These coatings may be applied to a substrate by spraying, applying with a brush or roller or electrostatically, such as powder coatings, etc. These 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 powders may be added to the coating compositions.
  • titanium dioxide pigments have been added to coating
  • Nano core/shell particles may be added to coating compositions as hiding or opacifiying agents.
  • dry-hiding power can be achieved by formulating the system above its critical pigment volume concentration (CPVC), thereby generating a network of air voids which create opacity.
  • CPVC critical pigment volume concentration
  • the disclosure provides a coating composition having improved opacity comprising a titanium dioxide ( ⁇ 2) particle chemically attached to one or more hollow particles, wherein each hollow particle's size has a volume ratio when compared to the titanium dioxide particle of between 0.008 and 8.
  • titanium dioxide particles we mean pigmentary sized titanium dioxide particles of average size which may or may not have organic or inorganic surface treatments. More typically the titanium dioxide particles have a particle size of about 100 to about 900nm in size, more typically between about 150 and about 600nm, and still more typically between about 180 and about 270nm.
  • the hollow particle(s) are chemically bound to the ⁇ 2 particle such that they at least partially coat the surface of the ⁇ 2 particle thereby separating it from adjacent ⁇ 2 particles in a crowded system.
  • “hollow particle” we mean a particle with a discernible density difference between the core and the shell materials of at least about 0.2 g/cm 3 in the dry paint film, or a precursor layered material that results in this density difference in the final paint film where the core material represents about 20 to about 90% of the total particle volume.
  • Figure 1 shows the attachment of hollow particles to the outer surface of a pigmentary T1O2 particle.
  • Figure 2A, 2B and 2C show TEM images of the hollow polymer/TiO2 composites.
  • T1O2 particle the T1O2 particle
  • T1O2 particle also includes a plurality of T1O2 particles.
  • This disclosure is particularly suitable for producing coating compositions comprising hollow inorganic or polymer particles, typically hollow silica particles, and in particular architectural paint formulations or ink formulations comprising hollow inorganic particles, typically hollow silica particles, having improved paint or ink performance.
  • the hollow inorganic particles or polymer particles, typically hollow silica particles, of this disclosure are produced using several different processes to generate core/shell particles.
  • the process of silica or polymer deposition is such that it allows tuning of the surface area and porosity of the silica shells, thereby allowing for synthesis of impervious core/shell particles.
  • the core material is removed to generate hollow particles.
  • the resulting hollow particles can be then functionalized with a variety of alkoxysilanes to generate functionalized hollow particles, with tunable porosity and surface area.
  • porosity and surface area can be tuned through iterative silica deposition to form a silica shell, thereby reducing the porosity and surface area of the hollow particles, as well as thermal treatment of the silica shell at high temperatures, usually over 500°C.
  • the use of polyvalent ions in the creation of the inorganic shell can allow for pH controlled porosity.
  • the disclosure describes the process for hollow silica or polymer particles with tunable porosity and surface area, as optionally functional group(s) on the hollow particles' surface.
  • the coating composition having improved opacity comprising a titanium dioxide (T1O2) particle chemically attached to at least one hollow particle, wherein an individual hollow particle's size has a volume ratio when compared to the titanium dioxide particle of between 0.008 and 8, more typically 0.02-2.
  • T1O2 titanium dioxide
  • the volume ratio of 0.008 corresponds to the volume ratio of a 50 nm diameter hollow particle to 250 nm diameter T1O2 particle as approximated by spheres.
  • the volume ratio of 8 corresponds to a 300 nm hollow particle attached to 150 nm diameter T1O2 or a 500 nm hollow particle attached to a 250 nm diameter ⁇ 2 particle as approximated by spheres. It is possible to prepare systems outside of our application window, but they are not efficacious.
  • glass microspheres we take the smallest of 3MTM's Glass Bubble product line. It has an average diameter of 30 micron. At this size its volume ratio to a ⁇ 2 particle would exceed 1 ,000,000. This would mean that each glass microsphere would have the same contribution to pigment volume contribution (PVC) as 1 ,000,000 or more T1O2 particles.
  • PVC pigment volume contribution
  • titanium dioxide particles we mean pigmentary sized titanium dioxide particles of average size which may or may not have organic or inorganic surface treatments.
  • the particles described herein are between about a 100 to about 900nm in size, more typically between about 150 and about 600nm, and still more typically between about 180 and about 270nm.
  • low particle we mean a particle with a discernible density difference between the core and the shell materials of at least about
  • attachment we mean the hollow particle(s) are attracted to the T1O2 particle such that they at least partially coat the surface of the T1O2 particle thereby separating it from adjacent T1O2 particles in a crowded system.
  • This attachment can be through chemical bonds (chemically bound) and additionally through supplementary attractive physical forces (physically bound).
  • a physical bond tends to be weaker, less robust, longer distance, and less selective than a chemical bond.
  • a physical bond is a bond mediated by physical forces, specifically electrostatic (Coulomb) and dispersion (Van der Waals) interactions.
  • Physical bonds include ionic bonds, dipole-dipole interactions, hydrogen bonds, ion-dipole interactions, ion-induced dipole interactions, dipole-induced dipole interactions, and dispersion (Van der Waals) interactions.
  • Examples of physical bonds include the interaction between metal cations and halide anions in salt (ionic) and the interaction of methanol with chloroform (dipole-dipole).
  • the interaction between the polar/charged surface of a ⁇ 2 pigment and the uncharged polymeric particle in US 7288146 is an example of ion-induced dipole class of physical bonds.
  • Non-polar and polar covalent bonds involve the sharing of electrons between atoms where one electron is contributed from each atom.
  • Non-polar covalent bonds describe those bonds where there is limited difference in electronegativity between the bound atoms (e.g. C-C), whereas polar covalent bonds describe those bonds where the difference in electronegativity is substantial (e.g, C-O).
  • Coordinate covalent bonds describe bonds where both electrons are contributed from a single atom (e.g. M + -O " or B-NR3).
  • Functionalization of either the T1O2 pigment or hollow particle allows for attachment of the particles via bonds formed through condensation with the available hydroxylated surface.
  • functional groups useful for this mode of attachment include but are not limited to phosphonic acids, sulfonic acids, boronic acids and their corresponding salts.
  • One example of chemical bonding is the incorporation of phosphate groups on the surface of the hollow particles so that they may, under appropriate conditions, interact with alumina species if present on the surface of an inorganically surface treated ⁇ 2 particle.
  • a further example of a polar covalent bond useful for this mode of particle attachment is the Si-O bond formed by the condensation of silanes with hydroxylated surfaces.
  • Another example of chemical bonding is the polar-covalent bond formed during the ring-opening of an epoxide with reactants including but not limited to thiols, amines, carboxylic acids, and alcohols. Placement of a separate reactant from the pair on the ⁇ 2 and the hollow particle results in attachment of the two particles post-reaction.
  • polar-covalent bonds useful for attachment of ⁇ 2 to hollow particles include but are not limited to amides, esters, urethanes, ureas, ethers and those bonds resulting from thiol-ene and azide-alkyne reactions.
  • An example of this attachment scheme that proceeds through formation of a non-polar covalent bond would be functionalization with a diene and a dienophile to facilitate a Diels-Alder reaction, forming a cyclic C-C based linker.
  • Hollow particles can be made using several different techniques described in more detail below.
  • a solvent-based silica precursor such as tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS) tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), tetrahexyl orthosilicate, diethoxydimethylsilane, ethoxytrimethylsilane, methoxytrimethylsilane, trimethoxy(octyl)silane, triethoxy(octyl)silane,
  • TEOS tetraethyl orthosilicate
  • TMOS tetramethyl orthosilicate
  • TPOS tetrapropyl orthosilicate
  • TBOS tetrabutyl orthosilicate
  • tetrahexyl orthosilicate diethoxydimethylsilane, ethoxytrimethylsilane, methoxytrimethylsilane, trimethoxy(oc
  • the recyclable template particle is removed by thermal depolymerization, typically by heating at temperatures of about 60°C to about 500°C, or by acid or base hydrolysis.
  • the recyclable template particle or core is prepared using typically an organic monomer which is polymerized to generate template particles.
  • Some monomes for the template include styrene, methyl methacrylate, a- methylstyrene, lactic acid, or formaldehyde, more typically methyl
  • a group of two monomers can be chosen for a copolymerization, such as a variety of diacids and dialcohols for polyester polymers (like polyethylene terephthalate, PET), diacids and diamides for various polyamides (like Nylon 6,6, or other Nylons), etc.
  • the monomers are present in the amount of about 1 to about 60wt%, more typically about 2 to about 50wt%, still more typically about 5 to about 40wt%, based on the total weight of the components used in the preparation of the recyclable template particle.
  • the particle size of the template is tunable, and the particle size distribution of the template particles achieved is narrow, which is advantageous.
  • preparation of the recyclable template particle or core by emulsion polymerization is achieved by
  • Radical initiators such as potassium- or ammonium persulfate, and 2,2-azobis(2- methylpropionamidine) hydrochloride (AIBA) can be used, more typically AIBA.
  • AIBA 2,2-azobis(2- methylpropionamidine) hydrochloride
  • surfactant can also typically be used.
  • suitable surfactants include sodium dodecylsulfate (SDS), cetyltrimethylammonium bromide (CTAB), poly-(vinylpyrrolidinone) PVP, etc.
  • copolymers in order to introduce charge on the surface of the particle, like for example vinyltimethylammonium chloride benzene, 2-(methacryloxy)ethyltrimethylammonium chloride, etc.
  • silica is deposited onto the template surface
  • comonomers that can crosslink two growing polymer chains, thereby strengthening the template particle-some of those materials include
  • the reaction temperature is kept between about 0 and about 100°C, more typically about 15 to about 90°C, still more typically about 25°C to about 70°C.
  • aqueous monomer dispersion we mean water or a mixture of water and surfactant, initiator, defoaming agent, or a suitable buffer in cases where pH needs to be kept in a particular range.
  • the recyclable template particle or core is then coated with a shell material to generate a core/shell particle.
  • a silica treatment or shell at least one solvent-based silica precursor or water-based silica precursor described earlier can be used.
  • the reaction is typically done in a dilute ethanol/water ammonia solution, with or without sonication.
  • the suspension of recyclable template particles in dilute ethanol/water solution of ammonia is treated with the solvent based silica precursor, which results in silica deposition on the recyclable template particles, generating core shell particles.
  • the pH is maintained at about 7 to about 10, more typically about 8 to about 10 to form a silica layer on the recyclable template particle and the reaction times are held between about 1 to about 24 hours, more typically about 1 .5 to about 18 hours, still more typically about 2 to about 12 hours.
  • the solids or core/shell particles are removed from the aqueous solution by centrifugation or filtration, more typically by centrifugation.
  • the recyclable template particle that constitutes the core can be recycled either through thermal depolymerization, or acid- or base hydrolysis.
  • core materials made out of poly-(a-methylstyrene), PMMA, various polyamides, as well as styrene are depolymerized at increased temperatures, with the temperatures of depolymerization varying with the polymer used.
  • Some suitable temperature ranges include about 250 to about 450°C, more typically about 275 to about 400°C, still more typically from 290-325°C, to generate hollow particles as well as core monomer. For example,
  • poly(methylmethacrylate)@silica core/shell particles can be heated above around about 300°C to generate methyl methacrylate monomer and hollow silica particles. Further, poly(a-methylstyrene)@silica can be heated to about above 60°C to generate hollow silica particles and a-methylstyrene monomer.
  • acid- or base-labile core materials can be hydrolyzed instead of thermally depolymerized to generate hollow particles with possibility of monomer recycling.
  • Polymers such as Delrin® (polyacetal), poly(lactic acid), as well as other polyesters can be depolymerized through acid hydrolysis.
  • treating polyacetal@silica with acid should generate hollow silica as well as aldehyde monomer that can be recycled in template particle synthesis.
  • polyesters or polyamides from core/shell particles can be recycled in the same fashion to generate diacid/dialcohol (diacid/diamine) monomer couples as well as hydroxylic or amino acids as monomers (like in the case of polylactic acid, for example).
  • functionalized hollow silica particles are prepared by a process comprising:
  • a core-shell silica particle comprising a template core particle and a silica treatment, more typically a coating, wherein the core-shell silica particle has an outer surface; and wherein the silica treatment is prepared using a solvent-based silica precursor;
  • the template core particle may be removed before or after
  • the core-shell silica particle comprising a template core particle and a silica treatment, typically a coating, is prepared by a process comprising: a) providing a template core particle, more typically prepared using emulsion polymerization;
  • the template particle or core is prepared using typically an organic monomer which is polymerized to generate template particles, or dispersed in water to generate template particles of the appropriate size. Monomers described earlier are also useful in this process.
  • the template particle or core may be inorganic, for example calcium carbonate, or other inorganic particles onto which silica can be deposited.
  • the template particle or core is then coated with a shell material to generate a core/shell particle.
  • a shell material to generate a silica treatment or shell.
  • at least one solvent-based silica precursor or water-based silica precursor described earlier can be used.
  • the suspension of template particles in dilute ethanol/water solution of ammonia is treated with the solvent based silica precursor, which results in silica deposition on the recyclable template particles, generating core shell particles.
  • a water-based silica precursor such as sodium- or potassium silicate
  • the template particles are suspended in water, and the silicate agent is added either dropwise, over a period of time, or all at once.
  • the pH is maintained at about 2 to about 10, more typically about 5 to about 8 to form a silica layer on the recyclable template particle and the reaction times are held between about 1 to about 24 hours, more typically about 1 .5 to about 18 hours, still more typically about 2 to about 12 hours. This results in the deposition of a silica treatment or shell on the recyclable template particle or core.
  • the solids are removed from the aqueous solution by centrifugation or filtration, more typically by centrifugation.
  • silica shells typically, in order to form impervious silica shells, surface area and porosity of the silica walls have to be tuned. Whether the silica shell is adequate can be determined by comparing the surface area of the particles with calculated surface area of a smooth sphere of the same diameter.
  • the shell impervious if its surface doesn't surpass about 130% of the calculated surface area of a smooth sphere of the same dimensions, i.e., it is about 30% or less higher than the surface of the core- shell silica particle prior to functionalization, more typically about 125% of the smooth sphere surface area, and still more typically about 120% of the smooth sphere surface area of the same dimensions.
  • Addition of various amounts of the silica precursor will lead to more or less porous silica layers, which can lead to control of the porosity and surface area of the particles.
  • the silica precursor may be added in stages to modulate the porosity of the particles as well as their surface.
  • calcination at temperatures higher than 500°C can decrease the porosity and surface area of the particles without increasing the thickness of the wall.
  • the core may then be removed before or after grafting of a variety of alkoxysilanes onto the surface of the silica particles to form hollow silica particles having a functionalized surface using techniques described earlier.
  • the functionalized surface on the silica particle may be prepared using sulfonic acid, phosphonic esters, carboxylic acids, amines, epoxides, boronic acids, quaternary amines, etc. Grafting of a variety of alkoxysilanes onto the surface of the hollow silica particles provides functionalized hollow silica particles.
  • a large spectrum of functionalities can be introduced onto the silica surface, for example silyl phosphonates, phosphonic acids, amines, alcohols, epoxides, carboxylic acids, thiols, thioethers, carbamates, isocyanates, quarternary ammonium ions, etc.
  • the grafting process includes mixing the grafting agent with silica particles, with or without the solvent, with optional heating of the material, in the temperature range 25-150°C, more typically 60-130°C, still more typically 80-120°C, with or without the application of vacuum, in order to remove the volatile byproducts, like water or alcohols.
  • the hollow silica particles were
  • silica particles were functionalized with diethoxyphosphoryl)methyl-2- ((triethoxysilyl)ethyl)carbamate, introducing phosphonate functionality on the surface.
  • the silica particles were functionalized with diethyl [2-(triethoxysilyl)ethyl]phosphonate to generate phosphonate-functionalized silica particles.
  • phosphonate ester functionality on the surface of the silica particles was hydrolyzed to generate phosphonic acid-functionalized hollow silica particles.
  • silica particles were treated with (3- glycidopropyl)trimethoxysilane, to generate epoxy functionality on the silica surface.
  • the epoxy silica was then treated, in one embodiment of the disclosure, with glycine, to introduce carboxylic acid functionality through an amine linkage on the particle.
  • the epoxy silica was treated with thioglycolic acid to introduce the carboxylic functionality through a thioether group.
  • nanospheres are prepared by a process comprising:
  • solvent at least one acrylic or styrenic monomer; at least one solvent based silica precursor or a polymerizable silane or combinations thereof or a water based silica precursor; an initiator; and at least one surfactant; (b) shearing the components of the mixture from (a) with high shear energy at an energy density of at least 10 ⁇ 6 J/m A 3 to form a mini- emulsion; and
  • silica/polymeric hybrid hollow nanosphere silica/polymeric hybrid hollow nanosphere.
  • non-reactive solvent we mean that the solvent does not substantially react, more typically does not react, with any of the other components added to the reaction.
  • These nanospheres have a particle size of about 5 nm to about 400 nm, more typically about 50 nm to about 300 nm, and still more typically about 100 nm to about 250 nm.
  • the non-reactive solvent may be an alkane, a hydrocarbon oil, aromatic hydrocarbon or halogenated hydrocarbon liquid, more typically alkane or hydrocarbon oil.
  • the at least one acrylic or styrenic monomer may be methyl methacrylate, methyl acrylate, n-butyl methacrylate, t-butyl methacrylate, t-butyl acrylate, ethyl glycol dimechacrylate, styrene or divinylbenzene; more typically methyl methacrylate or styrene.
  • Suitable initiators include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) or 2,2'-azobis(2-methylpropionamide) dihydrochloride (AIBA); metal persulfate such as potassium persulfate (KPS) or sodium persulfate; more typically AIBN or KPS.
  • AIBN 2,2'-azobisisobutyronitrile
  • AIBA 2,2'-azobis(2-methylpropionamide) dihydrochloride
  • metal persulfate such as potassium persulfate (KPS) or sodium persulfate
  • KPS potassium persulfate
  • sodium persulfate more typically AIBN or KPS.
  • Polymerizable silanes such as allyltriethoxysilane, allyltrimethoxysilane, diethoxy(methyl)vinylsilane, dimethoxymethylvinylsilane, tnethoxyvinylsilane, trimethoxy(7-octen-1 -yl)silane, 3-(trimethoxysilyl)propyl acrylate, 3- (trimethoxysilyl)propyl methacrylate, or vinyltrimethoxysilane are useful in this disclosure, more typically 3-(trimethoxysilyl)propyl acrylate or 3- (trimethoxysilyl)propyl methacrylate. At least one surfactant is part of the mixture in step (a).
  • Some suitable surfactants include cetyltrimethylammonium bromide (CTAB), lauryltrimethylammonium bromide, dodecyltrimethylammonium bromide, octyltrimethylammonium bromide, sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), dioctylsulfosuccinate , nonionic surfactants such as alkylphenol polyoxyethylene, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, octylphenol ethoxylates or poloxamers, more typically SDS, SDBS or CTAB.
  • Some useful commercially available surfactants series include Triton X ® manufactured by The Dow Chemical Company, Brij ® manufactured by Croda International PLC, or Pluoronic ® manufactured by BASF.
  • the mixture in step (a) may be prepared in any glass container or stainless steel reaction vessel.
  • the mixture of the above components is then sheared at an energy density of at least 10 ⁇ 6 J/m A 3, more typically about 10 ⁇ 7 J/m A 3 to about 5 * 10 ⁇ 8 J/m A 3, to form a mini-emulsion.
  • Some useful means for shearing include an ultrasonic disruptor, high speed blender, high pressure
  • homogenizer high shear disperser, membrane homogenizer or colloid mill, more typically an ultrasonic disruptor, high speed blender, or a high pressure homogenizer.
  • shearing occurs for a period of about 5 to about 120 minutes depending on amount of emulsion needed to be prepared and desired emulsion size range, more typically about 30 minutes to about 60 minutes.
  • shearing is accomplished at room temperature.
  • a defoamer may be needed to avoid foaming during emulsifying.
  • Some suitable defoamers include BASF Foamaster®, Dow Corning® 71 and 74 Antifoams.
  • step (i) The mini-emulsion formed in step (b) is then heated to at least about 50°C, more typically about 50°C to about 90°C; and still more typically about 60°C to about 80°C to form, in one step, a silica/polymeric hybrid network comprising a silica/polymeric hybrid hollow nanosphere. Heating may be accomplished using hot plate, heating mantle or any other heating method.
  • the non-reactive solvents and water may then be removed by heating or distillation before or after grafting of a variety of alkoxysilanes onto the surface of the silica particles to form hollow silica particles having a
  • the functionalized surface on the silica/polymer hybrid hollow particle may be prepared using sulfonic acid, phosphonic esters, carboxylic acids, amines, epoxides, boronic acids, quaternary amines, etc. Grafting of a variety of alkoxysilanes onto the surface of the hollow silica particles provides functionalized hollow silica particles.
  • a large spectrum of functionalities can be introduced onto the silica surface, for example silyl phosphonates, phosphonic acids, amines, alcohols, epoxides, carboxylic acids, thiols, thioethers, carbamates, isocyanates, quarternary ammonium ions, etc.
  • the grafting process includes mixing the grafting agent with silica particles, with or without the solvent, with optional heating of the material, in the temperature range 25-150°C, more typically 60-130°C, still more typically 80-120°C, with or without the application of vacuum, in order to remove the volatile
  • the hollow silica particles were functionalized with (diethoxyphosphoryl)methyl-2- ((triethoxysilyl)ethyl)carbamate, introducing phosphonate functionality on the surface.
  • the silica particles were functionalized with diethyl [2-(triethoxysilyl)ethyl]phosphonate to generate phosphonate-functionalized silica particles.
  • phosphonate ester functionality on the surface of the silica particles was hydrolyzed to generate phosphonic acid-functionalized hollow silica particles.
  • silica particles were treated with (3- glycidopropyl)trimethoxysilane, to generate epoxy functionality on the silica surface.
  • the epoxy silica was then treated, in one embodiment of the disclosure, with glycine, to introduce carboxylic acid functionality through an amine linkage on the particle.
  • the epoxy silica was treated with thioglycolic acid to introduce the carboxylic functionality through a thioether group.
  • the functionalized surface on the silica/polymer hybrid hollow particle can be achieved by adding at least one functionalized acrylic or styrenic monomer in step (a).
  • the at least one functionalized acrylic or styrenic monomer may be a monomer having one of the following formulas:
  • R H or Chb
  • X and Y are the functional groups that can be introduced onto the hollow particle surface.
  • boronic acid for example boronic acid, sulfonic acid, silyl phosphonates, phosphonic acids, amines, alcohols, epoxides, carboxylic acids, thiols, thioethers, carbamates, isocyanates, quarternary ammonium ions.
  • Some suitable functionalized acrylic or styrenic monomers are glycidyl methacrylate, phosphoric acid 2-hydroxyethyl methacrylate ester, 4- vinylbenzenephosphonic acid, 4-vinylbenzeneboronic acid, 4-vinylbenzene sulfonic acid and salts or esters.
  • the functional groups can be located in the either inner or outer surface of the hollow spheres.
  • the functionalized acrylic or styrenic monomer is present in the amount of about 0.1 wt% to about 20 wt%, more typically about 1 wt% to about 12 wt%, still more typically about 2 wt% to about 8 wt% based on the total weight of all monomers.
  • the inorganic hollow particle dispersions are prepared by a process comprising
  • silica precursor a) forming an oil-in-water or water-in-oil minemulsion by high energy shearing at least one non-reactive solvent; at least one solvent- or water-based silica precursor, described earlier; and at least one surfactant; at an energy density of at least 10 ⁇ 6 J/m A 3; wherein the concentration of silica precursor is about 2 to about 10 wt%, more typically about 2 to about 7 wt%, still more typically about 2 to about 5 wt%; in the absence of a catalyst or alcohol cosolvent; and wherein the silica precursor to non-reactive solvent ratio is about 0.1 to about 6, more typically about 0.5 to about 3, still more typically about 1 to about 2; oil to water or water to oil ratio is about 0.01 to 0.35, more typically 0.05 to 0.2; and surfactant concentration is about 0.001 wt% to about 5 wt%, more typically 0.1 wt% to about
  • silica precursors b) initiating a one-step sol-gel reaction, or to allow the silica precursors to diffuse to the oil/water interface, where they hydrolyze and condense to form a silica shell resulting in silica hollow particles having a particle size of less than about 400 nm being formed.
  • the one-step sol-gel reaction is initiated at room temperature, more typically about 20°C- to about 90°C.
  • the disclosure relates to a process for preparing an inorganic hollow particle dispersion at a solids concentration of at least 2% solids, more typically about 2 wt% to about 7 wt%, still more typically about 2 wt% to about 5 wt%.
  • These nanospheres have a particle size of less than about 400nm, more typically about 5 nm to about 400 nm, still more typically about 50 nm to about 300 nm, and most typically about 100 nm to about 250 nm.
  • the non-reactive solvent; solvent and water-silica precursors; and surfactants are defined earlier.
  • concentration of silica precursor is about 2 to about 10 wt%, more typically about 2 to about 7 wt%, still more typically about 2 to about 5 wt%,
  • the silica precursor to non-reactive solvent ratio is about 0.1 to about 6, more typically about 0.5 to about 3, still more typically about 1 to about 2; oil to water or water to oil ratio is about 0.01 to 0.35, more typically 0.05 to 0.2; and surfactant concentration is about 0.001 wt% to about 5 wt%, more typically 0.1 wt% to about 2 wt%, based on the total weight of all components. It is important because the combination of silica precursor to non-reactive solvent ratio, oil to water ratio and surfactant level determine the particle size, hollow or non-hollow particle structure, and allow high % solid hollow silica synthesis. The process is carried out in the absence of a catalyst or alcohol cosolvent.
  • the mixture in step (a) may be prepared in any glass container or stainless steel reaction vessel.
  • the mixture of the above components is then sheared at an energy density of at least 10 ⁇ 6 J/m A 3, more typically about 10 ⁇ 7 J/m A 3 to about 5 * 10 ⁇ 8 J/m A 3, to form a mini-emulsion.
  • Some useful means for shearing include an ultrasonic disruptor, high speed blender, high pressure
  • homogenizer high shear disperser, membrane homogenizer or colloid mill, more typically an ultrasonic disruptor, high speed blender, or a high pressure homogenizer.
  • shearing occurs for a period of about 5 to about 120 minutes depending on amount of emulsion needed to be prepared and desired emulsion size range, more typically about 30 minutes to about 60 minutes.
  • shearing is accomplished at room temperature.
  • a defoamer may be needed to avoid foaming during emulsifying.
  • Some suitable defoamers include BASF's Foamaster®, Dow Corning® 71 and 74 Antifoams.
  • a one-step sol-gel reaction is then initiated using the mini-emulsion formed in step (b), by allowing the silica precursors to diffuse to the oil/water interface, where they hydrolyze and condense to form a silica shell resulting in silica hollow particles having a particle size of less than about 400 nm being formed.
  • the one-step sol-gel reaction may be initiated at room temperature, more typically about 20°C to about 90°C, and still more typically about 20°C to about 70°C.
  • Heating may be accomplished using hot plate, heating mantle or any other heating method.
  • the non-reactive solvents and water may then be removed by heating or distillation before or after grafting of a variety of alkoxysilanes onto the surface of the silica particles to form hollow silica particles having a functionalized surface using techniques described earlier.
  • the functionalized surface on the silica particle may be prepared using sulfonic acid, phosphonic esters, carboxylic acids, amines, epoxides, boronic acids, quaternary amines, etc. Grafting of a variety of alkoxysilanes onto the surface of the hollow silica particles provides functionalized hollow silica particles.
  • a large spectrum of functionalities can be introduced onto the silica surface, for example silyl phosphonates, phosphonic acids, amines, alcohols, epoxides, carboxylic acids, thiols, thioethers, carbamates, isocyanates, quarternary ammonium ions, etc.
  • the grafting process includes mixing the grafting agent with silica particles, with or without the solvent, with optional heating of the material, in the temperature range 25-150°C, more typically 60-130°C, still more typically 80- 120°C, with or without the application of vacuum, in order to remove the volatile byproducts, like water or alcohols.
  • the hollow silica particles were functionalized with (diethoxyphosphoryl)methyl-2-((triethoxysilyl)ethyl)carbamate, introducing phosphonate functionality on the surface.
  • the silica particles were functionalized with diethyl [2-(triethoxysilyl)ethyl]phosphonate to generate phosphonate-functionalized silica particles.
  • silica particles were treated with (3- glycidopropyl)trimethoxysilane, to generate epoxy functionality on the silica surface.
  • the epoxy silica was then treated, in one embodiment of the disclosure, with glycine, to introduce carboxylic acid
  • the epoxy silica was treated with thioglycolic acid to introduce the carboxylic functionality through a thioether group.
  • surface functionalized polymeric and polymeric/silica hybrid hollow nanospheres are prepared by a process comprising:
  • the non-reactive solvent may be an alkane, a hydrocarbon oil, aromatic hydrocarbon or halogenated hydrocarbon liquid, more typically alkane or hydrocarbon oil.
  • the at least one acrylic or styrenic monomer may be methyl methacrylate, methyl acrylate, n-butyl methacrylate, t-butyl methacrylate, t- butyl acrylate, ethyl glycol dimechacrylate, styrene or divinylbenzene; more typically methyl methacrylate or styrene.
  • the monomer is present in the amount of about 5 wt% to about 30 wt%, more typically about 5 wt% to about 20 wt%, based on the total weight of all components.
  • the at least one functionalized acrylic or styrenic monomer may be a monomer having one of the following formulas:
  • R H or Chb
  • X and Y are the functional groups that can be introduced onto the hollow particle surface.
  • boronic acid for example boronic acid, sulfonic acid, silyl phosphonates, phosphonic acids, amines, alcohols, epoxides, carboxylic acids, thiols, thioethers, carbamates, isocyanates, quarternary ammonium ions.
  • Some suitable functionalized acrylic or styrenic monomers are glycidyl methacrylate, phosphoric acid 2-hydroxyethyl methacrylate ester, 4- vinylbenzenephosphonic acid, 4-vinylbenzeneboronic acid, 4-vinylbenzene sulfonic acid and salts or esters.
  • the functional groups can be located in the either inner or outer surface of the hollow spheres.
  • the functionalized acrylic or styrenic monomer is present in the amount of about 0.1 wt% to about 20 wt%, more typically about 1 wt% to about 12 wt%, still more typically about 2 wt% to about 8 wt% based on the total weight of all monomers.
  • initiators include azo compounds such as 2,2'- azobisisobutyronitrile (AIBN) or 2,2'-azobis(2-methylpropionamide) dihydrochloride (AIBA); metal persulfate such as potassium persulfate (KPS) or sodium persulfate; more typically AIBN or KPS.
  • AIBN 2,2'- azobisisobutyronitrile
  • AIBA 2,2'-azobis(2-methylpropionamide) dihydrochloride
  • metal persulfate such as potassium persulfate (KPS) or sodium persulfate
  • the initiator is present in the amount of about 0.05 wt% to about 0.5 wt%, more typically about 0.1 wt% to about 0.3 wt%, based on the total weight of all components.
  • Some suitable surfactants include cetyltrimethylammonium bromide (CTAB), lauryltrimethylammonium bromide, dodecyltrimethylammonium bromide, octyltrimethylammonium bromide, sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), dioctylsulfosuccinate , nonionic surfactants such as alkylphenol polyoxyethylene, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, octylphenol ethoxylates, or poloxamers, more typically SDS, SDBS or CTAB.
  • CTCAB cetyltrimethylammonium bromide
  • lauryltrimethylammonium bromide dodecyltrimethylammonium bromide
  • octyltrimethylammonium bromide sodium dodecyl sulfate (
  • Some useful commercially available surfactants series include Triton X ® manufactured by The Dow Chemical Company, Brij ® manufactured by Croda International PLC, or Pluoronic ® manufactured by BASF.
  • the surfactant concentration is about 0.001 wt% to about 5 wt%, more typically about 0.1 wt% to about 2 wt%, based on the total weight of all components.
  • a polymerizable silane may be needed if the polymeric/silica hybrid hollow particles are desired.
  • Some suitable polymerizable silanes are allyltriethoxysilane, allyltrimethoxysilane, diethoxy(methyl)vinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethoxy(7-octen-1 - yl)silane, 3-(trimethoxysilyl)-propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, or vinyltrimethoxysilane, more typically 3-
  • the monomers to non-reactive solvent ratio is about 0.1 to about 6, more typically about 0.5 to about 3, still more typically about 0.5 to about 2; oil to water ratio is about 0.01 to 0.3, more typically 0.05 to 0.2; and surfactant concentration is about 0.001 wt% to about 5 wt%, more typically 0.1 wt% to about 2 wt%, based on the total weight of all components. It is important because the combination of monomers to non-reactive solvent ratio, oil to water ratio and surfactant level determine the particle size, hollow or non- hollow particle structure, and the shell thickness.
  • the mixture in step (a) may be prepared in any glass container or stainless steel reaction vessel.
  • the mixture of the above components is then sheared at an energy density of at least 10 ⁇ 6 J/m A 3, more typically about 10 ⁇ 7 J/m A 3 to about 5 * 10 ⁇ 8 J/m A 3, to form a mini-emulsion.
  • Some useful means for shearing include an ultrasonic disruptor, high speed blender, high pressure
  • homogenizer high shear disperser, membrane homogenizer or colloid mill, more typically an ultrasonic disruptor, high speed blender, or a high pressure homogenizer.
  • shearing occurs for a period of about 5 to about 120 minutes depending on amount of emulsion needed to be prepared and desired emulsion size range, more typically about 30 minutes to about 60 minutes.
  • shearing is accomplished at room temperature.
  • a defoamer may be needed to avoid foaming during emulsifying.
  • Some suitable defoamers include BASF Foamaster®, Dow Corning® 71 and 74 Antifoams.
  • Heating may be accomplished using hot plate, heating mantle or any other heating method.
  • Coating compositions prepared from coating bases comprising
  • the coating base comprises a dispersion of resin, functionalized hollow silica particles of this disclosure and further comprises a colorant.
  • Other additives known to one skilled in the art may also be present.
  • the resin is selected from the group consisting of water-dispersible coating compositions such as latex coating compositions; alkyd coating compositions; urethane coating compositions; and unsaturated polyester coating compositions; and mixture thereof.
  • water-dispersible coatings as used herein is meant surface coatings intended for the decoration or protection of a substrate, comprising essentially an emulsion, latex, or a suspension of a film-forming material dispersed in an aqueous phase, and typically comprising 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.
  • Water-dispersed coatings are exemplified by, but not limited to, pigmented coatings such as latex paints.
  • the film forming material is a latex polymer of acrylic, styrene-acrylic, vinyl-acrylic, ethylene-vinyl acetate, vinyl acetate, alkyd, vinyl chloride, styrene-butadiene, vinyl versatate, vinyl acetate-maleate, 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).
  • Tex-Cote® and Super-Cote®, Rhopelx®, Vinnapas® EF500 are further examples of water based coating compositions comprising 100% acrylic resin.
  • the alkyd resins may be complex branched and cross-linked polyesters having unsaturated aliphatic acid residues.
  • Urethane resins typically comprise the reaction product of a polyisocyanate, usually toluene diisocyanate, and a polyhydric alcohol ester of drying oil acids. The resin is present in the amount of about 5 to about 40 % by weight based on the total weight of the coating composition. The amount of resin is varied depending on the amount of sheen finish desired.
  • the inorganic pigments may be used alone or in combination with conventional colorants. Any conventional colorant such as a pigment, dye or a dispersed dye may be used in this disclosure to impart color to the coating composition.
  • any conventional colorant such as a pigment, dye or a dispersed dye may be used in this disclosure to impart color to the coating composition.
  • about 0.1 % to about 40% by weight of conventional pigments, based on the total weight of the component solids can be added. More typically, about 0.1 % to about 25% by weight of conventional pigments, based on the total weight of component solids, can be added.
  • titanium dioxide is an especially useful powder in the products of this disclosure.
  • Titanium dioxide (TiO 2 ) powder useful in the present disclosure may be in the rutile or anatase crystalline form, more typically in predominantly rutile form, i.e., comprising at least 50% rutile, more typically at least about 75% rutile. It is commonly made by either a chloride process or a sulfate process. In the chloride process, TiCI 4 is oxidized to TiO 2 powders. In the sulfate process, sulfuric acid and ore containing titanium are dissolved, and the resulting solution goes through a series of steps to yield TiO 2 . Both the sulfate and chloride processes are described in greater detail in "The Pigment Handbook", Vol.
  • the powder may be pigmentary, nano or ultrafine particles.
  • Pigmentary refers to median primary particles in the size range typically about 200 nm to about 450 nm
  • nano refers to median primary particles in the size range typically less than 50 nm.
  • Conventional pigments are generally well known pigments and they may be used alone or in mixtures thereof in coating formulations of the disclosure, Suitable pigmnets are disclosed in Pigment Handbook, T. C. Patton, Ed., Wiley-lnterscience, New York, 1973.
  • any of the conventional pigments used in coating compositions can be utilized in these compositions such as the following: metallic oxides, such as titanium dioxide, zinc oxide, and iron oxide, metal hydroxide, metal flakes, such as aluminum flake, chromates, such as lead chromate, sulfides, sulfates, carbonates, carbon black, silica, talc, china clay, phthalocyanine blues and greens, organo reds, organo maroons, pearlescent pigments and other organic pigments and dyes. If desired chromate-free pigments, such as barium metaborate, zinc phosphate, aluminum triphosphate and mixtures thereof, can also be used.
  • metallic oxides such as titanium dioxide, zinc oxide, and iron oxide
  • metal hydroxide such as aluminum flake
  • chromates such as lead chromate, sulfides, sulfates, carbonates, carbon black, silica, talc, china clay, phthalocyanine blues and greens, organo reds, organ
  • additives may be present in the coating compositions of this disclosure as necessary, desirable or conventional.
  • These compositions can further comprise various conventional paint additives, such as dispersing aids, anti-settling aids, wetting aids, thickening agents, extenders, plasticizers, stabilizers, light stabilizers, antifoams, defoamers, catalysts, texture-improving agents and/or antiflocculating agents.
  • Conventional paint additives are well known and are described, for example, in "C-209 Additives for Paints" by George Innes, February 1998, the disclosure of which is incorporated herein by reference.
  • the amounts of such additives are routinely optimized by the ordinary skilled artisan so as to achieve desired properties in the wall paint, such as thickness, texture, handling, and fluidity.
  • Coating compositions of the present disclosure may comprise various rheology modifiers or rheology additives (such as Acrysol®), wetting agents, dispersants and/or co-dispersants, and microbicides and/or fungicides.
  • the present coating compositions may further comprise UV (ultra-violet) absorbers such as Tinuvin®.
  • Coating compositions of the present disclosure may further comprise ceramic or elastomeric substances, which are heat and/or infrared reflective, so as to provide additional heat reflective benefits.
  • the present disclosure provides a process for preparing a coating composition, such as a paint formulation, comprising mixing the pigment- containing components and functional ized hollow silica nanospheres or particles with the resin to form a coating base.
  • a vehicle may be present.
  • the vehicle may be aqueous or solvent based.
  • these coating compositions may comprise from about 30 to about 55% solids by weight and typically about 25% to about 45% solids by volume.
  • the coating compositions of this disclosure have a density of about 9.1 to about 1 1 .9 pounds per gallon, more typically about 9.5 to about 10.8 pounds per gallon.
  • Any mixing means known to one skilled in the art may be used to accomplish this mixing.
  • An example of a mixing device includes a high speed Dispermat®, supplied by BYK-Gardner, Columbia, MD.
  • Coating compositions of the present disclosure may be applied by any means known to one skilled in the art, for example, by brush, roller, commercial grade airless sprayers, or electrostatically in a particle coating.
  • Coating compositions presented herein may be applied as many times necessary so as to achieve sufficient coating on the coated surface, for example, an exterior wall. Typically, these coating compositions may be applied from about 2 mils to about 10 mils wet film thickness, which is equivalent to from about 1 to about 5 dry mils film thickness.
  • Coating compositions presented herein may be applied directly to surfaces or applied after surfaces are first coated with primers as known to one skilled in the art.
  • the coating compositions of this disclosure may be a paint, and the paint may be applied to a surface selected from the group consisting of building material, automobile part, sporting good, tenting fabric, tarpaulin, geo membrane, stadium seating, lawn furniture and roofing material.
  • the coating films may be substantially free of other conventional colorants and contain solely the treated titanium dioxide pigments of this disclosure.
  • Example 1 Polystyrene template particle synthesis
  • Example 2 Hollow silica particle synthesis
  • Example 5 Epoxide-functionalized hollow silica particles, followed by
  • Example 7 Hollow silica synthesis via interfacial miniemulsion method
  • the average particle size of the resulting hollow particles determined by dynamic light scattering is 97 nm with a polydispersity of 0.152.
  • the non- reactive solvents and water was then removed by filtration followed by distillation at 80°C to form ⁇ 25 g of dry hollow silica.
  • Example 8 Grafting the hollow silica with phosphonate ester
  • Solid hollow silica particles (25 g) generated from example 7 were dispersed in 125ml_ dimethyl formamide (DMF). To this suspension was added a diethyl-(2-(triethoxysilyl)ethyl)phosphonate (25 ml_, 77.5 mmol ), and the mixture was heated to 120 °C overnight. The resulting material was centrifuged to remove the DMF solvent, and washed with ethanol.
  • DMF dimethyl formamide
  • Example 9 Synthesis of Hollow Polymer with Boronic Acid Functional Group An oily mixture which contained 5.0 g of hexadecane, 36.8 g of octane, 28.8 g of methyl methacrylate, 3.6 g of ethylene glycol dimethacrylate, 3.6 g of styrene, 1 .8 g of 4-vinylbenzene boronic acid and 0.798 g of AIBN was first prepared, and added to a water solution which contains 420.0 g of water, 0.9 g of CTAB and 0.5 g of defoamer (Foamaster® 1 1 1 , BASF).
  • Miniemulsification was achieved by shearing the mixture for 30 minutes with a high speed blender at 9500 rpm. After forming a stable miniemulsion, the polymerization was started by heating to 70°C for at least 16 hours. The structure of the resulting particles was analyzed using transmission electron microscopy. The average particle size of the resulting hollow particles determined by dynamic light scattering is 146.5 nm with a polydispersity of 0.168.
  • Ti-Pure ® R-706 solution 3 wt% of Ti-Pure ® R-706 solution was mixed with equal amount of 7.5 wt% solution of hollow polymer with boronic acid functional group (from
  • Example 9 with the aid of sonication bath. Centrifugation was then performed to separate the free hollow polymers from the hollow polymer/TiO2 composites.
  • the TEM images ( Figures 2) of the hollow polymer/TiO2 composites showed that there were number of hollow particles surrounding the T1O2 pigment, suggesting a binding between T1O2 and hollow polymers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne une composition de revêtement ayant une opacité améliorée comprenant une particule de dioxyde de titane (TiO2) liée chimiquement à une particule creuse, la taille de la particule creuse ayant un rapport en volume par rapport à la particule de dioxyde de titane compris entre 0,008 et 8. Les compositions de revêtement selon l'invention renferment des particules creuses inorganiques qui sont utiles en tant qu'agents masquants ou opacifiants.
PCT/US2015/017323 2014-03-11 2015-02-24 Compositions de revêtement comprenant des particules de silice creuses ayant une faible porosité Ceased WO2015138117A1 (fr)

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EP3144354A1 (fr) * 2015-09-17 2017-03-22 Rohm And Haas Company Formulation de peinture pigmentée avec un liant de latex fonctionnalisé d'acide phosphoreux et un épaississant associatif
US10745574B2 (en) 2016-10-11 2020-08-18 Behr Process Corporation Hiding by using air voids encapsulated in hollow glass spheres
EP3728489A4 (fr) * 2017-12-19 2021-09-29 Sun Chemical Corporation Encre blanche à forte opacité
CN114539962A (zh) * 2022-02-24 2022-05-27 东来涂料技术（上海）股份有限公司 一种增强不饱和聚酯胶粘剂及其制备方法

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"The Pigment Handbook", vol. 1, 1988, JOHN WILEY & SONS
C. R. MARTENS: "Emulsion and Water-Soluble Paints and Coatings", 1965, REINHOLD PUBLISHING CORPORATION
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3144354A1 (fr) * 2015-09-17 2017-03-22 Rohm And Haas Company Formulation de peinture pigmentée avec un liant de latex fonctionnalisé d'acide phosphoreux et un épaississant associatif
US9745492B2 (en) 2015-09-17 2017-08-29 Rohm And Haas Company Pigmented paint formulation with a phosphorus acid functionalized latex binder and an associative thickener
AU2016222474B2 (en) * 2015-09-17 2021-01-14 Rohm And Haas Company Pigmented paint formulation with a phosphorus acid functionalized latex binder and an associative thickener
US10745574B2 (en) 2016-10-11 2020-08-18 Behr Process Corporation Hiding by using air voids encapsulated in hollow glass spheres
EP3728489A4 (fr) * 2017-12-19 2021-09-29 Sun Chemical Corporation Encre blanche à forte opacité
US11697742B2 (en) 2017-12-19 2023-07-11 Sun Chemical Corporation High opacity white ink
CN114539962A (zh) * 2022-02-24 2022-05-27 东来涂料技术（上海）股份有限公司 一种增强不饱和聚酯胶粘剂及其制备方法

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