Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B63/00—Lakes
• • 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
• • 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
  • C09C1/22—Compounds of iron
  • C09C1/24—Oxides of iron
• • 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
  • C09C1/22—Compounds of iron
  • C09C1/26—Iron blues
• • 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
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
  • D21H19/38—Coatings with pigments characterised by the pigments
  • D21H19/385—Oxides, hydroxides or carbonates
• • 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)
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
  • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
  • D21H19/38—Coatings with pigments characterised by the pigments

Definitions

• Inorganic pigments have been known for centuries, and have found use in enhancing the color of paints, coatings, ceramic and clay articles, molded plastic resins, and the like.
• Inorganic pigment compositions comprising surface-modified nanoparticles are described, along with methods of making such compositions. Such compositions may allow the inorganic pigment to be diluted to a significant extent with non-pigmented extenders, while preserving or enhancing the coloring power of the pigment.
• a method of preparing a nanoparticle-enhanced inorganic pigment composition comprising: providing a plurality of inorganic pigment particles; and, mixing the plurality of inorganic pigment particles with a plurality of surface-modified nanoparticles so that the plurality of surface-modified nanoparticles forms at least a monolayer upon at least a portion of the surface of at least some of the inorganic pigment particles.
• a nanoparticle-enhanced inorganic pigment composition comprising: a plurality of inorganic pigment particles; and, a plurality of surface-modified nanoparticles forming at least a monolayer upon at least a portion of the surface of at least some of the inorganic pigment particles
• inorganic pigment denotes any inorganic particulate material that may be used to impart a significant color or hue to a composition in which the pigment is present.
• pigments are defined herein as those substances that predominately impart a color other than white (e.g., that may impart a yellow, orange, red, green, blue, violet, black, etc. color), and do not include substances that impart a predominately white color (e.g., substances such as zinc oxide, titanium dioxide, barium sulfate, calcium carbonate, and the like).
• inorganic colored pigments A large number of naturally derived and synthetically produced inorganic colored pigments are known, and may be known by their specific chemical name and/or by their colloquial name.
• inorganic pigments include ferric ferrocyanide (commonly known as prussian blue), zinc ferrite, chromium oxide, chromium yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel-titanium yellow, raw umber, raw sienna, chromium orange, molybdenum orange, red iron oxide, cadmium red, red lead, mercury sulfide, cadmium permanent red 4R, cadmium sulfide, cadmium selenide, manganese violet, cobalt blue, cobalt stannate, potassium cobaltinitrite, calcium copper silicate, copper acetoarsenite, copper arsenite, barium copper silicate, lead chromate, lead oxide, chromium green, chromium
• inorganic pigments encompasses certain pigments that contain carbon, e.g. carbon present in cyano groups, as exemplified by ferric ferrocyanide, while excluding organic pigments such as those based on azo compounds and the like. Those of ordinary skill in the art will recognize many other inorganic pigments as also being suitable. Such inorganic pigments may be chosen, for example, from the pigments listed under "Chemical Type" as inorganic, in the PIRI
• compositions disclosed herein may be used to advantage in any pigment of any shade. However, results may be most striking for relatively dark-colored pigments (e.g., blue, purple, and the like).
• nanoparticles signifies particles with an average primary particle size of less than 100 nanometers and in which the primary particles are not present in the form of agglomerates that cannot be straightforwardly de-agglomerated to provide primary particles of the above-listed size.
• Average primary particle size refers to the average diameter obtained from measurements of multiple individual (non- agglomerated) particles. Nanoparticle size measurements can be performed, e.g., by transmission electron microscopy. In the case of nanoparticles that deviate from substantially spherical in shape, those of ordinary skill in the art will recognize the particle size to refer to an effective particle size (of a sphere of the same volume as the actual particle).
• the nanoparticles have an average particle size of less than about 40 nanometers, about 20 nanometers, or about 10 nanometers. In further embodiments, the nanoparticles have an average primary or agglomerate particle size diameter of at least 1, 2 or 3 nanometers.
• nanoparticles as defined herein will be distinguished from materials such as fumed silica, pyrogenic silica, precipitated silica, etc.
• silica materials are known to those of ordinary skill in the art as being comprised of primary particles that are essentially irreversibly bonded together in the form of aggregates which have an average size greater than 100 nm (e.g., typically of at least 200 nanometers) and from which it is not possible to straightforwardly extract individual primary particles.
• the nanoparticles used herein are inorganic nanoparticles.
• the nanoparticles comprise an inorganic material.
• inorganic materials that may be available in nanoparticulate form include for example metal phosphates, sulfonates and carbonates (e.g., calcium carbonate, calcium phosphate, hydroxy-apatite); oxides, e.g. metal oxides (e.g., zirconia, titania, silica, ceria, alumina, iron oxide, vanadia, zinc oxide, antimony oxide, tin oxide, and alumina-silica), and metals (e.g., gold, silver, or other precious metals).
• metal phosphates, sulfonates and carbonates e.g., calcium carbonate, calcium phosphate, hydroxy-apatite
• oxides e.g. metal oxides (e.g., zirconia, titania, silica, ceria, alumina, iron oxide, vanadia, zinc oxide, antimony oxide, tin oxide, and alumina-sili
• Nanoparticles e.g. silica nanoparticles
• nanoparticles may be obtained in the form of a colloidal dispersion.
• colloidal silica dispersions are available from Nalco Co. under the trade designations "NALCO 1040,” “NALCO 1050,” “NALCO 1060,” “NALCO 2326", “NALCO 2327,” and “NALCO 2329”.
• Zirconia nanoparticle dispersions are available from Nalco Chemical Co. under the trade designation “NALCO OOSS008” and from Buhler AG Uzwil, Switzerland under the trade designation “Buhler zirconia Z- WO”.
• Some colloidal dispersions can be dried to provide dry nanoparticles if desired for particular purposes.
• the nanoparticles may be fully condensed.
• Fully condensed nanoparticles typically have a degree of crystallinity (measured as isolated metal oxide particles) greater than 55%, preferably greater than 60%, and more preferably greater than 70%.
• the degree of crystallinity can range up to about 86% or greater.
• the degree of crystallinity can be determined by X-ray diffraction techniques.
• Condensed crystalline (e.g. zirconia) nanoparticles have a high refractive index whereas amorphous nanoparticles typically have a lower refractive index.
• the nanoparticles are surface modified so as to contain at least some organic (e.g., hydrocarbon) groups on their surface.
• a surface modification agent has a first end that will attach to the nanoparticle surface (covalently, ionically or through strong physisorption) and a second (e.g., organic) end that enhances the ability of the nanoparticles to resist agglomerating such as permanently fusing together.
• the inclusion of surface modification can also improve the compatibility of the nanoparticles with other materials.
• an organic end group such as the organic group of an organosilane can improve the compatibility of the nanoparticles with organic matrix material such as polymerizable and thermoplastic resins.
• nanoparticles modified with organic groups can be added to an inorganic pigment such that the nanoparticle-enhanced inorganic pigment displays enhanced pigmenting power, as disclosed herein, even though the surface-modified nanoparticles comprise a generally organic surface rather than an inorganic surface.
• Examples of surface modification (treatment) agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes and titanates.
• the preferred type of treatment agent is determined, in part, by the chemical nature of the (e.g. metal oxide) nanoparticle surface.
• Silanes may be preferred for silica and for other siliceous fillers.
• Silanes and carboxylic acids may be preferred for metal oxides such as zirconia.
• silanes include, but are not limited to, alkyltrialkoxysilanes such as n- octyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane,
• acryloxyalkyltrialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, 3- acryloxypropyltrimethoxysilane, and 3-(methacryloxy)propyltriethoxysilane;
• methacryloxyalkylalkyldialkoxysilanes or acryloxyalkylalkyldialkoxysilanes such as 3- (methacryloxy)propylmethyldimethoxysilane, and 3-
• aryltrialkoxysilanes such as styrylethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and p-tolyltriethoxysilane; vinyl silanes such as
• vinylmethyldiacetoxysilane vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane,
• vinyltriisopropoxysilane vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-t- butoxysilane, vinyltris(isobutoxy)silane, vinyltriisopropenoxysilane, and vinyltris(2- methoxyethoxy)silane; 3-glycidoxypropyltrialkoxysilane such as
• polyether silanes such as N-(3- triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate (PEG3TES), N-(3- triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate (PEG2TES), and
• the surface modification agent is a carboxylic acid and/or anion thereof that can impart a polar character to (e.g., zirconia-containing)
• the surface modification agent may comprise a volatile acid, i.e., monocarboxylic acids having six or less carbon atoms, such as acrylic acid, methacrylic acid, acetic acid, and mixtures thereof.
• a volatile acid i.e., monocarboxylic acids having six or less carbon atoms, such as acrylic acid, methacrylic acid, acetic acid, and mixtures thereof.
• acetic acid is non-reactive with the organic component; whereas acrylic acid and methacrylic acid are reactive volatile resins since the (meth)acrylate groups of these acids can copolymerize with the (meth)acrylate groups of the monomers of the organic components.
• the surface modification agent can be a carboxylic acid and/or anion thereof having a polyalkylene oxide group.
• the carboxylic acid surface modification agent is of the following formula. H 3 C-[0-(CH 2 ) y ] x -Q-COOH
• Q is a divalent organic linking group
• x is an integer in the range of 1 to 10
• y is an integer in the range of 1 to 4.
• the group Q is often an alkylene group, alkenylene group, arylene, oxy, thio, carbonyloxy, carbonylimino, or a combination thereof.
• Representative examples of this formula include, but are not limited to, 2-[2-(2- methoxyethoxy)ethoxy]acetic acid (MEEAA) and 2-(2-methoxyethoxy)acetic acid (MEAA).
• reaction product of an aliphatic or aromatic anhydride and a polyalkylene oxide mono-ether such as succinic acid mono-[2- (2-methoxy-ethoxy)-ethyl] ester, maleic acid mono-[2-(2-methoxy-ethoxy)-ethyl] ester, and glutaric acid mono-[2-(2-methoxy-ethoxy)-ethyl] ester.
• Still other carboxylic acid surface modifying agents are the reaction product of phthalic anhydride with an organic compound having a hydroxyl group.
• Suitable examples include, for example, phthalic acid mono-(2-phenylsulfanyl-ethyl) ester, phthalic acid mono-(2-phenoxy-ethyl) ester, or phthalic acid mono-[2-(2-methoxy- ethoxy)-ethyl] ester.
• the organic compound having a hydroxyl group is a hydroxyl alkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or hydroxylbutyl (meth)acrylate.
• Examples include, but are not limited to, succinic acid mono-(2-acryloyloxy-ethyl) ester, maleic acid mono-(2-acryloyloxy- ethyl) ester, glutaric acid mono-(2-acryloyloxy-ethyl) ester, phthalic acid mono-(2- acryloyloxy-ethyl) ester, and phthalic acid mono-(2-acryloyl-butyl) ester. Still others include mono-(meth)acryloxy polyethylene glycol succinate and the analogous materials made from maleic anhydride glutaric anhydride, and phthalic anhydride.
• the surface modification agent is the reaction product of polycaprolactone and succinic anhydride.
• the surface modification agent contains one or more linking groups (by way of which the agent can be covalently coupled to the surface of a nanoparticle) and one or more hydrocarbon groups (e.g., alkyl, phenyl, etc.). Such groups can impart a generally nonpolar organic character to the nanoparticles. Examples of such surface modification agents include e.g. isooctyltrimethoxy silane and methyltrimethoxy silane. Various other surface treatments are known in the art, such as described in WO2007/019229; incorporated herein by reference.
• the nanoparticles are typically combined with the surface modification agent, e.g., in a liquid that may act e.g. to disperse or suspend the nanoparticles and/or to disperse, suspend or dissolve the surface modification agent.
• the amount of surface modifier to be used may depend upon several factors such as nanoparticle size, nanoparticle type, molecular weight of the surface modifier, and modifier type. In general, it may be preferred that approximately a monolayer of modifier is attached to the surface of the nanoparticle. The attachment procedure or reaction condition may also depend on the surface modifier used. For silanes it is preferred to surface treat at elevated temperatures under acidic or basic conditions for about 1 -24 hours. Surface treatment agents such as carboxylic acids may not require elevated temperatures or extended time.
• the surface modification of nanoparticles e.g. in a colloidal dispersion can be accomplished in a variety of ways.
• the process may involves the mixing of an inorganic dispersion with one or more surface modifying agents.
• a co-solvent can be added, such as for example, l-methoxy-2-propanol, methanol, ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide, l-methyl-2-pyrrolidinone, and mixtures thereof.
• the co-solvent can enhance the solubility of the surface modifying agents as well as the dispersibility of the surface modified nanoparticles.
• the mixture comprising the colloidal dispersion and surface modifying agents may be subsequently reacted at room or an elevated temperature, with or without mixing.
• surface-modified nanoparticles resulting from the above-described surface modification may be provided as dry particles, or as a suspension or dispersion in a liquid. In whatever form obtained, they may be combined with inorganic pigments to form a nanoparticle-enhanced inorganic pigment composition as disclosed herein.
• the surface-modified nanoparticles may be combined with the inorganic pigment particles by wet blending. In this method, the surface-modified nanoparticles and the inorganic pigment particles may be combined in a liquid or liquid mixture.
• Typical liquids that may be employed include, for example, toluene,
• the liquid containing the surface- modified nanoparticles and inorganic pigment particles may be stirred, agitated, etc. with apparatus familiar to those of ordinary skill in the art. If desired, after the combination is complete the liquid may be removed (e.g. by filtration, evaporation, freeze-drying, etc.) to provide the nanoparticle-enhanced inorganic pigment composition in dry form. Or, particularly if the liquid is compatible with a particular vehicle into which it is desired to include the nanoparticle-enhanced inorganic pigment composition, the liquid may remain rather than being removed.
• the surface-modified nanoparticles may be present at less than 4 wt.%, less than 2 wt. %, or less than 1 wt. %, relative to the inorganic pigment particles. In additional embodiments, the surface-modified nanoparticles may be present at least at 0.2 wt.%, at least at 0.4 wt. %, or at least at 0.6 wt. %, relative to the inorganic pigment particles.
• the inorganic pigment particles may be provided with surface-modified nanoparticles in proximity to, and/or associated with, the outer surface of the inorganic pigment particle.
• the surface-modified nanoparticles are distributed so as to form at least a surface monolayer upon at least a portion of the surface of at least some of the inorganic pigment nanoparticles.
• the surface-modified nanoparticles may be bonded (e.g., covalently bonded) to the pigment particles. In other embodiments, the surface-modified nanoparticles may not be covalently bonded to the pigment particles.
• the nanoparticle-enhanced inorganic pigment compositions may provide advantageous color-imparting properties in comparison to the inorganic pigment without surface-modified nanoparticles.
• surface-modified nanoparticles may assist in more effectively causing agglomerates of pigment particles to be de-agglomerated into nonagglomerated pigment particles, may assist in more effectively dispersing pigment particles amongst extender particles, and/or may assist in more effectively dispersing pigment particles within an organic vehicle. Such effects may be visible upon inspection of the
• Such effects may also, or instead, be visible upon combining the nanoparticle-enhanced inorganic pigment composition with an extender, as demonstrated in Tables 1 , 2 and 3.
• Such effects may allow the achieving of similar color properties even at a much lower amount of pigment relative to extender, e.g. as may be seen in comparing Example 2-3 to Example 2-1 in Table 2.
• Such effects may allow the achieving of e.g. richer color properties at a given amount of pigment relative to extender, e.g. as may be seen in comparing Example 2-2 to Example 2-1 in Table 2.
• Such effects may also, or instead, be visible upon including the nanoparticle-enhanced inorganic pigment composition into a vehicle (e.g., paint, and the like), as demonstrated in Example 5.
• a vehicle e.g., paint, and the like
• surface-modified nanoparticles may provide the above-described enhancements in the color-imparting properties of inorganic pigments even though the surface-modified nanoparticles may comprise generally organic surface groups.
• Nanoparticle-enhanced pigment compositions as disclosed herein may be particularly advantageously used in combination with extenders.
• extender is used to denote any inorganic particulate additive that does not impart a significant (non-white) color or hue.
• extender is used to denote any inorganic particulate additive that does not impart a significant (non-white) color or hue.
• Suitable extenders may include e.g. any of the well-known inorganic fillers such as silicates and/or aluminosilicates (e.g., talc, clay, mica, and sericite), calcium carbonate, nepheline (available, for example, under the trade designation "MINEX” from Unimin Corp, New Canaan, CT), feldspar, wollastonite, kaolinite and the like.
• Suitable extenders may further include e.g. titanium dioxide, barium sulfate, zinc oxide, calcium carbonate, dicalcium phosphate, diatomaceous earth, and the like.
• Suitable extenders may further include e.g. glass bubbles and/or ceramic microparticles (e.g., beads, microspheres and the like).
• ceramics include aluminates, titanates, zirconates, silicates, doped (e.g., lanthanides, and actinide).
• Ceramic microparticles can be made using techniques known in the art and/or are commercially available. Examples of commercially available glass bubbles include those marketed by 3M Company, St. Paul, Minnesota, under the designation "3M
• SCOTCHLITE GLASS BUBBLES e.g., grades Kl, K15, S15, S22, K20, K25, S32, K37, S38, K46, S60/10000, S60HS, Al 6/500, A20/1000, A20/1000, A20/1000, H50/10000 EPX, and H50/10000 (acid washed)); glass bubbles marketed by Potter Industries, Valley Forge, Pennsylvania, under the trade designation
• SPHERICEL e.g., grades 110P8 and 60P18
• LXSIL LUXSIL
• Q-CEL hollow glass microspheres marketed under the trade designation "DICAPERL” by Grefco Minerals, Bala Cynwyd, Pennsylvania, (e.g., grades HP-820, HP-720, HP-520, HP-220, HP-120, HP-900, HP-920, CS-10-400, CS-10-200, CS-10-125, CSM-10-300, and CSM-10-150); and hollow glass particles marketed by Silbrico Corp., Hodgkins, Dlinois, under the trade designation "SIL-CELL” (e.g., grades SIL 35/34, SIL-32, SIL-42, and SIL-43).
• SIL-CELL e.g., grades SIL 35/34, SIL-32, SIL-42, and SIL-43
• Ceramic microspheres include ceramic hollow microspheres marketed by SphereOne, Inc., Silver Plume, Colorado, under the trade designation, "EXTENDOSPHERES” (e.g., grades SG, CG, TG, SF-10, SF-12, SF-14, SLG, SL-90, SL-150, and XOL-200); and ceramic microspheres marketed by 3M Company under the trade designation "3M CERAMIC MICROSPHERES” (e.g., grades G-200, G-400, G-
• the nanoparticle-enhanced inorganic pigment composition may be added directly to a vehicle, e.g. a vehicle containing one or more extenders, as described below.
• one or more extenders may be combined with the nanoparticle-enhanced inorganic pigment composition to provide an admixture that may be then added to a vehicle.
• the nanoparticle- enhanced inorganic pigment composition may be combined with one or more extenders, at a weight ratio of extender to nanoparticle-enhanced inorganic pigment composition of at least 2:1, at least 4: 1, or at least 8: 1.
• the extender is present at a weight ratio to the nanoparticle-enhanced inorganic pigment composition of at most 20:1, at most 15:1 , or at most 12:1.
• An admixture thus diluted with extender may exhibit the advantageous properties described previously herein; e.g., an admixture e.g.
• inorganic pigment containing only about 10% by weight inorganic pigment, but with the inorganic pigment being enhanced by the presence of surface-modified nanoparticles, may display similar visually perceived color characteristics to the undiluted inorganic pigment in the absence of the enhancing nanoparticles.
• Nanoparticle-enhanced inorganic pigment compositions as disclosed herein may be used to advantage in any vehicle (by which is generically meant any carrier, resin, material, matrix, syrup, varnish, paint, shellac, coating, adhesive, binder, etc.) into which the pigment may be included to provide a significant color.
• the nanoparticle-enhanced inorganic pigment composition may be added to a vehicle that already comprises extender (e.g., added to an existing paint).
• the nanoparticle-enhanced inorganic pigment composition may be mixed with extender to form a nanoparticle-enhanced inorganic pigment/extender admixture as described above, then added to a vehicle.
• Vehicles as disclosed herein may be applied to the surface of an item (e.g., as a paint or varnish), may be directly formed into shapes (e.g., molded, formed into particles (e.g., roofing granules)), and so on.
• an item e.g., as a paint or varnish
• shapes e.g., molded, formed into particles (e.g., roofing granules)
• Silica nanoparticles (16.6% solids in water) were obtained from Nalco Company, Naperville, Illinois under the trade designation NALCO 2326. These nanoparticles were reported by the supplier as having an average particle size of approximately 5 nm and were not reported by the supplier to be surface modified. Silica nanoparticles (41.45% solids in water) were obtained from Nalco Company under the trade designation
• NALCO 2327 These nanoparticles were reported by the supplier as having an average particle size of approximately 20 nm.
• Fumed silica was obtained under the trade designation Cab-O-Sil CT-1221 from Cabot Corporation, Billerica, MA.
• Iron oxide (red) inorganic pigment was obtained from Brenntag Specialties, South Plainfield, NJ, under the trade designation WCD Red.
• Ferric ferrocyanide (blue) inorganic pigment was obtained from Brenntag Specialties under the trade designation
• Iron oxide (red) inorganic pigment was also obtained from the 3M Industrial Minerals Products Division, St. Paul, MN, and is believed to be similar to, or equivalent to, WCD Red.
• Organic pigment was obtained from Sun Chemical, Cincinnati, OH, under the trade designation Indofast Violet 23.
• CM-1 1 1 Cosmetic Microspheres Semi-transparent, white spherical ceramic particles (extender) were obtained from 3M Company under the trade designation CM-1 1 1 Cosmetic Microspheres. The product is listed by the manufacturer as having a 50* percentile particle size of approximately 5 microns.
• NALCO 2326 silica nanoparticles were surface-modified with a mixture of isooctyltrimethoxy silane and methyltrimethoxy silane, according to the procedures outlined in U.S. Patent Application Serial Number 61/220698, entitled "Method of Milling Particles with Nanoparticles and Milled Free-flowing Powder.
• NALCO 2327 silica nanoparticles were likewise surface modified according to the procedures outlined in U.S. 61/220698.
• Nanoparticles were wet blended with inorganic pigments by combining the desired amounts of dried, surface modified nanoparticles and pigments with toluene and mixing overnight either with agitation by a magnetic stir bar or by rolling in a jar. Certain samples were wet blended in an isopropanol/water mixture rather than in toluene, as noted. The mixtures were then dried in an aluminum pan and were exposed to 120°C to ensure that the liquid was substantially removed. In various experiments, different weight ratios of nanoparticles to inorganic pigment particles were used, and are reported in the tables below as wt. % nanoparticles. Other materials (e.g., nanoparticles without surface modification, and fumed silica) were wet blended with the inorganic pigment in similar manner.
• the visually perceived color and appearance of the dried, inorganic pigment with surface-modified nanoparticles were recorded.
• the dried, inorganic pigment with surface-modified nanoparticles was mixed with CM-1 1 1 extender, using a mixing device available from FlackTek, Landrum, SC, under the trade designation SpeedMixer DAC 150 FVZ.
• CM-111 a weight ratio of 10% inorganic pigment with surface-modified nanoparticles, to 90% CM-111 was used; in other cases, a weight ratio of 7.5% inorganic pigment with surface-modified nanoparticles, to 92.5% CM-1 1 1 was used, and in some cases a weight ratio of 1.0% inorganic pigment with surface-modified nanoparticles, to 99% CM-111 was used.
• Optical color properties of the samples were also measured by use of a Hunter Lab D25A Optical Sensor (Hunter Associates, Reston, VA). These measurements provided an L* value (of the well-known L*a*b* scale) which is known to those of ordinary skill in the art as a measure of the lightness or darkness of a sample on a scale of 1-100 (where a value of 1 is black and a value of 100 is white).
• Table 1 are presented data for Iron Oxide Red pigment (WCD Red) with and without 5 nm surface-modified nanoparticles, extended with CM-111 at a ratio of 10% pigment to 90% CM-111, by weight.
• NALCO 2326 silica nanoparticles were surface-modified with a mixture of isooctyltrimethoxy silane and methyltrimethoxy silane as outlined above.
• the surface- modified nanoparticles were wet-blended with Ferric Ferrocyanide Blue pigment as outlined above, to provide 0.5 wt % surface-modified nanoparticles relative to the inorganic pigment.
• a paintbrush was then used to smear a small amount of each paint sample onto a glass slide.
• the painted samples were then allowed to dry. Visual inspection revealed that the paint sample with the nanoparticle-enhanced inorganic pigment composition displayed a noticeably more pronounced and more uniform blue color than the sample without nanoparticles.
• NALCO 2326 silica nanoparticles were surface-modified with a mixture of isooctyltrimethoxy silane and methyltrimethoxy silane as outlined above.
• the surface- modified nanoparticles were wet-blended with an organic pigment (available under the trade designation Indofast Violet 23 from Sun Chemical, Cincinnati, OH), in similar manner as outlined above, to provide 0.5 wt % surface-modified nanoparticles relative to the organic pigment.
• the organic pigment with surface-modified nanoparticles was mixed with CM-111 extender in similar manner as oudined above, using a mixing device available from FlackTek, Landrum, SC, under the trade designation SpeedMixer DAC 150 FVZ, at a weight ratio of 10% organic pigment with surface-modified nanoparticles, to 90% CM-111.
• the 90/10 mixture of CM-111 extender / organic pigment with surface- modified nanoparticles exhibited an L* value of 38.3.
• a 90/10 mixture of CM-111 extender / organic pigment without surface-modified nanoparticles exhibited an L* value of 23.0.
• the 90/10 extender-mixed sample with surface-modified nanoparticles appeared lighter in color with dark specs.

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