A cleaning wipe comprising a water insoluable substrate, wherein the substrate is a nonwoven fabric which is impregnated with a cleaning composition.

The present invention relates to a disposable single use dish cleaning wipe which is substantially dry to the touch. The product comprises of an insoluable single or multilayer substrate which has been impregnated with a cleaning composition. Use of the substrate enhances foaming, cleaning and grease removal for cleaning dishware, flatware, pots and pans.
The patent literature describes numerous wipes for both body cleaning and cleaning of hard surfaces but none describe wipes for cleaning dishware, flatware, pots and pans. U.S. Pat. Nos. 5,980,931, 6,063,397 and 6,074,655 teach a substantially dry disposable personal cleansing product useful for both cleansing and conditioning the skin and hair. U.S. Pat. No. 6,060,149 teaches a disposable wiping article having a substrate comprising multiple layers.
U.S. Pat. Nos. 5,756,612; 5,763,332; 5,908,707; 5,914,177; 5,980,922 and 6,168,852 teach cleaning compositions which are inverse emulsions.
U.S. Pat. Nos. 6,183,315 and 6,183,763 teach cleaning compositions containing a proton donating agent and having an acidic pH. U.S. Pat. Nos. 5,863,663; 5,952,043; 6,063,746 and 6,121,165 teaches cleaning compositions which are oil in water emulsions.
A substantially dry single use cleaning wipe for dishwashing application comprises a water insoluable substrate, impregnated with a cleaning composition containing an anionic sulfonate surfactant, a sulfate surfactant, a polyethylene glycol and at least one nonionic surfactant, wherein the liquid cleaning composition does not contain more than 10 wt. %, more preferably 7.0 wt. % of water and the composition is not an emulsion and does not contain proteins, enzymes, amides, sodium hypochlorite, dimethicone, a proton donating agent, N-methyl-2-pyrrolidone, monoalkyl phosphate or silicone based sulfosuccinate.
The present invention also relates to the method of manufacturing a disposable, single use cleaning wipe for cleaning dishware, flatware, pots and pans.
The present invention furthermore relates to the method for cleaning dishware, flatware, pots and pans with the cleaning wipe product described herein.
The present invention relates to a cleaning wipe for cleaning dishware, flatware, pots and pans which comprises approximately:
(a) 20 wt. % to 95 wt. % of a water insoluable substrate; and
(b) 5 wt. % to 80 wt. % of a cleaning composition being impregnated in said water insoluable substrate, wherein said cleaning composition comprises:
(i) 20 to 60 wt. % of at least one alkali metal salt of an anionic sulfonate surfactant;
(ii) 0 to 8 wt. %, more preferably 0.5 wt. % to 6 wt. % of an alkali metal salt of an anionic sulfate or an ethoxylated alkyl ether sulfonate surfactant;
(iii) 0 to 6 wt. %, more preferably 0.1 wt. % to 4 wt. % of a proton donating agent;
(iv) 0 to 3 wt. %, more preferably 0.25 wt. % to 2.5 wt. % of a C1-C4 alkanol such as ethanol;
(v) 30 wt. % to 65 wt. % of at least one nonionic surfactant; and
(vi) 1 wt. % to 10 wt. % of a polyethylene glycol, wherein the composition contains less than 10 wt. %, more preferably less than 7 wt. % of water has a pH of about 6.0 to about 7.5, at a concentration of about 10 grams of the composition in 100 ml. of water.
Suitable water-soluble non-soap, anionic surfactants used in the instant compositions include those surface-active or detergent compounds which contain an organic hydrophobic group containing generally 8 to 26 carbon atoms and preferably 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate and carboxylate so as to form a water-soluble detergent. Usually, the hydrophobic group will include or comprise a C8-C22 alkyl, alkyl or acyl group. Such surfactants are employed in the form of water-soluble salts and the salt-forming cation usually is selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or tri-C2-C3 alkanolammonium, with the sodium, magnesium and ammonium cations again being preferred.
Examples of suitable sulfonated anionic surfactants are the well known higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, C8-C15 alkyl toluene sulfonates and C8-C15 alkyl phenol sulfonates.
A preferred sulfonate is linear alkyl benzene sulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low.
Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents may be prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCHxe2x95x90CHR1 where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonating an xcex1-olefin.
Other examples of suitable anionic sulfonate surfactants are the paraffin sulfonates containing 10 to 20, preferably 13 to 17, carbon atoms. Primary paraffin sulfonates are made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Pat. Nos. 2,503,280; 2,507,088; 3,260,744; 3,372,188; and German Patent 735,096.
Examples of satisfactory anionic sulfate surfactants are the C8-C18 alkyl sulfate salts and the ethoxylated C8-C18 alkyl ether sulfate salts having the formula R(OC2H4)n OSO3M wherein n is 1 to 12, preferably 1 to 5, and M is a metal cation selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- and triethanol ammonium ions. The alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product.
On the other hand, the ethoxylated alkyl ether sulfates are obtained by sulfating the condensation product of ethylene oxide with a C8xe2x80x94C8 alkanol and neutralizing the resultant product. The alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product. The ethoxylated alkyl ether sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol. Preferred alkyl sulfates and preferred ethoxylated alkyl ether sulfates contain 10 to 16 carbon atoms in the alkyl group.
The ethoxylated C8-C12 alkylphenyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule also are suitable for use in the inventive compositions. These surfactants can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.
Other suitable anionic surfactants are the C9-C15 alkyl ether polyethenoxyl carboxylates having the structural formula R(OC2H4)nOX COOH wherein n is a number from 4 to 12, preferably 5 to 10 and X is selected from the group consisting of
CH2, (C(O)R1 and
wherein R1 is a C1-C3 alkylene group. Preferred compounds include C9-C11 alkyl ether polyethenoxy (7-9) C(O) CH2CH2COOH, C13-C15 alkyl ether polyethenoxy (7-9)
and C10-C12 alkyl ether polyethenoxy (5-7) CH2COOH. These compounds may be prepared by condensing ethylene oxide with appropriate alkanol and reacting this reaction product with chloracetic acid to make the ether carboxylic acids as shown in U.S. Pat. No. 3,741,911 or with succinic anhydride or phthalic anhydride. Obviously, these anionic surfactants will be present either in acid form or salt form depending upon the pH of the final composition, with salt forming cation being the same as for the other anionic surfactants.
The water soluble nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols, such a Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI). The nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water-soluble nonionic detergent. Further, the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
The nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
Preferred nonionic surfactants are the Neodol ethoxylates (Shell Co.) or Biosoft ethoxylates (Stephan) such as Biosoft 690 or Biosoft N23-6.5. These are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C9-C11 alkanol condensed with 7 to 10 moles of ethylene oxide (Neodol 91-8), C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like. Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
Other suitable nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from about 8 to 18 carbon atoms in a straight- or branched chain alkyl group with about 5 to 30 moles of ethylene oxide. Specific examples of alkyl phenol ethoxylates include nonyl condensed with about 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with about 12 moles of EO per mole of phenol, dinonyl phenol condensed with about 15 moles of EO per mole of phenol and di-isoctylphenol condensed with about 15 moles of EO per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic detergent ingredient in the described shampoo. These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
The polyethylene glycol is depicted by the formula:
HOxe2x80x94(CH2xe2x80x94CH2O)2xe2x80x94H
wherein n is about 8 to about 225, more preferably about 10 to about 100,000, wherein one preferred polyethylene glycerol is PEG1000 which is a polyethylene glycol having a molecular weight of about 1000.
Polyethylene glycol which is used in the instant composition has a molecular weight of 200 to 1,000 wherein the polyethylene glycol has the structure
HO(CH2CH2O)nH
wherein n is 4 to 52. The concentration of the polyethylene glycol in the instant composition is 0.1% to 7 wt. %, more preferably 0.1 wt. % to 5 wt. %.
The proton donating agent is selected from the group consisting of inorganic acids such as sulfuric acid and hydrochloric acid and hydroxy containing organic acid, preferably a hydroxy aliphatic acid, which are selected from the group consisting of lactic acid or citric acid, orthohydroxy benzoic acid or citric acid or glycolic and mixtures thereof.
The composition also preferably contains about 0.01 to about 1.5 wt. % of a perfume, more preferably about 0.1 to about 1.0 wt. %.
As used herein and in the appended claims the term xe2x80x9cperfumexe2x80x9d is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances. Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
In the present invention the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.
The cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Antibacterial agents such as 2,4,4xe2x80x2-trichloro-2xe2x80x2hydroxydiphenyl ether colors or dyes in amounts up to 0.5% by weight; preservatives or antioxidizing agents, such as formalin, 5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed.
The product of the present invention comprises a water insoluable substrate with one or more layers. Each layer may have different textures and abrasiveness. Differing textures can result from the use of different combinations of materials or from the use of different manufacturing processes or a combination thereof. A dual texture substrate can be made to provide the advantage of a more abrasive side for cleaning difficult to remove soils. A softer side can be used for fine dishware and flatware. The substrate should not dissolve or break apart in water. It is the vehicle for delivering the cleaning composition to dishware, flatware, pots and pans. Use of the substrate enhances lathering, cleaning and grease removal.
A wide variety of materials can be used as the substrate. It should have sufficient wet strength, abrasivity, loft and porosity. Examples include, non woven substrates, wovens substrates, hydroentangled substrates and sponges.
Examples of suitable non woven water insoluable substrates include, 100% cellulose Wadding Grade 1804 from Little Rapids Corporation, 100% polypropylene needlepunch material NB 701-2.8-W/R from American Non-wovens Corporation, a blend of cellulosic and synthetic fibres-Hydraspun 8579 from Ahlstrom Fibre Composites, and and0% Viscose/30% PES Code 9881 from PGI Nonwovens Polymer Corp.
The product of the present invention comprising mutliple layers may be ultrasonically bonded after applying the coating of one or more of the layers. Alternatively layers may be bonded together by needlepunch, thermal bonding, chemical bonding, or sonic bonding prior to applying the coating.
The cleaning compositions are prepared by mixing at 50xc2x0 C. to 65xc2x0 C. The cleaning composition is impregnated onto the substrate by spraying, dipping, extrusion coating or slot coating. It can be impregnated into the wipe in an even coating across the surface of the wipe, or in a random or definite pattern, such as stripes.
The product of the present invention is substantially dry and is intended to be wetted with water prior to use. The product is wetted by immersing in water or placing under a stream of water. Foam is generated from the product by mechanical action prior to or during contact with dishware, flatware, or pots and pans. Use of the product provides enhanced soil and grease removal.
The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.


Paint compositions and coatings having improved overall visual appearance, richness or depth of color and aesthetic properties such as for spraying-painting automobiles, boats, aircraft and home appliances. The present paint compositions are high solids content, heat-curable, transparent or translucent compositions containing embedded light-refractive colorless and/or tinted transparent glass beads preferably between about 10 to 20 microns diameter, and one or more color-enhancing agents such as pigments, dyes, aluminum flakes, mica, opaque glass beads, holographic flakes, and similar conventional light-enhancing agents. The present bead-containing refractive paint compositions may be based upon volatile organic solvents, water or may be solvent-free powder compositions, but in all cases the resinous binder material is cross-linkable at the baking temperature of the paint, or upon exposure to ultraviolet radiation, to cure as a hard, translucent, chip-resistant paint.

1. Field of the Invention
The present invention relates to the addition of microbeads to enhance the light emission, refraction or diffusion properties of heat-cured paint coatings. The invention relates to improved heat-curable paint compositions containing microbeads for producing painting surfaces, such as automobile bodies, having enhanced light-emission, light-refraction or light-diffusion properties, such as enhanced reflection, coloration, luminescence, phosphorescence and scattered light reflectability properties.
2. Description of Related Art
Microbeads and microspheres of glass, plastics and other materials, including those coated with conductive and reflective surface layers, are commercially-available for a variety of purposes, including use as light reflective fillers in paint and related coating compositions.
Reference is made to U.S. Pat. No. 5,650,213 for its disclosure of retroreflective coating compositions, such as for screen printing onto fabrics, containing hemispherical metallized microsphere beads of 20 to 200 micron size, and transparent pigment particles of less than 2 micron size, having a color corresponding to the color of the substrate or desired image, to provide an attractive daytime image and daytime unnoticability. The coatings contain an aqueous matrix or binder material and have a final thickness of matrix which is less than one-half the diameter of the reflective beads.
It is known to add light-reflective glass beads, including hemispherically-metallized glass beads to opaque paint compositions such as for highway signs in order to provide dried paint surfaces, at or above which the beads are exposed. Light directed thereat, such as from automobile headlights, is retroreflected or reflected directly back at the source by the metallic bead coating or by brightly-colored pigments or an aluminum flake layer underlying the beads, which function as transverse lenses.
Reference is made to U.S. Pat. Nos. 2,879,171; 2,963,378; 2,997,403 and 3,251,704 for their disclosures of opaque, low solids paint compositions containing film-forming binder materials which dry by solvent evaporation, glass beads and opaque pigments. In U.S. Pat. No. 2,879,171 the coating particles exceed 50 to 2,500 micron size and the coating physically retains the 3 to 10 mil (75 to 250 microns) glass beads exposed at the outer surface of the dried paint to act as light reflectors. In U.S. Pat. No. 2,963,378 the low solids paint composition contains a major amount by weight of volatile organic solvents, 35 weight percent of reflectorized glass beads of 10 to 500 micron diameter and solvent-drying, film-forming binder materials to provide reflex-reflecting, non-diffusing coatings. The reflectorized glass beads may be mixtures of glasses having different refractive indexes, and their surfaces may be coated with transparent pigment or dye to retro-reflect in color. The coatings have glass bead protrusions and are covered with a top coating of transparent varnish, which may be colored, to provide a flat glossy surface.
U.S. Pat. No. 2,997,403 also discloses solvent lacquer spray compositions containing 25 to 40% by volume of glass beads of 0.0017 to 0.0024xe2x80x3 (42.5 to 60 xcexc) diameter for application over painted surfaces to provide retroreflective surface coatings.
U.S. Pat. No. 3,251,704 discloses low solids spray paint compositions containing hemispherically-metallized glass beads of different refractive indexes and sized between about 15 and 75 microns, and opaque pigment particles which do not interfere with the required reflex-reflection properties. The dried composition contains exposed glass beads as reflex-reflective lens elements.
The present invention is based upon the discovery that the overall visual appearance, richness or depth of color and aesthetic properties of paint compositions, such as for spray-painting automobiles, boats, aircraft and home appliances, are substantially improved by formulating such paint compositions as high solids content, heat-curable, transparent or translucent compositions containing embedded or encapsulated light-refractive colorless and/or tinted transparent glass beads, preferably between about 10 to 20 microns diameter, and one or more color-enhancing agents such as pigments, dye aluminum flakes, colored aluminum flakes, mica, metallized mica, holographic flakes, phosphorescent glass beads and similar light-enhancing agents. Alternatively, some of the color enhancing agents may be present in a colored base coating over which the translucent light-refractive glass bead-embedded composition is applied, to cause light reflected by the base coat to be refracted and dissipated across the translucent glass bead layer, whereby the intensity and richness of the color or appearance of the combined layers is substantially enhanced.
While the present paint compositions may contain some beads which are opaque and/or retroreflective, such as hemispherically- or fully-metallized glass beads, or phosphorescent-coated beads, it is essential that a substantial content of the beads comprises light-refractive, clear or tinted glass beads which function as light diffusers within the light-transmissive or semi-opaque translucent paint layer to scatter direct and indirect light, including colored light, in all directions across the paint layer. The scattered light may have the color of a reflective base layer, or may become colored or enhanced by absorption and/or reflection by a color-enhancing ingredient also embedded within the beaded paint layer, such as metal flakes, mica, pigment, metallized beads or glass beads containing color, pigment, luminescent or phosphorescent coatings, holographic flakes or similar color enhancing additives. The most critical feature of the present light-refractive paint layers is that they scatter light across the paint layer, depending upon their degree of transluceny, due to the content of fully-embedded transparent or translucent beads, and do not merely retro-reflect or focus applied light directly back to the source. To the contrary the translucent glass beads refract direct and indirect light in all directions through the paint layer, to enhance the depth and richness of the color(s) of the paint layer or the underlying base layer.
The present bead-containing refractive paint compositions may be based upon volatile organic solvents, water or may be solvent-free spray powder compositions.
In the case of volatile organic solvent compositions, the solids content is maintained high, above about 60% solids, which is facilitated by the content of the inert, solid glass beads, pigment, aluminum flakes, mica, etc., and the film-forming binder material comprises a heat-curable resin system such as a polyester, acrylic, polyurethane or epoxy resin system including a cross-linking agent.
The present paint compositions may be water-borne or aqueous compositions comprising a water soluble heat-curable, cross-linking binder material such as an acrylic acid ester resin, a methacrylic acid ester resin, a polyurethane polymer, or the like, a microbead mixture comprising clear or translucent refractive beads and color enhancers such as pigmented, dyed, phosphorescent or luminescent reflective beads, pigments, metal flakes, mica, holographic flakes, etc.
In another embodiment of the invention the present compositions contain volatile organic solvent or vehicle, but are prepared as high solids compositions containing the refractive glass beads, color enhancers and a minor amount of resinous binder material and solvent or vehicle.
In yet another embodiment of the invention the present compositions do not contain any volatile organic solvent or aqueous vehicle, but are prepared as heat-fusible powder spray compositions containing the refractive glass beads, color enhancers and a fusible resinous binder material.
The most critical component of the present light-transmissive compositions is the mixture of color-enhancers and microbeads which comprises (a) translucent, preferably optically-clear, light-refracting microbeads; and (b) one or more color-enhancing additives such as reflective microbeads which are coated with or encapsulate a reflective material, such as aluminum microbeads or aluminum-coated glass microbeads, or which are coated with or encapsulate colored dye or pigment or luminescent or phosphorescent materials, or consist of pigments, dyes, metal flake, mica or holographic flake, to lend color, depth and intensity to the paint coatings.
The present refractive microbeads may be formed from clear or tinted glass, heat-resistant plastic, or other optical materials, and may have any desired shape such as spherical, oval, multi-facet, concave, convex, etc. However, spherical glass microbeads are preferred.
The present refractive microbeads preferably are glass bead mixtures having different particle sizes and different indexes of refraction. However, in all cases the maximum diameter of the refractive beads including refractive clear and/or colored beads is at least 10% less than the thickness of the cured paint layer, and preferably is within the range of 10 and 20xcexc for automotive paints, which preferably have a layer thickness up to about 25xcexc.
The microbeads may be formed in conventional manner from known glass compositions such as silica glass, quartz, soda lime glass, electroconductive glass, etc. The beads may be cast from molten glass compositions applied to corresponding cavities on a drum or plate, spraying of the molten composition through a nozzle for air cooling, or by any of the conventional processes currently used to produce commercially-available clear or tinted glass microbeads.
The light-refractive beads must be light-transmissive and preferably are optically clear and have an index of refraction of from about 1.5 to 2.5, preferably 1.9 to 2.1 and mixtures thereof.
The optional light reflective color-enhancing beads may be optically opaque, preferably vacuum-metallized, or phosphorescent- or luminescent-coated glass microspheres, which reflect or emit and disperse light from their surfaces into and through the refractive microbeads, or against color enhancing pigments, dyes, flakes, etc., and through the refractive microbeads in the form of scattered or dispersed colored light which gives added depth and intensity to the visual appearance and color of the paint layer.
In the case of luminescent, electroluminescent or phosphorescent reflective beads, the beads are surface coated with, or encapsulate, conventional luminescent, electroluminescent or phosphorescent compositions known to the art and, where necessary, are electroconductive.
The present paint compositions provide a novel and unexpected advantage with respect to the inclusion of mica as the color-enhancing particles. Mica is a preferred additive to conventional automotive paints since it imparts a pearlescent appearance. However because of the flat, lamelliform structure of mica crystals, the mica particles sometimes protrude at the dried paint surface to form imperfections of xe2x80x9cfish eyesxe2x80x9d. We have discovered that the mixture of glass beads and mica particles avoids these problems since the paint flows or levels to provide surface pattern control in which the mica particles are retained within the paint layer.
The common element of all of the present bead-containing compositions is the matrix or binder material for the light refracting, dispersing and enhancing microbead mixture.
Most commonly the present compositions are volatile vehicle-based coating compositions which are applied to a substrate, such as a light-transmissive, light-refractive paint composition applied to an anti-corrosion primed metallic automotive surface or to a colored base coating thereon, and dried. Such coating compositions may comprise water-soluble curable binder materials such as acrylic ester resins or polyurethane polyester resins. Such aqueous compositions generally contain about 60% to 70% water and 30% to 40% solids which includes between 10% and 20% of the refractive microbead mixture, 5% to 15% of the binder resin and the remainder consisting of one or more optional color-enhancing additives for imparting desired properties to the paint.
The formulation and application of the present compositions, such as paints for automobiles, boats, airplanes, appliances and a variety of other uses will be apparent to those skilled in the art in the light of the present disclosure. The present refractive paint compositions may be coated or printed as full or partial coverings, such as printed stripes, dots or other designs to produce light-scattering hazard signs, road lines, emergency vehicles, and a wide variety of other applications in which protective light-reflective materials are conventionally used to improve nighttime visibility under the application of light from headlights, flashlights, etc.
The present paint coatings may comprise a single light-refractive color layer covered by a clear top coat, or a colored base layer covered by a light-refracting tint layer and a clear top coat.
In the case of automotive paints, the base metal body is first bathed or showered with a corrosion-resisting conversion coating or electrocoat, such as of zinc or iron phosphate or chromates, and dried in an oven. Subsequently a primer coating may be applied by dipping or flow coating, using a resinous binder of epoxy or alkyd polyester in organic solvent, followed by baking to harden the primer layer.
Next, the paint layer is sprayed over the primer layer, either as a single bead-and color-containing curable resinous paint layer or as a color-containing curable resinous base layer covered by a curable resinous bead-containing light-refracting tint layer. Each layer is baked to heat cure the resinous binder material.
Finally a clear colorless or tinted curable resinous top coat is applied and baked to provide a hard protective, glossy exterior surface layer over the paint layer(s).
The preferred curable resinous binder system of the present coatings comprises the incorporation of both a cross-linkable polymer and a cross-linking agent which is reactive with groups on the polymer during heating or ultraviolet exposure to cure the polymer to a clear, hard, glasslike condition.
Water-based acrylic ester polymer-melamine formaldehyde cross-linking resin mixtures provide curable binder material coatings having good resistance to ultraviolet light. Similar systems based upon organic solvent-soluble acrylic polymers and aldehyde resins are also suitable.
Solvent-based polyurethane coatings are also suitable, comprising a urethane prepolymer containing isocyanate groups, as a polyisocyanate cross-linking agent, and an active hydrogen-containing polymer such as a polyester or polyether polymer.
Also conventional dry heat-fusible, curable resin powder coatings are suitable for use as binder materials according to the present invention, in combination with the glass beads and color-enhancing agents. Preferred resin systems of this type include aromatic polyester resins containing free carboxyl or hydroxyl groups in combination with polyisocyanates or blocked urethanes as cross-linking agents. Also suitable are curable epoxy mixtures of acid polyesters and bis-phenol-A, hydroxy acrylic polymers cross-linked with block urethanes, and hydroxy acrylic polymers cross-linked with diacid or dianhydride compounds.
A further advantage of the present glass-containing paint compositions, aside from the fact that the glass beads are inert, increase the solids content of the paint, and are easily reclaimable and recyclable, is that they provide the paint compositions with excellent spreadability, flow and leveling properties for ease and efficiency of application and surface pattern control.
The present glass bead paints containing color enhancers such as metallic flakes, including colored metallic flakes, and/or mica flakes, including colored mica flakes, provide richer, deeper automotive body colors and high specular flash or light scattering on the face of the color, i.e., when viewed directly, and a translucent rich deep elegant contrast when viewed at an angle, such on contoured body surfaces.
The glass spheres also provide surface pattern control for the color enhancers, particularly the metallic flakes and the mica, by enhancing uniform mixing, distribution and flow during application to assure uniformity of color and refractive consistency.
The content of the glass spheres must be controlled to optimize the surface color quality, and varies with paints of light or bright color and paints of dark color. With lighter, brighter colored paints such as silver-colored or light-colored metallic paints, the glass bead content should be in the range of 5-10% by weight of the cured paint, preferably about 7%, whereas with medium bright or darker colored paints the glass bead content should be in the range of 10-20% by weight of the cured paint, preferably 12-15%.
The glass bead particle sizes have a controlled micron size which permits smooth application by conventional automotive spray equipment, including robotic paint spraying devices, and which assures that the beads do not protrude at the surface of the bead-containing layer, whether it be a single paint layer, a base layer/tint layer combination or a clear top coat. The beads must be encased or encapsulated within their layer in order to produce the desired light-refraction and internal color enhancement properties. Otherwise light directed at exposed areas of the glass beads is retroreflected or reflected directly back to the source rather than being dissipated or scattered across the paint layer to permit color enhancement cooperation with the additives such as metallic flakes, mica flakes, pigment, phosphorescent beads, holographic flakes and/or metallic beads.
The present light-refracting beads preferably have a maximum diameter up to about 20xcexc for paint layers cured to a thickness of about 1 mil (25xcexc). Most preferably the glass bead maximum diameter is within the range of about 10 to 18xcexc for 1 mil coatings. However, paint layers of greater thickness, such as up to about 4 mils on boat surfaces, airplane/body surfaces, appliances, etc., will accommodate larger-diameter beads such as up to about 75xcexc. In all cases the maximum bead diameter must be at least 10% less than the thickness of the cured bead-containing layer.
The present light-refracting and scattering paints, particularly those containing phosphorescent pigments or phosphorescent-coated beads introduce added safety due to enhanced overall visibility of the painted body exposed to applied light, such as from headlights, spot lights, street lights, etc.
The following examples illustrate specific bead-containing paint compositions of different types coming within the present invention. It should be understood that such compositions are given by way of illustration only, and should not be considered limitative. In all cases, the layers are applied to conversion-coated or primed surfaces and are covered by conventional clear, glossy top coatings as currently used in the automotive paint industry.

Light-emission-enhancement microbead paint compositions and their preparation


A zero VOC aqueous coating composition comprising a halogen-free propylene/xcex1-olefin copolymer having an xcex1,xcex2-unsaturated dicarboxylic acid or anhydride grafted thereon, a neutralizing base, a water-dispersible resin containing at least two epoxy groups and an acid catalyst is applied to a plastic substrate comprising a propylene polymer. The dried coating promotes adhesion of a subsequent coating to the polypropylene-based surface of the article.

This invention relates to an adhesion-promoting thermoset coating for plastic substrates comprised of polyolefinic polymers. Because of their low surface energy and non-polar nature, such polymers are very difficult to paint with decorative and/or protective coatings. More particularly it relates to adhesion-promoting coatings which are halogen-free. Even more particularly, it relates to an aqueous coating composition having zero VOC (volatile organic compound-free) which improves the adherence of such a polyolefinic article to subsequent coatings when the adhesion-promoting composition is applied to the surface and cured by baking it at an elevated temperature.
The use of polyolefins such as polypropylene and polypropylene containing compounds modified with rubber called thermoplastic olefins (TPO) has grown significantly in areas such as the automotive market since the 1970""s because of their low cost, low weight, impact resistance, ease of molding and recyclability. They have been used in interior applications such as airbag covers and exterior ones such as fascia and trim.
The isotactic crystalline structure of polypropylene gives it a low surface energy of anywhere from 20 to 30 dynes/cm, resulting in a surface that most coatings will not wet out or adhere to. This surface must be physically or chemically altered to render it paintable with available coating technology. Plasma treatment and corona discharge employ ionized gases to oxidize the surface of the polypropylene or TPO which raises its surface energy and allows it to chemically and mechanically bond with the coating. However, the surface remains temporarily oxidized and must be coated before the energy lowers again. This process can be difficult and expensive in a production environment when complexly shaped automotive parts are involved. Flame treatment will also oxidize the surface but this requires a precise distance of flame to surface which is again hard to control on a production line that is coating components of different shapes and sizes. TCE (1,1,1 trichloroethane) is used to etch or dissolve the surface of the propylene or TPO but due to volatile organic compound (VOC) and toxicity concerns, this method is being phased out. A more common approach to the painting of polypropylene and TPO is the use of an adhesion promoting primer coating that uses a chlorinated polyolefin resin to gain adhesion to the surface. These coatings are easy to process in a production environment and can be topcoated after a short ambient flash or bake. However, solvent borne chlorinated polyolefin resins have limited solubility and are mainly compatible only with aromatic solvents such as xylene or toluene and must be sprayed at V.O.C.""s of 5.7 pounds per gallon or higher to properly coat the surface of the polypropylene or TPO. This can be a problem for a finisher that is required to comply with strict federal and state emissions standards.
Aqueous dispersions of chlorinated polyolefin resins have been formulated into adhesion promoter coatings with V.O.C.""s ranging from 1.0 to 0 pounds per gallon but the high cost of these materials has been a hindrance to their acceptance in the marketplace, despite the lower V.O.C.""s. The presence of chlorine in these aqueous adhesion promoting compositions is still an environmental concern.
It is an object of this invention, therefore, to provide a non-halogenated thermoset adhesion promoting coating for polypropylene-based substrates.
It is a related object of this invention to provide a zero VOC coating composition containing a non-halogenated resin which promotes adhesion of a subsequent coating to a polypropylene-based substrate.
It is a further related object of this invention to provide a zero VOC coating composition containing a non-halogenated adhesion promoting resin which is capable of sufficiently enhancing the adhesion of coatings on polypropylene based surfaces that such coatings comply with the standards, including those of humidity and gasoline resistance, required for using such coatings on the interior and exterior of automobiles as set by the automotive industry.
It is a still further object to provide such adhesion promoting resins that are relatively easy to formulate, store and use because they are sufficiently stable that they can be completely mixed to the composition in which they are intended to be applied and then stored in a single package for extended periods prior to use.
It is a related object of this invention to provide an article having a polypropylene-based surface which is coated with a zero VOC coating composition containing a non-halogenated resin which promotes adhesion of a subsequent coating to the surface.
It is a related object of this invention to provide an article having a polypropylene-based surface which is coated with an aqueous, zero VOC coating composition containing a non-halogenated resin which, when dry, promotes adhesion of a subsequent coating to the surface.
It is a related object of this invention to provide a polypropylene-based article having a coating which promotes adhesion of a subsequent coating in conditions of high humidity and when in contact with gasoline.
These and other objects which will become apparent from the following description thereof are provided by an article having a polyolefin resin surface which is coated with an aqueous composition comprising:
(a) a halogen-free copolymer of a higher xcex1-olefin and at least one monomer selected from the group consisting of ethylene and propylene, said copolymer having an xcex1, xcex2-unsaturated dicarboxylic acid or anhydride grafted thereon;
(b) a base;
(c) an acid catalyst, and
(c) a water-dispersible resin containing at least two epoxy groups.
Other polymers, including acrylics, polyurethanes, and melamines, to name a few, can be blended with the above mentioned composition. These resins are used to improve the physical properties of the system. In addition, pigments and additives can be employed to provide desired aesthetic or functional effects. The polyolefin surface may be that of an article made from a polyolefin or it may be that of a film on an article made from another material. The articles of particular interest for the purposes of this invention are polypropylene-based automotive parts that may be exposed to high humidity and may be subject to repeated contact with gasoline.
The olefin copolymer of component (a) in the aqueous coating composition of the invention is a random copolymer or block copolymer of the ethylene and/or propylene with a higher xcex1-olefin. Propylene/xcex1-olefin copolymers suitable for use in this invention are available from Eastman Chemical Products, Inc. and from the Rexene Company. Ethylene/xcex1-olefin copolymers suitable for use in this invention are available from Union Carbide under the trademark FLEXIMERS. They are exemplified by ethylene/butene, ethylene/hexene, and ethylene/butene/hexene copolymers. A random copolymer of a higher xcex1-olefin and propylene is preferred and the proportion of the propylene component is preferably not less than 10 weight percent. If it is less than 10 weight %, then adhesion to polypropylene is poorer, which is, of course, undesirable. Examples of the higher xcex1-olefins include, butene-1, pentene-1, and hexene-1. Among these, hexene-1 is preferable from the standpoint of physical properties of the polymer. Hexene-1 levels may range from 10 to 80 wt % but a preferable level is approximately 60 weight percent of the propylene/xcex1-olefin copolymer composition. Mixtures of two or more of the higher xcex1-olefins may be copolymerized with ethylene or propylene or with a mixture of ethylene and propylene.
The xcex1,xcex2-unsaturated dicarboxylic acids or their acid anhydrides to be graft copolymerized onto the propylene/xcex1-olefin copolymer are exemplified by maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid and aconitic acid, and their acid anhydrides. The amount of xcex1,xcex2-unsaturated dicarboxylic acid or its acid anhydride is preferably from about 1 to about 20% by weight of the grafted copolymer. If under 1% by weight, the stability of dispersion in water will become poor and, if over 20% by weight, the grafting efficiency decreases, which is uneconomical. From about 2 to about 10% by weight is particularly preferable and from about 4 to about 7% is even more preferable.
The number average molecular weight (determined by gel permeation chromatography or GPC) of the olefin copolymer after being grafted with the xcex1,xcex2-unsaturated dicarboxylic acid or its acid anhydride is preferably 3000 to 55,000. If under 3000, adhesion to the polyolefinic resin will be poorer and, if over 55,000, dispersion into water becomes difficult because of high viscosity. Bringing the molecular weight into this range is possible by selecting the molecular weight of the raw copolymer material or the conditions at the time of conducting the grafting reaction. Also, the grafting reaction may be conducted after the molecular weight of the raw copolymer material has been reduced.
Graft copolymerization of a xcex1,xcex2-unsaturated dicarboxylic acid or its acid anhydride onto the olefin copolymer may be conducted by a known method wherein the olefin copolymer is liquified by heating it above its melting point and the graft copolymerization is conducted in the presence of a free radical-generating agent. The product is referred to hereinafter as an acid grafted olefin copolymer.
When using this method, a reactor equipped with an intensive agitator, Banbury mixer, kneader, extruder or the like is employed and xcex1,xcex2-unsaturated dicarboxylic acid or its acid anhydride and a radical-generating agent or solution thereof in low boiling solvent are added at a temperature of not lower than about 150xc2x0 C. to not higher than about 300xc2x0 C. to react, and the product is pelletized by known methods after the low boiling solvent is removed.
It is also possible to dissolve the olefin copolymer in an organic solvent such as xylene under heat and conduct the reaction in the presence of a free radical-generating agent, but this method is less preferred because it is time-consuming to remove the organic solvent and the removal is not always complete.
The radical-generating agent to be used for the reaction can be appropriately selected from known materials, but an organic peroxide is particularly preferable. As the organic peroxides, for example, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,5-dimethyl-2, 5-di(t-butylperoxy) hexane, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate and cumene hydroperoxide can be used, depending on the reaction temperature.
The dispersion of components (a) and (b) in water can be performed by a method wherein component (a) is liquified by heating it to a temperature above its melting point, and the base (b), water and a surfactant, if needed, are added to the acid grafted copolymer with agitation. According to another embodiment of the method, a mixture of (a), (b), and, if needed, a surfactant, is added to water or all of the components including water are mixed and agitated under heat. A dispersion with good stability can be obtained at high temperature and pressures above atmospheric.
As noted, dispersion is possible either with or without using a surfactant, but it is desirable to use a surfactant when the amount of xcex1,xcex2-unsaturated dicarboxylic acid or its acid anhydride having been graft copolymerized is low. The use level is preferably not more than 25% by weight of component (a). If over 25% the water resistance of paint film will become poor.
Any type of surfactant can be used, but nonionic surfactants are desirable because of their low toxicity. Combinations of non-ionic surfactants, anionic surfactants and fluorosurfactants (if halogen-containing components can be tolerated in small amounts) in which the non-ionic is the main component may be used.
Polyoxyethylene alkyl esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, sorbitan alkyl esters, and polyglycerine esters are examples of the nonionic surfactants. A high molecular weight PLURONIC surfactant can be used.
Carboxylates, sulfonates, and phosphates are examples of the anionic surf actants. The fluorosurfactants may be anionic, nonionic or cationic.
Component (a) is neutralized with base in order to achieve good dispersion into water. Sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol and morpholine are examples of bases that may be used. The use of organic amines is suitable only when the introduction of small amounts of VOC must be tolerated in order to achieve other desirable properties.
Since the degree of hydrophilicity of the resin differs depending on the types of base being used, it is necessary to select one appropriate to the conditions. Amines having a hydroxyl group such as ethanolamine and 2-amino-2-methyl-1-propanol are preferable when their strong hydrophilicity is desired. Ammonia is preferable when the elimination of VOC from the paint system is of prime importance. The amount of base used is suitably in a range of 0.3 to 1.5 times as much as the equivalent weight to carboxyl group of component (a) and 0.5 to 1.2 times are preferable.
A preferred composition of the invention includes as the resin portion a maleated olefin copolymer crosslinked with at least one of the group consisting of a water-dispersible cycloaliphatic di-epoxy resin and a water-dispersible di-epoxy resin from the condensation of a bisphenol with epichlorohydrin.
Although different epoxies can be used, a cycloaliphatic di-epoxy is preferred. The epoxy should be used at levels so that enough crosslinking of the acid grafted propylene/xcex1-olefin copolymer occurs to assure complete integrity at high humidity but not at excessive levels so that adhesion to the substrate is prevented or interference with the crosslinking mechanism of the top coat applied over the coating of this invention occurs. The epoxy levels can range from approximately 50% to 600%, but preferably is from 100% to 200%, of the level of the acid grafted propylene/xcex1-olefin copolymer based on the theoretical equivalent weights of the two resins (i.e. a ratio of 0.5:1 to 6:1, preferably a ratio of 1:1 to 2:1, of epoxy equivalents to acid equivalents). These levels represent, by weight, approximately 12% to 75%, but preferably 25% of the level of a maleated propylene/xcex1-olefin copolymer when the di-epoxy resin has an equivalent weight of approximately 135.
The acid catalyst is preferably a sulfonic acid type catalyst, such as p-toluene sulfonic acid (PTSA), methane sulfonic acid, dodecylbenzene sulfonic acid, dinonylnapthalene sulfonic acid, trifluoromethane sulfonic acid or mixtures thereof. P-toluene sulfonic acid is the particularly preferred catalyst. Optionally, the acid catalyst may be blocked with such as an amine neutralizing agent. The acid catalyst is used at levels of 2-4 weight percent of the combined weight of the acid grafted olefin copolymer and epoxy resins. The curing temperature may be as high as about 150xc2x0 C.
The epoxy-crosslinked, acid grafted olefin copolymer of this invention comprises from about 40 to about 90 weight percent of the non-aqueous resin portion of the invention.
Various other resins are used in conjunction with the acid grafted olefin copolymer/epoxy resin/catalyst containing systems. Their main purpose is to improve the physical properties, such as hardness, of the coating of this invention. Acrylic emulsions and polyurethane emulsions are used at levels of from 0 to 100 weight percent, preferably about 50 weight percent, of the acid grafted olefin copolymer, on a solids basis. In addition to improving hardness, melamine resins can be used to further crosslink the epoxy crosslinked/acid grafted olefin copolymer coating. The melamine resins are used at levels up to 10 weight percent of the epoxy crosslinked/acid grafted olefin copolymer composition on a solids basis. Polymeric acids, such as those described in U.S. Pat. No. 5,759,703, which is hereby incorporated by reference, may also be included to assist in forming the aqueous dispersion of the acid-modified olefin copolymer as well as for their contribution to the physical and coating properties.
This invention employs pigments for aesthetic and functional effects. Conductive carbon black, talc and other organic and inorganic pigments may be employed. The carbon black and talc pigments may each comprise approximately 25 weight percent of the epoxy crosslinked/acid grafted olefin copolymer.

Chlorine-free, zero voc, waterborne adhesion promoter for polyolefinic substrates


Technologies and implementations for allocating datacenter resources are generally disclosed.

Unless otherwise indicated herein, the approaches described in this section are not prior art to the claims in this application and are not admitted to be prior art by inclusion in this section.
Current datacenters may perform tasks for clients by allocating resources at the datacenter to the tasks. With conventional datacenters, the resources may be inefficiently allocated and, in some instances, the colocation of certain tasks to shared hardware may stress and/or inefficiently utilize the shared hardware.

Datacenter database generation using task fingerprint and allocated resources


A method of treating a condition in a vertebrate animal characterized by bone having increased porosity and/or decreased bone mineral density. The porous bone is injected with an effective amount of a flowable bone composition. Also provided is a kit for the treatment of porous bone wherein a flowable bone composition is contained within an injectable delivery system.

This invention relates to methods for the treatment of porous bone, e.g., osteoporotic bone. The expression xe2x80x9cporous bonexe2x80x9d is intended herein to identify a condition of porosity and/or decreased bone mineral density that distinguishes the morphology of bone exhibiting a pathological condition from healthy bone. A common type of porous bone pathology is osteoporosis.
Osteoporosis is a pathologic state or disease involving some symptom or risk due to quantitative bone reduction exceeding a certain degree. Major symptoms are spinal kyphosis, fractures of dorsolumbar bones, vertebral centra, femoral necks, lower ends of radius, ribs, upper end of humerus, and others. In normal bone tissue, bone breakdown occurs constantly, but there is good balance between formation and resorption; osteoblasts and osteoclasts play key roles in bone formation and bone resorption, respectively. Upon deterioration of this balance, bone resorption surpasses bone formation, resulting in quantitative bone reduction.
Osteoporosis results in bone fractures in about 50% of postmenopausal women and is a leading cause of disability in an aging population. The decrease in bone mineral density and changes in architecture that accompany postmenopausal osteoporosis predisposes elderly women to fractures, particularly of the vertebral bodies. It is not elderly persons alone who suffer from this painful condition. Other individuals, such as transplant recipients, suffer fractures as a result of chronic steroid use. Current therapies include an adequate calcium and vitamin D intake as well as specific treatment with compounds such as estrogens, calcitonin and the bisphosphonates. However, each of these treatments has either troubling side effects or limited efficacy. Women fear the small increase in potential risk of breast cancer due to estrogens despite the dramatic reduction in myocardial infarctions and reduction in bone resorption. Calcitonin has a limited effect and is a protein and therefore needs to be injected or inhaled which is inconvenient. The new bisphosphonates such as alendronate have had encouraging results with an increase in bone density and decrease in fractures, however, some upper gastrointestinal irritation has been reported (Abraham et al., 1999, Mod. Pathol. Dec 12(12): 1152-1157). Current research for new compounds has concentrated on the systemic administration of bone anabolic compounds such as parathyroid hormone (PTH) or fragments of PTH or locally acting cytokines or bone growth factors such as bone morphogenic proteins. When these therapies are unable to prevent fractures of porous bone, the victims of such fractures suffer from persistent, often excruciating pain, which significantly impairs mobility and quality of life. External bracing, analgesics, and observation may be all that is necessary for pain control in some patients, but in others, a constant requirement for narcotics can be as life altering as the fracture itself.
Vertebroplasty has been described in the literature as a method of injecting materials into vertebral bodies via a pedicle approach. Patients with various problems including osteoporosis, tumor or trauma have deficiencies of the vertebral body leading to pain or other complications. By injecting methylmethacrylate (bone cement) into these areas interventional radiologists or other physicians are able to avoid further subsidence of the vertebrae and alleviate pain. This procedure can be done on an outpatient basis, but currently is reserved for patients with major problems. The current methods of vertebroplasty are directed toward treatment once a fracture occurs. Therefore, a prophylactic treatment directed toward reducing the tendency for porous vertebrae to fracture would be highly desirable
This invention describes the use of a flowable bone graft composition to induce bone growth at porous bone sites. A suitable bone graft for this indication would have the properties of flowability. i.e., allowing for injection through a 2-6 mm or larger trocar, and ability to support formation of new bone at the porous bone site. An ideal material would be flowable DBM (with or without enhancing substances such as BMP) such as that disclosed in U.S. Pat. Nos. 5,073,373, 5,236,456, 5,314,476, 5,405,390, 5,484,601 and 5,510,396 and commonly assigned PCT/US00/28462, filed Oct. 13, 2000, the contents of all of which are incorporated herein by reference.
It is an object of the invention to provide a method of treating a vertebrate animal having increased bone porosity and/or decreased bone mineral density.
It is a further object of the invention to provide a method for treating osteoporotic patients at risk for fracture of the vertebra or other sites.
It is a further object of the invention to provide a method for increasing the bone mineral density and/or decreasing bone porosity thereby decreasing the risk for future fracture.
It is a further object of the invention to provide a method of treating at risk vertebrae adjacent to a fractured vertebra.
The stated objects of the invention are not intended to be limiting in any way. Of course, further objects of the invention herein will be obvious to those skilled in the art in view of the above stated objects and the foregoing specification.
In keeping with these and related objects of the invention, there is provided a method of treating a condition in a vertebrate animal, the condition characterized by bone having increased porosity and/or decreased bone mineral density, which comprises injecting the porous bone with an effective amount of a flowable bone composition. The foregoing method applied to a site of increased bone porosity and/or decreased bone mineral density, e.g., one resulting from disease, malignancy or developmental malformation, leads to rapid new bone ingrowth by one or more mechanisms such as osteogenesis, osteoconduction and osteoinduction. The method of this invention is relatively simple, e.g., it can be performed on an outpatient basis, and relatively inexpensive, and avoids the major complications caused by vertebral fracture.
The method described herein is performed on individuals identified as being at risk for bone fracture due to increased bone porosity and/or decreased bone mineral density. Such individuals are identified using methods well known in the art, e.g., bone density scans, radiographic imaging, medical history. The conditions leading to decrease in bone density can include, e.g., osteoporosis, osteomalacia, osteotis fibrosa, Paget""s disease, bone deficiency, primary or secondary hyperparathyroidism, chronic inflammatory conditions, metastatic bone disease and osteolytic bone disease. When the condition is osteoporosis, the osteoporosis can be due to a number of conditions, e.g., age-related osteoporosis, post-menopausal osteoporosis, juvenile osteoporosis, Cushing""s syndrome osteoporosis, multiple myeloma osteoporosis, leukemia osteoporosis, Turner""s syndrome osteoporosis, alcohol osteoporosis, chronic liver disease osteoporosis, glucocorticoid-induced osteoporosis, chronic inflammatory disease induced osteoporosis and disuse osteoporosis. The site of decreased bone density can be trabecular bone, cortical bone, etc. When the bone site is trabecular bone the bone can include, e.g., vertebrae, rib, clavicle, sternum, femoral neck, hip, wrist and the distal ends of the long bones.
Once the site of decreased bone density is located utilizing methods well known in the art, e.g., bone density scans, radiographic imaging, medical history, a suitable amount of a flowable bone composition is injected into the bone site utilizing methods well known in the art, e.g., through a needle or cannula, e.g., a Jamshidi(copyright)11 gauge bone marrow biopsy/aspiration needle. In a preferred embodiment of the invention, a percutaneous vertebroplasty technique as described by Jensen et al. Diagnostic Imaging, pp. 68-72, September 1997, the contents of which are incorporated herein by reference, is used to inject the osteoinductive composition into the vertebra. This technique, a fluoroscopically guided transpedicular approach, has been found to be the easiest, safest and least time-consuming.
The bone component of the composition herein is a known type of material and is prepared in accordance with known procedures. The expressions xe2x80x9cpulverized bonexe2x80x9d, xe2x80x9cpowdered bonexe2x80x9d, xe2x80x9cbone particlesxe2x80x9d and xe2x80x9cbone powderxe2x80x9d as used herein shall be understood to include bone particles of a wide range of average particle size ranging from relatively fine powders to coarse grains and even larger chips or fibers. So, for example, the bone component present in the composition of this invention can range in average particle size from about 0.1 to about 1.2 cm and preferably from 0.2 to 1 cm. Bone particles whose median length to median thickness is at least about 10:1 are also suitable for use in the bone component useful herein. The bone component can be obtained from cortical, cancellous and/or corticocancellous allogenic, xenogenic or transgenic bone tissue. In general, allogenic bone tissue is preferred as the source of the bone component. The bone component may be mineralized, partially demineralized or demineralized as well as combinations thereof. Of course, it will be understood that any combination of the above-identified bone can be used in the preparation of flowable bone compositions useful in the practice of the invention herein.
In a preferred bone demineralization procedure, the bone is first pulverized to the desired average particle size followed by defatting/disinfecting and acid demineralization treatments. A preferred defatting/disinfectant solution, for example, is an aqueous solution of ethanol, the ethanol being a good solvent for lipids and the water being a good hydrophilic carrier to enable to solution to penetrate more deeply into the bone. The aqueous ethanol solution also disinfects the bone by killing vegetative microorganisms and viruses. Ordinarily at least about 10% to 40% water (i.e., about 60% to 90% defatting agent such as alcohol) should be present in the defatting, disinfecting solution to produce optimal lipid removal and disinfection within the shortest period of time. The preferred concentration range of the defatting solution is, for example, about 60% to 85% alcohol and most preferably 70% alcohol. Following defatting, the bone is immersed in acid over time to effect demineralization. Acids which can be employed in this operation include, for example, inorganic acids such as hydrochloric acid and organic acids such as peracetic acid. After acid treatment, the bone component is rinsed with water for injection, buffered with a buffering agent to a final predetermined pH and then finally rinsed with water for injection to remove residual amounts of acid and buffering agent. The demineralized bone component can be used immediately for preparation of the composition of this invention or it can be stored under aseptic conditions, advantageously in a freeze-dried state, prior to such preparation.
If desired, the bone component can be modified in one or more ways, e.g., the porosity of the bone component can be increased and/or the bone component can be treated with one or more modifying agents, e.g., gluturaldehyde, as disclosed in U.S. Pat. No. 4,678,470 the contents of which are incorporated herein by reference. Another optional treatment involves the augmentation of the bone protein content of the bone employing the procedure of U.S. Pat. Nos. 4,743,259 and 4,902,296 the contents of which are incorporated herein by reference. Any of a variety of medically and/or surgically useful substances can be incorporated in, or associated with, the bone component before, during, or after preparation of the osteoinductive composition. Thus, e.g., one or more of such substances can be introduced into the bone component, e.g., by soaking or immersing the bone component in a solution or dispersion of the desired substance(s), by adding the substance(s) to the carrier component of the osteoinductive composition of by adding the substances directly to the osteoinductive composition. Broad classifications of such substances would include, for example, agents that promote bone growth and/or inhibit bone resorption, e.g., bone morphogenetic factors, anti-resorption agents, osteogenic factors, cartilage-derived morphogenetic proteins, hormones, growth hormones and differentiating factors.
Medically/surgically useful substances, which can be readily combined with the bone component, fluid carrier and/or osteoinductive composition of this invention, include, e.g., demineralized bone powder as described in U.S. Pat. No. 5,073,373 the contents of which are incorporated herein by reference, all collagen types (not just type I), insoluble collagen derivatives, non-collagenous proteins such as osteopontin, osteonectin, bone sialo proteins, vitronectin, thrombospondin, proteoglycans, decorin, biglycan, aggrecan, veriscan, tenascin, matrix gla protein hyaluronan; hydroxyapatite, etc., and soluble solids and/or liquids dissolved therein, e.g., antiviricides, particularly those effective against HIV and hepatitis; antimicrobials and/or antibiotics such as erythromycin, bacitracin, neomycin, penicillin, polymyxin B, tetracyclines, viomycin, chloromycetin and streptomycins, cefazolin, ampicillin, azactam, tobramycin, clindamycin and gentamycin, etc.; amino acids, peptides, vitamins, inorganic elements, inorganic compounds, cofactors for protein synthesis, hormones; soluble and insoluble components of the immune system, soluble and insoluble receptors including truncated forms, soluble, insoluble and cell surface bound ligands including truncated forms; chemokines, bioactive compounds that are endocytosed; endocrine tissue or tissue fragments; synthesizers; enzymes such as collagenase, peptidases, oxidases, etc.; polymer cell scaffolds with paraenchymal cells; angiogenic drugs and polymeric carriers containing such drugs; collagen lattices; biocompatible surface active agents; antigenic agents; cytoskeletal agents; cartilage fragments, living cells such as chondrocytes, bone marrow cells, mesenchymal stem cells, natural extracts, tissue transplants, bioadhesives, bone morphogenic proteins (BMPs), transforming growth factor (TGF-beta), insulin-like growth factor (IGF-1) (IGF-2), platelet derived growth factor (PDGF), fibroblast growth factors (FGF), vascular endothelial growth factor (VEGF), epidermal growth factor (EGF), angiogenic agents, bone promoters, cytokines, interleukins, genetic material, genes encoding bone promoting action, cells containing genes encoding bone promoting action; hormones, growth hormones such as somatotropin; bone digestors; antitumor agents; fibronectin; cellular attractants and attachment agents; immuno-suppressants; bone resportion inhibitors and stimulators; angiogenic and mitogenic factors; bioactive factors that inhibit and stimulate second messenger molecules; cell-matrix and cell-cell adhesion molecules; clotting factors; externally expanded autograft or xenograft cells, permeation enhancers, e.g., fatty acid esters such as laureate, myristate and stearate monesters of polyethylene glycol, enamine derivatives, xcex1-keto aldehydes, etc.; and, nucleic acids and any combination thereof. The amounts of such optionally added substances can vary widely with optimum levels being readily determined in a specific case by routine experimentation.
The flowable bone composition can be modified to increase its suitability for this application. It can be rendered radiopaque by the addition of compositions containing barium, tungsten or mineralized bone. Optionally, agents that inhibit bone mineral loss or depress bone turnover can be added to the composition. Such agents include, for example, stable active analogs of pyrophosphate such as those known as bisphosphonates and estrogen and analogs thereof.
To provide the flowable bone composition useful in the practice of the invention herein, the bone component with or without any of the foregoing optional components mentioned above absorbed therein is combined with a biocompatible liquid organic material which functions as a carrier or suspension agent for the bone component.
The term xe2x80x9cliquidxe2x80x9d as employed herein is intended to include (1) organic materials which in the pure or highly concentrated state and at ambient temperature, e.g., 15 degree-40 degree C., are flowable liquids and (2) organic materials which in the pure or concentrated state and at ambient temperature are normally solid but dissolved in a suitable solvent, e.g., water or a biocompatible organic solvent such as ethanol, can be provided in liquid form. Functionally, the liquid component of the composition serves to provide a flowable material of widely varying consistency. The term xe2x80x9cflowablexe2x80x9d as used herein applies to compositions whose consistency range from those that can be described as shape-sustaining but readily deformable, e.g., those that behave like putty, to those which are runny. Specific forms of flowable bone compositions include cakes, pastes, putties, creams, fillers and gels. Suitable carriers can be any of a number of compounds and/or polymers, e.g., polymer sugars, proteins, long chain hydrophilic block copolymers, reverse phase block copolymers, hyaluronic acid, polymonic acid, mucopolysaccharide, proteoglycan, polyoxyethylene, surfactants, e.g., the Pluronics series of nonionic surfactants, and peptide thickener. Suggested classes of biocompatible fluid carrier would include polyhydroxy compound, polyhydroxy ester, fatty alcohol, fatty alcohol ester, fatty acid, fatty acid ester, liquid silicone, mixtures thereof, and the like. Examples of suitable biocompatible fluid carrier include, but are not limited to:
(i) Polyhydroxy compound, for example, such classes of compounds as the acyclic polyhydric alcohols, non-reducing sugars, sugar alcohols, sugar acids, monosaccarides, disaccharides, water-soluble or water dispersible oligosaccarides, polysaccarides and known derivatives of the foregoing. Specific polyhydroxy compounds include 1,2-propanediol, glycerol, 1,4,-butylene glycol trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, ethylene glycols, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol; polyoxyethylene-polyoxypropylene copolymer, e.g., of the type known and commercially available under the trade names Pluronic and Emkalyx; polyoxyethylene-polyoxypropylene block copolymer, eg., of the type known and commercially available under the trade name Poloxamer; alkylphenolhydroxypolyoxyethylene, e.g., of the type known and commercially available under the trade name Triton, polyoxyalkylene glycols such as the polyethylene glycols, xylitol, sorbitol, mannitol, dulcitol, arabinose, xylose, ribose, adonitol, arabitol, inositol, fructose, galactose, glucose, mannose, sorbose, sucrose, maltose, lactose, maltitol, lactitol, stachyose, maltopentaose, cyclomaltohexaose, carrageenan, agar, dextran, alginic acid, guar gum, gum tragacanth, locust bean gum, gum arabic, xanthan gum, amylose, mixtures of any of the foregoing, and the like.
(ii) Polyhydroxy ester, for example, liquid and solid monoesters and diesters of glycerol can be used to good effect, the solid esters being dissolved up to the limit of their solubilities in a suitable vehicle, e.g., propylene glycol, glycerol, polyethylene glycol of 200-1000 molecular weight, etc., Liquid glycerol esters include monacetin and diacetin and solid glycerol esters include such fatty acid monoesters of glycerol as glycerol monolaurate, glyceryl monopalmitate, glyceryl monostearate, etc. An especially preferred carrier herein comprises glyceryl monolaurate dissolved in glycerol or a 4:1 to 1:4 weight mixture of glycerol and propylene glycol, poly (oxyalkylene) glycol ester, and the like.
(iii) Fatty alcohol, for example primary alcohols, usually straight chain having from 6 to 13 carbon atoms, including caproic alcohol, caprylic alcohol, undecyl alcohol, lauryl alcohol, and tridecanol.
(iv) Fatty alcohol ester, for example, ethyl hexyl palmitate, isodecyl neopentate, octadodecyl benzoate, diethyl hexyl maleate, and the like.
(v) Fatty acid having from 6 to 11 carbon atoms, for example, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid and undecanoic acid. (vi) Fatty acid ester, for example, polyoxyethylene-sorbitan-fatty acid esters; e.g., mono-and tri-lauryl, palmityl, stearyl, and oleyl esters; e.g., of the type available under the trade name Tween from Imperial Chemical Industries; polyoxyethylene fatty acid esters; e.g., polyoxyethylene stearic acid esters of the type known and commercially available under the trade name Myrj; propylene glycol mono- and di-fatty acid esters such as propylene glycol dicaprylate; propylene glycol dilaurate, propylene glycol hydroxy stearate, propylene glycol isostearate, propylene glycol laureate, propylene glycol ricinoleate, propylene glycol stearate, and propylene glycol caprylic-capric acid diester available under the trade name Miglyol; mono-, di-, and mono/di-glycerides, such as the esterification products of caprylic or caproic acid with glycerol; e.g., of the type known and commercially available under the trade name Imwitor; sorbitan fatty acid esters, e.g., of the type known and commercially available under the trade name Span, including sorbitan-monolauryl, -monopalmityl, -monostearyl, -tristearyl, -monooleyl and trioleylesters; monoglycerides, e.g., glycerol mono oleate, glycerol mono palmitate and glycerol monostearate, for example as known and commercially available under the trade names Myvatex, Myvaplex and Myverol, and acetylated, e.g., mono- and di-acetylated monoglycerides, for example as known and commercially available under the trade name Myvacet; isobutyl tallowate, n-butylstearate, n-butyloleate, and n-propyloleate.
(vi) Liquid silicone, for example, polyalkyl siloxanes such as polymethyl siloxane and poly (dimethyl siloxane) and polyalkyl arylsiloxane.
In a preferred embodiment of the osteoinductive composition, the liquid carrier is a liquid polyhydroxy compound, liquid polyhydroxy compound derivative, liquid solution of solid polyhydroxy compound, liquid solution of solid polyhydroxy compound derivative or mixtures thereof. If necessary or desirable, the liquid carrier can be dissolved or diluted with an appropriate solvent such that when combined with the demineralized bone particles of the invention a readily flowable composition is provided. Thus, the polyhydroxy compound or polyhydroxy derivatives can be a liquid in the pure or highly concentrated state at ambient temperature, e.g., 1.5-50xc2x0 C., or it can be a solid or semi-solid at this temperature in which case it becomes necessary to dissolve the material in a solvent such as water, physiological saline, ethanol, glycerol, glucose, propylene glycol, polyethylene glycol of from 200-1000 molecular weight, polyvinyl alcohol, etc. Of course, the liquid carrier can be made up of one or more liquid polyhydroxy compounds or derivatives in solution with one or more solid polyhdroxy compounds or derivatives.
Of the foregoing polyhydroxy compounds, glycerol and its liquid monesters and diesters, e.g. monacetin and diacetin, fructose, glucose and sucrose, and mixtures thereof are preferred. Where the polyhydroxy compound is a solid, e.g., sucrose, a solvent such as water, glycerol, polyethylene glycol of from 200-1000 average molecular weight, or mixture thereof is used to provide a cohesive solution or paste of the compound.
Where, in a particular osteoinductive composition, the bone component exhibits a tendency to quickly or prematurely separate from the carrier component or to otherwise settle out from the composition such that application of a fairly homogeneous composition is rendered difficult or inconvenient, it can be advantageous to include within the composition a substance whose thixotropic characteristics prevent or reduce this tendency. Thus, e.g., where the carrier component is glycerol and separation of the component occurs to an excessive extent where a particular application is concerned, a thickener such as a solution of polyvinyl alcohol, polyvinylpyrrolidone, cellulosic ester such as hydroxypropyl methylcellulose, carboxyl methylcellulose, pectin, food-grade texturizing agent, gelatin, dextran, collagen, starch, hydrolyzed polyacrylonitrile, hydrolyzed polyacrylamide, polyelectrolyte such as polyacrylic acid salt, hydrogels, chitosan, other materials that can suspend particles, etc., can be combined with the carrier in an amount sufficient to significantly improve the suspension-keeping characteristics of the composition.
As previously indicated, the bone composition of this invention can be freshly prepared just prior to use by mixing of the bone component, carrier and optional component(s) in any suitable sequence of separate mixing operations or all at once. Thus, the bone component can be mixed with the optional ingredient(s) and thereafter combined with the liquid carrier component, the bone component can be mixed with the carrier followed by addition of the optional ingredient(s) or the optional ingredients can be added to the carrier followed by addition of the bone component. Variations of these sequences of mixing operations are of course, possible. The amount of bone component which can be incorporated into the composition of this invention can vary widely with amounts of from about 5 to 80 weight percent, and preferably from about 20 to about 65 weight percent, being entirely suitable in most cases. To facilitate on-site preparation of the composition herein, the bone component, preferably in lyophilized form, and carrier (the latter, containing any of the optional ingredients identified above) can be stored in separate packages or containers under sterile conditions and brought together in intimate admixture at the moment of use for immediate application to a bone defect site employing any suitable means, e.g., a syringe and cannula. U.S. Pat. No. 4,458,733, the contents of which are incorporated by reference herein, describes a combined storage, mixing and application device that can be adapted to perform the foregoing functions of storage, mixing and application. Alternatively, the bone composition can be prepared well in advance and stored under sterile conditions until required for use, e.g., in the barrel of a syringe or other suitable applicator device. In a preferred embodiment, the flowable demineralized bone powder composition of this invention is packaged in kit form to facilitate the treatment of porous bone.
The following examples are illustrative of the preparation of a preferred flowable bone composition useful in the practice of the invention herein and its use to treat osteoporotic vertebrae. The examples are intended to illustrate certain preferred embodiments of the invention but are not intended to limit the practice of the invention as disclosed by the specification and set forth in the claims herein.

Method of inducing new bone growth in porous bone sites


Microdermabrasion and suction massage apparatus are included in a single unit and alternatively connectable through a mode switch to a source of vacuum. The microdermabrasion section of the unit includes a crystal pick up station operating with a venturi effect to draw crystals through a hole into an air stream. The size of the hole is variable to control crystal density. A bleed valve is provided to control crystal velocity without controlling crystal density, while a bypass valve is provided to control crystal density without controlling crystal velocity. In an associated method, a microdermabrasion procedure is performed on the skin of a patient at an operative site. The mode switch is operated to activate the suction massage apparatus within the unit. This step is followed by performing a suction massage procedure at the operative site in order to promote healing of the abraded skin. The unit can be back-flushed by connecting various portions of the unit to a pressurized output of the source of vacuum.

1. Field of the Invention
This invention relates generally to cosmetic apparatus and method used by a plastic surgeon, and more specifically to skin abrasion apparatus and cellulite massage apparatus.
2. Discussion of the Prior Art
Traditional dermabrasion has been used successfully to treat various types of scarring, for example scarring caused by acne. Wire brush and diamond fraise techniques have been used both, requiring local anesthesia and highly skilled surgical techniques. Bleeding has typically occurred requiring the surgeons and technicians to protect themselves from blood spray while performing the procedure. Postoperative complications have also been encountered.
In a new technique referred to as crystal microdermabrasion, aluminum oxide crystals flowing in an air stream have been applied to the skin. In this technique, there is less bleeding, fewer complications, better compliance, and no need for local anesthesia or high surgical skills. In the microdermabrasion technique, the velocity and density of crystals within the stream of air is related to the degree of abrasion which can occur over a fixed period of time. In the past, the crystal velocity has been controlled primarily by providing a bleed valve for the introduction of additional air into the stream of air. In a suction system this tends to slow the velocity of the operative air stream and thereby reduce the degree of abrasion. Although the velocity is decreased, the crystal density tends to stay the same with this approach.
Microdermabrasion handpieces have typically been formed with handles and caps which deine an abrasion chamber. The flow of crystals and the stream of air has been introduced into the abrasion chamber through a nozzle and along a supply path having a distal component. A return orifice communicating with the abrasion chamber has drawn the flow of crystals along a return path haaving proximal compnent. In the past, an abrasion window has been formed in the cap of the handpiece with the window being disposed only in the supply path of the crystal flow. In the past the window has been provided only with a circular configuation, These structural limitations have not tended to maximize the abrasive qualities of the stream.
A system for cellulite massage has been used by the same surgeons and technicians in an apparatus heretofore separate from the microdermabrasion apparatus. This procedure is, commonly referred to as endermologie massage, has had as its primary purpose the reformation of collagen fibers particularly in cellulite. Cellulite occurs as a combination of several factors which may be hormonal, circulatory, and nutritional. Inherent genetics also contribute to this condition where the skin tends to take an orange-peel texture. Nippling of the skin is relieved during this treatment by the applied suction massage. Congestion is alleviated by increasing oxygenation in the blood circulation to the tissue altered by cellulite. The procedure also increases exchanges with the connective tissue and boosts the metabolism rate allowing the body to dispose of toxins naturally. Stretching the collagen fibers and strengthening the elastic fibers make the surface of the skin smoother and firmer. This procedure, requiring a source of vacuuming has been of particular advantage not only in the treatment of cellulite, but also in post-operative liposuction care. In the after instance, post-operative endermologie treatments have maximized results and offered the additional advantage of keeping patients in communication with the practice and focusing on long-term goals. Particularly when combined with a dietary program and exercise, repeated small-volume liposuction with endermologie following each procedure, has shown significant results. contribute to this condition where the skin tends to take an orange-peel texture. Nippling of the skin is relieved during this treatment by the applied suction massage. Congestion is alleviated by increasing oxygenation in the blood circulation to the tissue altered by cellulite. The procedure also increases exchanges with the connective tissue and boosts the metabolism rate allowing the body to dispose of toxins naturally. Stretching the collagen fibers and strengthening the elastic fibers make of the surface of the skin become smoother and firmer. This procedure, requiring a source of vacuuming has been of particular advantage not only in the treatment of cellulite, but also in post-operative liposuction care. In the latter instance, post-operative endermologie treatments have maximized results and offered the additional advantage of keeping patients in communication with the practice and focusing on long-term goals. Particularly when combined with a dietary program and exercise, repeated small-volume liposuction with endermologie following each procedure, has shown significant results.
In the endermologie procedure, a source of vacuum is applied to a conduit terminating at an endermologie handpiece. The handpiece has typically been provided in the configuration of a cylinder having a single fixed diameter.
While these two apparatus, the microdermabrasion apparatus, and the endermologie apparatus, have commonly been provided as separate instruments, they nevertheless have been used by the same surgeons and technicians. More recently, it has been found that the microdermabrasion procedure can be facilitated by the use of an aspiration system to promote tissue blood supply and thereby facilitate fast healing and scar tissue repair. Under these circumstances, the aspiration or suction system associated with the endermologie apparatus has been found of value in the microdermabrasion procedure. Notwithstanding this advantageous combination, the two instruments have not heretofore been combined in a single unit.
In accordance with the present invention, a single unit as adapted for use with a microdermabrasion handpiece as well as an endermologie handpiece. A stream of air is controlled by a 3-way valve which alternatively directs the air along a first air stream to the microdermabrasion handpiece or a second air stream to the endermologie handpiece. The first air stream is directed through a source of crystals which are introduced into the first air stream to provide a flow of crystals which is then sent to the microdermabrasion handpiece. With the advent of a single unit, the mere selection of the 3-way valve permits the unit to be used for both microdermabrasion techniques and endermnologie techniques. This advantage is of particular interest because the microdermabrasion technique can be facilitated by the suction and massage associated with the endermologie technique.
Further control over the degree of abrasion can be provided by a valve which bypasses the source of crystals. A reduction in the amount of air flowing through the source of crystals reduces the crystal density without necessarily affecting the crystal velocity at the handpiece.
At the source of crystals, the first air stream is directed through a tube which is provided with a hole in communication with the crystals. This hole is sized and configured to limit the amount of crystals which can flow into the first air stream. Accordingly, the hole can be sized to control the crystal density by limiting the amount of crystals which can be introduced into a given volume of air. A larger hole results in a higher crystal density. Using this structure in combination with a bypass valve is of significant advantage in maximizing control over the crystal velocity density, and hence the degree of skin abrasion.
In the microdermabrasion handpiece, the abrasion window is positioned along the cap so that it is disposed between the supply path and the return path of the crystals. In a particular environment, the nozzle is positioned to direct the flow of crystals directly into the abrasion window of the cap. This seems to provide the greatest control over the skin abrasion process. It has been found that rectangular holes can offer certain advantages over the circular holes of the past. In these embodiments, the long dimension of the rectangle is typically oriented generally parallel to a plane including the nozzle and the return orifice.

Microdermabrasion and suction massage apparatus and method


A solid oxide fuel cell which has a solid electrolyte having an air electrode and a fuel electrode on its upper and lower surfaces respectively. The fuel electrode is made of a mixture of nickel, zirconium oxide and chromium oxide.

1. Field of the Invention
The present invention relates to a solid oxide fuel cell.
2. Description of Related Art
One of the conventional types of solid oxide fuel cells is a plate type. This type of solid oxide fuel cell has a laminate structure of cell units and interconnectors. Each cell unit comprises a solid electrolyte having a fuel electrode on one side and an air electrode on the other side, and conductive distributors which distribute a fuel gas (such as hydrogen) and air (or oxygen) entirely and evenly to the fuel electrode and the air electrode, respectively, and which also act as transmitters of electricity generated on the electrodes. The plate type solid oxide fuel cell has an advantage of having a large output per a unit volume. This is for the following reasons: By using thinner components, namely, thinner electrolytes and thinner interconnectors, a solid oxide fuel cell which contains more cell units keeping the same thickness can be obtained. Additionally, an electric current generated by the solid oxide fuel cell flows in the vertical direction, that is, in the thicknesswise direction, and the resistance is small. As a method of producing a thinner solid oxide fuel cell of this plate type, it has been suggested to sinter the components together after lamination of the components.
The electrodes are required to be excellently conductive and to be porous in such a degree as to allow gases to diffuse therein. Conventionally, a cerment of nickel and zirconium oxide has been used as the material of the fuel electrode. Generally, solid oxide fuel cells are operated at a temperature of about 1000.degree. C. for a long time, and during the operation, the cerment of nickel and zirconium oxide is being sintered to excess and losing its porosity. Moreover, if the above-mentioned producing method (sintering after lamination), in which the sintering temperature is over 1300.degree. C., is adopted, the porosity of the fuel electrode cannot be guaranteed.