WO2009070802A1 - Hybrid pigments with coupling agents - Google Patents

Abstract

A hybrid pigment composition and method of producing the hybrid pigment composition is provided. The hybrid pigment composition includes a dye or pigment, a coupling agent, and a fibrous clay. The fibrous clay is palygorskite, sepiolite, or a combination thereof. The hybrid pigment composition is produced by reacting the dye or pigment, coupling agent, and clay.

Description

HYBRID PIGMENTS WITH COUPLING AGENTS

RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application

Serial No. 60/991,532, filed November 30, 2007. This application discloses subject matter similar to that disclosed in U.S. Patent No. 7,052,541 ; U.S. Patent No. 7,429,294; U.S. Application Serial No. 11/351,577, filed February 10, 2006; and U.S. Application Serial No. 11/424,758, filed June 16, 2006; and U.S. Application Serial No. 12/068,115 filed February 1, 2008, the contents of each herein incorporated by reference in their entirety.

FIELD OF THE INVENTION

[0002] This invention is directed to hybrid pigments comprising a coupling agent and a manufacturing process of producing hybrid pigments comprising a coupling agent that have desired properties in the industry.

BACKGROUND

[0003] In the scientific literature, the term Maya blue refers to a "turquoise" brilliant shade of blue that is found on murals and archaeological artifacts, for example, throughout Mesoamerica. It is described in the literature as being composed of palygorskite clay and indigo, that when mixed and heated, produce the stable brilliant blue color similar to that found in Mesoamerica. Proposed methods of preparation were performed with the intent of trying to replicate the blue color found at the historical sites and to reproduce the techniques employed by the original Maya.

[0004] H. Van Olphen, Rutherford Gettens, Edwin Littman, Anna Shepard, and Luis

Torres were involved in the examination of organic/inorganic complex paint from the 1960's to the 1980's. In early studies, Littman and Van Olphen published information specifically on the synthesis of the Mayan organic/inorganic complex (Littman, Amer. Antiquity, 45:87-101, 1980; Littman, Amer. Antiquity, 47:404-408, 1982; Olphen, Amer. Antiquity, 645-646, 1966; Olphen, Science, 154:645-646, 1966). Their work did not describe the technique for making the colorant, nor explain the stability of the organic/inorganic complex. However, the results of their two decades of studies with respect to the ancient paint laid a foundation of knowledge for future investigators.

[0005] Littman synthesized indigo-attapulgite complexes and verified that his synthetic version was indistinguishable from the original pigments found in the pre-Hispanic murals and artifacts (Littman, Amer. Antiquity, 45:87-101, 1980; Littman, Amer. Antiquity, 47:404-408, 1982). The prepared samples had the same physical and chemical characteristics as the authentic Maya blue examined. Littman concluded that the remarkable stability of the attapulgite was due to the heat treatment the attapulgite received during the synthesis. Others have also synthesized compounds similar to that of Maya blue by a number of routes (Torres, Maya Blue: How the Mayas Could Have Made the Pigment, Mat. Res. Soc. Symp., 1988). They employed the Gettens test to determine whether the laboratory synthesis of Maya blue was indeed authentic with the same chemical resistant properties (Gettens, Amer. Antiquity, 27:557-564, 1962). The test was necessary because initial attempts of simply mixing the palygorskite clay produced the color of Maya blue but the mixture did not possess the same chemical properties as the original organic/inorganic complex samples.

[0006] Previous literature discussions of pH pertain to the alkaline pH required to reduce the indigo prior to contacting it with the clay (Littman, Amer. Antiquity, 45:87-101, 1980; Littman, Amer. Antiquity, 47:404-408, 1982). Moreover, there was a lack of understanding regarding the chemistry for producing stable and nontoxic paint systems by combining dyes and pigments with fibrous clays. U.S. Patent 3,950,180 describes color compositions that involve cationic organic basic colored compounds complexed to alkali-treated inorganic substances. [0007] More recently, several patents and patent applications discussed indigo and related organic dyes complexed in an ionic interaction with inorganic supports. PCT Publication No. WO 01/04216 also describes ionic interactions in color compositions, wherein organic dyes undergo ion exchange with charged inorganic clays.

[0008] U.S. Patent 3,950,180 covers a method of manufacturing color compositions that include zeolite and montmorillonite. U.S. Patent 5,061,290 covers a method of using indigo derivatives as a dyeing agent. U.S. Patent 4,246,036 covers the method of manufacturing color compositions that are comprised of asbestos-cement. U.S. Patent 4,640,862 covers color compositions that are used for coating an expanded polystyrene "drop-out" ceiling tile. U.S. Patent 4,868,018 covers color compositions that are used with a mixture of epoxy resin, epoxy resin hardener, and portland cement to form a coating which can be applied to a surface to form simulated marble products. U.S. Patent 4,874,433 covers a method for encapsulating color compositions in and/or to a zeolite. U.S. Patent 5,574,081 covers a method of manufacturing waterborne clay-containing emulsion paints with improved application performance using color compositions. U.S. Patent 5,972,049 covers the method of manufacturing and using color compositions to form dye carriers used in the dyeing process for hydrophobic textiles. U.S. Patent 5,993,920 covers the method of manufacturing and using color compositions with stone powder and/or cement powder, fine sawdust and/or the heart of a kaoliang stalk and other materials to form an incombustible artificial marble. U.S. Patent 6,339,084 covers the method of manufacturing thiazine-indigo pigments. U.S. Patent 6,402,826 covers the method and manufacturing of color compositions for paper coating.

[0009] U.S. Patents 7,052,541 and 7,429,294 describe color compositions comprising neutral indigo derivative pigments and dyes complexed to the surface of inorganic clays. These materials are useful as paints and coatings for artistic and industrial purposes, including use in cements, plastics, papers and polymers. Upon grinding and heating, the organic and inorganic component as solid mixtures or in aqueous solutions, the resulting color compositions have unprecedented stability relative to the original starting materials. U.S. Serial No. 11/351,577 describes the use of similar starting materials in methods that rely on UV-light for preparing color compositions.

[0010] Currently, bleeding can be a problem with hybrid pigments. For example the indigo (vat blue 1) and thioindigo (vat red 41) used to produce the Mayacrom® Blue and Mayacrom® Violet hybrid pigments migrate in olefins and bleed in various solvents used in paint and coating and printing ink applications. It is believed that impurities, such as salts and unreacted starting materials, in commercially available textile grade vat dyes for example, may contribute to bleeding.

SUMMARY

[0011] The present disclosure provides hybrid pigment compositions and methods of forming hybrid pigment compositions with improved properties including decreased or elimination of bleeding, increased opacity, thermal stability, lightfastness, and unique new colors.

[0012] In certain embodiments of the present disclosure, a hybrid pigment composition is provided comprising a dye or pigment, a coupling agent, and a fibrous clay. In certain embodiments, the hybrid pigment is a reaction product of the dye or pigment, coupling agent, and fibrous clay. In certain embodiments the fibrous clay is palygorskite, sepiolite, or a combination thereof.

[0013] In certain embodiments of the disclosure, the dye or pigment is selected from the group consisting of vat dyes, quinacridones, solvent dyes, and optical brighteners. In certain embodiments, the dye or pigment is selected from the group consisting of vat blue 1, vat red 1, vat red 41, pigment red 4, pigment red 19, pigment red 254, solvent red 149, disperse red 277, pigment yellow 53, pigment yellow 83, pigment yellow 151, solvent yellow 33, solvent yellow

43, solvent yellow 94, disperse yellow 54, D&C yellow 10, vat orange 5, solvent orange 60, solvent orange 63, solvent green 28, solvent violet 13, vat violet 3, carmine, and combinations thereof.

[0014] In certain embodiments of the disclosure, the coupling agent is selected from the group consisting titanates, zirconates, and silanes. In certain embodiments, the coupling agent is a titanate. In certain embodiments, the titanate is an organic alkoxy titanate. In certain embodiments, the coupling agent is tetra-isopropyl titanate or tetra-2-ethylhexyl titanate.

[0015] In certain embodiments of the disclosure, the hybrid pigment has an average particle size of about 0.01 μm to about 40 μm.

[0016] In certain embodiments of the disclosure, the hybrid pigment composition comprises the dye or pigment in an amount of 0.01 wt.% to about 50 wt.% based on the total weight of the hybrid pigment composition. In certain embodiments, the composition comprises the coupling agent in an amount of about 1 wt.% to about 30 wt.% based on the total weight of the hybrid pigment composition.

[0017] In certain embodiments of the disclosure, the hybrid pigment composition further comprises a polymer, carrier liquid, or inorganic material.

[0018] In certain embodiments of the present disclosure, a method of forming a hybrid pigment composition is provided. The method comprises providing a dye or pigment, coupling agent, and a fibrous clay; and reacting the dye or pigment, coupling agent, and fibrous clay to form the hybrid pigment.

[0019] In certain embodiments of the disclosure, the step of reacting the dye or pigment, coupling agent, and fibrous clay further comprises mixing the coupling agent and a fibrous clay.

The coupling agent and clay are reacted to form a first reaction product. The first reaction product is mixed with the dye or pigment, and the first reaction product and the dye or pigment to are reacted to form the hybrid pigment.

[0020] In certain embodiments of the disclosure, the step of reacting the dye or pigment, coupling agent, and fibrous clay further comprises mixing the coupling agent, clay, and dye or pigment; and reacting the coupling agent, clay, and dye or pigment.

[0021] In certain embodiments of the disclosure, the step of reacting the dye or pigment, coupling agent, and fibrous clay further comprises mixing the dye or pigment and the fibrous clay. The fibrous clay and the dye or pigment are reacted to form a first reaction product. The first reaction product is mixed with the coupling agent. The first reaction product and the coupling agent are reacted to form the hybrid pigment.

[0022] In certain embodiments of the disclosure, the step of reacting the dye or pigment, coupling agent, and fibrous clay further comprises forming a vapor of the coupling agent. The vapor of the coupling agent is passed over a fibrous clay so that the coupling agent condenses onto the clay. Dye or pigment is mixed with the clay and coupling agent, and the coupling agent, clay, and dye or pigment are reacted to form the hybrid pigment.

[0023] In certain embodiments of the disclosure, the step of reacting includes heating at least two of the dye or pigment, coupling agent, and clay. In certain embodiments, heating is carried out at a temperature of between about 100 ⁰C and 450 ⁰C. In certain embodiments, the temperature is between 125 ⁰C and 360 ⁰C. In certain embodiments, the duration of heating is from about 10 minutes to about 24 hours.

[0024] In certain embodiments of the disclosure, in the method of forming a hybrid pigment composition, the fibrous clay is palygorskite, sepiolite, or a combination thereof.

[0025] In certain embodiments of the disclosure, in the method of forming a hybrid pigment composition, the dye or pigment is selected from the group consisting of vat dyes, quinacridones, disperse dyes, solvent dyes, and optical brighteners. In certain embodiments, the dye or pigment is selected from the group consisting of vat blue 1, vat red 1, vat red 41, pigment red 4, pigment red 19, pigment red 254, solvent red 149, disperse red 277, pigment yellow 53, pigment yellow 83, pigment yellow 151, solvent yellow 33, solvent yellow 43, solvent yellow 94, disperse yellow 54, D&C yellow 10, vat orange 5, solvent orange 60, solvent orange 63, solvent green 28, solvent violet 13, vat violet 3, carmine, and combinations thereof. [0026] In certain embodiments of the disclosure, in the method of forming a hybrid pigment composition, the coupling agent is selected from the group consisting titanates, zirconates, and silanes. In certain embodiments, the coupling agent is a titanate. In certain embodiments, the titanate is an organic alkoxy titanate. In certain embodiments, the titanate is tetra-isopropyl titanate or tetra-2-ethylhexyl titanate.

[0027] In certain embodiments of the disclosure, the method further comprises mixing a polymer, carrier liquid, or inorganic material with the hybrid pigment.

[0028] In certain embodiments of the disclosure, a method of forming a hybrid pigment composition is provide comprising (a) providing a dye or pigment, coupling agent, and a fibrous clay, and (b) heating a combination of at least two of the dye or pigment, coupling agent, and fibrous clay together to form the hybrid pigment. In certain other embodiments, step (b) comprises mixing the coupling agent and the fibrous clay, heating the coupling agent and clay, mixing the heated coupling agent and clay with the dye or pigment, and heating the mixture of the coupling agent and clay, and dye or pigment to form the hybrid pigment. In certain other embodiments, step (b) comprises mixing the coupling agent, clay, and dye or pigment; and heating the coupling agent, clay, and dye or pigment. In certain other embodiments, step (b) comprises mixing the dye or pigment and the fibrous clay, heating the fibrous clay and the dye or pigment, mixing the heated clay and dye or pigment with the coupling agent, and heating the mixture of clay and dye or pigment and the coupling agent to form the hybrid pigment. In certain other embodiments of the disclosure, step (b) comprises forming a vapor of the coupling agent, passing the vapor of the coupling agent over a fibrous clay so that the coupling agent condenses onto the clay, mixing the dye or pigment with the clay and coupling agent, and heating the coupling agent, clay, and dye or pigment to form the hybrid pigment. [0029] In certain embodiments of the disclosure, the step of heating comprises heating at a temperature of between about 100 ⁰C and 450 ⁰C. In certain embodiments, the temperature is between about 125 °C and 360 °C. [0030] These, and other, embodiments of the disclosure will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. It should be understood, however, that the following description, while indicating various embodiments of the disclosure and numerous specific details thereof, is given by way of illustration and not of limitation, and the invention includes appropriate substitutions, modifications, additions and/or rearrangements.

DETAILED DESCRIPTION

[0031] The present disclosure includes a composition of matter comprising organic pigments and/or dyes complexed with a solid support and a coupling agent. Such compositions can, in certain embodiments, be considered color compositions. In certain embodiments, the support is an inorganic support, such as a clay. Such materials have a wide range of uses including in paints and other coatings for artisan and industrial purposes, as well in cements, papers, and polymers. Various methods for making these compositions also are provided and include blending, grinding, and heating. Alteration of properties before synthesis, such as pH, particle size and support type, will change the color of the final composition. Because of the unique chemical nature of the resulting product, the compositions remain stable over time and under a variety of environmental conditions.

[0032] The selection of dyes or pigments, coupling agents, and a support is based on providing the desired stability. The present inventors have conducted experiments to identify classes of dyes which are capable of forming the necessary chemical structures to impart such stability, as well as providing the desired color.

[0033] In certain embodiments of the disclosure, hybrid pigment compositions were prepared by mixing dye or pigment, coupling agent, and fibrous clay using a blender, coffee grinder, or mortar and pestle. Once prepared, compositions according to the present disclosure can be heated in the temperature range of 100 ⁰C to 450 ⁰C using a tube furnace. In certain embodiments, the compositions are heated in the temperature range of 125 ⁰C to 360 ⁰C. Small ceramic boats that hold about 1 gram of hybrid pigment each were used for heating samples of the hybrid pigment composition in the tube furnace. Dyes or Pigments

[0034] In certain embodiments of the disclosure, the dyes or pigments include vat dyes, quinacridones and other pigments, disperse dyes, solvent dyes, and optical brighteners. In certain embodiments, the dye or pigment is wherein the dye or pigment is selected from the group consisting of vat blue 1, vat red 1 (laked form - soluble in H₂O), vat red 41, pigment red 4, pigment red 19, pigment red 254, solvent red 149, disperse red 277, pigment yellow 53, pigment yellow 83, pigment yellow 151, solvent yellow 33, solvent yellow 43, solvent yellow 94, disperse yellow 54, D&C yellow 10, vat orange 5, solvent orange 60, solvent orange 63, solvent green 28, solvent violet 13, vat violet 3, carmine, Uvitex® and Tinopal® optical brighteners, commercially available from Ciba®, Tico yellow 597 (a mixture of pigment yellow 53, pigment yellow 83, and pigment yellow 151), commercially available from Heubach GmbH, and combinations thereof.

Coupling Agents

[0035] In certain embodiments of the disclosure, the coupling agent is selected from the group consisting of titanates, zirconates and silanes. In certain embodiments, the coupling agent is a organic alkoxy titanate, zirconate, or silane. In certain embodiments of the disclosure, the coupling agent is a Tyzor® titanate or zirconate. Tyzor® titanates and zirconates are commercially available form DuPont™. In certain embodiments, the titanate coupling agent is an organic alkoxy titanate. In certain embodiments, the titanates are Tyzor® TOT and Tyzor® TPT. Tyzor® TOT and TPT are highly reactive organic alkoxy titanates, which can be used in crosslinking reactions. Tyzor® TPT is tetra-isopropyl titanate, and Tyzor® TOT, is tetra-2- ethylhexyl titanate.

[0036] Though not intending to be bound by any particular theory, it is believed the coupling agents tie up any loose molecules, even impurities, that may be causing vat dyes to bleed. Addition of the coupling agents also enhances desired properties such as opacity, thermal stability, lightfastness, and new unique colors.

Clays

[0037] In certain embodiments of the disclosure, the clays include fibrous clays including palygorskite, sepiolite, and combinations thereof. Temperature

[0038] In certain embodiments of the disclosure, the coupling agent, clay, and/or dye are reacted within the temperature range of about 100 ⁰C to about 450 ⁰C. In certain embodiments, the coupling agent, clay, and/or dye are reacted at one of the following temperatures: 170 ⁰C, 200 ⁰C, 250 °C, 300 °C, 360 °C.

Time

[0039] In certain embodiments of the disclosure, the coupling agent, clay, and/or dye or pigment are heated to the desired temperature for a time period ranging from about 1 minute to about 24 hours. In certain embodiments of the disclosure, the coupling agent, clay, and/or dye or pigment are heated to the desired temperature for a time period ranging from 10 minutes to 1 hour.

Reaction Methods

[0040] Several methods were used to form the hybrid pigments according to embodiments of the present disclosure, as explained below.

[0041] In one embodiment, the coupling agent and the clay are mixed together. The mixture of clay and coupling agent is heated to react the clay and coupling agent. The dye or pigment is subsequently mixed with the reaction product of the clay and coupling agent, and the mixture of dye and the reaction product is heated to react the dye or pigment with the reaction product to form the final hybrid pigment.

[0042] In another embodiment, the coupling agent, clay, and dye or pigment are mixed together, and all three components are reacted together by heating to form the final product.

[0043] In another embodiment, a hybrid pigment in which the dye or pigment is already reacted with clay, such as Mayacrom® Pigment, is mixed with coupling agent. The hybrid pigment and coupling agent are subsequently reacted by heating to form the final hybrid pigment.

[0044] In another embodiment, the coupling agent is vaporized and the coupling agent vapor is passed over clay, so that the coupling agent condenses onto the clay. Dye or pigment is subsequently mixed with the coupling agent and clay, and the mixture is heated to react the components to form the final hybrid pigment.

[0045] In certain embodiments of the present invention, mixing of the various components (e.g. - coupling agent, clay, and dye or pigment) is performed by grinding, blending, or mortar and pestle. In certain embodiments grinding is performed with a coffee grinder and blending is performed with a kitchen blender

[0046] The suitability of the hybrid pigments are determined by whether they bleed or migrate. Bleeding is determined by adding the hybrid pigments to a suitable solvent, such as isopropanol or acetone, and observing whether bleeding occurs. To determine whether the samples disclosed herein bleed, about 0.01 grams of hybrid pigment was placed in a vial with acetone or isopropanol. The mixture was shaken and the hybrid pigment was allowed to settle to the bottom of the vial. Bleeding was determined by observing whether the solvent over the hybrid pigment had color, (i.e. - the dye or pigment dissolved into the liquid phase in the vial). [0047] Compositions of the present disclosure may, in certain embodiments, refer to a pigment or dye complexed to a support, such as a fibrous clay. Non-limiting examples of uses of such compositions complexed to a support include colorants and coloring additives, coating purposes, paint powders and paints, cosmetic formulation ingredients, cement and printing inks, and plastics and leather colorants. Compositions according to the present disclosure may be a solid, such as the hybrid pigment or the hybrid pigment mixed with other solid material; or a liquid, such as a paint. Compositions may be resistant to decomposition due to light, acids, alkalis, and/or solvents.

[0048] Compositions of the present disclosure may, in certain embodiments, comprise a polymer, carrier liquid, and/or a binding agent, as described herein. The binding agent may be an organic binding agent. Compositions may comprise a cement, a polymer, an inorganic material, and/or an organic binding agent. A composition may be further defined as, for example, a shapeable molding material or a shapeable tile material. The terms "shapeable molding material" and "shapeable tile material" are well-known to those of skill in the art. Shapeable molding and/or tile materials may be made according to any method of the present disclosure. In such moldings and materials, the composition may further comprise a cement, inorganic binder, and/or a polymer. [0049] One or more binding agent or modifiers may be added to the composition to increase stability, uniformity, spread ability, adhesion, coating thickness, etc. Binding agents and modifiers are well known in the art of composition formulation, such as paints. Binding agents such as solvent-containing binding agents (acryl, cyclized rubber, butyl rubber, hydrocarbon resin, α-methylstyrene-acrylonitrile copolymers, polyester imide, acryl acid butyl esters, polyacrylic acid esters, polyurethanes, aliphatic polyurethanes and chlorosulfonated polyethylene), and thermoplastic materials (polyolefms, α-ethylstyrene-acrylonitrile copolymers, polyester imide and polyamide) may be added to the paint composition. Similarly, polymers such as acrylate, styrene acrylate, acrylonitrile copolymer, polyethylene, polyethylene oxide, chlorosulfonated polyethylene, ethylene-acrylic acid copolymer, methacrylate, vinylpyrrolidone- vinyl acetate copolymer, vinylidene chloride copolymer, polyvinylpyrrolidone, polyisopropyl acrylate, polyurethane, cyclized rubber, butyl rubber, hydrocarbon resin, α-methylstyrene- acrylonitrile copolymer, polyester imide, acryl acid butyl esters, or polyacrylic acid esters may be added.

[0050] The hybrid pigment can be used in a paint composition. The paint composition can be blended with a variety of other media including gum arabic, linseed oil, copal, egg tempura, and turpentine to create blended systems. The blended paint color can be altered depending on the medium in which it is blended.

Samples

[0051] The following Samples are included to demonstrate certain embodiments of the disclosure. It should be appreciated by those of skill in the art that the techniques disclosed in the Samples which follow represent techniques discovered by the inventor. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.

Sample 1

[0052] Mayacrom® Blue B 1000 was combined with Tyzor® TOT tetra-2-ethylhexyl titanate so that the composition was 10% by weight of Tyzor® TOT based on the total weight of the composition. The mixture was subsequently heated for 10 minutes at 360 ⁰C. The color of the resulting hybrid pigment was dark blue and the hybrid pigment bled.

Sample 2

[0053] Tyzor® TOT was vaporized and the vapor was passed over Mayacrom® Blue

BlOOO. The vapor condensed on the Mayacrom® Blue BlOOO. The mixture was heated for 10 minutes at 360 ⁰C. The color of the resulting hybrid pigment was a very dark blue and though the hybrid pigment bled, it bled much less than Sample 1.

Sample 3

[0054] Milled palygorskite clay was mixed with 5% by weight of Tyzor® TOT based on the total weight of the composition and then blended with 8% of vat red 41 by weight based on the total weight of the composition using a kitchen blender and heated at 170 ⁰C for 9 hours. 15% by weight Tyzor® TOT based on the total weight of the composition was ground together with the blended composition using a coffee grinder and the composition was subsequently heated for 10 minutes at 360 ⁰C. No bleeding of the hybrid pigment was observed.

Sample 4

[0055] 8% by weight vat red 41 based on the total weight of the hybrid pigment composition was blended with milled palygorskite clay using a kitchen blender and the resulting composition was heated at 170 ⁰C for 9 hours. The composition was subsequently heated for 10 minutes at 360 ⁰C. The color turned to a slightly darker violet and bleeding was observed.

Sample 5

[0056] 10% by weight Tyzor® TOT based on the total weight of the composition was ground with milled palygorskite clay using a coffee grinder. 8% by weight solvent yellow based on the total weight of the hybrid pigment composition was added to the TOT/palygorskite composition and ground using a mortar and pestle. The resulting mixture was heated for 10 minutes at 300 ⁰C. Bleeding of the hybrid pigment was observed. Sample 6

[0057] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight solvent red 19 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. No bleeding of the violet hybrid pigment was observed.

Sample 7

[0058] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight vat red 1 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. No bleeding of the violet hybrid pigment was observed.

Sample 8

[0059] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight vat orange 5 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The dark perylene red hybrid pigment bled slightly.

Sample 9

[0060] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight of vat blue 1 (indigo) based on the total weight of the hybrid pigment composition was ground together with the palygorskite/TOT mixture using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The dark blue pigment bled slightly.

Sample 10

[0061] Milled palygorskite clay was mixed with 5% by weight based on the total weight of the composition of Tyzor® TOT and then blended with 8% by weight of vat red 41 based on the total weight of the composition using a kitchen blender and heated at 170 ⁰C for 9 hours. The blended composition was subsequently heated for 60 minutes at 200 ⁰C. Bleeding of the purple hybrid pigment was observed.

Sample 11

[0062] Milled palygorskite clay was blended with 8% by weight based on the total weight of the composition of vat red 41 using a kitchen blender and heated at 170 ⁰C for 9 hours. The blended composition was subsequently heated for 60 minutes at 200 ⁰C. Bleeding of the purple hybrid pigment was observed.

Sample 12

[0063] Milled palygorskite clay was mixed with 5% by weight based on the total weight of the composition of Tyzor® TOT and then blended with 8% by weight of vat red 41 based on the total weight of the composition using a kitchen blender and heated at 170 ⁰C for 9 hours. The blended composition was subsequently heated for 60 minutes at 250 ⁰C. Unlike Sample 10, the color of the hybrid pigment changed from purple to blue, but it still bled.

Sample 13

[0064] Milled palygorskite clay was blended with 8% by weight based on the total weight of the composition of vat red 41 and then heated at 170 ⁰C for 9 hours. The blended composition was subsequently heated for 60 minutes at 250 ⁰C. Unlike Sample 11, the color changed to a bluer shade of purple, but it still bled.

Sample 14

[0065] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight vat red 41 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The color of the hybrid pigment turned blue, but bleeding was observed. Sample 15

[0066] Milled sepiolite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight vat red 41 based on the total weight of the hybrid pigment composition was ground together with sepiolite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The color of the hybrid pigment was a mix of blue and blue-purple. Bleeding was observed.

Sample 16

[0067] Milled sepiolite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight solvent yellow 33 based on the total weight of the hybrid pigment composition was ground together with sepiolite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The yellow hybrid pigment bled and there was some sublimation of the composition visible after about 5 minutes.

Sample 17

[0068] Milled sepiolite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight vat blue 1 (indigo) based on the total weight of the hybrid pigment composition was ground together with sepiolite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The dark blue hybrid pigment bled slightly.

Sample 18

[0069] Milled sepiolite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight vat orange 5 based on the total weight of the hybrid pigment composition was ground together with sepiolite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The brown hybrid pigment bled slightly.

Sample 19 [0070] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight vat red 41 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The color of the hybrid pigment was a dark violet and it bled a violet color.

Sample 20

[0071] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight vat orange 5 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The hybrid pigment was strongly red in color and it bled.

Sample 21

[0072] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight vat blue 1 (indigo) based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The hybrid pigment was strongly blue in color and it bled.

Sample 22

[0073] Milled palygorskite clay, 10% by weight Tyzor® TOT, 8% by weight solvent yellow 33 based on the total weight of the hybrid pigment composition combined and heated for 15 minutes at 300 ⁰C. The hybrid pigment bled. The color of the hybrid pigment was a darker yellow than Sample 5 and sublimation was observed within 5 minutes.

Sample 23 [0074] An additional 40% by weight Tyzor® TOT based on the total weight of the pigment composition was added to Sample 22 and the composition was subsequently heated for 15 minutes at 300 ⁰C. The hybrid pigment turned brown and bled.

Sample 24

[0075] Milled palygorskite clay and 10% by weight Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight vat red 1 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TOT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The greyish-light purple hybrid pigment did not bleed.

Sample 25

[0076] Milled palygorskite clay was mixed with 5% by weight of Tyzor® TOT based on the total weight of the composition and then blended with 8% by weight of vat red 41 based on the total weight of the composition and heated at 170 ⁰C for 9 hours. The blended composition was heated for 15 minutes at 300 ⁰C. The blue hybrid pigment bled.

Sample 26

[0077] Milled palygorskite clay was blended with 8% by weight of vat red 41 based on the total weight of the composition and heated at 170 ⁰C for 9 hours. The blended composition was heated for 15 minutes at 300 ⁰C. The violet hybrid pigment had a slight blue tone and it bled.

Sample 27

[0078] Milled Palygorskite clay was mixed with 10% by weight of Tyzor® TOT based on the total weight of the composition and heated at 300 ⁰C for 15 minutes. After heating, the palygorskite/Tyzor® composition was ground together using a mortar and pestle with 8% by weight of vat red 41 based on the total weight of the composition and subsequently heated at 300 ⁰C for 15 minutes. The hybrid pigment was a duller blue than unheated palygorskite/Tyzor® TOT composition. The hybrid pigment bled less than Sample 14. Sample 28

[0079] Milled sepiolite clay was mixed with 10% by weight of Tyzor® TOT based on the total weight of the composition and heated at 300⁰C for 15 minutes. After heating, the sepiolite/Tyzor® composition was ground together using a mortar and pestle with 8% by weight of vat red 41 based on the total weight of the composition and subsequently heated at 300 ⁰C for 15 minutes. The hybrid pigment turned purple and was as bright as unheated sepiolite and dye. The hybrid pigment bled less than Sample 15.

Sample 29

[0080] Milled palygorskite clay was ground together with 10% by weight of Tyzor®

TOT based on the total weight of the composition using a coffee grinder and subsequently heated at 300 ⁰C for 15 minutes. The composition became darker after heating.

Sample 30

[0081 ] Milled sepiolite clay was ground together with 10% by weight of Tyzor® TOT based on the total weight of the composition using a coffee grinder and heated at 300 ⁰C for 15 minutes. The composition did not change color after heating.

Sample 31

[0082] Milled palygorskite clay was mixed with 5% by weight of Tyzor® TOT based on the total weight of the composition and then blended with 8% by weight of vat red 41 based on the total weight of the composition and heated at 170 ⁰C for 9 hours. The blended composition was heated for 15 minutes at 360 ⁰C. The dull blue hybrid pigment did not bleed.

Sample 32

[0083] Milled palygorskite clay was ground together with 10% by weight of Tyzor®

TOT based on the total weight of the hybrid pigment composition using a coffee grinder. The palygorskite/Tyzor® composition was ground together with 8% by weight of vat red 41 based on the total weight of the composition using a mortar and pestle and subsequently heated at 360 ⁰C for 10 minutes. The hybrid pigment was a dark blue and did not bleed. Sample 33

[0084] Milled sepiolite clay was ground together with 10% by weight of Tyzor® TOT based on the total weight of the hybrid pigment composition using a coffee grinder. The palygorskite/Tyzor® composition was ground together with 8% by weight of vat red 41 based on the total weight of the composition using a mortar and pestle and subsequently heated at 360 ⁰C for 10 minutes. The hybrid pigment was a dark purple and did not bleed.

Sample 34

[0085] Milled Palygorskite clay was blended with 8% by weight of vat red 41 based on the total weight of the composition using a kitchen blender and subsequently heated at 170 ⁰C for 9 hours. The composition was subsequently heated at 360 ⁰C for 10 minutes. The composition turns blue. The hybrid pigment bleeds slightly, but less than the same composition heated at lower temperatures.

Sample 35

[0086] Milled palygorskite clay was ground together with 10% by weight of Tyzor®

TOT based on the total weight of the composition using a coffee grinder and subsequently heated at 360 ⁰C for 10 minutes. The composition turned a dark grey after heating.

Sample 36

[0087] Milled sepiolite clay was ground together with 10% by weight of Tyzor® TOT based on the total weight of the composition using a coffee grinder and subsequently heated at 360 ⁰C for 10 minutes. The composition turned a slightly dark beige after heating.

Sample 37

[0088] Milled palygorskite clay was heated at 360 ⁰C for 10 minutes. The composition turned light grey after heating.

Sample 38

[0089] Milled sepiolite clay was heated at 360 ⁰C for 10 minutes. The color of the composition changed very little, taking on a slightly more yellow tone after heating. Sample 39

[0090] Milled palygorskite clay was ground together with 10% by weight of Tyzor®

TOT based on the total weight of the hybrid pigment composition using a coffee grinder. The palygorskite/Tyzor® composition was ground together with 8% by weight of vat orange 5 based on the total weight of the composition using a mortar and pestle and subsequently heated at 360 ⁰C for 10 minutes. The dark red hybrid pigment bled, but bled less than the same hybrid pigment heat treated at lower temperatures.

Sample 40

[0091] Milled palygorskite clay was ground together with 10% by weight of Tyzor®

TOT based on the total weight of the hybrid pigment composition using a coffee grinder. The palygorskite/Tyzor® composition was ground together with 60% by weight of Uvitex® optical brightener based on the total weight of the composition using a mortar and pestle and subsequently heated at 200 ⁰C for 30 minutes. The hybrid pigment appeared brighter and appeared to fluoresce more than compositions without Tyzor® TOT.

Sample 41

[0092] Milled sepiolite clay was ground together with 10% by weight of Tyzor® TOT based on the total weight of the hybrid pigment composition using a coffee grinder. The palygorskite/Tyzor® composition was ground together with 60% by weight of Uvitex® optical brightener based on the total weight of the composition using a mortar and pestle and subsequently heated at 200 ⁰C for 30 minutes. The hybrid pigment appeared brighter and appeared to fluoresce more than Sample 40.

Sample 42

[0093] Milled palygorskite clay was ground together with 10% by weight of Tyzor®

TOT based on the total weight of the composition using a coffee grinder and subsequently heated at 200 ⁰C for 10 minutes. The composition did not change color after heating.

Sample 43 [0094] Milled sepiolite clay was ground together with 10% by weight of Tyzor® TOT based on the total weight of the composition using a coffee grinder and subsequently heated at 200 ⁰C for 10 minutes. The composition did not change color after heating.

Sample 44

[0095] The final composition from Sample 42 was ground together with 8% by weight of vat red 41 based on the weight of the total composition using a mortar and pestle. The composition was subsequently heated for 30 minutes at 200 ⁰C. The hybrid pigment appeared to bleed much less than compositions prepared without titanate.

Sample 45

[0096] The final composition from Sample 43 was ground together with vat 8% by weight of vat red 41 based on the weight of the total composition using a mortar and pestle. The composition was subsequently heated for 30 minutes at 200 ⁰C. The hybrid pigment appeared to bleed much less than compositions prepared without titanate.

Sample 46

[0097] Tyzor® TOT was placed in the middle in a boat in the middle of a tube. 0.5 grams of milled palygorskite clay was placed in a vial at the end of the tube so that the TOT vapor condensed into vial and coat the palygorskite clay. The TOT and the palygorskite were heated for 15 minutes at 300 ⁰C. No color change of the composition was observed after heating.

Sample 47

[0098] The composition of Sample 46 was ground together with 8% by weight of vat red

41 based on the total weight of the composition using a mortar and pestle and subsequently heated for 15 minutes at 300 ⁰C. The hybrid pigment turned blue and it appeared to bleed less than compositions prepared without titanate.

Sample 48 [0099] Prior to heating at 300 ⁰C, 1/2 of the composition of Sample 47 was heated at 200

⁰C for 30 minutes. The hybrid pigment retained its violet color after heating and bled less than compositions prepared without titanates.

Sample 49

[0100] Milled palygorskite clay and 10% by weight Tyzor® TPT, a tetra-isopropyl titanate, based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 8% by weight solvent yellow 33 based on the total weight of the hybrid pigment composition was ground together with palygorskite/TPT composition using a mortar and pestle. The resulting mixture was heated for 15 minutes at 300 ⁰C. The hybrid pigment turned blue and appeared not to initially bleed, but bled slightly the next day.

Sample 50

[0101] Prior to heating at 300 ⁰C, 1/2 of the composition of Sample 49, was heated at 200

⁰C for 30 minutes. The color of the hybrid pigment remained violet and appeared not to initially bleed, but bled slightly the next day.

Sample 51

[0102] Milled palygorskite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, commercially available from Day GIo Color Corp. as Day GIo D- 149, based on the total weight of the hybrid pigment composition was ground together with the palygorskite/TPT mixture using a mortar and pestle. The resulting mixture was heated at 200 ⁰C for 15 minutes. The dark, bright pink hybrid pigment bled.

Sample 52

[0103] Milled sepiolite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149 based on the total weight of the hybrid pigment composition was ground together with the sepiolite/TPT mixture using a mortar and pestle. The resulting mixture was heated at 200 ⁰C for 15 minutes. The dark, bright pink hybrid pigment bled. Sample 53

[0104] Milled palygorskite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, based on the total weight of the hybrid pigment composition was ground together with the Palygorskite/TPT mixture using a mortar and pestle. The resulting mixture was heated at 360 ⁰C for 15 minutes. The hybrid pigment composition decomposed.

Sample 54

[0105] Milled sepiolite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, based on the total weight of the hybrid pigment composition was ground together with the Sepiolite/TPT mixture using a mortar and pestle. The resulting mixture was heated at 360⁰C for 15 minutes. The hybrid pigment composition decomposed.

Sample 55

[0106] Milled sepiolite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, based on the total weight of the hybrid pigment composition was ground together with the Sepiolite/TPT mixture using a mortar and pestle. The resulting mixture was heated at 250 ⁰C for 15 minutes. The dark pink hybrid pigment bled.

Sample 56

[0107] Milled palygorskite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, based on the total weight of the hybrid pigment composition was ground together with the palygorskite/TPT mixture using a mortar and pestle. The resulting mixture was heated at 250 ⁰C for 15 minutes. The dark pink hybrid pigment bled.

Sample 57 [0108] Milled palygorskite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, based on the total weight of the hybrid pigment composition was ground together with the palygorskite/TPT mixture using a mortar and pestle. The resulting mixture was heated at 300 ⁰C for 15 minutes. The hybrid pigment bled slightly, but started decomposing.

Sample 58

[0109] Milled sepiolite clay and 10% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, based on the total weight of the hybrid pigment composition was ground together with the sepiolite /TPT mixture using a mortar and pestle. The resulting mixture was heated at 300 ⁰C for 15 minutes. The hybrid pigment bled slightly, but started decomposing.

Sample 59

[0110] Milled sepiolite clay and 10% by weight of Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149 based on the total weight of the hybrid pigment composition was ground together with the sepiolite /TOT mixture using a mortar and pestle. The resulting mixture was heated at 240 ⁰C for 10 minutes. The dark pink hybrid pigment bled.

Sample 60

[0111] Milled palygorskite clay and 10% by weight of Tyzor® TOT based on the total weight of the hybrid pigment composition were ground together using a coffee grinder. 20% by weight solvent red 149, based on the total weight of the hybrid pigment composition was ground together with the palygorskite /TOT mixture using a mortar and pestle. The resulting mixture was heated at 240 ⁰C for 10 minutes. The dull-purplish hybrid pigment bled.

Sample 61

[0112] Milled palygorskite clay and 5% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were blended together using a kitchen blender. The blended mixture was heated at 200 ⁰C for 30 minutes. The resulting stable mixture was clay colored.

Sample 62

[0113] Milled palygorskite clay and 20% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were blended together using a kitchen blender. The blended mixture was heated at 200 ⁰C for 30 minutes. The resulting stable mixture was clay colored.

Sample 63

[0114] Milled sepiolite clay and 5% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were blended together using a kitchen blender. The blended mixture was heated at 200 ⁰C for 30 minutes. The resulting stable mixture was clay colored.

Sample 64

[0115] Milled sepiolite clay and 20% by weight of Tyzor® TPT based on the total weight of the hybrid pigment composition were blended together using a kitchen blender. The blended mixture was heated at 200 ⁰C for 30 minutes. The resulting stable mixture was clay colored.

Sample 65

[0116] The palygorskite/TPT mixture of Sample 61 was ground together with 8% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 200 ⁰C for 60 minutes. The purple hybrid pigment appeared not to bleed, but bled slightly overnight. The hybrid pigment was a brighter purple than the hybrid pigment of Sample 66.

Sample 66

[0117] The palygorskite/TPT mixture of Sample 62 was ground together with 8% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 200 ⁰C for 60 minutes. The dull purple hybrid pigment appeared not to bleed, but bled slightly overnight. The purple hybrid pigment was bluer than the hybrid pigment of Sample 68.

Sample 67

[0118] The sepiolite/TPT mixture of Sample 63 was ground together with 8% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 200 ⁰C for 60 minutes. The bright violet hybrid pigment appeared not to bleed, but bled slightly overnight.

Sample 68

[0119] The sepiolite/TPT mixture of Sample 64 was ground together with 20% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 200 ⁰C for 60 minutes. The bright violet hybrid pigment appeared not to bleed, but bled slightly overnight.

Sample 69

[0120] The palygorskite/TPT mixture of Sample 61 was ground together with 8% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 360 ⁰C for 15 minutes. The purplish-blue hybrid pigment did not bleed.

Sample 70

[0121] The palygorskite/TPT mixture of Sample 62 was ground together with 8% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 360 ⁰C for 25 minutes. The dark blue hybrid pigment did not bleed, but appeared to begin decomposing.

Sample 71

[0122] The sepiolite/TPT mixture of Sample 63 was ground together with 8% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 360 ⁰C for 25 minutes. The blue hybrid pigment did not bleed.

Sample 72

[0123] The sepiolite/TPT mixture of Sample 64 was ground together with 8% by weight vat red 41 based on the total weight of the hybrid pigment composition using a coffee grinder. The resulting mixture was heated at 360 ⁰C for 15 minutes. The dull, dark purplish-blue colored hybrid pigment did not bleed.

Sample 73

[0124] Vat red 41 was heated for 60 minutes at 390 ⁰C. The heated dye had a black color with fiber crystals collected from the tube after sublimation. When subsequently ground the material retains its purple color.

Sample 74

[0125] Vat red 41 was heated for 10 minutes at 360 ⁰C. The heated dye had a black color with fiber crystals collected from the tube after sublimation. When subsequently ground the material retains its purple color.

Sample 75

[0126] Vat red 41 was heated for 10 minutes at 300 ⁰C. No crystals developed by heating. The heated dye has a little metallic color, but is not black.

Sample 76

[0127] The palygorskite/TPT mixture of Sample 62 was mixed with 8% by weight of the heated vat red 41 of Sample 75 based on the total weight of the hybrid pigment composition using a mortar and pestle. The resulting mixture was heated at 200 ⁰C for 60 minutes. The dull violet hybrid pigment bled slightly.

Sample 77 [0128] Milled palygorskite clay was ground together with 20% by weight Tyzor®TPT based on the total weight of the hybrid pigment composition. The palygorskite/TPT mixture was ground with 8% by weight of the heated vat red 41 of Sample 75 based on the total weight of the hybrid pigment composition using a mortar and pestle. The resulting mixture was heated at 200 ⁰C for 60 minutes. The dull violet hybrid pigment bled slightly.

[0129] The samples tested are listed in Table 1.

TABLE 1-1

Table 1-2

Table 1-3

[0130] In certain embodiments of the disclosure, bleeding was reduced in hybrid pigments comprising solvent dyes. Vat orange 5 and vat blue 1 exhibited minimal bleeding when heated at 360°C and the color of the final hybrid pigments was much darker. In certain embodiments, solvent red 19 and vat red 1 do not bleed, but the colors of the final hybrid pigments were much darker than hybrid pigments without the titanate coupling agent. The samples with optical brighteners both appeared much brighter under fluorescence with the titanates. The use of the coupling agents can eliminate bleeding when using vat red 41. [0131] Vat red 41 changes from a pink to a violet color when reacted with palygorskite clay and no titanate at 170 ⁰C. When the palygorskite clay is reacted with titanate and dye using different reaction methods at 200 °C, the color also changes to a violet, and the bleeding is reduced. The best results at this temperature (200 ⁰C) involved reacting the clay (either sepiolite or palygorskite) with the titanate, Tyzor TPT, and heating at 200 ⁰C for 30 minutes then reacting the vat red 41 with the clay (already reacted with titanate) and heating at 200 °C for 1 hour. [0132] As explained in the Samples and shown in Table 1, heating at 300 °C using different reaction methods caused the violet pigment to turn blue; this was observed with and without the titanate. The sample bled much less, but bleeding was still evident. In certain embodiments, heating at 360 °C with the titanate eliminated all bleeding. The elimination of bleeding only occurred when the titanate is used. Without the titanate there was still slight bleeding. The color of the pigment is a dark blue when using palygorskite clay and it is a dark violet when using sepiolite clay.

[0133] In certain embodiments of the disclosure, the clays were tested at 360 ⁰C with and without titanate. The palygorskite becomes darker and is a light grey color without titanate and a very dark grey color with titanate. Sepiolite does not change color without titanate, but does turns slightly darker and more beige with titanate. The change in color of vat red 41 with palygorskite at 360 ⁰C from violet to blue may be due to the palygorskite clay changing color not the vat red 41. In certain embodiments of the invention sepiolite clay is mixed with the titanates at temperatures above 300 °C because it appears to withstand higher temperatures than the palygorskite clay.

[0134] In certain embodiments of the disclosure, the best result for eliminating bleeding occurred at 360 °C when heated for 10 min with either titanate. Heating the dyes alone with the titanate does not eliminate bleeding, and heating the dyes with the clays without the titanate does not eliminate bleeding. Because TPT reacts much faster than TOT, it appears to work better at minimizing bleeding at the lower temperatures. Based on the test date, it appears that 5%-10% titanate by weight is sufficient to eliminate bleeding. 20% titanate causes the pigment to begin decomposing slightly at 360 °C and the color of the final pigment is also much duller. The sepiolite clay seems to be more heat stable than the palygorskite clay and is preferable when reacting at temperatures over 360 °C

[0135] The embodiments illustrated in the instant disclosure are for illustrative purposes only. They should not be construed to limit the claims. As is clear to one of ordinary skill in the art, the instant disclosure encompasses a wide variety of embodiments not specifically illustrated herein. While the compositions and methods of this disclosure have been described in terms of exemplary embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention.

Claims

What is claimed is:

1. A hybrid pigment composition comprising a dye or pigment, a coupling agent, and a fibrous clay.

2. The hybrid pigment composition of claim 1, wherein the hybrid pigment is a reaction product of the dye or pigment, coupling agent, and fibrous clay.

3. The hybrid pigment composition of claim 1, wherein the fibrous clay is palygorskite, sepiolite, or a combination thereof.

4. The hybrid pigment composition of claim 1, wherein the dye or pigment is selected from the group consisting of vat dyes, quinacridones, solvent dyes, disperse dyes, and optical brighteners.

5. The hybrid pigment composition of claim 1, wherein the dye or pigment is selected from the group consisting of vat blue 1, vat red 1, vat red 41, pigment red 4, pigment red 19, pigment red 254, solvent red 149, disperse red 277, pigment yellow 53, pigment yellow 83, pigment yellow 151, solvent yellow 33, solvent yellow 43, solvent yellow 94, disperse yellow 54, D&C yellow 10, vat orange 5, solvent orange 60, solvent orange 63, solvent green 28, solvent violet 13, vat violet 3, carmine, and combinations thereof.

6. The hybrid pigment composition of claim 1, wherein the coupling agent is selected from the group consisting titanates, zirconates, and silanes.

7. The hybrid pigment composition of claim 6, wherein the coupling agent is a titanate.

8. The hybrid pigment composition of claim 7, wherein the coupling agent is an organic alkoxy titanate.

9. The hybrid pigment composition of claim 8, wherein the coupling agent is tetra- isopropyl titanate or tetra-2-ethylhexyl titanate.

10. The hybrid pigment composition of claim 1, wherein the hybrid pigment has an average particle size of about 0.01 μm to about 40 μm.

11. The hybrid pigment composition of claim 1, wherein the composition comprises said dye or pigment in an amount of 0.01 wt.% to about 50 wt.% based on the total weight of the hybrid pigment composition.

12. The hybrid pigment composition of claim 1, wherein the composition comprises said coupling agent in an amount of about 1 wt.% to about 30 wt.% based on the total weight of the hybrid pigment composition.

13. A composition comprising the hybrid pigment composition of claim 1 and a polymer, carrier liquid, or inorganic material.

14. A method of forming a hybrid pigment composition comprising: providing a dye or pigment, coupling agent, and a fibrous clay; and reacting the dye or pigment, coupling agent, and fibrous clay to form the hybrid pigment.

15. The method of forming a hybrid pigment composition of claim 14, wherein said reacting the dye or pigment, coupling agent, and fibrous clay further comprises: mixing the coupling agent and the fibrous clay; reacting the coupling agent and clay to form a first reaction product; mixing the first reaction product with the dye or pigment; and reacting the first reaction product and the dye or pigment to form the hybrid pigment.

16. The method of forming a hybrid pigment composition of claim 14, wherein said reacting the dye or pigment, coupling agent, and fibrous clay further comprises: mixing the coupling agent, clay, and dye or pigment; and reacting the coupling agent, clay, and dye or pigment.

17. The method of forming a hybrid pigment composition of claim 14, wherein said reacting the dye or pigment, coupling agent, and fibrous clay further comprises: mixing the dye or pigment and the fibrous clay; reacting the fibrous clay and the dye or pigment to form a first reaction product; mixing the first reaction product with the coupling agent; and reacting the first reaction product and the coupling agent to form the hybrid pigment.

18. The method of forming a hybrid pigment composition of claim 14, wherein said reacting the dye or pigment, coupling agent, and fibrous clay further comprises: forming a vapor of the coupling agent; passing the vapor of the coupling agent over a fibrous clay so that the coupling agent condenses onto the clay; mixing a dye or pigment with the clay and coupling agent; and reacting the coupling agent, clay, and dye or pigment to form the hybrid pigment.

19. The method of forming a hybrid pigment composition of claim 14, wherein said reacting includes heating at least two of said dye or pigment, coupling agent, and clay.

20. The method of forming a hybrid pigment composition of claim 14, wherein said heating comprises heating at a temperature of between about 100 ⁰C and 450 ⁰C.

21. The method of forming a hybrid pigment composition of claim 20, wherein the temperature is between about 125 °C and 360 °C.

22. The method of forming a hybrid pigment composition of claim 19, wherein the duration of heating is from about 10 minutes to about 24 hours.

23. The method of forming a hybrid pigment composition of claim 14, wherein the fibrous clay is palygorskite, sepiolite, or a combination thereof.

24. The method of forming a hybrid pigment composition of claim 14, wherein the dye or pigment is selected from the group consisting of vat dyes, quinacridones, solvent dyes, and optical brighteners.

25. The method of forming a hybrid pigment composition of claim 24, wherein the dye or pigment is selected from the group consisting of vat blue 1, vat red 1, vat red 41, pigment red 4, pigment red 19, pigment red 254, solvent red 149, disperse red 277, pigment yellow 53, pigment yellow 83, pigment yellow 151, solvent yellow 33, solvent yellow 43, solvent yellow 94, disperse yellow 54, D&C yellow 10, vat orange 5, solvent orange 60, solvent orange 63, solvent green 28, solvent violet 13, vat violet 3, carmine, and combinations thereof.

26. The method of forming a hybrid pigment composition of claim 14, wherein the coupling agent is selected from the group consisting titanates, zirconates, and silanes.

27. The method of forming a hybrid pigment composition of claim 26, wherein the coupling agent is a titanate.

28. The method of forming a hybrid pigment composition of claim 27, wherein the coupling agent is an organic alkoxy titanate.

29. The method of forming a hybrid pigment composition of claim 28, wherein the coupling agent is tetra-isopropyl titanate or tetra-2-ethylhexyl titanate.

30. The method of forming a hybrid pigment composition of claim 14, further comprising mixing a polymer, carrier liquid, or inorganic material with the hybrid pigment.

31. A method of forming a hybrid pigment composition comprising:

(a) providing a dye or pigment, coupling agent, and a fibrous clay; and

(b) heating a combination of at least two of the dye or pigment, coupling agent, and fibrous clay together to form the hybrid pigment.

32. The method of forming a hybrid pigment composition of claim 31 , wherein (b) comprises: mixing the coupling agent and the fibrous clay; heating the coupling agent and clay; mixing the heated coupling agent and clay with the dye or pigment; and heating the mixture of the coupling agent and clay, and dye or pigment to form the hybrid pigment.

33. The method of forming a hybrid pigment composition of claim 31 , wherein (b) comprises: mixing the coupling agent, clay, and dye or pigment; and heating the coupling agent, clay, and dye or pigment.

34. The method of forming a hybrid pigment composition of claim 31 , wherein (b) comprises: mixing the dye or pigment and the fibrous clay; heating the fibrous clay and the dye or pigment; mixing the heated clay and dye or pigment with the coupling agent; and heating the mixture of clay and dye or pigment and the coupling agent to form the hybrid pigment.

35. The method of forming a hybrid pigment composition of claim 31, wherein (b) comprises: forming a vapor of the coupling agent; passing the vapor of the coupling agent over the fibrous clay so that the coupling agent condenses onto the clay; mixing a dye or pigment with the clay and coupling agent; and heating the coupling agent, clay, and dye or pigment to form the hybrid pigment.

36. The method of forming a hybrid pigment composition of claim 31 , wherein said heating comprises heating at a temperature of between about 100 ⁰C and 450 ⁰C.

37. The method of forming a hybrid pigment composition of claim 36, wherein the temperature is between about 125 ⁰C and 360 °C.