IMPROVED EFFECT PIGMENT BACKGROUND OF THE INVENTION This application is a continuation in part of the pending North American application serial number 10,335,303 filed on December 31, 2002. The use of effect pigments, also known as pearlescent pigments or pearlescent pigments, with The purpose of imparting a pearl luster, metallic luster and / or multicolored effect that approximates the iridescent, is well known. The effect pigments are composed of a plurality of lamellar platelets, each of which is coated with one or more reflection / transmission layers. Pigments of this type are first based on metal oxides, as described in U.S. Patent Nos. 3,087,828 and 3, 087, 829, and a description of their properties can be found in the Pigment Handbook, Volume I, Second Edition, pages 829-858, John Wiley · & Sons, NY 1988. More recently, the use of other coating layers has been developed to perform optically variable effects. The unique appearance of the effect pigments is the result of multiple reflections and light transmissions. The platelet substrate usually has a refractive index that is different from the coating and usually also has a degree of transparency. The coating is in the form of one or more thin films that have been deposited on the surfaces of the platelets. There are a number of important aspects for the effect pigments. One is that they are commonly composed of a plurality of particles that are platelet-shaped. If there is a different size or shape, the pearly or pearly appearance is significantly diminished and usually lost to a degree that the material does not work any longer as an effect pigment. An important aspect of the coating on the plate is that it must be smooth and uniform in order to obtain the optimum pearl appearance. The reason is that if an irregular surface is formed, light scattering occurs and the coated plate will no longer function as an effect pigment. In addition, the coating must adhere strongly to the platelet or else the coating will become separated during processing, resulting in considerable breakage and loss of luster. The particles that do not get to join the platelet during the preparation of the coatings on the platelets or that are the result of the separation cause dispersion of light that impart opacity to the pigment. When there are too many such small particles, the pearly appearance can be reduced or lost. The addition of the coatings to a platelet so that the luster, color and color homogeneity are maintained is a very complex process and originally, the only laminated substrate that obtained some significant use in commerce was mica. Thus, historically, the largest class of effect pigments based on thin film interference were those based on a mica substrate. With the advent of synthetic substrates, for example synthetic mica, aluminum oxide, silica and glass, it became apparent that other substrates could be used since each substrate itself contributes to certain effect attributes, due to variations in transparency, refraction, volumetric color, thickness and characteristics of surface and edge. The substrate effect pigments coated in this manner provide different but similar visual effects when they are identical except for the identity of the platelet material due to these considerations. Glass flakes are desirable in the industry because they are very resilient and can also be optically attractive. In one method, the glass flakes are made by stretching a molten glass into thin sheets, beads or glass tubes, followed by crushing the glass into flakes. The resulting flakes have a size and shape that mimics the mica platelets used in the mica pearlescent pigments coated with metal oxide and thus have an average particle size in a range of about 1 to 150 microns and a thickness of about 0.1 to 10 microwaves A commercially viable method for preparing glass plates coated with metal oxide is described in US Pat. No. 5, 753,371, the description of which is incorporated herein by reference. That patent discloses the coating of glass C in preference to glasses A or E. A glass is a glass of soda-lime, commonly used to be windows and contains more sodium than potassium and also contains calcium oxide. C glass, also known as chemical glazing, is a form that is resistant to corrosion by acid and moisture. E or electric glass is, as the name implies, designed for electronic applications and although it is very stable at high temperatures it can be susceptible to chemical attack. See also commonly assigned US Patent No. 6,045,914. The international publications WO 03/006558 A2 and WO 02/090448 A2 disclose a glass flake-based pigment wherein the glass flakes have a softening point of >; _ 800 ° C; a preferred glass is quartz. The ENGELHARD REFLECKS ™ Pearl and Iridescent Pigments brochure dated 2000 shows a borosilicate pigment with Ti02. See also Japanese Patent Publication No. 11340 published January 16, 2001, which teaches a pearlescent pigment of glass flakes. The mica effect pigment coated with metal oxide and a coated glass effect pigment. with metal oxide provides different visual effects even if they are identical except for the platelet substrate material. The reason is that mica and glass differ with respect to both due to their degree of transparency, refractive index and volumetric color. Also, while the surfaces of both are sufficiently smooth for the use of the effect pigment, the surface of the glass is the smoothest of the two substrates and thus provides a different optical appearance. Laminated aluminum oxide has a smooth surface similar to glass. The glass pigments derive their appearance by the reflection and transmission of light and the difference in transparency and the refractive index cause the amount of transmitted reflected light to differ. However, both types of effect pigments are highly attractive and commercially valuable. The preparation of coated glass platelets, while highly desirable, is also expensive. For commercial acceptability, C glass is usually required and this type of glass is expensive. In addition, the calcining temperatures employed should be kept low since the coated glass plates tend to melt starting at about 650 ° C and any significant amount of melting, generally initiating about 1% by weight of the glass platelets results in the formation of large masses that do not provide the desired pearlescent effect due to their size and irregular shape. The separation of the fused platelets from the separated platelets is both time consuming, costly and impractical. In addition, the required lower calcination temperature means that the temperature must be maintained for a longer period of time, which is also added to the cost. Efforts have been made to find a way to reduce the production cost of the coated effect pigment. Theoretically, this could be done by mixing the coated glass pigment with coated mica pigment. However, this procedure has not been proven to be effective because of the difference in transparency and the refractive index between the two platelet materials, in addition to the process variations, making it extremely difficult to equalize the two mixed materials with respect to to the apparent color. Therefore, as a practical matter, it has not been possible to provide a degree of visual homogeneity with a mixture that approximates the visual homogeneity of each member of the mixture when considered in isolation. This result is not surprising in view of the knowledge of the technique. When two or more effect pigments using different substrates are combined together, the attributes of each are present which results in a unique appearance. One problem with the combination of the effect pigments is that, since the color effects are generated by an additive mechanism instead of a subtractive mechanism, small variations in the color of the effect pigments can result in varying degrees of layered appearance of their mixture. This overrides the basic appearance value of the pigment. However, it may be useful to obtain some attribute, for example, to simultaneously obtain an acceptable degree of concealment and glossiness as described in U.S. Patent No. 6,267,810. U.S. Patent No. 5,277,711 describes a mixture of aluminum flake coated with iron oxide and mica coated with iron oxide with or without a precoating of a highly refractive metal oxide, colorless The purpose of the mica is to reduce the ignition in the air and the danger of dust explosion otherwise exhibited by the aluminum flake. The mixture is made by co-coating the aluminum and mica particles with iron oxide in fluidized lump by the decomposition of the gas phase of the iron carbonyl. The appearance of the mixture, homogeneous or otherwise, was not a consideration.
It has now been surprisingly discovered that a visually homogeneous mixture of coated effect pigments in which the platelets of substrates are of different laminated materials can be obtained despite differences in thickness, the refractive index and the transparency of the materials of platelets. It was also surprisingly discovered that with regard to glass platelets re-mixed with mica, a visually homogeneous product could be made by a process in which the calcination temperature was higher than that used with the platelets only of coated glass , in order to reduce the time necessary to complete the calcination and also reduce the production cost of the product. BRIEF DESCRIPTION OF THE INVENTION This invention relates to an effect pigment comprising a coated mixture of at least two different materials, wherein the effect pigment exhibits visual homogeneity. Each of the at least two different materials is present of at least about 5 weight percent to about 95 weight percent based on total of the at least two different materials. This minimum of about 5 weight percent differs over prior art products where an impure substrate is used and. such impure substrate can be considered a mixture. The present invention intentionally adds the second different material in order to obtain the unexpected results discussed below. . In another example, the present invention relates to an effect pigment which is a mixture of platelets coated with different materials that is visually homogeneous and the method for producing the effect pigment. More particularly, the effect pigment is a mixture of coated lamellar platelets, preferably lamellar platelets coated with metal oxide, in which the platelets are a mixture of different materials, for example glass and mica, and in which the pigment of The effect exhibits visual homogeneity that is produced by mixing the different platelets before they are coated. The same degree of color homogeneity appearance is not obtained from a combination of separately coated substrates that are mixed after the substrates are coated. DESCRIPTION OF THE INVENTION The phrase "coated mixture of at least two different materials" as used herein, means that at least two different materials are first mixed together and then-the mixture is coated. An effect pigment is formed according to the present invention by any process known in the art. This can be done, as an example, by precipitating the metal ion onto lamellar platelets and then calcining the coated platelets to provide platelets coated with metal oxide. The most widely used metal oxide is titanium dioxide, followed by iron oxide. Other usable oxides include (but are not limited to) tin, chromium and zirconium oxides as well as mixtures and combinations of oxides. For convenience the description of this process that follows will be mainly related to titanium and iron as the oxide metal but it will be understood that any other known metal or combination of metals can be used. Other useful combinations of metal oxides include SiO2 on calcium borosilicate aluminum and then TiO2 on it; substrate / Si02 / Fe203; substrate / Ti02 / Si02; substrate / Ti02 / Si02 / Ti02; substrate / Ti02 / Si02 / Fe203: substra-to / Ti02 / Si02 / Cr203; substrate / Fe203 / Si02; substra-to / Fe203 / Si02 / Fe203; substrate / Fe203 / Si02 / Ti02; substrate / Fe203ASi02 / Cr203; substrate / Cr203 / Si02 / Cr203; and substrate / Cr203 / Si02 / Fe203. Other combinations of the layers mentioned in the above are obvious to one skilled in the art. An interlayer to increase performance attributes can also be used. Useful interlayer materials include Al hydroxides and oxides, Ce, Cr, Fe, Mg, Si, Ti and Zr. Essentially any organic or inorganic substance can be a useful interlayer for the promotion of adhesion, mechanical integrity, product improvement or other desirable attributes. In general, the method involves dispersing the particulate material (flakes) and combining that dispersion with a precursor which results in the formation of a precursor coating of titanium oxide or iron oxide on the flakes, usually the particulate material or the flakes it is dispersed in water, which is preferably distilled. The average particle size of the flakes of preference used may vary from an average of about 3 microns to an average of about 100 microns, but smaller flakes below about 1 miera or less or larger flakes of up to 150 micras or more They can also be used if desired. Platelets have a thickness of approximately 0.1 to 10 μ? T? and a dimensional ratio (particle size / thickness) of at least about 10. The concentration of the particulate material in the water can vary from about 5 to 60%, although the generally preferred concentrations vary between about 10 and 20%. ? the water / particulate material suspension is added with an appropriate metal ion source material. In the case of titanium, titanium chloride or titanium tetrachloride is preferably used and in the case of iron, the source material is preferably ferric chloride. The pH of the resulting suspension is maintained at an appropriate level during the addition of the titanium iron salt by the use of a suitable base such as sodium hydroxide, in order to cause precipitation of a precursor of titanium dioxide or oxide of iron on the particulate material. The increase in thickness gives rise to interference colors. If desired, the layers of titanium and iron and / or oxide hydroxide (or other metals) can be deposited sequentially. If it is necessary to lower the pH, an aqueous acid such as hydrochloric acid can be used. The coated platelets can be washed, if desired and dried before being calcined to the final effect pigment. When preparing products coated with titanium dioxide, modifications of both anatase and rutile crystal are possible. The highest quality and most stable pearlescent pigments are obtained when the titanium dioxide is in the rutile form. Some substrates, including both mica and glass, are directly for anatase and therefore it is necessary to modify the above procedure if a rutile product is used. The modifications necessary to make a rutile Ti02 are known in the art. One method involves the precipitation of a hydroxide or tin oxide entity on the surface of the particulate material prior to the formation of titanium dioxide precursor layer. The stratified combination is processed and calcined. This process is described in U.S. Patent No. 4,038,099, which is incorporated herein by reference, an alternative procedure is described in U.S. Patent No. 5,433,779, the description of which is also incorporated by reference and involves the deposition of the precursor of titanium dioxide on the substrate in the presence of iron and calcium, magnesium and / or zinc salts without the use of tin. While rutile coatings are preferred, it may be desirable to produce anatase coatings and this is also within the scope of the present invention. Other coating processes, such as, for example, chemical vapor deposition processes, can also be used. Optically variable effect pigments have been developed more recently. These are built with the substrate that is coated with a reflection layer (eg, silver, gold, platinum, palladium, rhodium, ruthenium, osmium, iridium or its alloys) which is overcoated with a low refractive index material, typically having a refractive index of 1.3 to 2.5, which provides a variable path length for light dependent on the angle of incidence of the light hitting it (eg, Mg 2 or S1O2), which in turn can be coated with a selectively transparent third layer to direct light on it (eg, silicon, oxide of iron, chromium oxide, a mixed metal oxide, titanium dioxide, titanium nitride and aluminum, as well as the same materials as the first layer, provided they are sufficiently thin to be selectively transparent). Examples of such pigments and the processes by which they can be produced can be found inter alia, in U.S. Patent Nos. 5,135,812, 4,434,010 (teaching for example alternating layers of, Ti02 and Si02), 5,059,245, 5,281,480, 5,958,125, 6, 160.208, 6,325,847 and 6,440,208, the descriptions of which is also incorporated by reference. The different materials are substrates used in the present invention can have any morphology including platelet, spherical, cubic, circular, hairy or fibrous. Examples of useful laminate materials include rolled aluminum oxide, laminated glass, aluminum, mica, bismuth oxychloride, laminated iron oxide, laminated graphite, laminated silica, bronze, stainless steel, natural bead, boron nitro, silicon dioxide, flake copper, copper alloy flake, zinc flake, zinc alloy flake, zinc oxide, enamel, china clay and porcelain and the like. Any combination of the preceding laminate materials or at least one of the preceding laminate materials and at least one non-laminate material can be used. For convenience, the following description will focus on the combination of glass and mica, although other combinations may be used. Mica is desirable due to its high transparency, strong reflectance and strong chromaticity, mainly due to the presence of small, coated flakes. The glass flakes have the attributes of high transparency, very white voluminous color and a flash effect in strong light but, as mentioned in the above, their high cost and melting point prevent their use in many applications. Examples of useful spherical materials include glass, plastic, ceramic, metal or an alloy and the spheres can be solid or hollow. Useful glass spheres are disclosed in U.S. Patent 5,217,928, incorporated herein by reference in its entirety. Useful cubic materials include glass cubes. In one example, the present invention uses a mixture of two or more laminar substrates. Preferably, one of the substrates is either rolled aluminum oxide or laminated glass. Individually, each substrate can constitute approximately 5 to 90% of the mixture although it is preferred that most of the mixture is constituted by a substrate, for example mica. More preferably, the mixture contains at least about 65% mica and even more preferably at least about 75% mica. Individually, mica platelets and glass platelets have an average particle size and thickness in the ranges specified above. The particle sizes are selected so that the resulting coated product exhibits visual homogeneity, ie, exhibits an increase relative to a mixture of the same proportion of the substrates coated with at least 5 chromates (CieLab) or at least five percent (5%) increase in the chroma units when evaluated with an X-Rite MA 68 at 25 ° from the specular angle. Preferably, the increment is at least 10 chroma units (CieLab) and to obtain that result, the average particle size of the smallest of the glass and mica platelets is preferably within approximately 25% of the size of the largest of the glass and mica platelets. While it is preferable to use glass C, as in the prior art, any type of glass and morphology can be used in the present invention. Other useful glass flakes have a thickness of <; 1.0 pin and a softening point of > 800 ° C. The glass can be classified, for example as glass A, glass C, glass E and glass ECR. The types of glass that meet the required softening point characteristic are quartz glass, and any other glass composition that has a softening point of > 800 ° C. The glass flakes that meet the requirements are similar special glass, for example Schott Duran or Supremax types. The softening point is defined, according to ASTM C 338 as the temperature at which a uniform glass fiber with a diameter of 0.55-0.75 mm and a length of 23.5 cm increases its length by 1 mm./min when the 10 cm higher temperatures are heated at a rate of 5 ° C / min. Examples of useful mixtures of at least two different materials are in the following table: FIRST MATERIAL SECOND MATERIAL Glass A Glass C Glass A Glass E Glass A Glass ECR Glass A Glass Quartz Glass C Glass E Glass -C Glass ECR Glass C Glass Quartz Glass E Glass ECR Glass E Quartz Glass Silicon Carbide Mica Mica Glass Spheres Predominantly Glass Spheres oxide iron containing other oxides Predominantly Mica oxide iron containing other oxides Zinc Oxide Glass Metal or alloy Glass Ceramic microspheres Mica Mica Glass Bubbles Suitable glass flakes are characterized in that they contain an average particle size in the range of 5-1000 p and a thickness of 0.1-5 p.p., preferably 0.1-0.3 p.m. The dimensional relation of the glass flakes are in intervals of 10-300, preferably in the range of 50-200. The method of coating the substrate used is adjusted such that the two or more substrate materials are coated substantially in the same proportion to thereby develop a coating of similar quality and thickness. This may involve temperature control, reagent addition ratio, reagent identity, pretreatment of the substrate and the like. Frequently, this control is obtained more easily as the platelets become closer to each other in the average thickness size. The necessary or appropriate modifications can be easily established by those skilled in the art or a few preliminary runs to establish the appropriate parameters. The procedure described in the foregoing, in which the glass and mica platelets are mixed before being coated, unexpectedly results in a product exhibiting visual homogeneity showing a uniform color, which can not be obtained by forming a platelet mixture. of coated mica and pre-coated glass prepared. This result is obtained in spite of the fact that the mica and glass substrates have different degrees of transparency, surface chemistry and refractive index and usually have a different thickness. The calcination of coated glass flakes is typically done in the vicinity of 600 ° C because the glass platelets fuse at about 650-700 ° C creating a dough that has greatly diminished quality. Surprisingly, it has been found that a mixture of glass and mica, coated with a metal oxide precursor, is capable of being calcined at temperatures of 650 ° C to about 850 ° C without causing the glass flakes to fuse. . Preferably, the calcination temperature is about 675 to 825 ° C and much more preferably about 800 ° C when the metal oxide is TiO2 and about 700 ° C when the metal oxide is Fe203. Another advantage of using the present co-precipitated effect pigment is the ability to have the product color space that is the same for the different materials of the mixture. To obtain an exact color matching of the two different materials and then the post-mixing of the products is a difficult and not practical process. The factors such as particle size, surface chemistry, refractive index and reflectivity of the substrates influence the final optical properties of the pigments such that they are difficult to evaluate their equivalent hue values. With the co-precipitated process present, the hue values of both substrates are automatically controlled in the coating process. The coated substrates, however produced can be post-treated by any method known in the art. Examples of such treatments can be found, for example, in U.S. Patent Nos. 4,134,776, 5,091,011, 5,156,889, 5,326,392, 5,423,912, 5,759,255 and 6,325,846, which are incorporated herein by reference, but are not limited to those methods. Depending on the proposed use, the present effect pigment may benefit from some form of a surface treatment. Non-limiting examples would be a coupling agent with or without a metal hydroxide for increased exterior stability. Frequently, metal compounds are added as surface treatments with or without organic compounds to vary the surface charge of the particles and / or the various tactile properties. The resulting pigment can be used in any application for which the pigments of Effects have been used so far, such as, for example, in cosmetics, plastics, safety markings, inks and coatings including automotive paint systems that carry water and solvent. The products of this invention have unlimited use in all types of automotive and industrial paint applications, especially in the coating field and organic color inks where deep color intensity is required. For example, these pigments can be used in the mass tone or as styling agents for spray paints of all types of automotive and non-automotive vehicles. Similarly, they can be used on all clay / formica / wood surfaces (glass / metal / enamel / ceramic and non-porous or porous.) Pigments can be used in powder coating compositions. plastic, ready for the toy or home industry, safety applications such as inks and coatings are a valuable use for these products, these pigments can be impregnated into fibers to impart a new and aesthetic coloration to clothes and carpets. Use to improve the appearance of shoes, rubber and vinyl / marble floors, vinyl lining boards and all other vinyl products, and these colors can be used in all types of modeling hobbies. The foregoing, in which the compositions of this invention are useful, are well known to those of ordinary skill in the art. for printing, nail enamels, lacquers, thermoplastic and thermosetting materials, natural resins and synthetic resins. Some non-limiting examples include polystyrene and its mixed polymers, polyolefins, in particular, polyethylene and polypropylene, polyacrylic compounds, polyvinyl compounds, for example polyvinyl chloride and polyvinyl acetate, polyesters and rubber, and also filaments made of viscose and ethers of cellulose, cellulose esters, polyamides, polyurethanes, polyesters, - for example, polyglycolterephthalates and polyacrylonitrile. For a complete introduction to a variety of pigment applications, see Temple C. Patton, editor, The Pigment Handbook, volume II, Applications and Markets, John Wiley and Sons, New York (1973). In addition, see for example, with respect to inks: R. H. Leach, editor, The Printing Ink Manual, Fourth Edition, Van Nostrand Reinhold (International) Co. Ltd., London (1988), particularly pages 282-591; with respect to paints: C. H. Hare, Protective Coatings, Technology Publishing Co., Pittsburgh (1994), particularly at pages 63-288. The above references are incorporated herein by reference for their teachings of ink, paint and compositions. plastic, formulations and vehicles in which the compositions of this invention can be used including the amounts of colorants. For example, the pigment can be used at a level of 10 to 15% in an offset lithographic ink, with the remainder being a vehicle containing gelled and ungelled hydrocarbon resins, alkyd resins, wax compounds and aliphatic solvent. The pigment may also be used, for example, at a level of 1 to 10% in an automotive paint formulation together with other pigments which may include titanium dioxide, acrylic latexes, coalescing agents, water or solvents. The pigment can also be used, for example, at a level of 20 to 30% in a colored plastic concentrate in polyethylene. In the cosmetic field, these pigments can be used in the area of the eyes and in all external and rinsing applications. Thus, they can be used in hair brushes, face powder, leg makeup, insect repellent lotion, mascara coating / cream, nail polish, nail polish remover, perfume lotion and shampoos of all types (gel or liquid). In addition, - can be used in shaving cream (spray concentrate without brush, foam), shiny bar for skin, makeup for the skin, hair alignment, eye shadow (liquid, ointment, powder, bar, pressed or cream), eyeliner, cologne bar, cologne, cologne emollient, bubble bath, body lotion (moisturizer, cleansing, analgesic, astringent), after-shave lotion, after-bath cream and lotion of sunscreen. For a review of cosmetic applications, see Cosmetics: Science and Technology, 2nd Edition, Eds: MS Balsam and Edward Sagarin, Wiley-Interscience (1972) and deNavarre, The Chemistry and Science of Cosmetics, 2-Edition, Volumes 1 and 2 (1962), Van Nostrand Co. Inc., Volumes 3 and 4 (1975), Continental Press, both of which are incorporated herein by reference. In order to further illustrate the invention, several non-limiting examples will be set forth below. In these examples, as well as throughout the remainder of this specification and the claims, all parts and percentages are by weight and all temperatures are degrees centigrade unless otherwise indicated. Examples 1-4 A mixture of 50 grams of glass flakes C having an average particle size of about 140 microns (by scattering laser light) were mixed with 50 grams of muscovite mica having an average particle size. of approximately 80 micras. The mixture was dispersed in 750 ml of water and iron and zinc were introduced in the form of 1 ml of a 39% aqueous solution of ferric chloride and 7 ml of a 9% aqueous zinc chloride solution. The pH of the suspension was adjusted to 3.0 using a 35% aqueous sodium hydroxide solution and the suspension was heated to a temperature of 76 ° C. The pH was then lowered to 1.6 by the addition of hydrochloric acid and a 40% aqueous solution of titanium tetrachloride was added at a rate of 100 ml / hour while the pH was maintained at 1.6 by the addition of aqueous sodium hydroxide. to 35%. The introduction of titanium was continued until an appearance of either a white bead or the gold, red and blue interference colors has been achieved. When the desired endpoint was obtained, the suspension was filtered in a Buchner funnel and washed with additional water. The coated platelets were then dried and calcined at approximately 800 ° C. The microscopic evaluation - of the resulting pigments shows that the platelets are coated with a smooth homogenous layer of titanium dioxide. The coated pigments were visually homogeneous. The luster and color of the resulting pigments were evaluated visually and instrumentally using spreads in a cover diagram (opacity diagrams of Form 2-6 of The Leneta Company), half of which is black and half of which is white. A coating on the black part of this diagram exhibits the color of reflection and luster when examined specularly, while the coating on the white portion exhibits the transmission color when viewed at non-specular angles. Spreads are prepared by incorporating pigment at a concentration of 12% in a nitrocellulose lacquer and by applying the suspension to the black and white diagram with a Bird film applicator bar. The stretches prepared in these examples show a series of high quality, vibrant colors with high chromaticity and coverage. Examples 5-9 100 grams of the glass / mica mixture of Examples 1-4 were dispersed in 330 ml of distilled water which was then heated to 74 ° C and the pH adjusted to 1.6 using dilute hydrochloric acid. Then 7 ml of a solution of 18% aqueous stannous chloride was slowly added followed by a 40% aqueous solution of titanium tetrachloride at a rate of 100 ml / hour. The pH was maintained at 1.6 during the addition of tin and titanium by simultaneously adding a dilute aqueous solution of sodium hydroxide. The addition of titania was continued until a white bead or the gold, red, blue or green interference color was observed. When the desired endpoint was reached, the suspension was filtered and washed with additional water and calcined at 800 ° C. The microscopic evaluation of the resulting pigments shows that the platelets are coated with a smooth homogenous layer of titanium dioxide. The coated pigments were visually homogeneous. The extensions prepared in the pigments of these examples show a series of high quality, vibrant colors with high chromaticity and coverage. Examples 10-17 75 grams of the glass / mica mixture of the
Examples 1-4 were dispersed in 300 ml of distilled water. The dispersion was heated to 76 ° C and the pH adjusted to 3.2 with dilute hydrochloric acid. An aqueous ferric chloride solution was added to the suspension. at 0.2 ml / min. , while maintaining the pH at 3.2 using dilute sodium hydroxide. The addition of ferric chloride was continued until a desired color was observed, at which point the suspension was filtered, washed with water and calcined at 800 ° C to produce an effect pigment coated with ferric oxide. Since the ferric oxide has an inherent red color, the flakes coated with this oxide have both a reflection color and an absorption color. The interference color is due to the interference of light, while the absorption color is due to the absorption of light. The color of reflection changes from gold to red to blue to green as in accordance with increased amounts of iron oxide (III) are coated on the leaflets. As even more iron oxide (III) is added, the thicker coatings of Fe2Ü3 are obtained which produce another series of interference colors known as second observable interference colors. The second colors have a higher color intensity than the first colors. If the coating process is still further continued, a third series of interference colors can be obtained. When the flakes coated with iron oxide were extended, a series of high quality colors are observed alive. The interference colors made in these examples were bronze, first orange, first red, first violet-blue, first green, second orange, second red and second green.
Examples 18-20 Titanium dioxide can produce a series of interference colors as the thickness of the titanium dioxide layer increases. This produces a whitish reflection that appears pearly or silver initially, and according to the layer of Ti02 that becomes thicker, golden, red, blue and green interference colors are observed. As the coating becomes even thicker, a series of second observable colors are observed. The second colors have more color intensity than the first colors described in the previous Examples. The second colors were prepared by dispersing 50 grams of the mica / glass mixture used in Examples 1-4 in 333 ml of distilled water. The pH was adjusted to 1.6 with dilute hydrochloric acid and the suspension was heated to 74 ° C. Then 7 ml of a solution of 18% tin chloride was added followed by the addition of 40% titanium chloride at a rate of 0.33 ml / min. The pH was maintained at 1.6 by simultaneously adding dilute sodium hydroxide. The titanium addition was continued until the desired color was obtained, at which point the suspension was filtered, washed with water and calcined at 800 ° C. In this way, the second colors, golden, orange and red are obtained. When they are extended, the products have higher intensity of color than their first observable, affordable interference colors. Examples 21-25 The procedures of Examples 5-9 were repeated except that the lamellar platelet mixture was constituted by 75 parts of muscovite mica having an average particle size of about 25 microns and 25 parts of glass chips C which it has an average particle size of approximately 25 microns. Examples 26-33 The procedure of Examples 10-17 was repeated except that the. Laminar platelet mixture was constituted by 75 parts of muscovite mica having an average particle size of about 25 microns and 25 parts of glass flakes C having an average particle size of about 25 microns. Example 34-41 The procedure of Examples 10-17 was repeated except that the lamellar platelet mixture consisted of a mixture of 50 grams of rolled aluminum oxide having an average particle size of about 20 microns (by dispersion). of laser light) and 50 grams of muscovite mica that has an average particle size of approximately 25 microns. Example 42 A mixture of 150 grams of muscovite mica having an average particle size of about 25 um, was mixed with 50 grams of glass flakes with a nominal thickness of 1 um and a larger dimension (D50) of 20 um. The mixture was dispersed in 2,000 ml of distilled water and heated to 78 ° C. At that temperature, the pH of the suspension was reduced to 1.5 with a diluted HC1 solution and 20 grams of an 18% SnCl solution were added at 0.4 ml / min while maintaining the pH at 1.5 with the NaOH solution . After the addition of the SnCl 4 solution, the pH was raised 3.2 with dilute NaOH and 39% FeCl 3 was added at 1.5 ml / min, until the desired color was obtained. The product was then washed, dried and heat treated at 650 ° C. Example 43 The product of Example 42 was dispersed in a new automotive urethane topcoat paint formulation and evaluated with an X-Rite ™ 68 for the 25 ° and 15 ° chroma from the specular angle. The sample, where the substrates have been pre-mixed before the coating and a sample prepared in a similar manner, with the same proportions of individually coated substrates are set forth in the tables below.The premixed sample showed an increase in chroma above 10. units (CieLab) at each angle, specifically 76.1 vs. 59.7 at 15 ° and 62.4 vs. 51.8 at 25 ° 15 ° from Specular L to BC Example 42 76.8 64.4 40.5 76.1 Mix 80.0 56.5 19.1 59.7
from the Specular
Example 44 A mixture of 50 grams of rolled aluminum oxide having an average particle size of about 20 microns (by laser light scattering) is mixed with 50 grams of muscovite mica having an average particle size of about 25 microns. mieras The mixture is dispersed in 750 ml of water and iron and zinc are introduced in the form of 1 ml of a 39% aqueous solution and ferric chloride and 7 ml of a 9% zinc chloride solution. The pH of the suspension was adjusted to 3.0 using a 35% aqueous sodium hydroxide solution and the suspension is heated to a temperature of 76 ° C. The pH is lowered to 1.6 by the addition of hydrochloric acid and a 40% aqueous solution of titanium tetrachloride is added at a rate of 100 ml / hour while the pH is maintained at 1.6 by the addition of aqueous sodium hydroxide. to 35%. The introduction of titanium is continued until an appearance of a white pearl has been achieved. When the desired end point is obtained, the suspension is filtered in a Buchner funnel and washed with additional water. The coated platelets are then dried and calcined at about 800 ° C. Using 45 one hundred grams of a mixture of equal weight of glass flakes (100 μ average larger dimension) and mica (100 μ average larger dimension) is placed in a 1 liter basin equipped with a magnetic stir bar and containing 393 grams of a 2% dextrose solution. The suspension is stirred at room temperature. One solution, which contains 7.87 grams of silver nitrate crystals, 375 ml of water and enough 29% ammonium hydroxide solution to dissolve any precipitate, is quickly added to the solution. The supernatant liquid is tested for the silver ion by the addition of a few drops of concentrated hydrochloric acid. The test is a visual estimate of any precipitate and / or turbidity and when none is found, the suspension is filtered and rinsed several times with distilled water and the press cake is dried at 100 ° C. to a constant mass. The dried sample is a lustrous, opaque and silver colored material. 50 · grams of the silver-coated material are suspended in 600 ml of isopropanol at 25 ° C. To the suspension are added 75 grams of distilled water, 3.5 grams of 29% NH4OH and 75 grams of tetraethoxysilane. The suspension is stirred for 7 hours at room temperature and then filtered, and the product is washed and dried in an oven. 10 grams of this silica-coated material is suspended in 50 grams of 1% dextrose solution. A solution of 0.4 grams of AgN03, 40 grams of water and slight excess of 29% ammonium hydroxide solution are added quickly to the solution. When the supernatant liquid of the suspension is tested negative for the silver ion, it is filtered and the product is washed and dried at 120 ° C. The product exhibits a sharp change of very clean color from blue to violet in a change in the viewing angle of a lacquer film containing the product and the pigment is visually homogeneous. Example 46 The pigment of Example 1 can be formulated in a powder eye shadow as follows: the following materials are mixed and dispersed completely: Ingredients by weight
MEARLTALC TCA® (Talc) 18
MEAR MICA® SVA (Mica) 20
Myristat of Magne 5
Silica 2 CLOISONNÉ® Red 424C (mica coated with red Ti02) 20 CLOISONNÉ® Violet 525C (mica coated with Ti02 violet) 13 CLOISONNÉ® Nu-Antique Blue 626CB (mica coated with Ti02 mica / coated, with iron oxide) 2 CLOISONNÉ® Cerise Flambe 550Z (mica coated with iron oxide) - 2
Conservatives and Antioxidant q. s. MEARLTALC TCA®, MEARLMICA® SVA and CLOISONNÉ® are all registered trademarks of Engelhard Corporation. Then 7 parts of octyl palmitate 1 part of isostearyl neopentanoate are heated and mixed until uniform, time in which the resulting mixture is sprayed in the dispersion and mixing is continued. The mixed material is pulverized and then 5 parts of Cloisonne Red 424C and 5 parts of the pigment of Example 1 are added and mixed until a uniform powder eye shadow is obtained. Example 47 The pigment of Example 1 can be formulated in a lipstick as follows. The following quantities of the following listings are placed in a heated container and the temperature rises to 85 + 3 ° C.
parts in pe Candelilla wax 2.75 Carnauba wax 1.25 Beeswax 1.00 Ceresin wax 5.90 Ozokerite wax 6.75 Microcrystalline wax 1.40 Olethyl alcohol 3.00 Isostearyl palmitate 7.50 Isostearyl isostearate 5.00 Capric / Capricho triglyceride 5.00 Bis-Diglicerilpolyalcohol adipate 2.00 Acetylated lanolin 2.50 Sorbitan tristearate 2.00 Aloe Vera 1.00 Risino oil 37.50 Red lacquer 6 0.25 Tocopheryl acetate 0.20 Phenoxyethanol, isopropylparaben, and butylparaben 1.00 Antioxidant qs Then, 14 parts of the pigment of Example 1 are added and mixed until all the pigment is well dispersed. Fragrance is added as desired and mixed with agitation. The resulting mixture is emptied in molds at 75 ± 5 ° C, allowed to cool and flamed in lipsticks. Example 48 and Comparative A 115 g of muscovite mica with an average particle size of 20 μp? They were suspended in 2 liters of deionized water. To this suspension, 30 g of glass of a similar particle size of Nippon Sheet Glass were added and the pH was adjusted to 1.4 with dilute HC1. To this suspension, 2.7 grams of a 77% solution of SnCl4.5H20 were added and the suspension was heated to 83 degrees centigrade. Ti02 was added to the suspension at this time by the addition of a 40% TÍCI4 solution at a rate of 2.8 grams per minute. The suspension was maintained at pH and constant temperature during this deposition. The addition of T1O2 was continued until the desired color was obtained. The coating was then filtered, washed and calcined for 20 minutes at 800 ° C. The pigment of Example 48 obtained from this coating process, when compared with another of equal hue value but prepared by dry blending the TiO2 coated mica and the TiO2 coated glass (Comparative A), showed improved chromaticity values as It is mentioned right away. The phrase "improved chromaticity" as used herein, means that it exhibits an increased chromaticity value with a mixture of the first substrate coated with oxide and the second different substrate coated with oxide in the same shade. The color characteristics of the two pigments were defined using a X-Rite? 68 II Multi-Angle Spectrophotometer with readings at 15 degrees from the spectral angle. The samples were prepared using 1 gram of pigment in 33.3 grams of NC varnish. The mixture was applied to a black letter with a controlled application device. X-RITE MA68 II COLORIMETRIC DATA SPECTRAL A REFLECTANCE OF 15 DEGREES
From the data, it is evident that the chromaticity value (C *) for the pigment of Example 48 is almost 10% greater than the Comparative pigment A at the same hue value (h *). The product of Example 48 also exhibited visual homogeneity compared to Comparative A. Example 49 and Comparative B Another advantage of the present co-precipitated mixture of 25% mica and glass with TiO? has been the best in the volumetric color of the final calcined product. It is known that mica products coated with titanium dioxide, when calcined, have a yellow volumetric color. The term "volumetric" color refers to the color observed when observed in the calcined powder. When the glass is added to the mica suspension, it is coated and calcined, the volumetric color of the resulting product is considerably less yellow. The glass that is a purer substrate has less color impurities, which can add color to the pigment coated with 1O2. This can be documented by observing the color characteristics of the present glass / mica product covered with Ti02 / Example 42) to a white pearl interference color with those of a similar coating made with only mica and Ti02. (Comparative B). Using an X-Rite spectrophotometer model SP62 that is capable of measuring the Whiteness Index as set forth in ASTME 313 of powder substances, the index was measured in a powder of a mica sample coated with Ti02 (Comparative B) and a mixture of 25% glass / 75% mica coated in a similar manner (Example 49). The Whiteness Index value was 23.3 for the mica sample (Comparative B) while the Whiteness Index value was 33.9 for the glass mixing sample (Example 49). It is obvious that this is a significant improvement in the color of the inventive mixed glass product. The phrase "improved whiteness index" as used herein means that it exhibits an increased Whiteness Index compared to a mica sample.
Example 50 and Comparative C Example 50 was another mixture of 25% mica flake and glass co-precipitated with Ti02 which was prepared following Example 48 above. Comparative example C was prepared by dry mixing the mica coated with Ti02 and the glass flake coated with Ti02. The color characteristics of the pigments were defined using an X-Rite MA68 II Multi-Angle Spectrophotometer with readings at 15 degrees from the spectral angle and are as follows
These results demonstrate that the product of Example 50 had improved chromaticity and visual homogeneity compared to Comparative C. Example 51 Another 25% mixture and glass co-precipitated with Ti02 was prepared following Example 48 above except that the glass flake (supplied by Nippon Sheet Glass) had an average particle size of 30 microns. The color characteristics of the pigments were defined using a X-Rite MA68 II Multi-Angle Spectrophotometer with readings at 15 degrees from the spectral angle and are as follows X-Rite MA 68 II COLORIMETRIC DATA AT A REFERENCE OF 15 DEGREES
Example 52 and Comparative D Example 52 was another mixture of 25% mica and glass flake co-precipitated with 10 2 which was prepared following Example 48 above. Comparative D was prepared by dry mixing TiO2-coated mica and Ti-coated glass (¾.) The color characteristics of the pigments were defined using a X-Rite MA68 II Multi-Angle Spectrophotometer with readings at 15 degrees from the spectral angle and they are as follows
These results show that the product of the
Example 52 had improved chromaticity and exhibited visual homogeneity compared to Comparative D. Example 53 A suspension of 210 grams of mica (the average particle size D (50) = 50 microns); 30 grams of glass jugs (D (50) = 100 microns, supplied by Nippon Glass); and 2 liters of distilled water was prepared and stirred at 350 revolutions per minute. The pH was lowered to 1.4 with 1: 1HC1. 2.7 grams of SnCl4-5H20 at 77% were added drop by drop. The composition was heated to 83 ° C. 180 grams of 40% TiCl 4 at 2.1 ml / min were added while controlling the pH to 1.4 with 35% NaOH. The pH was raised to 8.2 with 35% NaOH. 2500 grams of 28% Na2Si03-9H20 were added at 3.5 ml / min while the pH is controlled at 8.2 with 1: 1HC1. The pH was lowered to 1.9 with 1: 1HC1 at 0.5 ml / min. 180 grams of 40% TiCl4 were added at 2.1 ml / min while the pH was controlled at 1.9 with 35% NaOH. The product 1 had the following composition :. 12.5% of Ti02, 33.4% of Si02, 47.3% of mica and 6.8% of glass. Product 2 had the following composition: 13.5% Ti02, 33.0% Si02, 46.8% mica and 6.7% glass. The product 3 had the following composition: 16.6% of Ti02, 31.8% of Si02, 45.2% of mica and 6.4% of glass. The X-Rite properties of the resulting products are as follows. Product 1 Product 2 Product 3
L * 77.01 79.27 82.76 a * -23.64 -25.01 -17.19 b * -12.6 -5.99 10.78 C * 26.79 25.72 20.29 h ° 208.06 193.46 147.91 25 'D65 / 100 L * 44.13 45.81 48.35 to -12.28 -12.3 -9.21 -8.79 - 5.96 3.86 c * 15.1 13.67 9.99 h ° 215.58 205.83 157.27
45 ° D65 / 100 L * 21.69 23.58 25.15 * a -3.72 -3.96 -4.8 -9.09 -8.21 -1.76 9.82 9.11 5.11 h ° 247.76 244.21 200.18
75 ° D65 / 100 L * 14.4 15.91 17.16 * a -1.37 -1.36 -2.6 -7.99 '-7.83 -5.12 c * 8.1 7.95 5.74 h ° 260.27 260.14 243.02
110 ° D65 / 100 L * 11.88 13.25 14.45 * to -0.45 -0.38 -0.46 b * -8.3 -8.27 -7.94
C * 8.31 8.28 7.95 h ° 266.86 267.39 266.67
Various changes and modifications can be made to the products and process of the present invention without departing from the spirit and scope thereof. The various embodiments disclosed herein were for the purpose of further illustrating the invention but are not intended to limit it.