KR101132502B1 - Improved Effect Pigment Comprising a Mixture of at Least 2 Substrate Materials - Google Patents

Abstract

The effect pigments consist of a coated layered plate which is a mixture of different plate-like materials called plate-like glass or plate-shaped aluminum oxide, which pigments exhibit visual uniformity.

Effect pigment, plate glass, plate aluminum oxide, C glass

Description

Improved Effect Pigment Comprising a Mixture of at Least 2 Substrate Materials

This application is part of US Patent Application No. 10 / 335,303, filed December 31, 2002.

The use of effect pigments, also known as pearlescent pigments or nacreous pigments, to provide pearlescent luster, metallic luster and / or iridescent multicolor effects is known. The effect pigments consist of a plurality of layered plates each coated with one or more reflective / transmissive layers. Pigments of this type are based on metal oxides first, as described in US Pat. Nos. 3,087,828 and 3,087,829, and descriptions of their properties are given in Pigment Handbook, Volume I, Second Edition, pp. 829-858, John Wiley & Sons, NY 1988. More recently, the use of other coating layers that exhibit photovariable effects has been developed.

 The unique appearance of the effect pigments is the result of multiple reflections and transmission of light. Plate-like substrates generally have a refractive index that is different from the coating and also generally have transparency. The coating is in the form of one or more thin films deposited on the surface of the plate.

There are many important points in effect pigments. One is that they consist of a large number of particles that are generally plate-shaped. In different sizes or shapes, the appearance of nacres or pearlescents is significantly reduced, and is generally lost to such an extent that the material no longer functions as an effect pigment.

One of the important aspects of the plate coating is that it must be smooth and uniform in order to obtain an optimal pearlescent appearance. The reason is that when an irregular surface is formed, light is scattered and the coated plate will no longer function as an effect pigment.

In addition, the coating must adhere strongly to the plate or it will separate during processing and will cause severe cracking and loss of gloss. Particles that do not adhere to them or are produced by separation during coating to the plate result in light scattering and render the pigment opaque. If there are too many such small particles, the nacre appearance may be reduced or lost.

Adding coatings to the plates in order to maintain gloss, color and color uniformity is a very complex process, and the only plate-like substrate that is of commercial importance, originally commercially, is mica. Thus, historically, the largest class of effect pigments based on thin film interference has been the class based on mica substrates. With the advent of synthetic substrates such as synthetic mica, aluminum oxide, silica and glass, each substrate itself contributes to specific effect properties due to variations in transparency, refractive index, bulk color, thickness, and surface and edge shapes, It has been evident that other substrates may be used. Thus, the coated substrate effect pigments provide different visual effects even if they are similar for the above reasons if they are identical except for the nature of the plate material.

Glass flakes are industrially desirable because they can be very elastic and optically attractive. In one method, glass flakes are prepared by spreading the molten glass into thin plates, beads or glass tubes, and then grinding the glass into flakes. The resulting flakes have a size and shape similar to the mica plates used for the pearlescent pigments of metal oxide-coated mica, thus having an average particle size in the range of about 1 to 150 microns and thickness of about 0.1 to 10 microns.

Conventional viable methods of making metal oxide-coated glass plates are described in US Pat. No. 5,753,371, the disclosure of which is incorporated herein by reference. The patent discloses coating of C glass, preferably A or E glass. A glass is a soda-lime glass that is generally used to make windows and contains more sodium than potassium and also contains calcium oxide. C glass, also known as chemical glass, is a form that is corrosion resistant by acids and moisture. E or electrical glass, as the name implies, is designed for electrical equipment, which is very stable at high temperatures but can be sensitive to chemical attack (see also commonly assigned US Pat. No. 6,045,914).

WO 03/006558 A2 and WO 02/090448 A2 disclose pigments based on glass flakes having a softening point of 800 ° C. or higher, with preferred glass being quartz. The 2000 ENGELHARD REFLECKS (R) pearlescent and iridescent pigments brochure teaches borosilicate pigments with TiO ₂ (also known as glass flake pearlescent pigments, published January 16, 2001). See Japanese Patent Publication No. 11340).

The metal oxide-coated mica effect pigments and metal oxide-coated glass effect pigments are identical except for the material of the plate base, but provide different optical effects. The reason is that mica and glass differ from each other in the degree of their transparency, refractive index and bulk color. In addition, although the surface of the two is smooth enough for the effect pigment, the glass surface is smoother than that of the two substrates, providing a different optical appearance. Plate-shaped aluminum oxide has a smooth surface similar to glass. Effect pigments induce their appearance by reflection and transmission of light, and the amount of light reflected or transmitted is different due to the difference in transparency and refractive index. Nevertheless, both types of effect pigments are very attractive and of commercial value.

The production of coated glass plates is very desirable but also expensive. C glass is generally required for commercial use, and this type of glass is expensive. In addition, the coated glass sheet begins to melt at about 650 ° C. and tends to form large materials that start at a significant amount of the melt, typically about 1 weight percent of the glass sheet and do not provide the desired pearlescent effect because of its size and irregular shape. Therefore, the calcination temperature used should be kept low. Separating the molten plate from a separate plate is time, expensive and impractical. In addition, the lower required calcination temperature means that the temperature must be maintained for a longer time, which also adds cost.

Efforts have been made to find ways to reduce the cost of producing coated glass effect pigments. In theory, this can be achieved by combining the coated glass pigment with the coated mica pigment. However, this approach has proven ineffective because not only the method variations but also the difference in transparency and refractive index between the two plate materials makes it very difficult to match the two blended materials in appearance color. Thus, as a practical matter, it is impossible to provide a formulation with a visual uniformity similar to that of each member of the formulation when considering isolation. The results are not surprising in view of the art. When combining two or more effect pigments using different substrates together, each property is present, resulting in a unique appearance. One problem with combining effect pigments is that small color changes in the two effect pigments can cause various faded appearances in their formulations, since color effects are caused by additive mechanisms instead of subtractive mechanisms. This negates the basic appearance brightness of the pigment. However, it may be useful to obtain some other properties, such as obtaining a satisfactory hiding power and gloss simultaneously, as described, for example, in US Pat. No. 6,267,810.

U. S. Patent 5,277, 711 describes a mixture of iron oxide-coated aluminum flakes and iron oxide-coated mica with or without precoating of a colorless, high refractive metal oxide. The purpose of mica is to reduce the risk of ignition and dust explosions in the air represented by aluminum flakes in the absence of mica. The mixture is prepared by coating aluminum and mica particles together with iron oxide in a fluidized bed by gas phase decomposition of iron carbonyl. The appearance of the mixture is not a problem to consider even if it is uniform or not.

It has now been surprisingly found that visually uniform blends of coated effect pigments in which the base plate is a different plate material can be obtained despite the thickness, refractive index and transparency of the different plate materials. Surprisingly, the glass plates premixed with mica are treated with calcination temperatures higher than those used in only coated glass plates to produce a visually uniform product, thereby reducing the time required for complete calcination and also producing the product. It turns out that the cost can be reduced.

Summary of the Invention

The present invention relates to a visually uniform effect pigment comprising a coated mixture of two or more different materials. Each of the two or more different materials is present at least about 5% to about 95% by weight based on the total amount of the two or more different materials. At least about 5% by weight is different from prior art products in which impure substrates are used and such impure substrates can be considered mixtures. The present invention intentionally adds a second different material to achieve the unexpected results discussed below.

In another embodiment, the present invention relates to a visually uniform effect pigment and a method of making the same, which is a mixture of coated plates of different materials. More particularly, the effect pigment is a mixture of coated layered plates, preferably metal oxide-coated layered plates, wherein the plate is a mixture of different materials, such as glass and mica, and the effect pigments are formulated by combining different plates before coating It shows visual uniformity. The same degree of color uniformity and appearance is not obtained with a combination of separately coated substrates which are formulated after coating the substrate.

As used herein, the phrase "coated mixture of two or more different materials" means first mixing two or more different materials together and then coating the mixture.

Effect pigments are formed according to the present invention by any method known in the art. In one embodiment, this can be achieved by depositing metal ions on the layered plate and then calcining the coated plate to obtain a metal oxide-coated plate. The most widely used metal oxide is titanium dioxide, followed by iron oxide. Other available oxides include, but are not limited to, tin, chromium and zirconium oxides, as well as mixtures and combinations thereof. For convenience, the methods described below relate primarily to titanium and iron as metal oxides, but it will be appreciated that any other known metal or combination of metals may be used.

Other useful metal oxide combinations include SiO ₂ on calcium aluminum borosilicate and then TiO ₂ ; Base material / SiO ₂ / Fe ₂ O ₃ ; Base material / TiO ₂ / SiO ₂ ; Base material / TiO ₂ / SiO ₂ / TiO ₂ ; Base material / TiO ₂ / SiO ₂ / Fe ₂ O ₃ ; Base material / TiO ₂ / SiO ₂ / Cr ₂ O ₃ ; Base material / Fe ₂ O ₃ / SiO ₂ ; Base material / Fe ₂ O ₃ / SiO ₂ / Fe ₂ O ₃ ; Substrate / Fe ₂ O ₃ / SiO ₂ / TiO ₂ 2; Base material / Fe ₂ O ₃ / SiO ₂ / Cr ₂ O ₃ ; Base material / Cr ₂ O ₃ / SiO ₂ / Cr ₂ O ₃ ; And base materials / Cr ₂ O ₃ / SiO ₂ / Fe ₂ O ₃ . Other combinations of the above mentioned layers are also apparent to those skilled in the art.

Interlayers may also be used to enhance performance characteristics. Useful interlayer materials include hydroxides and oxides of Al, Ce, Cr, Fe, Mg, Si, Ti and Zr. Basically, any organic or inorganic material can be an interlayer useful for promoting adhesion, mechanical preservation, product reinforcement or other desirable properties.

Generally, the method involves dispersing the fine particles (flakes) and combining the dispersion with the precursor to form a titanium oxide or iron oxide precursor coating on the foil. Usually, the particulates or flakes are preferably dispersed in water to be distilled off. While the average particle size of the flakes preferably used may vary from an average of about 3 microns to an average of about 100 microns, smaller flakes of at least about 1 micron or less, or larger flakes of at least 150 microns, may also be used if desired. The thickness of the plate is about 0.1 to 10 μm, and the aspect ratio (average particle size / thickness) is about 10 or more. The concentration of particulates in water can vary from about 5 to 60%, but generally the preferred concentration can vary from about 10 to 20%.

A suitable metal ion feed material is added to the water / particulate slurry. In the case of titanium, titanyl chloride or titanium tetrachloride is preferably used, and in the case of iron, ferric chloride is preferred as a feed material. The pH of the resulting slurry is maintained at a suitable level with the use of a suitable base such as sodium hydroxide during the addition of titanium or iron salts, resulting in the deposition of titanium dioxide or iron oxide precursors on the particulates. Increasing the thickness causes an interference color. If desired, layers of hydroxides and / or oxides of titanium and iron (or other metals) may be deposited successively. If it is necessary to lower the pH, an aqueous acid such as hydrochloric acid can be used. The coated plate can be washed and dried, if desired, before calcining with the final effect pigment.

When preparing titanium dioxide-coated products, both anatase and rutile crystal modifications are possible. The highest quality and most stable pearlescent pigments are obtained when titanium dioxide is in rutile form. Some substrates, including mica and glass, are directly anatase, so if the rutile product is desired, it is necessary to modify the method above. Modifications necessary to obtain rutile TiO ₂ are known in the art. One method involves depositing tin hydroxide or tin oxide on the surface of the particulate and then forming a titanium dioxide precursor layer. The layered combination is processed and calcined. The process is described in detail in US Pat. No. 4,038,099, which is incorporated herein by reference. The alternative is described in US Pat. No. 5,433,779, the disclosure of which is also incorporated herein by reference, which deposits a titanium dioxide precursor on a substrate in the presence of iron and calcium, magnesium and / or zinc salts without the use of tin. It involves making. Although rutile coatings are preferred, it may be desirable to produce an anatase coating, and is also within the scope of the present invention.

Other coating methods can also be used, for example chemical vapor deposition methods.

Optically variable effect pigments have been developed more recently. It is generally coated with a reflective layer (eg silver, gold, platinum, palladium, rhodium, ruthenium, osmium, iridium or alloys thereof), which provides a variable path length for light depending on the angle of occurrence of light impinging upon it. And a third layer (eg, silicon, iron oxide) that is overcoated with a low index of refraction with a refractive index of 1.3 to 2.5 (eg, MgF ₂ or SiO ₂ ) and then selectively permeable to direct sunlight thereon. Chromium oxide, mixed metal oxides, titanium dioxide, titanium nitride and aluminum, as well as the same material as the first layer, which is selectively thin) to selectively permeate). Examples of individual pigments and methods of producing them, in particular, teach alternating layers of US Pat. Nos. 5,135,812, 4,434,010 (eg TiO ₂ and SiO ₂ , the disclosure of which is also incorporated by reference). ), 5,059,245, 5,281,480, 5,958,125, 6,160,208, 6,325,847, and 6,440,208.

Different materials or substrates used in the present invention may have any form, including plate-shaped, spherical, cube-shaped, needle-shaped, single crystal or fibrous. Examples of useful plate materials include plate aluminum oxide, plate glass, aluminum, mica, bismuth oxychloride, plate iron oxide, plate graphite, plate silica, bronze, stainless steel, natural pearls, boron nitride, silicon dioxide, copper flakes, copper alloy flakes Zinc flakes, zinc alloy flakes, zinc oxide, enamel, china clay and porcelain. Any combination of the platelets, or one or more of the platelets and one or more non-platelets, may be used. For convenience, the following substrate will focus on the combination of glass and mica, but other combinations may be used. Mica is preferred because of its high transparency, strong reflectivity and strong chromaticity due to the presence of small coated flakes. Glass flakes have the property of gloss effect in high transparency, very white bulk and strong light, but as described above, they are expensive and have a high melting point, making them difficult to use in many applications.

Examples of useful spherical materials include glass, plastics, ceramics, metals or alloys, and the spheres may be hollow or empty. Useful glass spheres are disclosed in US Pat. No. 5,217,928, which is incorporated herein by reference in its entirety.

Useful cube materials include free cubes.

In one embodiment, the present invention uses a blend of two or more layered substrates. Preferably, one of the substrates is plate aluminum aluminum or plate glass.

Individually, although each substrate may comprise about 5 to 90% of the mixture, it is preferred that the majority of the formulation consists of one substrate, such as mica. More preferably the blend contains at least about 65% mica, and even more preferably at least about 75% mica. Individually, the mica and glass plates have an average particle size and thickness in the range specified above. Particle dimensions are measured in chroma units (CieLab) for the formulation of the same proportion of coated substrate so that the resulting coating product exhibits visual uniformity, ie measured by X-Rite MA at 25 ° from the angle of reflection. ) An increase of at least 5 or an increase of at least 5% in chromaticity units. Preferably, the increase is greater than or equal to the chromaticity unit (CieLab) 10 and the smaller average particle size of the glass and the mica plate is preferably within about 25% of the larger particle size of the glass and the mica plate. It is preferred to use C glass as in the prior art, but any type of glass and form can be used in the present invention. Other useful glass flakes have a thickness of 1.0 μm or less and a softening point of 800 ° C. or more.

Glass can be classified, for example, into A glass, C glass, E glass, and ECR glass. Glass types that meet the characteristics of the required softening point are quartz glass and any other glass composition having a softening point of at least 800 ° C. Glass flakes that meet these requirements are of particular glass type, such as the Scott Duran or Supermax type. Softening point is defined according to ASTM C 338 at a temperature at which its length increases by 1 mm per minute when the top 10 cm of the uniform fibers of glass 0.55 to 0.75 mm in diameter and 23.5 cm in length are heated at a rate of 5 ° C. per minute. .

Examples of mixtures of two or more different materials that are useful are in the table below.

First substance Second material 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 glass Quartz glass Silicon carbide mica Glass sphere mica Contains other oxides
Mainly iron oxide Glass sphere Contains other oxides
Mainly iron oxide mica Zinc oxide Glass Metal or alloy Glass Ceramic microspheres mica Glass bubble mica

Suitable glass flakes are characterized by an average particle size in the range of 5 to 1000 μm and a thickness of 0.1 to 5 μm, preferably 0.1 to 0.3 μm. The aspect ratio of the glass flakes is in the range of 10 to 300, preferably 50 to 200.

The substrate coating method used is adapted to coat two or more substrate materials at substantially the same rate, resulting in coatings of similar quality and thickness. This may include control of temperature, reagent addition rate, reagent type, substrate pretreatment, and the like. Often, the adjustment is made easier as the plates get closer to each other in average size and thickness. Necessary or suitable modifications can be readily performed by those skilled in the art along with some preparatory work to obtain suitable parameters.

The above-described method of blending glass and mica plates prior to coating results in unexpectedly obtained products exhibiting visual uniformity in uniform color, which cannot be achieved by the formation of a combination of pre-coated coated mica and coated glass plates. . The results are obtained despite the fact that mica and glass substrates have different transparency, surface chemistry and refractive index, and usually different thicknesses.

The calcination of the coated glass flakes is generally done at around 600 ° C. as the glass plate melts at about 650 to 700 ° C., resulting in a material of significantly degraded quality. Surprisingly, it has been found that a combination of glass and mica, coated with a metal oxide precursor, can be calcined without melting glass flakes at temperatures of 650 ° C. up to about 850 ° C. Preferably, the calcination temperature is about 675 to 825 ° C., most preferably about 800 ° C. when the metal oxide is TiO ₂ and about 700 ° C. when the metal oxide is Fe ₂ O ₃ .

Another advantage of using the co-deposited effect pigments of the present invention is the ability to have the same product color space for different materials of the mixture. Accurately matching the colors of two different materials and then compounding the product is a difficult process and not practical. Factors such as particle size, surface chemistry, refractive index, and reflectance of the substrate affect the final optical properties of the pigment, making it difficult to measure its corresponding hue value. In the co-deposition method of the present invention, the color values for both substrates are automatically adjusted in the coating process.

However, the coated substrate obtained can be worked up by any method known in the art. Examples of such treatments are found, for example, in US Pat. Nos. 4,134,776, 5,091,011, 5,156,889, 5,326,392, 5,423,912, 5,759,255, and 6,325,846, all of which are incorporated herein by reference. You can, but you're not limited to this method.

Depending on the intended use, the effect pigments of the invention can benefit from some form of surface treatment. Non-limiting examples would be coupling agents with or without metal hydroxide for enhanced external stability. Often, as a surface treatment, metal compounds are added with or without organic compounds to change the surface charge and / or tactile properties of the particles.

The pigments obtained can be used in any application so far such as effect pigments, for example cosmetics, plastics, safety signs, inks and solvents including solvents, and waterborne automotive paint systems. The products of the present invention have unlimited use in all types of automotive and industrial paint applications, especially in the field of organic color coatings and inks where dark color strength is required. For example, the pigments can be used as massons in all types of automotive and non-automobile vehicles or as styling agents for spraying paints. Similarly, they can be used on all clay / formica / wood / glass / metal / enamel / ceramic and nonporous and porous surfaces. The pigments can be used in powder coating compositions. They can be incorporated into plastic articles that are installed for the toy industry or for home use. Safety uses such as inks and coatings are useful uses of these products. The pigments penetrate into the fibers and provide new, aesthetic colors to clothing and carpets. The pigments are used to improve the appearance of shoes, rubber and vinyl / marble flooring, vinyl wallboards and all other vinyl products. In addition, these colors can be used for all types of hobby models.

The abovementioned compositions in which the compositions of the invention are useful are well known to those skilled in the art. Examples include printing inks, nail enamels, lacquers, thermoplastic and thermosetting materials, natural resins and synthetic resins. Some non-limiting examples include polystyrene and mixed polymers thereof, polyolefins, in particular polyethylene and polypropylene, polyacrylic compounds, polyvinyl compounds such as polyvinyl chloride and polyvinyl acetate, polyesters and rubbers, and also viscose and Filaments made of cellulose ethers, cellulose esters, polyamides, polyurethanes, polyesters such as polyglycol terephthalate, and polyacrylonitrile.

For various introductions to various pigment applications, see Temple C. Patton, editor, The Pigment Handbook, volume II, Applications and Markets, John Wiley and Sons, New York (1973). Further, for example, regarding ink, R. H. Leach, editor, The Printing Ink Manual, Fourth Edition, Van Nostrand Reinhold (International) Co. Ltd., London (1988), especially pp. 282-591; For paints, see C. H. Hare, Protective Coatings, Technology Publishing Co., Pittsburgh (1994), in particular pages 63-288. These documents are incorporated herein by reference to teach the inks, paints and plastic compositions, formulations and vehicles in which the compositions of the present invention may be used, including the amount of colorants. For example, the pigments can be used with vehicles containing residual amounts of gelled and ungelled hydrocarbon resins, alkyd resins, wax compounds and aliphatic solvents at levels of 10-15% in offset lithography inks. The pigments can also be used at levels of 1 to 10% in automotive paint formulations with other pigments which may include, for example, titanium dioxide, acrylic lattice, binders, water or solvents. The pigments can also be used at levels of 20 to 30%, for example in plastic color concentrates in polyethylene.

In the cosmetic field, the pigments can be used in the eye area and in all external and cleansing applications. Thus, they can be used in hair sprays, face powders, leg-makes, pest control lotions, mascara cakes / creams, nail enamels, nail enamel removers, perfume lotions, and all types of shampoos (gels or liquids). In addition, they are shaving creams (concentrates for aerosols, no brushes, foams), skin gloss sticks, skin makeup, hair groom, eyeshadows (liquid, pomade, powder, sticks, compressed or creams), It can be used in eyeliners, lotion sticks, lotions, lotion softeners, bubble baths, body lotions (moisturizing, cleansing, pain relief, astringent), after shave lotions, post bath milk and sunscreen lotions.

Cosmetics: Science and Technology, 2nd Ed., Eds: MS Balsam and Edward Sagarin, Wiley-Interscience (1972), and deNavarre, The Chemistry and Science of Cosmetics, incorporated herein by reference for review of cosmetic uses. , 2nd Ed., Vols 1 and 2 (1962), Van Nostrand Co. Inc., Vols 3 and 4 (1975), Continental Press.

To further illustrate the invention, various non-limiting examples will be described below. In addition to these examples, throughout this specification and the following claims, all parts and proportions are by weight unless otherwise indicated, and all temperatures are in degrees Celsius.

Example 1-4

A blend of 50 g of C glass flakes having an average particle size of about 140 microns (measured with a laser light scatterer) was mixed with 50 g of white mica having an average particle size of about 80 microns. The mixture was dispersed in 750 ml of water and iron and zinc were charged in the form of 1 ml of 39% ferric chloride aqueous solution and 7 ml of 9% zinc chloride aqueous solution. The pH of the slurry was adjusted to 3.0 using 35% aqueous sodium hydroxide solution, and heated to a temperature of 76 ° C. Then, the pH was lowered to 1.6 by adding hydrochloric acid, and 40% aqueous titanium tetrachloride solution was added at a rate of 100 ml per hour while maintaining the pH at 1.6 by adding 35% aqueous sodium hydroxide solution. The titanium loading was continued until white pearly color, or gold, red and blue interference color appeared. When the desired end point was reached, the slurry was filtered through a Buchner funnel and washed with additional water. The coated plate was then dried and calcined at about 800 ° C.

Microscopic evaluation of the obtained pigment showed that the plate was coated with a smooth and uniform layer of titanium dioxide. The coated pigment was visually uniform.

The gloss and color of the obtained pigment is black and the other half is white and visually and mechanically using a drawdown on a concealment test paper (Type 2 to 6 opacity test paper of the Leneta Company). Measured. The coating of the white portion of the test paper showed a transmissive color when viewed from non-reflective angles, while the coating of the black portion showed a reflective color and gloss when viewed from the reflection angle. The pigment was added to the nitrocellulose lacquer at a concentration of 12%, and the suspension was applied to black and white test paper with a Bird film applying rod to prepare a drawdown. The drawdown prepared in this example exhibited a series of vivid high quality colors with high chromaticity and range.

Example 5-9

100 g of the glass / mica blend of Examples 1-4 were dispersed in 330 ml of distilled water, then heated to 74 ° C. and the pH adjusted to 1.6 using dilute hydrochloric acid. Then, 7 ml of 18% tin-chloride aqueous solution was slowly added, followed by 40% titanium tetrachloride aqueous solution at a rate of 100 ml per hour. During the addition of tin and titanium, dilute aqueous sodium hydroxide solution was added simultaneously to maintain the pH at 1.6. The titania addition was continued until white pearly color, or yellow, red, blue or green interference color appeared. When the desired end point was reached, the slurry was filtered, washed with additional water and calcined at about 800 ° C.

Microscopic evaluation of the obtained pigment showed that the plate was coated with a smooth and uniform layer of titanium dioxide. The coated pigment was visually uniform.

The drawdowns made in the pigments of this example showed a series of vivid high quality colors with high chromaticity and range.

Example 10-17

75 g of the glass / mica blend of Examples 1-4 were dispersed in 300 ml of distilled water. The dispersion was heated to 76 ° C and the pH was adjusted to 3.2 with dilute hydrochloric acid. Aqueous ferric chloride solution was added to the suspension at a rate of 0.2 ml per minute while maintaining the pH at 3.2 using dilute sodium hydroxide. Ferric chloride was continuously added until the desired color was observed, and the slurry was filtered, washed with water and calcined at 800 ° C. when the desired color appeared, to obtain the ferric oxide coated effect pigment.

Since ferric oxide was originally red, the flakes coated with the oxide had both reflective and absorbing colors. Absorption color is the color due to light absorption, while interference color is the color due to light interference. The reflection color changes from gold to red and again from blue to green as the amount of iron (III) coated on the layered flakes increases. Further addition of iron (III) oxide yielded a thicker coating of Fe ₂ O ₃ , yielding another series of interference colors known as the second observable interference color. The second color had a higher color intensity than the first color. Further continuing the coating process can yield a series of third interference colors.

When the iron oxide-coated flakes were drawn down, a clear, high-quality series of colors was observed. The interference colors shown in the above examples were bronze, first orange, first red, first violet, first green, second orange, second red and second green.

Example 18-20

Titanium dioxide can produce a series of interference colors as the thickness of the titanium dioxide layer increases. Initially a pale white reflection occurred with pearly or silvery appearance, and gold, red, blue and green interference colors were observed as the TiO ₂ layer thickened. As the coating became thicker, a series of second observable colors were observed. The second color had a higher color intensity than the first color described in the above examples.

A second color was prepared by dispersing 50 g of the mica / glass blend 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 18% stannous chloride solution was added, followed by 40% titanium chloride at a rate of 0.33 ml per minute. Dilute sodium hydroxide was added simultaneously to maintain the pH at 1.6. Titanium addition was continued until the desired color was obtained and the slurry was filtered, washed with water and calcined at 800 ° C. when the desired color appeared. The second index gold, orange and red color were obtained by the above method. When drawn down, the product had a higher color intensity compared to its first observable interference color.

Example 21-25

The methods of Examples 5-9 were repeated except that the lamellar formulation consisted of 75 parts of white mica with an average particle size of about 25 microns and 25 parts of C glass flakes having an average particle size of about 25 microns.

Example 26-33

The methods of Examples 10-17 were repeated except that the lamellar formulation consisted of 75 parts of mucosa with an average particle size of about 25 microns and 25 parts of C glass flakes having an average particle size of about 25 microns.

Example 34-41

The methods of Examples 10-17, except that the layered plate blend consisted of a blend of 50 g lamellar aluminum with an average particle size of about 20 microns (measured with a laser light scattering machine) and 50 g of white mica with an average particle size of about 25 microns. Was repeated.

Example 42

A blend of 150 g of white mica with an average particle size of about 25 μm was mixed with 50 g of glass flakes having a nominal thickness of 1 μm and a major dimension (D ₅₀ ) of 20 μm. The mixture was dispersed in 2000 ml of distilled water and heated to 78 ° C. At this temperature, the pH of the slurry was reduced to 1.5 with dilute HCl solution and 20 g of 18% SnCl ₄ solution was added at 0.4 ml per minute while maintaining the pH at 1.5 with NaOH solution. After addition of the SnCl ₄ solution, the pH was increased to 3.2 with dilute NaOH and 1.5 ml of 39% FeCl ₃ was added per minute 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 commercially available automotive urethane repaint formulation and chromaticity was measured with X-Lite MA 68 at 25 ° and 15 ° from the angle of reflection. The values obtained from pre-blended substrate samples before coating and samples prepared in a similar manner with the same fraction of individually coated substrates are shown in the table below. The premixed samples showed a chromaticity increase of at least 10 units (Cielab) at each angle, 76.1 vs 59.7 at 15 ° and 62.4 vs 51.8 at 25 °.

Example 44

A blend of 50 g of plated aluminum oxide having an average particle size of about 20 microns (measured with a laser light scatterer) was mixed with 50 g of white mica having an average particle size of about 25 microns. The mixture was dispersed in 750 ml of water and iron and zinc were added in the form of 1 ml of 39% ferric chloride aqueous solution and 7 ml of 9% zinc chloride aqueous solution. The pH of the slurry was adjusted to 3.0 using 35% aqueous sodium hydroxide solution, and heated to a temperature of 76 ° C. Then, the pH was lowered to 1.6 by adding hydrochloric acid, and a 40% aqueous titanium tetrachloride solution was added at a rate of 100 ml per hour while maintaining the pH at 1.6 by adding 35% aqueous sodium hydroxide solution. Titanium dosing was continued until white pearl color appeared. When the desired end point was reached, the slurry was filtered with Buchner funnel and washed with additional water. The coated plate was then dried and calcined at about 800 ° C.

Example 45

100 g of the same mixture of glass flakes (average major dimension 100 µm) and mica (average major dimension 100 µm) were placed in a 1 L beaker equipped with a magnetic stir bar and containing 393 g of a 2% dextrose solution. The slurry was stirred at room temperature. A solution containing 7.87 g of silver nitrate crystals, 375 ml of distilled water, and 29% ammonium hydroxide solution sufficient to dissolve any deposits was quickly added to the slurry. The supernatant was tested for silver ions by adding a few drops of concentrated hydrochloric acid. The test was a visual assessment of any deposits and / or turbidity, when nothing was found, the slurry was filtered, washed several times with distilled water, and the presscake dried at 100 ° C. to constant mass. The dried sample was a shiny, opaque silver material.

50 g of silver-coated material was slurried with 600 ml of isopropanol at 25 ° C. 75 g of distilled water, 3.5 g of 29% NH ₄ OH and 75 g of tetraethoxysilane were added to the slurry. The slurry was stirred at rt for 7 h, then filtered, the product was washed and oven dried.

10 g of the silica-coated material was slurried with 50 g of a 1% dextrose solution. A slight excess of 0.4 g AgNO ₃ , 40 g water and 29% ammonium hydroxide solution was quickly added to the slurry. When the slurry supernatant was negatively tested for silver ions, it was filtered off, the product was washed and dried at 120 ° C. The product showed a very clear color flop from blue to purple as the viewing angle of the lacquer film containing the product changed, and the pigment was visually uniform.

Example 46

The pigment of Example 1 can be formulated into a powder eye shadow as follows.

The following materials were combined thoroughly and dispersed.

ingredient Parts by weight Multalc TCA (Trademark) (talcum) 18 MEARLMICA (trademark) SVA (Mica) 20 Magnesium myristate 5 Silica 2 CLOISONNE '(registered trademark) red 424C
(Red TiO ₂ -coated mica) 20 Clujone Violet 525C (purple TiO ₂ -coated mica) 13 Clujone Nu-Antique Blue 626CB (TiO ₂ -coated mica / iron oxide-coated mica) 2 Cluazone Ceris Flambe '550Z (iron oxide-coated mica) 2 Preservatives and Antioxidants  Quantity Multalk TCA, Mulmica SVA and Kluazone are all registered trademarks of Engelhard Corporation.

Subsequently, 7 parts by weight of octyl palmitate and 1 part by weight of isostearyl neopentanoate were heated, mixed until uniform, the resulting mixture was sprayed with a dispersion, and the compounding was continued. The blended material was ground and then 5 parts by weight of Cloazone Red 424C and 5 parts by weight of the pigment of Example 1 were added and mixed until homogeneous to obtain a powder eyeshadow.

Example 47

The pigment of Example 1 can be formulated into a lipstick as follows.

The amount of ingredients listed below was placed in a heating vessel and the temperature was increased to 85 ± 3 ° C.

Parts by weight Candelilla Wax 2.75 Carnauba Wax 1.25 Beeswax 1.00 Ceresine Wax 5.90 Ozokerite Wax 6.75 Microcrystalline wax 1.40 Oleyl alcohol 3.00 Isostearyl Palmitate 7.50 Isostearyl isostearate 5.00 Capryl / Capre Triglycerides 5.00 Bis-Diglyceryl Polyalcohol Adipate 2.00 Acetylated Lanolin Alcohol 2.50 Sorbitan tristearate 2.00 Aloe vera 1.00 Castor oil 37.50 Red 6 Lake 0.25 Tocopheryl acetate 0.20 Phenoxyethanol, isopropylparaben and butylparaben 1.00 Antioxidant Quantity

Then 14 parts by weight of the pigment of Example 1 were added and mixed until all the pigments were well dispersed. Aroma ingredients were added if necessary and mixed with stirring. The resulting mixture was poured into a mold at 75 ± 5 ° C., cooled and burned with lipstick.

Example 48 and Comparative Example A

115 g of white mica with an average particle size of 20 μm was suspended in 2 L of deionized water. To the slurry was added 30 g of glass of similar particle size to Nippon Sheet Glass and the pH was adjusted to 1.4 with dilute HCl. It was added 77% SnC1 _4? 5H ₂ O solution is 2.7 g to the suspension, followed by heating the slurry to 83 ℃.

TiO ₂ was added to the suspension at this time by adding a 40% TiCl ₄ solution at a rate of 2.8 g per minute. The slurry was maintained at a constant pH and temperature during the deposition. TiO ₂ addition was continued until the desired color was reached. The coating was then filtered, washed and calcined at 800 ° C. for 20 minutes.

Have the same color value, as compared with TiO _2, mica, and TiO pigment (Comparative Example A) prepared by dry mixing the glass a _second coating coated, as described for the pigment of Example 48 obtained by the above coating method Improved chromaticity values are shown. As used herein, the phrase "improved chromaticity" is meant to indicate an increased chromaticity value in comparison with a mixture of an oxide coated first substrate and an oxide coated second substrate at the same color.

The color characteristics of the two pigments are defined by reading at 15 ° from the spectral angle using an X-lite MA 68 II Multi Angle spectrophotometer. Samples were prepared using 1 g of pigment in 33.3 g of NC varnish. The mixture was applied to the black card with a controlled applicator.

From the data, it was proved that the chromaticity value (C ^* ) for the pigment of Example 48 is almost 10% larger than the pigment of Comparative Example A at the same color value (h ^* ). The product of Example 48 also exhibited visual uniformity compared to Comparative Example A.

Example 49 and Comparative Example B

Another advantage of the 25% mica and glass formulations co-deposited with TiO ₂ of the present invention is that the bulk color of the final calcined product is improved. It is known that when calcined the titanium dioxide coated mica product has a yellow bulk color. The term “bulk color” refers to the color observed when viewing the calcined powder. When glass is added to the mica slurry, coated and calcined, the bulk of the product obtained is significantly reduced yellow. Glass, which is a pureer substrate, has fewer color impurities that can add color to TiO ₂ coated pigments. This can be demonstrated by observing the color characteristics of the TiO ₂ coated glass / mica product of the present invention (Example 49) and the similar coating product made only of mica and TiO ₂ (Comparative Example B) against the white pearl interference color.

TiO ₂ coated mica sample powder (Comparative Example B) and 25% glass / coated in a similar manner, using an X-lite SP62 model spectrophotometer capable of measuring whiteness index as described in ASTME 313 of powder material The index was measured for 75% mica blend powders (Example 49).

The whiteness index value for the glass blend sample (Example 49) was 33.9, while the whiteness index value for the mica sample (Comparative Example B) was 23.3. It is evident that the color of the blended glass product of the present invention was significantly improved. As used herein, the phrase “improved whiteness index” is meant to indicate an increased whiteness index compared to mica samples.

Example 50 and Comparative Example C

Example 50 was another combination of 25% mica and glass flakes co-deposited with TiO ₂ prepared according to Example 48 above. Comparative Example C was prepared by dry blending the glass flakes a TiO ₂ coated mica coated with TiO _2. The color characteristics of the pigments were defined by reading at 15 ° from the spectral angle using an X-lite MA 68 II multi-angle spectrophotometer, as follows.

The results demonstrated that the product of Example 50 had improved chromaticity and showed visual uniformity compared to Comparative Example C.

Example 51

Another blend of glass with 25% mica co-deposited with TiO ₂ was prepared according to Example 48 above except that the average particle size of the glass flakes (purchased from Nippon Sheet Glass) was 30 microns. The color characteristics of the pigments were defined by reading at 15 ° from the spectral angle using an X-lite MA 68 II multi-angle spectrophotometer, as follows.

Example 52 and Comparative Example D

Example 52, another combination of 25% mica and glass co-deposited with TiO ₂ was prepared according to Example 48 above. Comparative Example D was prepared by dry mixing the TiO ₂ coated mica and TiO ₂ coated glass. The color characteristics of the pigments were defined by reading at 15 ° from the spectral angle using an X-lite MA 68 II multi-angle spectrophotometer, as follows.

The results demonstrated that the product of Example 52 had improved chromaticity and showed visual uniformity compared to Comparative Example D.

Example 53

A slurry of mica (medium particle size D (50) 50 micron) 210 g, glass flakes (D (50) 100 micron, purchased from Nippon Glass) and 2 L of distilled water was made and stirred at 350 rpm. The pH was lowered to 1.4 with 1: 1 HCl. 77% SnCl _4? Dropwise 5H ₂ O 2.7 g. The composition was heated to 83 ° C. While adjusting the pH to 1.4 with 35% NaOH, 180 g of 40% TiCl ₄ was added at 2.1 ml per minute. The pH was raised to 8.2 with 35% NaOH. 2500 g of 28% Na ₂ SiO ₃ -9H ₂ O was added at a rate of 3.5 ml per minute, adjusting the pH to 8.2 with 1: 1 HCl. The pH was lowered to 1.9 by adding 1: 1 HCl at 0.5 ml per minute. While adjusting the pH to 1.9 with 35% NaOH, 180 g of 40% TiCl ₄ was added at 2.1 ml per minute. Product 1 had a composition of 12.5% TiO ₂ , 33.4% SiO ₂ , 47.3% Mica, and 6.8% Glass. Product 2 had a composition of 13.5% TiO ₂ , 33.0% SiO ₂ , 46.8% Mica, and 6.7% Glass. Product 3 had a composition of 16.6% TiO ₂ , 31.8% SiO ₂ , 45.2% mica and 6.4% glass. The X-lite characteristics of the obtained product are as follows.

Various changes and modifications can be made in the products and methods thereof without departing from the spirit and scope of the invention. The various embodiments disclosed herein are intended to further illustrate the present invention, but are not intended to be limiting.

Claims (20)

An effect pigment exhibiting visual uniformity comprising a coated mixture of two or more different materials, each present at least 5% to 95% by weight based on the total amount of two or more different materials. The effect pigment of claim 1, wherein the coating comprises a plurality of layers, and at least one of the layers comprises an oxide. The effect pigment of claim 2, wherein the oxide layer comprises silicon hydroxide and silicon oxide. The method of claim 3, wherein the plurality of layers comprise SiO ₂ / Fe ₂ O ₃ ; TiO ₂ / SiO ₂ ; TiO ₂ / SiO ₂ / TiO ₂ ; TiO ₂ / SiO ₂ / Fe ₂ O ₃ ; TiO ₂ / SiO ₂ / Cr ₂ O ₃ ; Fe ₂ O ₃ / SiO ₂ ; Fe ₂ O ₃ / SiO ₂ / Fe ₂ O ₃ ; Fe ₂ O ₃ / SiO ₂ / TiO ₂ ; Fe ₂ O ₃ / SiO ₂ / Cr ₂ O ₃ ; Cr ₂ O ₃ / SiO ₂ / Cr ₂ O ₃ ; Or an effect pigment comprising Cr ₂ O ₃ / SiO ₂ / Fe ₂ O ₃ . The effect pigment of claim 1, wherein the coated mixture comprises at least three different materials. The effect pigment of claim 1 further comprising a surface treatment to said coated mixture. The effect pigment of claim 1, wherein at least one of the different materials is plate-shaped, spherical, cubed or fibrous. 8. An effect pigment according to claim 7, wherein at least one of said different materials is glass. 8. An effect pigment according to claim 7, wherein at least one of said different materials is a plate material. A cosmetic comprising the effect pigment of claim 1. The method of claim 1, i) the at least two different materials are selected from the group consisting of cube and spherical materials and the coating is a metal oxide; ii) the two or more different materials are two different glasses; or iii) the at least two different materials are plate metal materials Effect pigments. delete delete delete delete delete delete delete delete delete