# Patent

## Title
Multilayer effect pigment

## Abstract

A multilayer effect pigment includes a transparent substrate, a layer of high refractive index material on the substrate, and alternating layers of low refractive index and high refractive index materials on the first layer, the total number of layers being an odd number of at least three, all adjacent layers differing in refractive index by at least about 0.2 and at least one of the layers having an optical thickness which is different from all of the other layers. The resulting multilayer effect pigment is not a quarter-wave stack.
The present multilayer effect pigment may be used in cosmetics or personal care products.

## Background
This application is a continuation-in-part of U.S. Ser. No. 11/056,560 filed Feb. 12, 2005, which is a continuation in-part of U.S. Ser. No. 10/346,076, filed Jan. 17, 2003, now U.S. Pat. No. 6,875,264, issued Apr. 5, 2005.


BACKGROUND OF THE INVENTION
Effect pigments, also known as pearlescent or nacreous pigments, are based on the use of a laminar substrate such as mica or glass flake which has been coated with a metal oxide layer. These pigments exhibit pearl-like luster as a result of reflection and refraction of light, and depending on the thickness of the metal oxide layer, they can also exhibit interference color effects.
Titanium dioxide-coated mica and iron oxide-coated mica effect pigments are the effect pigments which are encountered most often on a commercial basis. Pigments in which the metal oxide has been over-coated with another material are also well known in the art.
The commercially available effect pigments which contain only a single coating of a high refractive index material provide only two reflecting interfaces between materials. These two material interfaces (and reflections) are therefore solely responsible for the reflectivity achieved from the platelet surface. A substantial percentage of the incident light is thus transmitted through the platelet and while this is necessary to create the nacreous appearance of the pigment, it also diminishes other desirable properties of the effect pigments such as luster, chromaticity and hiding power. To counteract this consequence, the art has either mixed the effect pigments with other pigments or added additional layers of transparent and/or selectively absorbing materials onto the effect pigment.
Examples of prior art describing multi-coated effect pigments include JP 7-246366, WO 98/53011, WO 98/53012 and U.S. Pat. No. 4,434,010. All of such prior art requires that each coated layer possess an optical thickness equal to a whole number multiple of a one-quarter of the wavelength at which interference is expected. Such construction of the so-called quarter-wave stacks is a widely accepted and implemented condition in the thin-film industries. Because of this limitation, a unique layer thickness combination is essential in order to create each individual one of the interference colors of the visible spectrum. The base substrate is the only dimension common to all of the compositions displaying different interference colors.
It has now been discovered that the adherence to the quarter-wave stack approach is unnecessary and suitable products, even with substantial gains in luster, chromaticity and hiding power, can be achieved without observing that requirement. Further, numerous other advantages can be realized.
It is accordingly the object of this invention to provide a new multilayer effect pigment, including having improved luster, chromaticity and/or hiding power relative to other effect pigments.
SUMMARY OF THE INVENTION
This invention relates to a multilayer effect pigment and more particularly, to a multilayer effect pigment which includes a transparent substrate having a transparent high refractive index material layer thereon and at least one pair of layers which are a transparent high refractive index material and a transparent low refractive index material, in which the total number of layers is an odd number, in which every two adjacent non-substrate layers differ in refractive index by at least about 0.2 and in which at least one layer has an optical thickness which is different from all of the other layers, whereby the pigment is not a quarter-wave stack.
The present patent application is directed to a multilayer effect pigment comprising a transparent substrate having a layer of titanium dioxide thereon. The titanium dioxide layer has an optical thickness of about 85 to 385 nm. A layer of a low refractive index material is on the titanium dioxide layer and an outermost layer of a high refractive index material placed on the low refractive index layer. The high refractive index material comprises titanium dioxide having an optical thickness of from about 45 to 420 nm and the low refractive index material is silicon dioxide having an optical thickness of about 30 to 120 nm. At least one layer has an optical thickness which is different from all of the other layers, whereby the pigment is not a quarter-wave stack.


DESCRIPTION OF THE INVENTION
In accordance with the present invention, the effect pigment is a multilayered product composed of a transparent substrate having an odd number of layers thereon and in which at least one of the layers has an optical thickness which is different from all of the other layers causing the pigment not to be a quarter-wave stack.
Any encapsulatable smooth and transparent platelet can be used as the substrate in the present invention. Examples of useable platelets include mica, whether natural or synthetic, kaolin, glass flakes and the like. The substrate need not be totally transparent but should, preferably, have at least about 75% transmission. The size of the platelet shaped substrate is not critical per se and can be adapted to the particular use. Generally, the particles have largest major dimensions averaging about 5-250 microns, preferably 5-100 microns, and an aspect ratio greater than about 5. Their specific free surface area (BET) is, in general, from about 0.2 to 25 m2/g.
The layers encapsulating the substrate alternate between high refractive index materials and low refractive index materials. High refractive index materials include those with a refractive index from about 2.00 to about 3.10. Low refractive index materials include those with a refractive index from about 1.30 to about 1.80. The high refractive index materials may be anatase titanium dioxide, rutile titanium dioxide, iron oxide, zirconium dioxide, zinc oxide, zinc sulfide, bismuth oxychloride or the like.

    
    
        The CRC Handbook of Chemistry and Physics, 63rd edition reports refractive indices for these high refractive index materials as follows.
    
    















Material
Refractive Index








TiO2 - anatase
2.55



TiO2 - rutile
2.90



Fe2O3 - hematite
3.01



ZrO2
2.20



ZnO
2.03



ZnS
2.38



BiOCl
2.15









The low refractive index material may be silicon dioxide, magnesium fluoride, aluminum oxide, a polymer such as polymethyl methacrylate, polystyrene, ethylene vinyl acetate, polyurea, polyurethane, polydivinyl benzene and the like.

    
    
        The CRC Handbook of Chemistry and Physics, 63rd edition reports refractive indices for these low refractive index materials as follows.
    
    















Material
Refractive Index








SiO2 - amorphous
1.46



MgF2
1.39



Al2O3
1.76



Polymers
1.4-1.6 is typical









Any combination of materials may be selected provided that adjacent layers differ in refractive index by at least about 0.2, and more preferably at least about 0.6. The materials are transparent but may, like iron oxide and chromium oxide, have an absorption component.

The phrase “a transparent substrate having a layer of titanium dioxide thereon” as used herein means that the titanium dioxide may be in direct contact with the transparent substrate or additives or other layers may be present between the transparent substrate and the layer of titanium dioxide. Additives include rutile directors for titanium dioxide such as tin. The phrase “a layer of a low refractive index material on said titanium dioxide layer” as used herein means that the low refractive index material may be in direct contact with the titanium dioxide or additives or other layers may be present between the titanium dioxide and the low refractive index material. The phrase “outermost layer of a high refractive index material placed on said low refractive index material layer” as used herein means that the outermost layer of a high refractive index material may be in direct contact with the low refractive index material layer or additives or other layers may be present.
The individual layers can be applied to the substrate and to each other using techniques well known in the art. Any such technique can be utilized. One of the advantages of the invention is that sol-gel techniques can be used to apply the coatings. Such techniques are well known and widely practiced for thin film deposition, and are safe, economical and amenable to a wide variety of particle shapes and sizes. Chemical vapor deposition techniques which have been used in some prior art have a litany of negative aspects including safety hazards, expensive reagents and infrastructure and substrate particle size limitations. Monolithic web-based multilayer coating techniques have also been used in the prior art and suffer from the disadvantages that pigment particles are formed after the coatings are applied and therefore have discontinuities in the layers at the fracture points. The particles must also be classified according to size after the monolith is fractured, whereas in the present invention the particle size can be predetermined before the coating and can be constant.
Another advantage of the present invention is that the substrate and all layers have an appreciable degree of transparency and therefore the resulting pigments can exhibit unique angle dependent reflectivity ranging from nearly totally reflecting to substantially transmitting as the viewing angle is changed. Many multi-coated pigments in the prior art use metal flakes as substrates and such metal layers are not capable of transmitting light and the resulting pigment is therefore totally opaque.
Because the pigment is not a quarter-wave stack, the first layer which is adjacent the substrate can be given a fixed thickness and by varying the thickness of the other layers, it is possible to prepare all of the interference colors desired.
While any odd number of layers equal to or greater than three can be employed, it has been found that substantial advantages are present when there are three layers and this is therefore preferred.
As described below, the thicknesses of each of the individual layers applied to the substrate are described as the optical thickness values. Optical thickness is the product of the actual physical or geometric thickness (t) of the layer and the refractive index (n) of the material of the layer. While it may be possible to measure the physical thickness of the deposited layer on the substrate, the refractive index of the applied material will vary from published values depending on the density and uniformity of the deposited layer. Typically, the tabulated values of refractive index are well known but such values are determined from a uniform and highly packed structure and are almost always higher than the refractive index values of the actual layers deposited via the techniques of this invention. Accordingly, it may be difficult to obtain the desired color by simply applying the respective materials at a prescribed physical thickness of the layer in as much as the refractive index may vary widely depending on the density and uniformity of the coating. However, the optical thickness can be indirectly determined by measuring the wavelengths at which interferences occur in the sample and then solving for “nt” in the well-known constructive interference and/or destructive interference equations. The equations as written below are for normal angle incidence of light only, in which the cosine θ term reduces to 1 and does not need to appear, in the interest of simplifying the present discussion.
Constructive interference equation: nt=m λ/4 where in m=odd integer

    
    
        n=refractive index of the film material
        t=geometric (physical) thickness of the film material, in nanometers
        λ=the wavelength of maximum reflection, in nanometers
        nt=optical thickness of the film material, in nanometers
    
    


Destructive interference equation: nt=m λ/2 where in m=any positive integer

    
    
        λ=the wavelength of minimum reflection, in nanometers
    
    


By measuring the interference wavelength λ from samples having the desired color after each layer deposition, the optical thickness of each layer can be readily determined. It is important to note that in this invention, the optical thicknesses of all the layers are not the same and as such, the pigment of the present invention does not represent the typical quarter wave stack. A layer having the appropriate whole integer multiple for the coefficient “m” in the equations is considered to possess the same optical thickness as the m=1 case, and therefore construction of a stack of layers in which the integer m is varied at a constant λ is still considered a quarter-wave stack based on its function. This practice is therefore avoided in this invention. Surprisingly, it has been found that non-quarter wave stack pigments can yield desired colors contrary to what was long considered in the art, that the optical thicknesses of all the layers had to be the same.
The low refractive index is preferably silica and while this can have other optical thicknesses, the silica layer preferably has an optical thickness in the range of about 30-120 nm, and more preferably about 60-120 nm. This minimizes the degree of angle dependent color travel, which is inherent in silica films. Silica layers which have an optical thickness greater than about 180 nanometers produce a wider range of angle dependent colors which is not always desirable.
The first layer on the substrate and the outermost layer can be the same or different, but are preferably the same, and are further preferably titanium dioxide. It will be appreciated that where the first or innermost layer has a fixed optical thickness and the low refractive index layer also has a predetermined optical thickness, the outermost high refractive index layer will control the interference color as a result of its optical thickness. The substrate/first layer/second layer combination thus acts as a universal base from which all interference colors can be realized by simply varying the optical thickness of the third layer. The transparent substrate will have a first layer of titanium dioxide thereon, the first layer having an optical thickness of about 80 to 400 nm. The optical thickness of the third layer, when it is titania, in such an arrangement generally varies from about 45 to 600 nm, and preferably about 140-420 nm. Preferably, the first layer will have a optical thickness of from about 85 to 385 nm.
While the approach of using a universal substrate/first layer/second layer base yields products superior to single-layer TiO2-coated substrates, optimum pigments of this invention can be derived by employing a variety of unique optical thickness combinations. Examples of such products are provided in Table 2 below.
It is further part of the present invention that the pigments have first and outermost layers which have different optical thicknesses from each other and still yield the unexpected color which has been achieved by these materials which do not follow the standard quarter-wave theory. Moreover, the TiO2 layers may have the same optical thickness. In such case, it is the optical thickness of the low refractive index layer, e.g., SiO2, which provides the non-quarter wave stack. The most useful pigments of this invention will have a chromacity (0° C.*) of at least 40.0.
The products of the present invention can be used in any application where pearlescent pigments have been used heretofore. Thus, the products of this invention have an unlimited use in all types of automotive and industrial paint applications, especially in the organic color coating and inks field where deep color intensity is required. For example, these pigments can be used in mass tone or as styling agents to spray paint all types of automotive and non-automotive vehicles. Similarly, they can be used on all clay/formica/wood/glass/metal/enamel/ceramic and non-porous or porous surfaces. The pigments can be used in powder coating compositions. They can be incorporated into plastic articles geared for the toy industry or the home. These pigments can be impregnated into fibers to impart new and esthetic coloring to clothes and carpeting. They can be used to improve the look of shoes, rubber and vinyl/marble flooring, vinyl siding, and all other vinyl products. In addition, these colors can be used in all types of modeling hobbies.
The above-mentioned compositions in which the compositions of this invention are useful are well known to those of ordinary skill 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 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 cellulose ethers, cellulose esters, polyamides, polyurethanes, polyesters, for example polyglycol terephthalates, and polyacrylonitrile.
For a well-rounded 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 regard to ink: R. H. Leach, editor, The Printing Ink Manual, Fourth Edition, Van Nostrand Reinhold (International) Co. Ltd., London (1988), particularly pages 282-591; with regard to paints: C. H. Hare, Protective Coatings, Technology Publishing Co., Pittsburgh (1994), particularly pages 63-288. The foregoing references are hereby incorporated by reference herein for their teachings of ink, paint and plastic compositions, formulations and vehicles in which the compositions of this invention may be used including amounts of colorants. For example, the pigment may 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 along with other pigments which may include titanium dioxide, acrylic lattices, coalescing agents, water or solvents. The pigment may also be used, for example, at a level of 20 to 30% in a plastic color concentrate in polyethylene.
In the cosmetic and personal care field, these pigments can be used in the eye area and in all external and rinse-off applications. They are restricted only for the lip area. Thus, they can be used in hair sprays, face powder, leg-makeup, insect repellent lotion, mascara cake/cream, nail enamel, nail enamel remover, perfume lotion, and shampoos of all types (gel or liquid). In addition, they can be used in shaving cream (concentrate for aerosol, brushless, lathering), skin glosser stick, skin makeup, hair groom, eye shadow (liquid, pomade, powder, stick, pressed or cream), eye liner, cologne stick, cologne, cologne emollient, bubble bath, body lotion (moisturizing, cleansing, analgesic, astringent), after shave lotion, after bath milk and sunscreen lotion.
In order to further illustrate the invention, various examples are set forth below. In these examples, as well as throughout this specification and claims, all parts and percentages are by weight and all temperatures are in degrees Centigrade, unless otherwise indicated.
Example 1
Into a 1 liter Morton flask is added a solution of 420 ml of isopropanol, 32 ml of distilled water and 4 ml of a 29% NH4OH aqueous solution. To this stirred solution is added 300 grams of a white reflecting TiO2 coated glass flake powder (G130L, Reflecks Pinpoints of Pearl, Engelhard Corporation). The resulting suspension is stirred and heated to 60° C.
A charge of 33.2 grams of tetraethoxysilane is added to the suspension, which is stirred for 18 hours. The suspension is then vacuum filtered, and the presscake dried in a 120° C. oven for 16 hours. The yield of the dried product is 307.4 grams, and the bulk color is a weak red which is not visible in the reaction suspension.
Into a 2 liter Morton flask equipped with heating, stirring, and temperature control is added 550 ml of demineralized water and 278 grams of silica coated intermediate prepared above. The stirring suspension pH is adjusted to 1.5, and the temperature set at 79° C. While maintaining the pH at 1.5, 16.7 grams of an 18% SnCl45H2O solution is added at a constant rate over 60 minutes, and then the suspension is stirred at the temperature and pH set points for 30 minutes beyond the addition. While maintaining the pH at 1.5, and the temperature at 79° C., 50 ml of a 40% TiCl4 aqueous solution is then added over 60 minutes. The suspension is filtered, and the presscake rinsed with water and dried for 16 hours at 120° C. The yield of final product is 315 grams.
A small portion (5 grams) of the final TiO2 coated product is calcined at 600° C. for 20 minutes. Both the 120° C. dried product and the 600° C. calcined product is compared to the singly coated starting material (G130L, Engelhard Corporation) as drawdowns of 12% powder in nitrocellulose lacquer. The reflectivity of all the samples is evaluated both visually and instrumentally. A large increase in the reflectivity is imparted to the G130L starting material by the application of the 2 additional coatings.
Example 2
Into a 2 liter Morton flask is added a solution of 900 ml of isopropanol, 190 ml of distilled water, and 17 ml of a 29% NH4OH aqueous solution. To this stirred solution is added 300 grams of a white reflecting TiO2 coated mica powder (Timica SparkleTM, 110P, Engelhard Corporation).
A charge of 176.8 grams of tetraethoxysilane is added to the 60° C. suspension, which is stirred for 18 hours. The suspension is then vacuum filtered, and the presscake dried at 120° C. for 16 hours. The yield of silica coated product is 355 grams. The material displays a weak red reflection color in bulk form, which is not visible in the reaction suspension.
Into a 3 liter Morton flask equipped with heating, stirring, and temperature control is added 1000 ml of demineralized water and 150 grams of the silica coated intermediate obtained from the previous coating procedure. While stirring at a constant rate, the suspension is heated to the 74° C. set point, and the pH was adjusted to 1.6. Next, 23.5 grams of an 18% SnCl45H2O solution is pumped into the suspension over 15 minutes while maintaining the pH at 1.6. The suspension is allowed to stir for 30 minutes following the addition.
While maintaining the temperature, stirring rate and pH of the suspension at the values for the previous reagent addition, an aqueous solution of 40% TiCl4 is added to the suspension at a rate of 0.65 ml per minute. During the addition, small aliquots of the suspension get spread onto a black glass plate to monitor the luster and color of the pigment platelets. After 100 ml of TiCl4 solution is added, there is still no increase in the luster of the particles, the addition is terminated, and the suspension filtered and the product dried at 120° C. The yield of product is 170 grams. The product is compared to the singly coated starting material (Timica Sparkle) as a drawdown of 3% pigment in nitrocellulose lacquer. The dried paint displays inferior luster to the starting material, and severe particle agglomeration.
Example 3
A slurry of 420 grams of iron oxide coated borosilicate flake (G270L, REFLECKSTM Blazing Bronze, Engelhard Corporation), 590 mls. of isopropanol, 45 mls. of water, and 5.6 mls. of 29% NH4OH solution is heated to 60° C. and stirred in a reaction vessel. Then, 46.5 grams of tetraethoxysilane is added to the slurry and stirred at that temperature for 20 hours. The slurry is vacuum-filtered and the product dried for 24 hours at 135° C., yielding 432.2 grams. A slurry of 416 grams of the aforementioned silica coated product in 756 mls. of water is stirred in a reaction vessel and heated to 79° C. The slurry pH is adjusted to 1.5. An aqueous solution containing 8.93 grams of SnCl45H2O is pumped into the slurry over a 2 hour period while maintaining the pH at 1.5 with 10% Na2CO3 solution. After the addition is completed, the slurry temperature is raised to 82° C. and the pH is adjusted to 3.0 with 10% Na2CO3 solution. An aqueous 39% FeCl3 solution is pumped in at 0.4 g/min while controlling the pH at 3.0 with the 10% Na2CO3 solution. The addition is stopped after 81.8 grams of the iron solution is added, and the slurry is then vacuum-filtered, the presscake washed with water, and then calcined for 90 minutes at 650° C.
Both the calcined product and base iron oxide-coated glass flake are compared as drawdowns of 12% powder in nitrocellulose lacquer. The calcined product is seen to exhibit a bronze shade with superior reflectivity and chromaticity to that of the base material.
Example 4
A slurry of 420 grams of titanium dioxide coated borosilicate flake (G130L, REFLECKSTM Pinpoints of Pearl, Engelhard Corporation), 590 mls. of isopropanol, 45 mls. of water, and 5.6 mls. of 29% NH4OH solution is heated to 60° C. and stirred in a reaction vessel. Then, 46.5 grams of tetraethoxysilane is added to the slurry and stirred at that temperature for 20 hours. The slurry is vacuum-filtered and the product dried for 24 hours at 135° C., yielding 432.2 grams. A slurry is prepared with 416 grams of the aforementioned silica coated product in 756 mls. of water, stirred in a reaction vessel and heated to 79° C. The slurry pH is adjusted to 1.5. An aqueous solution containing 8.93 grams of SnCl45H2O is pumped into the slurry over a 2 hour period while maintaining the pH at 1.5 with 10% Na2CO3 solution. After the addition is complete, the slurry temperature is raised to 82° C. and the pH adjusted to 3.0 with 10% Na2CO3 solution. An aqueous 39% FeCl3 solution is pumped in at 0.4 g/min while controlling the pH at 3.0 with 10% Na2CO3 solution. The addition is stopped after 81.8 grams of the iron solution is added, and the slurry is vacuum-filtered, the presscake washed with water, and calcined for 90 minutes at 650° C.
Both the calcined product and base iron oxide-coated glass flake are compared as drawdowns of 12% powder in nitrocellulose lacquer. The calcined product is seen to exhibit a bronze shade with superior reflectivity and chromaticity to that of the base material.
Example 5
The following samples with non-zero layers represent computer simulations on the specific pigments described employing a 1 micron thick glass substrate. Samples with zero thicknesses for the silica layer and second TiO2 layer are simulations of singly coated commercial pigments and serve as comparisons to the inventive samples. Samples 1 and 3 represent pigments that were prepared as described above. The actual properties measured and observed agreed with the simulated properties.














TABLE 1









Second







First TiO2
Silica
TiO2


Sample
Target
Layer,
Layer,
Layer,


No.
Color
Nm1
Nm2
Nm1
L*
a*
b*






















1
White
148
117
136
90.6
−2.6
0.2


2
White
148
0
0
75.5
0.6
0.4


3
Yellow
148
117
208
84.2
−1.2
54.0


4
Yellow
208
0
0
64.3
5.2
37.6


5
Yellow3
165
165
165
84.3
−4.0
67.5


6
Red
148
117
241
74.7
33.5
−0.7


7
Red
241
0
0
51.4
28.3
0.1


8
Violet
148
58
308
57.1
54.0
−53.3


9
Violet
265
0
0
44.6
36.2
−36.7


10
Blue
148
58
343
59.0
1.1
−56.3


11
Blue
305
0
0
51.7
−0.3
−45.4


12
Green
148
58
410
78.1
−44.2
0.5


13
Green
374
0
0
70.9
−19.1
−0.5


14
Green3
370
370
370
72.1
−58.8
−1.2





1±12 nm


2±8 nm


31⁄4 wave pigment


The L*, a* and b* data are for normal incidence and specular reflection.






Example 6
The following data represent computer simulations on the specific pigments optimized with respect to C* magnitude and employing a 1 micron thick glass substrate. All samples represent pigments that were prepared by the sol-gel technique as described above. The actual properties measured and observed agreed with the simulated properties.















TABLE 2







First

Second






Sam-

TiO2
Silica
TiO2


ple
Target
Layer,
Layer,
Layer,


No.
Color
Nm1
Nm2
Nm1
0° L*
0° a*
0° b*
0° C*























1
Yellow
203
117
203
81.0
1.0
83.0
83.0


2
Yellow
203
58
227
80.0
−3.0
75.0
75.1


3
Orange
243
58
243
64.0
32.0
34.0
46.7


4
Red
243
58
267
53.0
50.0
1.0
50.0


5
Violet
270
117
274
43.2
66.1
−24.9
70.6


6
Blue
143
58
72
47.0
3.0
−60.0
60.1


7
Blue
119
58
86
49.3
2.7
−59.2
59.3





1±12 nm


2±8 nm






Example 7
The following data represent computer simulations on specific pigments employing a 1 micron thick glass substrate.














TABLE 3






First

Second







TiO2
Silica
TiO2


Normal
Layer,
Layer,
Layer,


Color
Nm1
Nm2
Nm1
0° L*
0° a*
0° b*
0° C*






















White
134
117
134
90.7
−6.0
−0.2
6.00


White
134
114
136
90.7
−6.2
−0.1
6.20


White
134
111
138
90.7
−6.6
−0.1
6.60


White
134
108
141
90.6
−6.9
0.03
6.90


White
134
105
143
90.5
−7.2
0.13
7.20


White
134
102
143
90.3
−7.7
−0.33
7.71


White
134
99
145
90.1
−7.9
−0.27
7.91


White
134
96
148
89.9
−8.2
−0.24
8.20


White
143
58
155
86.0
−10.0
−1.0
10.0


Yellow
203
114
205
80.4
0.78
84.7
84.7


Yellow
203
111
208
80.2
1.15
85.7
85.7


Yellow
203
108
208
80.2
0.73
86.1
86.1


Yellow
203
105
210
80.3
0.35
86.2
86.2


Yellow
203
102
212
80.0
0.97
85.8
85.8


Yellow
203
99
212
80.0
0.70
85.5
85.5


Yellow
203
96
215
80.0
0.47
85.0
85.0


Red
243
117
248
49.0
57.0
3.0
57.1


Red
489
117
489
75.0
43.0
6.0
43.4


Violet
372
58
67
42.0
61.0
−64.0
88.4


Violet
143
58
45
31.0
55.0
−56.0
78.5


Violet
83
58
72
33.0
54.0
−51.0
74.3


Violet
95
58
72
30.0
60.0
−67.0
89.9


Violet
107
58
64
27.0
67.0
−71.0
97.6


Violet
265
117
265
38.0
71.0
−51.0
87.4


Blue
131
58
79
48.3
2.6
−60.3
60.4


Green
374
117
374
77.8
−59.8
0.2
59.8


Green
372
58
417
71.0
−45.0
−2.0
45.0





1±12 nm


2±8 nm






Example 8
The pigment of this invention can be formulated into a powder eye shadow by thoroughly blending and dispersing the following materials:












Wt.


Ingredients
Parts
















Mearltalc TCA ® (Talc)
18


Mearlmica ® SVA (Mica)
20


Magnesium Myristate
5


Silica
2


Cloisonne ® Red 424C (Red TiO2-coated mica)
20


Cloisonne ® Violet 525C (Violet TiO2-coated mica)
13


Cloisonne ® Nu-Antique Blue 626CB
2


(TiO2-coated mica/iron oxide-coated mica)



Cloisonne ® Cerise Flambé 550Z (iron oxide-coated mica)
2


Preservatives & Antioxidant
q.s.









Then 7 parts of octyl palmitate and 1 part of isostearyl neopentanoate are heated and mixed until uniform, at which time the resulting mixture is sprayed into the dispersion and the blending continued. The blended material is pulverized and then 5 parts of Cloisonne Red 424C and 5 parts of the pigment of this invention added and mixed until a uniform powder eye shadow is obtained.
Example 9
The pigment can be formulated into a lipstick by placing the following amounts of the listed ingredients into a heated vessel and raising the temperature to 85.+−0.3° C.:











Ingredients
Wt. Parts
















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


Caprylic/Capric Triglyceride
5.00


Bis-Diglycerylpolyalcohol 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
q.s.









A mixture of 13 parts of the pigment of this invention and 1 part of kaolin are added and mixed until all of the pigment is well dispersed. Fragrance is added as desired and mixed with stirring. The resulting mixture is poured into molds at 75.+−0.5° C., allowed to cool and flamed into lipsticks.
Various changes and modifications can be made in the present invention without departing from the spirit and scope thereof. The various embodiments which were illustrated herein were set forth in order to illustrate the invention but were not intended to limit it.

## Claims

1. A multilayer effect pigment comprising:
a transparent substrate having a layer of titanium dioxide thereon, said layer having an optical thickness of about 85 to 385 nm,
a layer of a low refractive index material on said titanium dioxide layer and an outermost layer of a high refractive index material placed on said low refractive index material layer,
said high refractive index material comprises titanium dioxide having an optical thickness of from about 45 to 420 nm and the low refractive index material is silicon dioxide having an optical thickness of about 30 to 120 nm, and wherein at least one layer has an optical thickness which is different from all of the other layers, whereby the pigment is not a quarter-wave stack.

2. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 134 to 148±12 nm, said silicon dioxide layer has an optical thickness of 105 to 117±8 nm, and the outermost titanium dioxide layer has an optical thickness of 134 to 143±12 nm, said pigment being white.

3. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 134±12 nm, said silicon dioxide layer has an optical thickness of 496±8 nm, and the outermost titanium dioxide layer has an optical thickness of 148±12 nm, said pigment being white.

4. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 143±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and the outermost titanium dioxide layer has an optical thickness of 155±12 nm, said pigment being white.

5. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 148±12 nm, said silicon dioxide layer has an optical thickness of 117±8 nm, and the outermost titanium dioxide layer has an optical thickness of 208±12 nm, said pigment being yellow.

6. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 203±12 nm, said silicon dioxide has an optical thickness of 105 to 117±8 nm and the outermost titanium dioxide layer has an optical thickness of 203 to 210±12 nm, said pigment being yellow.

7. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 203±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm or 96±8 nm, and said outermost layer titanium dioxide layer has an optical thickness of 215 to 227±12 nm, said pigment being yellow.

8. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 243±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and said outermost titanium dioxide layer has an optical thickness of 243±12 nm, said pigment being orange.

9. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 243±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm or 117±8 nm, and said outermost titanium dioxide layer has a thickness of 267 or 248±12 nm, respectively, said pigment being red.

10. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 148±12 nm, said silicon dioxide layer has an optical thickness of 117±8 nm, and the outermost titanium dioxide layer has a optical thickness of 241±12 nm, said pigment being red.

11. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 143 to 148±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and the outermost titanium dioxide layer has a optical thickness of 45±12 nm or 308±12 nm, said pigment being violet.

12. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 265 to 270±12 nm, said silicon dioxide layer has an optical thickness of 117±8 nm, and said outermost titanium dioxide layer has an optical thickness of 265 to 274±12 nm, said pigment being violet.

13. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 372±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and said outermost titanium dioxide layer has an optical thickness of 267±12 nm, said pigment being violet.

14. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 83±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and said outermost titanium dioxide layer has an optical thickness of 72±12 nm, said pigment being violet.

15. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 107±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and said outermost titanium dioxide layer has an optical thickness of 64±12 nm, said pigment being violet.

16. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 143 to 148±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and the outermost titanium dioxide layer has a optical thickness of 72±12 nm or 343±12 nm, said pigment being blue.

17. The multilayer effect pigment of claim 1 wherein said titanium dioxide layer has an optical thickness of 119±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and said outermost titanium dioxide layer has an optical thickness of 86±12 nm, said pigment being blue.

18. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 148±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and the outermost titanium dioxide layer has an optical thickness of 410±12 nm, said pigment being green.

19. The multilayer effect pigment of claim 1 wherein said inner titanium dioxide layer has an optical thickness of 374±12 nm, said silicon dioxide layer has an optical thickness of 117±8 nm, and the outermost titanium dioxide layer has a optical thickness of 374±12 nm, said pigment being green.

20. The multilayer effect pigment of claim 1 wherein said titanium dioxide layer has an optical thickness of 372±12 nm, said silicon dioxide layer has an optical thickness of 58±8 nm, and the outermost titanium dioxide layer has a optical thickness of 417±12 nm, said pigment being green.

21. The multilayer effect pigment of claim 1 wherein said transparent substrate is glass flake.

22. A multilayer effect pigment comprising:
a transparent substrate having a layer of titanium dioxide thereon, said layer having a optical thickness of 489±12 nm;
a layer of silicon dioxide on said titanium dioxide layer, said silicon dioxide layer having an optical thickness of 117±8 nm; and
an outermost titanium dioxide layer placed on said silicon dioxide layer and having an optical thickness of 489±12 nm, said pigment being red.

23. A cosmetic comprising liquid or powder and said multilayer effect pigment of claim 1.

24. The multilayer effect pigment of claim 1, wherein the pigment has a chromaticity of at least 40.0.