DE3001272A1 - METHOD FOR THE PRODUCTION OF MOTHER-OF-PEARL-TYPE WISMUTOXYCHLORIDE, COMPRISING ULTRAVIOLET LIGHT - Google Patents

Description

The invention relates to pearlescent bismuth oxychloride pigments and, more particularly, to an improved method for Production of a bismuth oxychloride pigment which is stable to ultraviolet light and which is produced at high temperatures and with high productivity.

Since bismuth oxychloride has a high refractive index and in In pearlescent form, bismuth oxychloride is widely used as a pearlescent pigment in cosmetic Products such as lipsticks, shadows under the eyes, blush preparations and nail polish preparations. The main disadvantage of using the nacreous bismuth oxychloride in such cosmetic products but is that the material tends to lose its characteristic white color, and that it darkens when exposed to light, especially ultraviolet light. There are already several ways of working used to try to reduce the tendency of bismuth oxychloride to become significantly darker when exposed, to minimize. Such an operation requires special and expensive packaging materials for the product used that shield the light »Another common way of working is organic ultraviolet light absorbers, e.g., 2-hydroxybenzophenone, added to the bismuth oxychloride pigment. Such a way of working is described, for example, in U.S. Patent No. 2,974,053. However, such additives are expensive and they add to contributes to the final cost of the cosmetic product.

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US Pat. No. 3,917,671 describes a process for stabilizing bismuth oxychloride in which the bismuth oxychloride is heated to a temperature of about 300 to about 800 ^° C., preferably 400 to 700 ^° C., over a period of time sufficient for the pigment to be stabilized, is heated. This method is far superior to the previously known methods. In this process, however, it is necessary to avoid excessively high temperatures in order to prevent sintering and thus agglomeration of the bismuth oxychloride pigment. When the pigment is sintered, it becomes sandy and loses its lubricity. Furthermore, it suffers losses in gloss and in opacity, as can easily be shown, for example, by a standard paint tensile test on a dark background. At the temperatures that can be tolerated in this process, the heating must be carried out for at least 1 hour, for example 6 to 12 hours, in order to achieve stabilization against ultraviolet light. The productivity of this process is therefore limited by these relatively strict heating time requirements.

The invention is based on the object of an improved process for the production of ultraviolet light stable To provide bismuth oxychloride pigments. In this process, the pigments are said to be highly productive and without sintering taking place. The desired bismuth oxychloride should continue a high degree of ultraviolet light stability, the shine, the pearlescent appearance and the opacity.

030031 / ΟθδΟ BATH ORIGINAL

The invention therefore provides a "process for the production of a pearlescent bismuth oxychloride which is stable to ultraviolet light and in which there is minimal sintering of this material containing refractory material is heated. As the refractory material is mica and / or talc is used. the heating is carried out at a temperature of at least about 35O ⁰ C for a period of time sufficient that the bismuth oxychloride is stabilized against ultraviolet light.

According to the invention it has been found that the sintering, which normally occurs when heating bismuth oxychloride to high levels Temperature occurring can be avoided if the pigment is both bismuth oxychloride and a particulate contains refractory material such as mica or talc. The bismuth oxychloride can therefore be stabilized against ultraviolet light by heating it to a high temperature for relatively short periods of time. This creates a get significant productivity improvement. The refractory material preferably serves as a support on which the bismuth oxychloride is deposited. Surprisingly, however, it was found that the inventive The method is effective and that sintering is substantially avoided when the pigment is a simple physical one Is a mixture or mixture of bismuth oxychloride and a particulate refractory material.

When carrying out the process according to the invention, the pigment is in air to a temperature of at least about

030031 / 068Ö

350 ° C. for a period sufficient to stabilize the bismuth oxychloride against ultraviolet light. Un to avoid heating for too long, the fiction, modern process is preferably carried out at a temperature of at least 500 ⁰ C. It was also found that even at temperatures above 800 ^° C., no significant sintering of the pigment was found. The main advantage that is obtainable by the process according to the invention is obtained at temperatures above 700 ^° C., at which stabilization is completed in 3 to 4 h, and in particular at temperatures above 800 ^° C., at which ultraviolet light stabilization is obtained in one h or less is realized. This takes place without sintering or agglomeration of the pigment taking place. When the heating temperature is about 900 to 925 ° C, the stability can be obtained in a heating period of half an hour or less. A multiple increase in productivity compared to the process according to US Pat. No. 3,917,671 can therefore be obtained. The maximum permissible temperature in the method according to the invention is approximately 95O ° C. Thermal decomposition of the bismuth oxychloride occurs above this temperature.

Because of the time / temperature dependency of the ultraviolet light stabilization treatment of the bismuth oxychloride, the method according to the invention can alternatively be used, in order to obtain higher degrees of stability by using periods similar to those of the known method are comparable, but at temperatures which are considerably higher than those in the known process, is heated. By suitable selection of the temperature and

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30Q1272

of the period of time, advantages in terms of both productivity and ultraviolet light stability can be obtained will.

The refractory component of the pigment is preferably in the muscovite form of mica. However other natural and synthetic mica can also be used. Furthermore, talc, which has a high degree of lubricity and which is adapted for cosmetic preparations can be used as the refractory component of the pigment. It has been shown to remove minor impurities commonly found in commercial grades of mica or talc do not have any significant adverse effects on the gloss and the stability of the pigment. For example, mica contains iron, the oxides of which are strong pigments with a red, black or yellow color. Despite the exposure of the mica to oxidation during heating, it occurs during or as a result of the heating process no significant discoloration or no significant darkening of the pearlescent pigment. Furthermore, commercially available mica or talc calcium stearate can be used as a lubricant or anti-agglomeration agent contain. A slight yellowing will appear as a result of the pyrolysis of the stearate during the heating process observed. However, the effect is not enough, the pearlescent appearance of the pigment for use for cosmetic Adversely affecting purposes.

As stated above, it is preferred that the particulate Refractory material acts as a support on which the pearlescent bismuth oxychloride is deposited. These Shape is preferred because it shows the concentration gradient

830Ö31 / 068Q

avoids that can occur in a mixture. It this is believed to result in more consistent ultraviolet light stability is obtained. Although the mixture has been found to be resistant to sintering is considerably more stable than bismuth oxychloride alone, the deposition of the bismuth oxychloride on the refractory support provides further security against agglomeration. In this way, a more consistent opacity can be obtained. Furthermore shows at the same Proportion of bismuth oxychloride that applied to the support Pigment a slightly greater luster.

The deposition of the bismuth oxychloride on a refractory substrate can be carried out in such a way that one a base to an aqueous suspension of the refractory material, which is a soluble bismuth salt and a Containing excess chloride ions adds to the bismuth oxychloride on the surface of the refractory material to be deposited. Thus, for example, the particulate refractory material can be in a mixed solution of nitric acid and hydrochloric acid (which may optionally contain bismuth nitrate) are suspended. After that you can at the same time another solution of bismuth nitrate in the said mixed acid and a third solution, the sodium hydroxide contains, are added to this. Such a process is described, for example, in US Pat. No. 3,597,250.

The refractory component of the pigment should typically have an average particle size im Range from 2 to 100 µm. Preferably 75% by weight of the particulate refractory material has one - Particle size less than 44 µm and 100% are smaller

than 85 um. If a mixture is made, then it should the bismuth oxychloride component is typically an average Particle sizes ranging from 2 to 40 µm with 100% of the bismuth oxychloride being less than 44 µm are.

Both in the case that a bismuth oxychloride applied to a support is used, as well as in the case that mixtures are used, the bismuth oxychloride content should be used of the pigment are in the range from 10 to 90% by weight. For an equivalent gloss a slightly higher proportion of bismuth oxychloride is required in the case of the mixture than in the case of the pigment applied to a carrier. In general, the pigment prepared according to the invention has has a low degree of agglomeration and it has high hiding power, high gloss and excellent Stability against ultraviolet light.

The invention is illustrated in the examples. example 1

A pigment consisting of bismuth oxychloride which has been deposited on muscovite and which is approximately 40% by weight Containing bismuth oxychloride was by precipitation of Bismuth oxychloride prepared on the muscovite in the manner described below.

The following solutions were made:

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solution A. Bismuth
ENT, HCl H ₂ O solution B. H ₂ O
NaOH solution C. H ₂ O
mica HCl ENT,

Bismuth nitrate liquid, 51 ° Baume 1085.3 g

52.9 g 95.2 g 0.26 1

1.7 1,333.9 g

1.0 l

417.4 g 14.2 g 24.9 g

Solution C was placed in a glass jar and heated to reflux. This was followed by the addition of the solution A started and this was further added at a constant rate so that its addition was complete in 180 minutes was. 15 min after the start of the addition of solution A, the addition of solution B continued at a constant rate started, so that the addition of the latter solution was completed within 180 minutes.

The reaction mixture was stirred for an additional 15 minutes and then cooled to 45 ° C. The product was through Filtration collected. The product filter cake was washed with water and dried. The product was from that

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Type, which under the Viaren designation Bi-Lite 20 from MaI-linckrodt, Inc. is distributed. Separate portions of this pigment each weighing 50 g were in heated in an air oven under controlled temperature and time conditions.

After taking out of the oven, the reflective properties of each part of the pigment were measured using a Standard compressed powder tests measured. Each part was then exposed to ultraviolet light for 16 hours. Thereupon were the reflective properties measured again.

In the press powder test, the dry powdered pigment is placed in a 7.6 cm press sample holder. The latter is provided with a quartz lens. The measurement of the reflection properties of the molding powder is carried out using a commercially available reflection spectrophotometer. The spectrophotometer is provided with a reflective integrated sphere 18 inches long and it comes with a Standard reflective surface calibrated so that the standard with a Y value of the tristimulus of 100% under exposure a standard CIE (Commission Internationale de l'Eclairage) illuminating light source C yields.

The Y value of the tristimulus of each sample was measured on a white background before and after exposing the dried paint to an ultraviolet light source (General Electric F-15T8 / BLB Black Light) for 16 hours at a distance of 42 cm. The Y-value of the tristimulus is a direct measure of the luminous reflection relative to the standard reflective surface. The greater the percentage change in Y (J \% Y) , the greater the color deterioration of the sample.

030031/0660

Using the methods described above, several other pigments of bismuth oxychloride on a mica support were heated to stabilize against ultraviolet light and tested for the effect of exposure to ultraviolet light. The other pigments included additional batches of Bi-Lite 20, a pigment containing 10% bismuth oxychloride on mica sold under the trademark Ul tralite by Mallinckrodt, Inc., a pigment containing 58% by weight bismuth oxychloride and k% titanium dioxide , bound with calcium stearate on a mica substrate sold under the tradename Ultrawhite by Mallinckrodt, Inc., a pigment containing 40% by weight bismuth oxychloride and 1% calcium stearate on a mica carrier sold under the tradename Ultrapress by Mallinckrodt, Inc. and a pigment containing 40% by weight bismuth oxychloride on a talc carrier sold under the trade name Bital by Rona Corporation (division of Ε-Merck, Darmstadt). The heat treatment conditions and the results of the optical tests of this example are shown in Table I.

030031

Tabel

Conditions of heat treatment and results of powder molding tests for on a carrier

applied BiOCl

Book a
wear no. material 20th 1070D-18 number
the
Versu
che Test condition
worked
Tempe Erhit
ratur zungs
Time
in the
Oven,
H 16 Bilite 20th 1070D-18 not
ge
burns 16 · 368-37 Bilite 20th 1070D-18 1 225 ⁰ C 16 368-17 Bilite 20th 1070D-18 4th 525 ⁰ C 368-29 Bilite 20th 1070D-31 1 820 ⁰ C 16 Bilite 20th 1070D-31 not
ge
burns 16 368-98 Bilite 20th 1070D-31 1 225 ⁰ C 368-100 Bilite 20th 1070E-9 2 525 ° C 16 Bilite 20th 1070E-9 not
ge
burns 16 368-98 Bilite 20th 1070E-9 2 225 ⁰ C 368-100 Bilite 20th 1070E-10 1 525 ° C Bilite not
ge
burns

Set the results of the powder test before UV after UV exposure
Pure color luster Pure color luster % Y means % Y χ y χ y

0.3144 0.3204 87.2 0.3132 0.3192 77.8 9.4

0.3165 0.3223 83.74 0.3154 0.3215 80.20 3.54 0.3189 0.3256 81.44 0.3163 0.3233 74.63 6.81 0.3251 0.3379 86.2 0.3270 0.3371 84.4 1.8 «0.3140 0.3201 84.52

0.3171 0.3223 82.60 0.3147 0.3209 78.06 4.54 0.3180 0.3254 78.34 0.3176 0.3249 76.22 2.12 0.3137 0.3203 83.71

0.3154 0.3200 80.67 O.3144 0.3197 78.36 0.3186 0.3267 79.76 0.3187 0.3266 78.32 0.3132 0.3194 84.6

ro

NJ

Ultrawhite EEB 0.3109 0.3174 86.06 0.3239 0.3353 82.36 11.37

Table I continued

approx 368-105 * 368-43 Ultra white EEB 1 525 ⁰ C a Ultrapress DGR not ge
burns 1/0680 368-41 Ultrapress DGR 2 525 ⁰ C Ultralite EAY not ge
burns 368-41 Ultralite EAY 1 525 ⁰ C Bit 3181 not ge
burns BAC Bit 3181 2 525 ⁰ C ¹ ORIGINAL

16 0.3107 0.3172 74.68 0.3232 0.3341 81.12 1.24

0.3113 0.3183 85.65 0.3066 0.3139 55.33 30.32

16 0.3223 0.3332 80.08 0.3213 0.3314 77.27 2.81

0.3165 0.3229 80.1 0.3147 0.3209 76.21 3.9

16 0.3219 0.3287 72.23 0.3218 0.3287 71.68 0.35

0.3125 0.3190 88.46 0.3115 0.3182 75.74 12.72

16 0.3172 0.3256 85.39 0.3171 0.3244 80.28 5, ^ 1

/ Ib

Example 2

A variety of bismuth oxychloride pigments are applied on a mica carrier, and also several pigments, "consisting of a mixture of bismuth oxychloride and Mica containing 40 wt% bismuth oxychloride was heated for ultraviolet light stabilization. Thereafter they were exposed to ultraviolet light and subjected to optical tests. The methods for ultraviolet light stabilization and the exposure to ultraviolet light are the same as in Example 1. Those used here however, optical tests were paint pull tests instead of press powder tests.

In the paint pull test, a paint suspension is produced that contains 10% by weight of pigment in a conventional nail polish solution contains. This contains nitrocellulose, resins and plasticizers as well as a solvent that contains acetone, dibutyl phthalate, Toluene and butyl alcohol. The paint is then applied to a standard test card. A Part of the card surface is white and another part is black, allowing measurements of the properties of the paint can be obtained on both background types.

In the experiments of this example, the measurement of the reflective properties was carried out using a different one commercially available reflection spectrophotometer. This was provided with an integrated reflection sphere measuring 20.3 cm. The calibration was carried out with a standard reflective surface, so that the standard has a tristimulus Y value of 100% under exposure to a standard CIE light source C.

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In Table II are the heat treatment conditions and the results of the tests of this example are compiled.

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Table II

Conditions of heat treatment and results of paint pulling test when applied to a substrate BiOCl

CO O O

Book a
wear no.
*
ο material 20th IO7OE-IO At
number
the
Ver
see below
che Test condition
gene
Tempera- heating
tur ning
Time
in the
Oven,
H 4th Results of the
before the UV
Expose
Color pure
Ness
χ y 0.3304 Paint pull tests
after UV exposure
Pure color gloss
is called % YJ \% Y
Shine χ y
^ Y 0.3085 0.3165 29.90 52.06 32.96 ^ Bilite 20th IO7OD-I8 not ge
burns 16 0.3234 0.3308 81.96 0.3073 0.3155 29.10 51.6S 32.99 * ^ 368-34 Bilite 20th IO7OD-I8 3 425 ⁰ C 64 0.3237 0.3311 80.71 0.3070 0.3153 27.63 52.43 ' 34.73 ^l 0 368-34 Bilite 20th IO7OD-I8 4th 425 ⁰ C 8th 0.3240 0.3321 80.08 0.3158 0.3239 46.40 33.78 34.47 % 368-34 Bilite 20th IO7OD-I8 1 425 ⁰ C 4th 0.3246 0.3309 80.26 0.3059 0.3140 26.71 53.70 3 ?, 78 ⁰ 368-34 Bilite 20th IO7OD-I8 2 425 ⁰ C 8th 0.3239 0.3317 80.41 0.3167 0.3247 54.24 26.06 32.75 368-17 Bilite 20th IO7OD-I8 3 525 ⁰ C 16 0.3244 0.3325 80.30 0.3204 0.3283 63.61 17.13 32.58 368-17 Bilite 20th IO7OD-I8 2 525 ⁰ C 16 0.3249 0.3337 80.47 0.3222 0.3302 67.21 14.21 32.71 368-17 Bilite 20th IO7OE-IO 4th 525 ⁰ C 4th 0.3257 0.3330 81.42 0.3241 0.3318 72.56 8.17 25.29 368-175 Bilite 20th IO7OD-I8 1 550 ⁰ C 4th 0.3251 0.3335 80.73 0.3218 0.3304 65.53 16.50 24.75 368-17 Bilite 20th IO7OD-I8 6th 65O ⁰ C 8th 0.3252 0.3378 82.03 0.3288 0.3392 78.64 2.81 11.73 368-27 Bilite 20th IO7OD-I8 3 725 ⁰ C 0.5 0.3274 0.3398 81.45 0.3305 0.3416 79.61 1.77 11.30 368-27 Bilite 20th IO7OE-IO 2 725 ⁰ C 1 0.3285 0.3344 81.38 0.3254 0.3338 70.59 10.58 14.32 368-164 Bilite 20th 1070E-10 1 850 ⁰ C 0.25 0.3262 0.3375 81.17 0.3289 0.3380 77.20 3.28 12.34 368-164 Bilite 20th 1070E-10 2 85O ⁰ C 0.3284 0.3369 80.48 0.3270 0.3362 70.42 10.17 12.88 368-165 Bilite 1 90O ⁰ C 0.3280 80.59

Table II continued

0.3398 77.23 2.88 11.92 0.3423 77.55 1.75 12.11 0.3232 32.98 47.08 20.34

0.3414 71.67 4.27 15.12

0.3431 77.61 1.61 11.73

0.3426 77.66 1.63 r. , 03

0.3389 77.51 3.46 10.52

0.3194 41.34 40.92 25.86

0.3369 77.24 3.31 33.43 0.3259 55.42 27.37 26.13

0.3323 77.71 4.15 16 _V 6O

* The information is obtained by removing the black section of 10% trains that are not exposed have been read.

Gt
approx 368-165 Bilite 20 IO7OE-IO 3181 2 90O ⁰ C 0.5 0.3294 0.3389 80.11 0.3303 ο
ο 368-171 Bilite 20 IO7OE-IO 3181 1 95O ⁰ C 1.25 0.3316 0.3409 79.31 0.3328 368-168 Blend not ge
burns 0.3265 0.3339 80.06 0.3148 O
ös 368-175 Blend 368-168 2 550 ⁰ C 16 0.3334 0.3407 75.94 0.3341 a 368-169 Blend 368-168 850 ⁰ C 1 0.3322 0.3417 79.22 0.3335 .- - 368-170 Blend 368-168 900 ⁰ C 0.5 0.3320 0.3416 79.29 0.3332 368-171 Blend 368-168 2 95O ⁰ C 0.25 0.3289 0.3383 80.97 0.3295 1 Ultrapress DGR not ge
burns 0.3203 0.3273 82.26 0.3118 S. 368-41 Ultrapress DGR 2 525 ⁰ C 16 0.3267 0.3367 80.55 0.3269 Ω
> Bital not ge
burns 0.3212 0.3286 82.79 0.3182 368-43 Bital 2 525 ⁰ C 16 0.3231 0.3309 81.86 0.3246

CO
O
O

As can be seen from Table II, the optical tests of this example included measurements of % Y on a black surface prior to exposure to ultraviolet light. The paint pull tests and the measurements of the% Y value on the black surface give both quantitative and observational values relating to the extent of sintering and agglomeration. Visual inspection indicated that the sintering that occurred was minimal in all cases. This was confirmed by the quantitative tests which showed that the reflectance on a black surface was consistently greater than 10 -6. This is a reflectance that is generally not obtainable when there has been significant agglomeration of the pigment particles.

030Ö31 / 06SÖ

Claims (9)

Process for the production of pearlescent bismuth oxychloride which is stable to ultraviolet light 1. Method of making pearlescent, opposite Ultraviolet light stable bismuth oxychloride with minimal sintering of this product, characterized in that a pearlescent pigment, which is both nacreous bismuth oxychloride and a particulate refractory material selected from the group Contains mica and talc over a sufficient period of time that the bismuth oxychloride is stable against ultraviolet light. Ö30Ö31 / 06 & Ö 7624 - -. . ". vHTV. _3: rr · - , is siert, to a temperature of at least about 350 ° C heated. 2. The method according to claim 1, characterized in that the pigment is brought to a temperature heated between about 800 and about 95O ° C. 3. The method according to claim 1, characterized in that the pigment is heated to a temperature which is sufficient that the bismuth oxychloride
is stabilized against ultraviolet light after less than about an hour of heating. 4. The method according to claim 1, characterized in that the pigment comprises bismuth oxychloride which is deposited on a carrier which
particulate refractory material. 5. The method according to claim 4, characterized in that the carrier consists of mica. 6. The method according to claim 5, characterized in that the proportion of pigment between is about 10 to 90 weight percent of the bismuth oxychloride. 7. The method according to claim 6, characterized in that the pigment has an average particle size of between about 2 and about 100 lim
both before and after heating the pigment. 8. The method according to claim 7, characterized in that after heating at least 75 030031/0680 W / 6% of the pigment has a particle size less than about 44 to have. 9. The method according to claim 1, characterized shows that the carrier is made of talc. 030031 / 06ÖQ BAD ORIG (MAL