JP2000265154A - Lamellar barium sulfate coated with iron oxide and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored ultraviolet absorbing composition which can provide cosmetic pigments which have no color unevenness and good slipperiness and also ultraviolet rays absorbing effect by coating lamellar barium sulfate with red oxide, black iron oxide and yellow iron oxide. SOLUTION: This composition is obtained by coating (A) lamellar barium sulfate with (B) red oxide (Fe2O3), (C) black iron oxide (Fe3O4), and (D) yellow iron oxide (FeOOH). The component A is preferably one with a mean particle size of 3-70 p m and an average thickness of 0.05-2 μm. The amount of each of the components B, C and D to be coated is preferably 0.1-50 pts.wt. based on 100 pts.wt. of the component A. The component A coated with the component B is obtained by such a method that a water-soluble ferric salt is dissolved in an aqueous suspension of the component A, followed by neutralization reaction by gradually adding an alkaline solution to the suspension to effect deposition of ferric hydroxide on the component A surface followed by filtration and washing the deposits with water, drying and then burning the deposits to remove the crystal water of the ferric hydroxide to make the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Industrial applications]

[0002] Iron oxide is widely used as an inorganic color pigment in makeup cosmetics such as foundations and eye shadows.

[0003]

2. Description of the Related Art When formulating cosmetics such as foundations, organic pigments and inorganic coloring pigments such as iron oxide have been mixed.

[0004]

SUMMARY OF THE INVENTION Bengala, yellow iron oxide,
Powders with fine or needle-like particles, such as black iron oxide, or with magnetic properties are difficult to disperse uniformly, hindering the slipperiness of cosmetics and causing color unevenness. Was also the cause. In addition, there was a limit to the amount of the composition due to the inhibition of the slipperiness.

[0005]

Means for Solving the Problems The average particle diameter is 3 to 70 μm.
m and a mean thickness of 0.05 to 2 μm are excellent in slipperiness, and have a feature that a cosmetic having a good feeling in use can be obtained by blending it into a cosmetic. I have. Because barium sulfate is excellent in dispersibility,
By coating it with iron oxide, the pigment can be dispersed uniformly, and a pigment for cosmetics free from color unevenness and having good slip properties can be obtained. Further, pigments obtained by coating plate-like barium sulfate with iron oxide also have an ultraviolet absorbing effect and are useful as an ultraviolet absorbing agent.

By coating iron oxide on a plate-like barium sulfate simultaneously with or separately from an ultraviolet absorbing substance such as titanium oxide, zinc oxide, cerium oxide, etc., a colored pigment having a higher ultraviolet absorbing effect and excellent in slipperiness can be obtained. You can get it.

[0007] Bengala-coated barium sulfate is obtained by dissolving a water-soluble ferric salt such as ferric chloride in a solution of barium sulfate suspended in water, and adding sodium hydroxide, ammonia water, and sodium carbonate. A neutralization reaction is carried out by gradually adding an alkali solution such as the above, and is deposited as ferric hydroxide on the surface of barium sulfate, followed by filtration, washing and drying. Further calcination to remove the water of crystallization of ferric hydroxide.
₂ O ₃ ).

The ferric salt is not particularly limited as long as it is water-soluble, such as ferric sulfate and ferric nitrate, but ferric chloride having high solubility is industrially desirable.

The neutralization reaction temperature is not limited, but is 20 to 50 ° C.
Is industrially desirable. The sintering temperature may be 300 ° C. or higher. However, at 300 ° C., 400 ° C. or higher is preferable because iron hydroxide partially remains and good color formation cannot be obtained.

[0010] The color of the obtained bengala-coated plate-like barium sulfate powder can be arbitrarily adjusted by the amount of bengala-coated, as shown in Table 1. The amount of bengala-coated exceeds 50 parts by weight per 100 parts by weight of barium sulfate. This is not preferred because the slip property deteriorates.

[0011]

[Table 1] This Table 1. In Table ₂ , the coating amount indicates parts by weight of Fe ₂ O _{3 based} on 100 parts by weight of barium sulfate.

Black iron oxide-coated barium sulfate is prepared by adding a water-soluble ferrous salt such as ferrous chloride or ferric chloride and a ferric salt to a barium sulfate solution suspended in warm water. Was dissolved in a molar ratio of 1: 2, and a neutralization reaction was carried out by gradually adding an alkali solution such as sodium hydroxide, aqueous ammonia, sodium carbonate, etc., and deposited on the surface of barium sulfate as hydrous magnetite, followed by filtration and washing with water. And dried to black iron oxide. The ferrous salt and the ferric salt are not particularly limited as long as they are water-soluble, as in the case of bengala production, but ferrous chloride and ferric chloride having high solubility are desirable. The neutralization reaction temperature is not limited, but the reaction is slow at 30 ° C. or lower, and a part of ferrous iron is oxidized to α-iron oxide. 30-80 ° C is industrially preferred. Hydrous magnetite is partially oxidized in air,
Drying is carried out in an atmosphere of an inert gas such as N ₂ gas, because it easily becomes α-iron oxide. The drying temperature may be a normal drying temperature of 100 to 200 ° C.

The color of the obtained barium sulfate powder coated with black iron oxide is approximately as shown in Table 2 depending on the coating amount of black iron oxide.

[0014]

[Table 2] This Table 2. In Table 1, the coating amount indicates parts by weight of Fe ₃ O ₄ with respect to 100 parts by weight of barium sulfate.

[0015] The coating amount of black iron oxide is 5 to barium sulfate.
Exceeding 0 parts by weight is not preferable because the slipperiness deteriorates. Yellow iron oxide (FeOOH) coated plate barium sulfate is
In a barium sulfate solution suspended in water, ferrous sulfate,
A water-soluble ferrous salt such as ferrous chloride is dissolved and neutralized with an alkali solution such as sodium hydroxide, aqueous ammonia, and sodium carbonate to obtain a mixed slurry of ferrous hydroxide and barium sulfate. This is gradually oxidized with oxygen gas, air, aqueous hydrogen peroxide or the like to deposit yellow iron oxide on the surface of barium sulfate, followed by filtration, washing and drying. The ferrous salt is not particularly limited as long as it is water-soluble, such as ferrous chloride, ferrous sulfate, and ferrous nitrate. The oxidation reaction temperature is not limited, but is 20
~ 50 ° C is industrially desirable. Yellow iron oxide becomes α-iron oxide by dehydration at 250 ° C or higher.
00-200 degreeC is preferable. The color of the yellow iron oxide is yellow to yellow-orange, and becomes darker as the coating amount increases. However, if it exceeds 50 parts by weight with respect to barium sulfate, the sliding property deteriorates, which is not preferable.

[0016]

EXAMPLES Examples will be described below, but the present invention is not limited to these examples.

[0017]

Example 1 1 L of pure water and 50 g of plate-like barium sulfate having an average particle size of 20 μm and an average thickness of 1 μm were placed in a 2 L glass beaker coated with barley sulfate and adjusted to 25 ° C. and stirred with a stirrer. 1.7 g of ferric chloride (hexahydrate) was added thereto and dissolved therein (plate-like barium sulfate 10).
0 parts by weight and 1 part by weight of Bengala). The slurry pH at this time was 3.0. At 25 ° C., 1N sodium hydroxide was added at a flow rate of 5 ml / min using a microtube pump to neutralize to pH 8.0 and stirring was continued for another 30 minutes. It was filtered and washed by a conventional method, dried at 105 ° C. for 2 hours, and baked in an electric furnace maintained at 500 ° C. for 1 hour to obtain about 50 g of a flesh-colored powder.

[0018]

EXAMPLE 2 In Example 1, the amount of ferric chloride was changed to 3.4.
g (100 parts by weight of barium sulfate plate)
Parts by weight), and about 54 g of red powder was obtained.

[0019]

Example 3 850 mL of hot pure water and 50 g of plate-like barium sulfate having an average particle diameter of 30 μm and an average thickness of 1 μm were placed in a 2 L glass beaker on a black iron oxide-coated plate-like barium sulfate heater, and stirred with a stirrer while maintaining the temperature at 60 ° C. did. FeCl adjusted to 100 g / L
13.7 ml of an aqueous solution _{2 and} 32 ml of an aqueous solution of FeCl ₃ were added and mixed (5 parts by weight of black iron oxide with respect to 100 parts by weight of barium sulfate plate), and the liquid volume was adjusted to 1 L with pure water. The slurry PH at this time was 3.0. 1N sodium hydroxide was added at a flow rate of 5 ml / min using a microtube pump to neutralize to pH 8.0 and stirring was continued for another 30 minutes. Filtration was carried out by a conventional method, and the filtrate was washed with water until no chloride ion was observed (when the filtrate was turbid when 1-2 drops of a 10% barium chloride aqueous solution was added). , N ₂
Dry at 150 ° C for 3 hours in an atmosphere to obtain about 54 black powders.
g was obtained.

[0020]

Example 4 In Example 3, the aqueous solution of FeCl ₂ was
The same operation was carried out except that 7.4 ml of the FeCl ₃ aqueous solution and 64 ml of the aqueous FeCl ₃ solution (10 parts by weight of black iron oxide with respect to 100 parts by weight of barium sulfate in the form of plate) to obtain about 58 g of a red powder.

[0021]

EXAMPLE 5 1 L of pure water at 25 ° C. and an average particle size of 3 were placed in a 2 L glass beaker coated with barium sulfate coated with iron oxide yellow.
50 g of plate-like barium sulfate having an average thickness of 0 μm and 1 μm was added and stirred with a stirrer. To this, 43 ml of an aqueous solution of FeSO ₄ adjusted to 25 ° C. and 100 g / L was added and mixed (5 parts by weight of yellow iron oxide with respect to 100 parts by weight of barium sulfate plate). The slurry pH at this time was 3.2. 30%
Neutralized with sodium hydroxide and adjusted the pH to 7.0.
Addition of 1% aqueous hydrogen peroxide at 25 ° C. was continued using a microtube pump at a flow rate of 5 ml / min until the pH reached 3.5. After stirring was continued for further 30 minutes, the mixture was filtered by a conventional method, and washed with water until no sulfate group was found in the filtrate (it did not become cloudy when 1 to 2 drops of a 2% silver nitrate aqueous solution was added to the filtrate). Thereafter, drying was performed at 105 ° C. for 2 hours to obtain about 54 g of a yellow powder.

[0022]

Example 6 The same procedure as in Example 5 was repeated except that the aqueous FeSO ₄
ml (100 parts by weight of barium sulfate in a plate) and the same operation except that the amount was changed to about 58 parts by weight of yellow powder.

[0023]

Example 7 After coating with titanium oxide, 4 L of a titanyl sulfate solution adjusted to a sulfuric acid concentration of 6 g / L and a titanium oxide concentration of 1.5 g / L was placed in a 5 L beaker and stirred with a stirrer. Here, 50 g of plate-like barium sulfate similar to that in Example 1 was suspended (BaSO4: TiO2 = 25:
3). The mixture was further heated by a heater and kept boiling for 2 hours. During this time, the liquid volume was kept constant while adding pure water.
Thereafter, suction filtration was performed, and the residue was washed with water until no sulfate group was found in the filtrate. Next, the same operation as in Example 1 was carried out except that the whole amount of the residue was suspended in pure water to make a liquid volume of 1 L, instead of the barium sulfate suspension, to obtain about 54 g of flesh-colored powder.

Slipperiness test Plate-like barium sulfate used in Examples 1 to 7 and Example 1
Table 3 shows the results of a sensory test performed on the slipperiness of the powders obtained in Nos. To 7 by seven panelists. The evaluation was performed on a 5-point scale (5 points: good, 4 points: slightly good, 3 points: normal, 2 points: slightly poor, 1 point: bad), and the average value was taken.

Evaluation of ultraviolet absorption effect Plate-like barium sulfate used in Examples 1 to 7 and Example 1
The powders obtained in Steps No. 7 to No. 7 were formed into a paint by the following method, and the light transmittance of a coating film sample stretched on a transparent film was measured using a V-550 U.S.M. V. It was measured using a VISS Victory photometer.

Preparation of light transmittance measurement sample <Formulation> 7 g of sample powder 2.5 g of nitrocellulose liquid (nitrocellulose: isopropyl alcohol = 1: 1)
(Weight ratio) 9 g of xylene 9 g of isopropyl alcohol 9 g of butyl acetate 9 g of dioctyl phthalate 1.2 g of the above composition was weighed into a 100 ml mayonnaise bottle, and dispersed in a red devil paint conditioner for 10 minutes to obtain a paint. This paint was applied to a biaxially oriented polypropylene film using a No. 22 bar coater, and dried at room temperature.

Light Transmittance Measurement Results For barium sulfate plate and Examples 2 and 7, wavelength 29
The light transmittance measurement results of the coating film sample at 0 to 800 nm are shown in FIGS. The measurement results of other samples were 350
Table 3 shows the value obtained by subtracting the light transmittance (100 fraction) at 100 nm from 100 as the ultraviolet absorptivity.

[0027]

[Table 3]

[0028]

[Brief description of the drawings]

FIG. 1 shows the results of measuring the light transmittance of the coated sample at a wavelength of 290 to 800 nm for the barium sulfate plate used in Examples 1 to 7 and Examples 2 and 7. FIG. 2 is a scanning electron micrograph of the barium sulfate used in Examples 1 to 7 (magnification: 5,000 times). FIG. 3 shows the second embodiment.
It is a scanning electron micrograph of the powder obtained by (magnification:
5,000 times). It can be observed that Fe ₂ O ₃ is precipitated on the surface of the plate-like barium sulfate. However, since the shape of the plate-like barium sulfate (FIG. 2) has not changed, the slipperiness is not impaired.

Continued on front page F-term (reference) 4C083 AB231 AB232 AB241 AB242 AB361 AB362 BB25 BB46 EE06 EE17 FF01 4G076 AA14 AA18 BC08 BF05 BF08 CA26 DA16 4J037 AA08 AA09 CA05 CA09 DD05 EE03 EE04 EE26 EE33 FF35 FF05

Claims (5)

[Claims] 1. A plate-like barium sulfate is coated with red iron (Fe)
₂ O ₃ ), black iron oxide (Fe ₃ O ₄ ), yellow iron oxide (FeO
OH) and a method for producing the same. 2. After coating the plate-like barium sulfate with titanium oxide,
Further, a colored ultraviolet absorbing composition characterized by being coated with one of red iron oxide, black iron oxide and yellow iron oxide, and a method for producing the same. 3. A plate-like barium sulfate having a bengara (Fe)
₂ O ₃ ), black iron oxide (Fe ₃ O ₄ ) or yellow iron oxide (Fe
OOH) and titanium oxide, and a method for producing the same. 4. The barium sulfate plate has an average particle diameter of 3 to 70.
3. The process for producing a colored ultraviolet absorbing composition according to claim 1, wherein the colored ultraviolet ray absorbing composition has a thickness of 0.05 to 2 [mu] m. 5. The coating amount of each of red iron oxide, black iron oxide, and yellow iron oxide is 0.1 to 100 parts by weight of plate-like barium sulfate.
5. The method according to claim 1, wherein the amount is 1 to 50 parts by weight.