Black iron oxide for use with cosmetics, production method thereof, and cosmetic materials comprising the same

Abstract

To solve the problem of providing a black iron oxide that can yield sufficient blackness, opacifying effect and covering ability even if it is only added in a small amount for use with cosmetic materials, the invention provides a black iron oxide with a high tinting strength having an octahedral shape, a specific surface in a range of 8.0 to 20.0 m.sup.2/g, and a particle surface coated with a layer containing one type or two or more types of inorganic compounds, wherein an L*value of a color on reduction is 31.0 or lower and a b*value of a color on reduction is 1.5 or lower, a production method thereof, and cosmetic materials that incorporate the same.

Claims

1. A method, comprising: reacting a ferrous salt solution with an alkali hydroxide to form a ferrous hydroxide slurry; adding a ferric salt solution to the ferrous hydroxide slurry to produce a ferrous hydroxide slurry comprising a nucleus of black iron oxide; adjusting a pH of the ferrous hydroxide slurry comprising the nucleus of black iron oxide to 12.0 to 13.0; introducing an oxygen-containing gas over the ferrous hydroxide slurry comprising the nucleus of black iron oxide and heating the slurry to grow the nucleus of black iron oxide and form a slurry comprising a black iron oxide particle; and adding an inorganic metal salt to the slurry comprising the black iron oxide particle to foiln a black iron oxide particle having a layer comprising a hydroxide or an oxide of the inorganic metal salt coated on a surface thereof and having an octahedral shape and a specific surface area of 8.0 to 20.0 m.sup.2/g, wherein an L*value of a colour on reduction of the black iron oxide particle having a layer containing an hydroxide or an oxide of the inorganic metal salt on a surface thereof according to JIS K5101-3-1 is 31.0 or lower and a b*value of a colour on reduction of the black iron oxide particle having a layer containing a hydroxide or an oxide of the inorganic metal salt on a surface thereof according to JIS K5101-3-1 is 1.5 or lower.

2. The method according to claim 1, wherein the hydroxide or oxide of the inorganic metal salt coated on the surface of the black iron oxide particle is a hydroxide or an oxide of one or more of aluminum, silicon, zinc, titanium, zirconium, cerium, or tin.

3. The method according to claim 1, further comprising incorporating the black iron oxide particle having a layer containing a hydroxide or an oxide of the inorganic metal salt on a surface thereof into a cosmetic material.

4. The method according to claim 3, wherein the cosmetic material is in the form of a makeup base, foundation, concealer, face powder, control color, sun screen, lipstick, lip cream, eye shadow, eye liner, mascara, cheek color, manicure, body powder, perfume powder, baby powder, solid soap, bath powder, or peel-off mask.

5. The method according to claim 1, wherein the ferric salt is selected from ferric chloride, ferric sulfate, and ferric nitrate.

6. The method according to claim 1, wherein the ferric salt solution is added to the slurry in an amount of 0.8 to 5.0 wt % as Fe.sup.3+ against 100 wt % of Fe.sup.2+.

7. The method according to claim 1, wherein the inorganic metal salt is added to the slurry containing the black iron oxide particle in an amount that can form the layer containing the hydroxide or the oxide of the inorganic metal salt in an amount of 0.5 to 5.0 wt % against 100 wt % of the black iron oxide particle.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a scanning electron microscope (SEM) image showing the particle shape of the black iron oxide with a high tinting strength obtained in Example 1.

(2) FIG. 2 is a SEM image showing the particle shape of the black iron oxide obtained in Comparative Example 1.

(3) FIG. 3 is a SEM image showing the particle shape of a major black iron oxide, BL-100P (product of Titan Kogyo, Ltd.).

DESCRIPTION OF EMBODIMENTS

(4) Detailed explanation is provided below of the black iron oxide with a high tinting strength of the present invention, a production method thereof, and cosmetic materials incorporating said black iron oxide.

(5) The present invention relates to a black iron oxide with a high tinting strength having an octahedral shape, a specific surface in a range of 8.0 to 20.0 m.sup.2/g, and a particle surface coated with a layer containing one type or two or more types of inorganic compounds, wherein an L*value of a colour on reduction is 31.0 or lower and a b*value of a colour on reduction is 1.5 or lower, a production method thereof, and cosmetic materials incorporating said iron oxide pigment. The particle shape of the black iron oxide of the present invention is the shape observed by a scanning electron microscope (SEM) image. As shown in FIG. 1, the particle shape of the black iron oxide of the present invention is a clear octahedral shape.

(6) The specific surface of the black iron oxide of the present invention is a value measured by the single point BET method using Gemini 2360 (a product of Micromeritics) after deaeration of the sample in nitrogen at 150 C. for 30 minutes.

(7) An L*value of the colour on reduction and a b*value of the colour on reduction of the black iron oxide of the present invention are color indices (L*value and b*value) shown according JIS Z 8781-4 based on values obtained by stirring 0.125 g of the sample, 0.375 g of titanium dioxide and 1.0 ml of styresol with a hoover muller to form a paste, adding 2.0 ml of styresol to the paste, then mulling and forming a paint from the mixture, coating a cast coat paper with the mixture using a 150 m (6 mil) applicator to form a coated fragment (thickness of the film: about 30 m), and air drying the fragment, followed by baking at 130 C. for 30 minutes, then measuring the color using a SM-7 type color tester by Suga Test Instruments. In addition, the colour on reduction is that according to the definition of the tinting strength of a pigment in JIS K5101-3-1 (Test methods for pigmentsPart 3: Tinting strengthSection 1: Determination of relative tinting strength and colour on reduction of coloured pigmentsVisual comparison method). Namely, colour on reduction means colour of reduction of a coated film made of a reduction paste, and reduction paste means paste obtained by mixing white pigment paste with colored pigment dispersed in a binder. In the present invention, the black iron oxide of the present invention corresponds to colored pigment

(8) The L*value of the colour on reduction is an index of the tinting strength, and the smaller the L*value of the colour on reduction, the higher the tinting strength. The L*value of the colour on reduction of the conventional black iron oxide for cosmetics is about 38. An L*value of the colour on reduction of 31.0 or lower provides a sufficiently high tinting strength.

(9) The b*value of the colour on reduction is an index of blackness, and a higher b*value of the colour on reduction makes the brownish color more visible and reduces blackness. When the b*value of the colour on reduction exceeds 1.5, the brownish color becomes too strong to be called black. When the b*value of the colour on reduction becomes a negative value, the blue color becomes strong, but a bluish black is also included in the scope of the present invention.

(10) <Production Method of Black Iron Oxide with High Tinting Strength>

(11) The production method of black iron oxide with a high tinting strength of the present invention is described in detail.

(12) The ferrous salt solution was set to a predetermined temperature in the inert gas atmosphere, and an alkali solution at a neutralization equivalent or higher was added to the solution to generate a ferrous hydroxide slurry. Then, a predetermined amount of ferric salt solution is added to the ferrous hydroxide slurry to induce nucleation of black iron oxide. Subsequently, an alkali solution is added to the slurry containing nuclei of black iron oxide to adjust the pH of the slurry to a range of 12.0 to 13.0, and preferably, an oxygen-containing gas is passed over the slurry while it is heated to a range of 60 to 100 C. to induce the growth of the nucleus of black iron oxide. A predetermined amount of metal salt is added to the slurry after generation of black iron oxide has ended, and the pH of the mixture is adjusted by acid or alkali to obtain an insoluble hydroxide of the metal salt to be deposited onto the particle surface of the black iron oxide. Then, the slurry containing black iron oxide coated with an inorganic compound is filtered out, washed to remove salt impurities, and subsequently dried to obtain black iron oxide particles coated with an inorganic compound, preferably an inorganic metal hydroxide or oxide, of the present invention.

(13) The ferrous salts used in the present invention include ferrous chloride, ferrous sulfate, and ferrous nitrate. In addition, hydroxides such as sodium hydroxide, potassium hydroxide, and ammonium hydroxide, carbonates such as sodium carbonate, potassium carbonate, and ammonium carbonate, or ammonia gas can be used as the alkali source, but an alkali source that contains ammonia vaporizes at a high neutralization temperature, so hydroxides are preferable.

(14) The ferric salt that can be used in the present invention includes ferric chloride, ferric sulfate, and ferric nitrate. The amount of ferric salt to be added is 0.8 to 5.0 wt % as Fe.sup.3+ against 100 wt % of Fe.sup.2+. When the amount of ferric salt to be added is too small, the specific surface of the black iron oxide becomes smaller than 8.0 m.sup.2/g. On the other hand, when the amount of ferric salt to be added is too large, the specific surface becomes higher than 20.0 m.sup.2/g.

(15) When the pH of the slurry containing nucleus of black iron oxide is lower than 12.0, the black iron oxides will not grow sufficiently, and particles having an octahedral shape will not be formed. An octahedral shape is also obtained when the slurry pH is higher than 13.0, but such case requires more alkali to be used and is not economic. When the temperature for heating slurry containing nucleus of black iron oxide is lower than 60 C., crystals of materials that are not black iron oxide such as goethite are generated, and the tinting strength and blackness declines. The black iron oxide with a high tinting strength desired in the present invention can be obtained at a temperature above 100 C., but it is not economic.

(16) The slurry after completing the generation of black iron oxide with a high tinting strength is coated with a layer of one type or two or more types of inorganic compounds on the particle surface to suppress the decline of blackness due to oxidation in the drying step. A predetermined amount of inorganic metal salt can be added to the slurry containing black iron oxide to transform the inorganic metal salt into an insoluble hydroxide, and this process allows the surface of the black iron oxide particle to be coated with an inorganic compound. The inorganic metal salt to be used in the present invention is not particularly limited as long as they can be formed into a hydroxide or oxide of metals, such as aluminum, silicon, zinc, titanium, zirconium, cerium and tin, but it is preferably sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, sodium silicate, potassium silicate, silicon tetrachloride, zinc sulfate, zinc chloride, titanium sulfate, titanium tetrachloride, zirconium oxychloride, zirconium sulfate, zirconium nitrate, cerous chloride, cerium nitrate, cerium acetate, tin chloride, stannous sulfate, and sodium stannate.

(17) The amount of inorganic metal salt to be added is desirably an amount that can form a coating of an inorganic compound, preferably a coating of metal hydroxides or oxides in an amount of 0.5 to 5.0 wt % against 100 wt % of black iron oxide. When the amount of inorganic compound to be coated is lower than 0.5 wt %, the black iron oxide particle is oxidized in the drying step, the color tone becomes brownish, and the decline in blackness cannot be regulated. When the amount of inorganic compound for coating exceeds 5.0 wt %, the proportion of back iron oxide decreases and the tinting strength decreases.

(18) <Organic Surface Treatment>

(19) The surface of the black metal oxide particles of the present invention can be made water repellent and/or oil repellent by an organic matter to improve the dispersion stability and durability in the dispersion medium in the production of cosmetics that incorporate the black iron oxide particle of the present invention. The organic matter used herein may include dimethylpolysiloxane, methylhydrogenpolysiloxane and other silicone compounds, silane coupling agents, aluminum coupling agents, titanium coupling agents, zirconium coupling agents and other coupling agents, perfluoroalkyl phosphate compounds and other fluorine compounds, hydrocarbon, lecithin, amino acid, polyethylene, wax or lauric acid, stearic acid, isostearic acid and other fatty acids.

(20) <Cosmetic Material>

(21) The present invention provides a cosmetic material, in which black iron oxide particles that are surface coated with an inorganic compound (black iron oxide with a high tinting strength) are added in a predetermined amount against the main component of the cosmetic material. The amount of black iron oxide with a high tinting strength to be added in the cosmetic material may be set freely according to the required characteristics of the various cosmetic materials, and preferably in a range of 0.01-50 wt %, more preferably in a range of 0.02-40 wt % against the cosmetic material.

(22) <Inorganic Pigment and Organic Pigment that can be Combined for Use>

(23) The cosmetic material of the present invention can be combined for use with various additive components used in common cosmetic materials, such as inorganic pigments, and organic pigments. Inorganic pigments that can be combined for use may include titanium oxide, zinc oxide, iron red, yellow iron oxide, ultramarine blue, iron blue, cerium oxide, talc, muscovite, synthetic mica, bronze mica, black mica, synthetic fluorphlogopite, titanium-mica, mica-like iron oxide, sericite, zeolite, kaoline, bentonite, clay, silica, silica anhydride, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium sulfate, magnesium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, boron nitride, bismuth oxychloride, alumina, zirconium oxide, magnesium oxide, chromium oxide, calamine, hydroxyapatite and composites thereof. Likewise, organic pigments that can be combined for use include silicone powder, silicone elastic powder, polyurethane powder, cellulose powder, nylon powder, urethane powder, silk powder, PMMA powder, starch, polyethylene powder, polystyrene powder, tar dye, natural dye, metal soaps, such as zinc stearate and composites thereof.

(24) <Components that can be Added>

(25) Note that the cosmetic material of the present invention can incorporate components other than those above in quantitative and qualitative ranges that do not impair the effect of the present invention in view of the purpose of use. For example, oil-based components, dyes, pH adjustors, humectants, thickeners, surfactants, dispersants, stabilizers, colorants, preservatives, antioxidants, sequestering agents, astringents, extinguishing agents, UV absorbers, perfumes and the like can be added in a range that achieves the object of the present invention.

(26) <Form of Cosmetic Materials>

(27) The cosmetic material of the present invention can be produced by a known method, and it can be in any form including powder, solid powder, cream, emulsion, lotion, liquid oil, solid oil, paste. For example, it can be in the form of cosmetics for make-up, cosmetics for skin care, cosmetics for hair care and the like including makeup base, foundation, concealer, face powder, control color (makeup base), sun screen, lipstick, lip cream, eyeshadow, eye liner, mascara, cheek color, manicure, body powder, perfume powder, baby powder, solid soap, bath powder, peel-off mask, without being limited thereby.

EXAMPLES

(28) The present invention is described in more detail by Examples shown below. The following examples are given merely to provide examples, and they do not limit the scope of the invention.

Production Example 1

(29) A ferrous sulfate solution (2.15 L) containing 1.50 mol/L of Fe.sup.2+ was added to a 1.67 mol/L NaOH solution (3.85 L) in an inert gas atmosphere to generate ferrous hydroxide. (The amount of sodium hydroxide to be used is 1.04 equivalent against Fe.sup.2+.) Then, a ferric sulfate solution at 1.7 wt % as Fe.sup.3+ against Fe.sup.2+ was added to the aqueous solution containing ferrous hydroxide to generate a crystal nucleus of black iron oxide. Subsequently, a NaOH solution was added to a ferrous hydroxide slurry containing nucleus of black iron oxide to adjust the pH to 12.3. The ferrous hydroxide slurry containing the nucleus was mechanically stirred at 90 C., then 2 L/min. of air was passed over for 120 minutes to induce growth of black iron oxide particles. Next, sodium aluminate at 1.5 wt % as Al.sub.2O.sub.3 was added slowly to the obtained black iron oxide while the mixture was stirred, and after 1 hour of stirring, diluted sulfuric acid was added to adjust the pH to 8.0. The mixture was filtered and washed, then dried at 100 C. to obtain Sample A. The scanning electron microscope (SEM) image of Sample A is shown in FIG. 1. As shown in FIG. 1, the particle shape of the obtained Sample A is an octahedron. The specific surface of Sample A measured by the BET method was 13.3 m.sup.2/g. Further, the L*value of the colour on reduction of Sample A is 27.4, and the b*value of the colour on reduction is 1.1.

Production Example 2

(30) A ferrous sulfate solution (2.15 L) containing 1.50 mol/L of Fe.sup.2+ was added to a 1.67 mol/L NaOH solution (3.85 L) in an inert gas atmosphere to generate ferrous hydroxide. (The amount of sodium hydroxide to be used is 1.04 equivalent against Fe.sup.2+.) Then, a ferric sulfate solution at 4.2 wt % as Fe.sup.3+ against Fe.sup.2+ was added to the aqueous solution containing ferrous hydroxide to induce nucleation of black iron oxide. Subsequently, a NaOH solution was added to a ferrous hydroxide slurry containing nucleus of black iron oxide to adjust the pH to 12.5. The ferrous hydroxide slurry containing the nucleus was mechanically stirred at 85 C., then 2 L/min. of air was passed over for 120 minutes to induce growth of black iron oxide particles. Next, sodium aluminate at 3.0 wt % as Al.sub.2O.sub.3 was added to the obtained black iron oxide slowly while the mixture was stirred, and after 1 hour of stirring, diluted sulfuric acid was added to adjust the pH to 8.0. The mixture was filtered and washed, then dried at 100 C. to obtain Sample B. The particle shape of the obtained Sample B is an octahedron, and the specific surface of Sample B measured by the BET method was 18.8 m.sup.2/g. Further, the L*value of the colour on reduction of Sample B was 27.7, and the b*value of the colour on reduction was 1.1.

Production Example 3

(31) A ferrous sulfate solution (2.15 L) containing 1.50 mol/L of Fe.sup.2+ was added to a 1.67 mol/L NaOH solution (3.85 L) in an inert gas atmosphere to generate ferrous hydroxide. (The amount of sodium hydroxide to be used is 1.04 equivalent against Fe.sup.2+.) Then, a ferric chloride solution at 0.9 wt % as Fe.sup.3+ against Fe.sup.2+ was added to the aqueous solution containing ferrous hydroxide to induce nucleation of black iron oxide. Subsequently, a NaOH solution was added to a ferrous hydroxide slurry containing nucleus of black iron oxide to adjust the pH to 12.1. The ferrous hydroxide slurry containing the nucleus was mechanically stirred at 95 C., then 2 L/min. of air was passed over for 120 minutes to induce growth of black iron oxide particles. Next, sodium aluminate at 1.5 wt % as Al.sub.2O.sub.3 was added slowly to the obtained black iron oxide while the mixture was stirred, and after 1 hour of stirring, diluted sulfuric acid was added to adjust the pH to 8.0. The mixture was filtered and washed, then dried at 100 C. to obtain Sample C. The particle shape of Sample C is an octahedron, and the specific surface of Sample C measured by the BET method was 8.6 m.sup.2/g. Further, the L*value of the colour on reduction of Sample C was 28.8, and the b*value of the colour on reduction was 2.9.

Production Example 4

(32) A ferrous sulfate solution (2.15 L) containing 1.50 mol/L of Fe.sup.2+ was added to a 1.67 mol/L NaOH solution (3.85 L) in an inert gas atmosphere to generate ferrous hydroxide. (The amount of sodium hydroxide to be used is 1.04 equivalent against Fe.sup.2+.) Then, a ferric sulfate solution at 1.7 wt % as Fe.sup.3+ against Fe.sup.2+ was added to the aqueous solution containing ferrous hydroxide to induce nucleation of black iron oxide. Subsequently, a NaOH solution was added to a ferrous hydroxide slurry containing nucleus of black iron oxide to adjust the pH to 12.7. The ferrous hydroxide slurry containing the nuclei was mechanically stirred at 80 C., then 2 L/min. of air was passed over for 120 minutes to induce growth of black iron oxide particles. Next, sodium silicate at 3.0 wt % as SiO.sub.2 was added slowly to the obtained black iron oxide while the mixture was stirred, and after 1 hour of stirring, diluted sulfuric acid was added to adjust the pH to 5.0. The mixture was filtered and washed, then dried at 100 C. to obtain Sample D. The particle shape of the obtained Sample D is an octahedron, and the specific surface of Sample D measured by the BET method was 13.0 m.sup.2/g. Further, the L*value of the colour on reduction of Sample D was 27.5, and the b*value of the colour on reduction was 1.0.

Production Comparative Example 1

(33) A process similar to Production Example 1, other than that the pH after nucleation was adjusted to 8.8, was performed to obtain Sample E. The scanning electron microscope (SEM) image of Sample E is shown in FIG. 2. As shown in FIG. 2, the particle shape is a sphere. The specific surface of Sample E was 12.0 m.sup.2/g. Further, the L*value of the colour on reduction of Sample E was 31.5, and the b*value of the colour on reduction was 1.6.

Production Comparative Example 2

(34) A process similar to Production Example 1, other than that a ferric sulfate solution was added at an amount of 0.7 wt % as Fe.sup.3+ against Fe.sup.2+, was performed to obtain Sample F. The particle shape of Sample F was an octahedron, and the specific surface was 7.5 m.sup.2/g. Further, the L*value of the colour on reduction of Sample F was 31.7, and the b*value of the colour on reduction was 3.4.

Production Comparative Example 3

(35) A process similar to Production Example 1, other than adding a ferric sulfate solution at an amount of 7.0 wt % as Fe.sup.3+ against Fe.sup.2+, was performed to obtain Sample G. The particle shape of Sample G was an octahedron, and the specific surface was 22.0 m.sup.2/g. Further, the L*value of the colour on reduction of Sample G was 27.5, and the b*value of the colour on reduction was 2.4.

Production Comparative Example 4

(36) A process similar to Production Example 1, other than that no surface treatment was performed after generating black iron oxide (addition of sodium aluminate), was performed to obtain Sample H. The particle shape of Sample H was an octahedron, and the specific surface was 13.1 m.sup.2/g. Further, the L*value of the colour on reduction of Sample H was 28.9, and the b*value of the colour on reduction was 1.7.

Examples 1-4, Comparative Examples 1-5: Pressed Eyeshadows

(37) 20.0 wt % of either of Samples A-D obtained in Production Examples 1-4 and Samples E-H obtained in Production Comparative Examples 1-5, and BL-100P produced by Titan Kogyo, Ltd. shown in the picture of FIG. 3 as a typical black iron oxide (particle shape: edgeless cube, specific surface 6.6 m.sup.2/g, L*value of the colour on reduction: 39.0, b*value of the colour on reduction: 4.2), 35.0 wt % of sericite, 14.9 wt % of talc, 20.0 wt % of titanium-mica (produced by BASF: Flamenco Super Pearl 120C) and 0.1 wt % of methylparaben were mixed/ground, and mixed. Then, 7.0 wt % of dimeticone 1000 cs (viscosity of 1000 mm.sup.2/s) and 3.0 wt % of diisostearyl malate that were mixed in a different container were added and stirred/mixed to homogenize the mixture. The mixture was dispersed in isopropyl alcohol to achieve a suitable viscosity, and pressed/filled in a gold plate having a diameter of 57 mm and a depth of 4 mm using a slurry filler. Then the mixture was dried at 40 C. for 12 hours to obtain the desired pressed eyeshadow.

(38) [Assessment Items and Assessment Method Using Black Iron Oxide with a High Tinting Strength]

(39) <Sensory Assessment>

(40) The obtained pressed eyeshadow was subjected to a sensory assessment concerning the covering ability, blackness, gloss and the like.

(41) <Assessment and Assessment Standard>

(42) The pressed eyeshadows created in Examples 1-4 and Comparative Examples 1-5 were tested on 10 panels; a sensory assessment was performed by rating the sensory assessment items of Table 1 in a scale of 1 to 5; and the average score was used for judgment.

(43) <Assessment Standard>

(44) Very good: 5 Good: 4 Acceptable: 3 Not good: 2 Bad: 1
<Judgment Standard> 4.0-5.0 points: 3.0-lower than 4.0 points: 2.0-lower than 3.0 points: 1.0-lower than 2.0 points:

(45) The results are shown in Table 1.

(46) TABLE-US-00001 TABLE 1 Comp. Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Applied black Sample A Sample B Sample C Sample D Sample E Sample F Sample G Sample H BL- iron oxide 100P Test Items Covering ability X Blackness X X Gloss X

(47) As a result of the sensory assessment, the pressed eyeshadows obtained in Examples 1-5 of the present invention all had good covering ability and blackness, as well as gloss, compared to Comparative Examples 1-4 or Comparative Example 5, which incorporates a conventional black iron oxide. A cosmetic material that has good covering ability and blackness, and produces a glossy finish was obtained by incorporating a black iron oxide with high tinting strength having an octahedral shape, a specific surface in a range of 8.0 to 20.0 m.sup.2/g, a particle surface coated with a layer containing one or two or more types of inorganic compounds, and an L*value (colour on reduction) of 31.0 or lower and a b*value (colour on reduction) of 1.5 or lower.

Example 5: Aqueous Eyeliner

(48) TABLE-US-00002 TABLE 2 <Components> Weight (%) 1. Production Example 2 (Sample B) black iron oxide 7.0 with high tinting strength 2. Purified water 21.5 3. Decaglyceryl laurate 1.0 4. Glycerine 6.0 5. Carboxymethyl cellulose 10% solution 18.0 6. Phenoxyethanol 0.5 7. Pentylene Glycol 1.0 8. Vinyl acetate resin emulsion 45.0 (Nisshin Chemical Industry Co., Ltd. Vinyblan GV-5651)
<Production Method> A: Components 1-3 were weighed out, and the black iron oxide was finely dispersed using a bead mill. B: Components 4-7 were weighed out in a different container, and after A was added at 70 C. to the components and the mixture was dispersed homogenously, it was cooled to room temperature. Component 8 was added to obtain an aqueous eyeliner.

(49) The obtained aqueous eyeliner had high blackness and opacifying effect.

Example 6: Emulsified Mascara

(50) TABLE-US-00003 TABLE 3 Weight <Components> (%) 1. Purified water 23.1 2. Polyvinyl pyrrolidone 2.0 3. Propanediol 2.0 4. Cationized cellulose 1% solution 10.0 5. Bentonite 0.5 6. Triethanolamine 1.7 7. Methylparaben 0.2 8. Talc 4.0 9. Production Example 2 (Sample B) black iron oxide with a 10.0 high tinting strength 10. Carnauba wax 5.5 11. Beeswax 9.0 12. Stearic acid 2.0 13. Self-emulsifiable glyceryl stearate 2.0 14. Propylene glycol stearate 2.0 15. Hydrogenated polyisobutene 2.0 16. Cyclomethicone 4.0 17. Acrylate resin emulstion <Daito Kasei Kogyo 20.0 Co. DAITOSOL 5000AD>
<Production Method> A: Components 8-10 were stirred/mixed using a Henschel mixer. B: A was added to Components 1 to 7, and the mixture was dispersed homogenously using a stirrer. C: After heated/dissolved Components 11-16 were added to B and emulsified, the mixture was cooled to 40 C., Component 17 was added, and the mixture was cooled to room temperature to obtain an emulsified mascara.

(51) The obtained emulsified mascara was an emulsified mascara with a somewhat reddish blackness and a good opacifying effect.

Example 7: Eyebrow Pencil

(52) TABLE-US-00004 TABLE 4 <Components> Weight (%) 1. Production Example 4 (Sample D) black iron oxide 20.0 with a high tinting strength 2. Titanium oxide 5.0 3. Talc 10.0 4. Kaoline 15.0 5. Japan wax 21.0 6. Stearic acid 10.0 7. Beeswax 5.0 8. Hydrogenated castor oil 5.0 9. Vaseline 3.0 10. Lanolin 3.0 11. Squalane 3.0 12. Preservative suitable amount 13. Antioxidant suitable amount
<Production Method> A: Components 1 to 4 were mixed/ground. B: To heated/dissolved Components 5 to 13, A was added and the mixture was homogenously kneaded using a three roll mill. C: The mixture was molded into a core and surrounded by wood into a pencil shape to obtain an eyebrow pencil.

(53) The obtained eyebrow pencil had a smooth use, since it not only had high blackness, but it could also be added in a smaller amount.

Example 8: Cheek

(54) TABLE-US-00005 TABLE 5 <Components> Weight (%) 1. Triethoxycaprylylsilane-treated talc 25.0 2. Triethoxycaprylylsilane-treated sericite 61.0 3. Stearic acid treated titanium oxide particle (Titan 3.0 Kogyo, Ltd. STV-455) 4. Triethoxycaprylylsilane-treated titanium oxide 2.0 5. Black iron oxide with a high tinting strength of 0.05 Production Example 1 (Sample A) treated with triethoxycaprylylsilane at an amount of 1.5 wt % 6. Triethoxycaprylylsilane-treated iron red 0.15 7. Triethoxycaprylylsilane-treated yellow iron oxide 0.8 8. Ethylhexyl methoxycinnamate 3.0 9. Ethylhexyl palmitate 5.0 10. Preservative suitable amount 11. Antioxidant suitable amount
<Production Method> A: Components 1-7 were mixed using a Henschel mixer. B: Components 8 to 11 were heated/dissolved and added to A, then it was ground with an atomizer. C: The mixture was press-molded on an aluminum plate to obtain the desired check.

(55) The obtained cheek had good usability.

Example 9: Nail Enamel

(56) TABLE-US-00006 TABLE 6 Weight <Components> (%) 1. Nitrocellulose ( sec.) 10.0 2. Modified alkyd resin 10.0 3. Acetyl tributyl citrate 5.0 4. Ethyl acetate 20.0 5. Ethanol 5.0 6. Toluene 34.0 7. Production Example 2 (Sample B) black iron oxide with a 3.0 high tinting strength 8. Black iron oxide-coated titanium-mica (Timica 10.0 Nu-Antique Silver by BASF) 9. Organically modified montmorillonite 3.0
<Production Method> A: A half amount of each of Components 2, 3 was collected, and they were mixed with Components 7-8 and kneaded together. B: Residue of Components 2, 3 and Components 1, 4-6 and 9 were added to A, and mixed until the mixture was homogenized to obtain nail enamel.

(57) The obtained nail enamel had good blackness and opacifying effect.

Example 10: O/W Emulsified Foundation

(58) TABLE-US-00007 TABLE 7 <Components> Weight (%) 1. Stearic acid 1.0 2. Isostearic acid 0.3 3. Ethyl hexanoic acid cetyl 4.0 4. Liquid paraffin 70cs 11.0 5. Steareth-10 2.0 6. Cetyl alcohol 1.5 7. Triethoxycaprylylsilane-treated talc 5.0 8. Black Iron oxide with a high tinting strength of 0.2 Production Example 3 (Sample C) treated with Triethoxycaprylylsilane at an amount of 1.0 wt % 9. Triethoxycaprylylsilane-treated iron red 0.3 10. Triethoxycaprylylsilane-treated yellow iron oxide 1.8 11. Triethoxycaprylylsilane-treated titanium oxide 8.0 12. Triethanolamine 1.2 13. Propanediol 5.0 14. Xanthan gum 0.2 15. Purified water 58.0 16. Phenoxyethanol 0.5
<Production Method> A: Components 7 to 11 were mixed/ground. B: To Components 1 to 6 heated/dissolved at 85 C., A was added and the mixture was dispersed homogenously. C: Components 12 to 16 were heated/dissolved at 85 C. and gradually added to B to obtain an emulsified mixture, and the mixture was stirred/cooled to room temperature to fill a suitable container and to obtain an O/W emulsifying foundation.

(59) The obtained O/W emulsifying foundation spreads well, and it has a good covering ability as well as a fresh feel.

Example 11: Two-Way Cake Foundation

(60) TABLE-US-00008 TABLE 8 <Components> Weight (%) 1. Dimethicone-treated talc residue 2. Dimethicone-treated titanium oxide 10.0 3. Dimethicone-treated mica 20.0 4. Dimethicone-treated sericite 36.0 5. Nylon powder 10.0 6. Dimethicone-treated yellow iron oxide 1.0 7. Dimethicone-treated iron red 0.5 8. Black iron oxide with a high tinting strength of 0.1 Production Example 4 (Sample D) treated with 1.0 wt % dimethicone 9. Dimethicone 1000cs 6.0 10. Isotridecyl isononanoate 3.0 11. Squalane 3.0 12. Tocopherol 0.1 13. 1,3-Butylene glycol 1.0
<Production Method> A: Components 1-8 were mixed using a Henschel mixer. B: Components 9 to 13 were heated/dissolved and added to A. C: B was ground in an atomizer, and press-molded in an aluminum plate to obtain a two-way foundation.

(61) The obtained two-way foundation had a smooth feel, and a fresh feel.

Example 12: Lipstick

(62) TABLE-US-00009 TABLE 9 Weight <Components> (%) 1. Ceresin 10.0 2. Microcrystalline wax 3.2 3. Paraffin 5.0 4. Pentaerythrityl tetraisostearate 20.0 5. Diisostearyl malate 15.0 6. Hydrogenated polydecene 10.0 7. Vaseline 10.0 8. Polyglyceryl Triisostearate-2 22.1 9. Simethicone 0.1 10. Propylparaben 0.1 11. Red 202 0.6 12. Production Example 1 (Sample A) black iron oxide with a 0.1 high tinting strength 13. Titanium oxide 0.4 14. Iron red 0.4 15. Titanium-Mica (BASF: Flamenco Sparkle Gold 220J) 2.0 16. Silica 1.0
<Production Method> A: Components 1-16 were weighed out, and heated/mixed. B: A was dispersed evenly using a three roll mill, then it was further heated and stirred to a homogenous state. C: After defoaming, a bulk of A was poured into a mold, and quenched. The bulk was fixed in a suitable container to obtain a lipstick.

(63) The obtained lipstick exhibited a deep red color, and showed a unique color tone.

Example 13: Body Shampoo

(64) TABLE-US-00010 TABLE 10 <Components> Weight (%) 1. Lauric acid 11.5 2. Myristic acid 7.7 3. Palmitic acid 4.8 4. Potassium hydroxide (48%) 12.2 5. Lauryl hydroxy sulfo betaine 10.0 6. Cocamide monoethanolamide 1.0 7. Ethylene glycol distearate 2.0 8. Purified water 50.2 9. EDTA-4Na 0.1 10. Production Example 1 (Sample A) black iron oxide 0.1 with a high tinting strength 11. Talc 0.4
<Production Method> A: Components 1 to 3 were heated/dissolved at 70 to 80 C. B: Components 10 to 11 were mixed/ground. C: Component 4 was added gradually to A to perform saponification. After saponification was completed, Components 5 to 9 were added, and the mixture was stirred until it reached a homogenous state. D: C was cooled to 40 C., then B was added to it and the mixture was cooled to room temperature while it was being stirred/mixed to obtain a body shampoo.

(65) The obtained body shampoo was colored with only a small amount of pigments, so pigments were prevented from precipitating under a high temperature environment.

Example 14: Solid Soap

(66) TABLE-US-00011 TABLE 11 Weight <Components> (%) 1. Fatty acid alkali metal salt (lauric acid 38%, myristic acid 94.5 37%, palmitic acid 15%, stearic acid 10%) (potassium:sodium = 1:5) 2. Cocamidopropyl betaine 3.0 3. Glycerine 2.0 4. Production Example 2 (Sample B) black iron oxide with a 0.5 high tinting strength
<Production Method> A: Sodium hydroxide (48%) and potassium hydroxide (48%) were added to a fatty acid of a composition of Component 1, then the mixture was stirred/mixed at a high temperature to prepare a fatty acid alkali metal salt of Component 1. B: Components 2 to 4 were added to A, and mixed together, then the mixture was homogenized using a three roll mill. C: B was kneaded/pressurized and extruded into a stick soap with an extruder, then molded with a stamping machine to obtain a solid soap.

(67) The obtained solid soap had a water content of 11.5%, and it had a stable blackness and somewhat of a red tint.

Example 15: Bath Powder

(68) TABLE-US-00012 TABLE 12 Weight <Components> (%) 1. Sodium sulfate 86.0 2. Sodium hydrogen carbonate residue 3. Sodium glutamate 2.0 4. Silica (AGC Si-Tech Co., Ltd. SUNSPHERE H-52) 1.0 5. Production Example 1 (Sample A) black iron oxide with a 0.5 high tinting strength 6. Vanillylbutyl ether 0.2 7. Capsicum extract 0.1
<Production Method>

(69) Components 1 to 7 were weighed out and mixed evenly using a Henschel mixer to obtain a bath powder.

(70) A use of the obtained bath powder made the warm water in the bath tub turn a translucent black color.

Example 16: Peel-Off Mask

(71) TABLE-US-00013 TABLE 13 Weight <Components> (%) 1. PEG1500 8.0 2. PEG/PPG-25/30 copolymer 6.0 3. Xanthan gum 0.2 4. Sodium citrate 0.3 5. Citric acid 0.1 6. Purified water 49.0 7. Polyvinyl alcohol 10.0 8. Polysorbate-80 0.2 9. Silica (AGC Si-Tech Co., Ltd. SUNSPHERE H-51) 4.0 10. Talc 8.0 11. Production Example 1 (Sample A) black iron oxide with a 1.0 high tinting strength 12. Alkyl acrylate copolymer emulsion 5.0 13. Methylparaben 0.2 14. Ethanol 8.0
<Production Method> A: Components 9 to 11 were mixed/ground. B: To heated/dissolved Components 1 to 8, A was added and evenly dispersed, then, the mixture was cooled to 40 C. C: Components 12 to 14 were added to B, then stirred/cooled to room temperature to prepare a peel-off mask.

(72) The obtained peel-off mask exhibited a homogenous black color, and it made sebum and dirt visible after the mask was removed.