KR100598496B1 - Dye for cosmetics, the preparation thereof, and the cosmetic composition containing the same - Google Patents

Abstract

The present invention relates to a cosmetic pigment and a cosmetic composition containing the same, and more particularly, to make-up and sunburn prevention prepared by partially replacing titanium ions (Ti ⁴⁺ ) in titanium dioxide with manganese ions (Mn ²⁺ ). It relates to a cosmetic pigment, a method for producing the same, and a cosmetic composition containing the pigment.

Whitening phenomenon, titanium ion, manganese ion, cosmetic pigment, manganese titanium oxide

Description

Cosmetic pigments and preparation method thereof, and a cosmetic composition containing the same {Dye for cosmetics, the preparation honey, and the cosmetic composition containing the same}

       1 is a graph showing the spectral distribution of general skin.

2 is a distribution, color, lightness and saturation analysis results of skin color by race.

3 is a schematic diagram showing the crystal lattice structure of the manganese titanium oxide according to the present invention.

4 is a result of comparing the spectral transmittance (Spectral Transparency) of the manganese-titanium oxide of Example 1 of the present invention and the general pigment grade titanium dioxide.

5 is a result of comparing the spectral reflectance (Spectral Reflectance) of the manganese-titanium oxide of Example 1 of the present invention and the general pigment grade titanium dioxide.

Figure 6 is a photograph taken after the application of Formulation Example 1 and Comparative Formulation Example 1 to the skin.

The present invention relates to a cosmetic pigment and a cosmetic composition containing the same, and more particularly, to make-up and sunburn prevention prepared by partially replacing titanium ions (Ti ⁴⁺ ) in titanium dioxide with manganese ions (Mn ²⁺ ). It relates to a cosmetic pigment, a method for producing the same, and a cosmetic composition containing the pigment.

In general, human skin color is manifested by the optical absorption of translucent skin tissue and the scattering and interaction of the skin's brown pigment melanin with hemoglobin in the blood, but not all but race, sex, seasonal and cosmetic As there are many variables in relation to the presence or absence of, it is difficult to define exactly and objective data is difficult. However, with scientific and objective data on color, research on skin color has been made naturally, and research data on more objective and average skin color have been accumulated to obtain spectral distribution of skin color as shown in FIG. ( Figure 1 ; Edward & Duntley, The Pigments and Color of Living Human Skin, Am, J. Anat 65 (1) No. 1, P 1-33, (1939)).

There was also a study of differences in racial skin color by applying Munsell color system ( FIG. 2 ;; 方明博, 肌 色 と 化粧, 齒科 蕃 美, 6, (2) p53 ~ 57, (1994)). As a result of the measurement of the skin color, there was a small difference in the preferred color when corrected through the skin color and makeup of the real face.

For example, white people prefer a slightly yellowish skin color because their skin color feels white and red like white hair, while women in the Far East, such as Korea and Japan, feel that their skin color is yellow, which is why they are red. Psychological tendency to prefer makeup (CJ Bartleson: Memory Color of Familiar Object, J. Opt. Soc. Am. , 50 (1), p73-77 (1960)). The difference between the actual skin color and the preferred color satisfies psychological needs in a form that complements the production through makeup.

In order to produce the skin color of the makeup, a combination of white pigments such as titanium dioxide (Titaniuum Dioxide), iron oxide (Iron Oxide Yellow), iron oxide (Iron Oxide Red) and iron oxide black (Iron Oxide Black) natural skin color Directing. Titanium dioxide is used as a white pigment to adjust brightness and saturation, yellow and red iron oxide to adjust color, and black iron oxide to adjust brightness and saturation.

Titanium dioxide is also an indispensable material in makeup and anti-burning cosmetic compositions due to its high whiteness and high refractive index.

However, the high index of refraction and high whiteness of titanium dioxide may cause other disadvantages. The first disadvantage is that the makeup has a high whiteness due to the high reflection of visible light, which makes the makeup look thick. This can lead to unnatural color expression, such as the appearance of the skin dull.

Another disadvantage is that when taking a picture in a dark place, the flash light source of the camera itself emits light, hits the surface of titanium dioxide and scatters and reflects, causing a whitening effect that is unusually white in the picture (Kunihiko Mohri & Naoki). Nakamura: New Pseudobrookite Pigment, C & T Magazine V111 p65 (1996)).

In order to solve this drawback, a new material has been developed which eliminates whitening by sintering iron oxide to titanium dioxide. However, this is a result of sintering yellow iron oxide on general titanium dioxide, but it can reduce whitening phenomenon, but it cannot reduce the feeling of thick coating that makeup expresses.

The present inventors have studied to overcome the above disadvantages, manganese-titanium oxide prepared by partially replacing titanium ions (Ti ^{4 +} ) in titanium dioxide with manganese ions (Mn ^{2 +} ), natural color representation and transparency The present invention was found to give a light feeling and to reduce the whitening phenomenon and to complete the present invention.

Accordingly, an object of the present invention is to provide a manganese titanium oxide and a method for producing the same as a pigment for cosmetics.

Another object of the present invention is to provide a makeup and anti-burning cosmetic composition containing the manganese-titanium oxide.

In order to achieve the above object, in the present invention, manganese-titanium oxide is produced using neutral hydrolysis, which is a general method for producing ultrafine titanium oxide. More specifically, the manganese titanium oxide according to the present invention was prepared by dissolving titanium tetrachloride (TiCl ₄ ) and manganese chloride (MnCl ₂ ) in purified water and neutralizing the aqueous solution with sodium hydroxide (NaOH). Same as 1.

The starting material of the neutralization hydrolysis method used in the present invention is titanium tetrachloride (TiCl ₄ : 98% Wako Chemical) and manganese chloride (MnCl ₂ : Sigma M8530), the mixing ratio of the titanium tetrachloride and manganese chloride is 97.0: 3.0 to 96.0: It is preferable to mix in a weight ratio of 4.0, and the molar ratio of Ti: Mn of the final product is prepared to be 9: 1. After dissolving each substance in purified water, neutralize the solution by adding a certain amount of purified water to a round-bottomed flask and maintaining the temperature at 75 to 80 ° C. while maintaining a pH of 1.8 to 2.0 while slowly adding sodium hydroxide solution to the aqueous titanium tetrachloride / manganese chloride solution. Causes a reaction.

After the neutralization reaction, the final product in the form of a hydrate was calcined by heating at 900 ° C., filtered, washed twice, dried at 120 ° C. for 16 hours, and then ground to prepare manganese-titanium oxide.

Manganese-titanium oxide made in the present invention is a white pigment material having a tetragonal system structure in the form of rutile and anatase, which are crystal structures of general titanium dioxide, as shown in FIG. 3. It is characterized by having a lattice structure as it loses, and doubled the role of enhancing transparency with 60nm-class ultrafine titanium oxide.

In addition, the manganese-titanium oxide according to the present invention ^replaces a part of titanium ions (Ti ⁴⁺ ) with manganese ions (Mn ²⁺ ) to change the natural beige color, thereby improving the spectral reflectance in the short wavelength and visible light range. It was effective in reducing whiteness of skin color and reducing whitening (PWE) caused by fresh lighting when taking pictures in dark places.

The manganese-titanium oxide pigments prepared in the above steps have a natural beige color, and are not thick and give natural beige color and clarity, and are effective in reducing whitening when photographing in a dark place.

In addition, the present invention can be prepared as a cosmetic formulation for makeup and anti-nitrogen containing the manganese-titanium oxide pigment, and specific examples of the formulation include two-way cakes, foundations, face powders, skin covers, and sun creams. .

The content of manganese and titanium oxide pigments in the manufacture of the makeup and anti-fog cosmetics is preferably 1 to 20% by weight of the total weight of the composition, and when the content is less than 1% by weight, sufficient concealment effect and UV protection effect cannot be obtained. When it exceeds 20% by weight, there is a possibility of causing problems such as skin adhesion, molding state and usability.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited only to these examples.

Example 1 Preparation of Manganese Titanium Oxide Pigment

34.15 g of titanium tetrachloride (TiCl ₄ : 98% Wako Chemical) and 2.52 g of manganese chloride (MnCl ₂ : Sigma M8530) were each prepared as a 30% aqueous solution.

2 liters of purified water was added to a round bottom flask and the temperature was maintained at 75 to 80 ° C., while 113.84 g of the 30% titanium tetrachloride (TiCl ₄ ) solution prepared above and 29.40 g of 30% manganese chloride solution (MnCl ₂ ) were slowly added thereto. The reaction was neutralized with a sodium hydroxide aqueous solution (NaOH.H ₂ O) while maintaining the pH at 1.8 to 2.0.

Upon completion of the neutralization reaction, the resulting hydrate was calcined at 900 ° C., washed twice, dried at 120 ° C. for 16 hours, and then ground to prepare 27.15 g of manganese-titanium oxide (TiMnO ₃ ).

In order to confirm the content of manganese in the prepared manganese titanium oxide (TiMnO ₃ ), it was quantitatively analyzed by inductively coupled spectroscopy (Inductively Coupled Plasma: Perkin-Elmer (USA) OPTIMA 3000 DV).

<Analysis Condition>

1) Plasma view: Axial.

2) Wavelength (nm): Mn; 257.610

<Analysis Result>

Manganese content: 3.5%

Test Example 1 Transparency Confirmation Experiment of Manganese Titanium Oxide Pigment

The spectral transmittance of the manganese-titanium oxide pigment prepared in Example 1 was measured using an FT-IR spectrometer (Perkin Elamer, Paragon 1000), and the results are shown in FIG. 4.

As shown in FIG. 4, the transmittance in the visible light region of the manganese-titanium oxide pigment according to the present invention is compared with that of the general pigment grade titanium dioxide. As a result, the transmittance in the visible light region of the manganese-titanium oxide pigment is much higher. As a result, it was confirmed that a more natural feeling can be produced in terms of transparency.

[Test Example 2] Experiment of confirming the reduction rate of whitening phenomenon (PWE) of manganese titanium oxide pigment

Spectral reflectance of the manganese-titanium oxide pigment of Example 1 was measured by UV / VIS / NIR spectrometer (Perkin Elamer / Lamda 9), the results are shown in FIG.

As shown in FIG. 5, the spectral reflectance in the short wavelength region and visible light region of the manganese-titanium oxide of the present invention was confirmed to be significantly lower than that of the general pigment grade titanium dioxide, and thus the whitening phenomenon of the conventional titanium dioxide By reducing the reflectance in the short wavelength and visible light, which is the cause, it was found that the skin was loosened.

Test Example 3 Sensory Test on Skin Color Expression and Transparency

In order to confirm skin color tone and clarity of the manganese-titanium oxide pigments prepared in Example 1, 20 female panelists 20 to 40 years old were subjected to sensory tests to express their natural expressiveness and clarity. Evaluation was conducted.

First, the manganese-titanium oxide pigment of Example 1 was applied to the skin of the back of each panel several times, and the natural expressive power and the degree of expression of the transparency of the skin were determined in five stages according to the following evaluation criteria. Indicated.

<Evaluation Criteria>

5: very good 4: excellent 3: moderate 2: slightly poor 1: bad

Natural color expression Skin transparency Example 1 4.70 4.80

As can be seen in Table 1, when using the manganese-titanium oxide pigment of the present invention it was confirmed that the overall excellent results in terms of expressing the natural color and clarity of the skin.

[Formulation Example 1 and Comparative Formulation Example 1]

Formulation Example 1 and Comparative Formulation Example 1 were prepared as two-way cake formulations using the compositions shown in Table 2 below.

Prize number Name Formulation Example 1 (wt%) Comparative Formulation Example 1 (wt%) A One Example 1 7.0 - 2 Do this car 15.0 15.0 3 Silica 8.0 8.0 4 Nylon powder 4.0 4.0 5 Titanium dioxide - 7.0 6 Iron oxides Quantity Quantity B 7 Dimethicone 5.0 5.0 8 Spices Quantity Quantity C 9 Talc Remaining amount Remaining amount

<Production method>

1) Phase A and phase C were added to a Henschel mixer, mixed and stirred at a constant speed.

2) Mixing and stirring while spraying phase B into the Henschel mixer.

3) The bulk in which the A, B and C phases were mixed and stirred was pulverized twice with an atomizer.

4) The semi-finished product was aged for a certain time and then molded (tableted).

Formulation Example 2 and Comparative Formulation Example 2

Formulation Example 2 and Comparative Formulation Example 2 were prepared as a liquid foundation formulation using the composition of Table 3 below.

Prize number Name Formulation Example 2 (wt%) Comparative Formulation Example 2 (wt%) A One Ceresin 1.0 1.0 2 Candelilla wax 0.3 0.3 3 Cetyl Dimethicone Copolyol 2.0 2.0 4 Cyclomethicone 15.0 15.0 5 Dimethicone 2.0 2.0 B 6 Bentonite 1.0 1.0 7 Example 1 7.0 - 8 Titanium dioxide - 7.0 9 Iron oxides Quantity Quantity C 10 Propylene glycol 5.0 5.0 11 Purified water Remaining amount Remaining amount D 12 Spices Quantity Quantity

<Production method>

1) Phase B was dispersed three times with a three-stage roller.

2) The prepared phases A and B were added to the kiln and then heated to 80 ° C.

3) When the prepared phase C was warmed to 80 ° C., the emulsion was gradually added to the kiln.

4) When the emulsification is completed, it was cooled and the D phase was introduced at 40 ° C, and then cooled to 25 ° C to float.

Formulation Example 3 and Comparative Formulation Example 3

Formulation Example 3 and Comparative Formulation Example 3 were prepared as a skin cover formulation using the composition of Table 4 below.

Prize number Name Formulation Example 3 (wt%) Comparative Formulation Example 3 (wt%) A One Ceresin 9.0 9.0 2 Squalene 8.0 8.0 3 Ranollin 10.0 10.0 4 Polyethylene 2.0 2.0 5 Phenyltrimethicone 10.0 10.0 6 Dimethicone 1.0 1.0 7 Glyceryl Trioctanoate Remaining amount Remaining amount B 8 Example 1 15.0 - 9 Titanium dioxide - 15.0 10 Iron oxides Quantity Quantity C 11 Spices Quantity Quantity

<Production method>

1) The phase A was heated to 80 ° C. to completely melt the wax phase.

2) The B phase was added to the A phase, followed by simple stirring, and then treated three times with a three-stage roller.

3) The mixed phases A and B were heated again to be completely dissolved, and then phase C was added and stirred.

4) When the A, B, and C phases were evenly mixed, the contents were filled in Sara and cooled at room temperature.

Formulation Example 4 and Comparative Formulation Example 4

Formulation Example 4 and Comparative Formulation Example 4 were prepared as sunscreen formulations using the compositions of Table 5 below.

Prize number Name Formulation Example 4 (wt%) Comparative Formulation Example 4 (wt%) A One Fiji 100 Stearate 1.2 1.2 2 Dicaprylyl Maleate 10.0 10.0 3 C12-C15 Alkylethylhexanoate 10.0 10.0 4 Polyglyceryl-3-methylglucose disitrate 2.0 2.0 5 C18-C36 Acid Glycol Ester 2.0 2.0 6 Tocopherol Acetate 0.1 0.1 7 Octylmethoxycinnamate 2.0 2.0 8 Example 1 5.0 - 9 Titanium dioxide - 5.0 B 10 Potassium cetylphosphate 0.5 0.5 11 Xanthan Gum 0.2 0.2 12 Magnesium Aluminum Silicate 1.0 1.0 13 Purified water Remaining amount Remaining amount C 14 Spices Quantity Quantity

<Production method>

1) The phase A was uniformly dispersed with a homo mixer while warming up to 80 ° C.

2) Disperse | distribute evenly, adding the said components 10-12 while heating the purified water of phase B.

3) The phase B warmed up to 80 ° C. was emulsified while slowly added to the heated A phase.

4) After the emulsification was completed, the mixture was cooled and the C phase was added at 40 ° C.

5) The solution of 4) was cooled to 25 ° C and filtered.

[Test Example 4]

The visual expression of the natural color expression and clarity of Formulation Example 1 and Comparative Formulation Example 1 was applied to the facial skin of 50 female panels from 25 to 40 years old, and then natural color expression and transparency through sensory evaluation. Judgment was made by relative evaluation, and the results are shown in Tables 6 to 9 below.

<Evaluation Criteria>

Formulation Example 1 and Comparative Formulation Example 1 were compared to evaluate the number of favorable populations.

Two-way cake preference division Natural color expression Transparent Formulation Example 1 47 people 45 persons Comparative Formulation Example 1 3 people 5 people

Liquid Foundation Preference division Natural color expression Transparent Formulation Example 1 45 persons 41 people Comparative Formulation Example 1 5 people 9 persons

Skin cover rating division Natural color expression Transparent Formulation Example 1 47 people 40 persons Comparative Formulation Example 1 3 people 10 people

Sun Cream Preference division Natural color expression Transparent Formulation Example 1 48 people 47 people Comparative Formulation Example 1 2 people 3 people

As can be seen from Tables 6 to 9, it was confirmed that Formulation Example 1 containing the manganese-titanium oxide pigment of the present invention exhibited superior and superior preference to natural color expression and transparency expression than Comparative Formulation Example 1.

[Test Example 5]

The model coated with Formulation Example 1 on the skin and the model coated with Comparative Formulation Example 1 on the skin were photographed using a digital camera (Canon EOS 20D) in a slightly dark place, and sensory to 50 female panelists aged 25 to 40 years. The evaluation examined the preference of the reduced state of the whitening phenomenon, the results are shown in Table 10 and FIG.

Whitening phenomenon reduction evaluation division Very good Great usually Bad Very bad Formulation Example 1 25 persons 20 people 5 people - - Comparative Formulation Example 1 - - 7 people 23 persons 20 people

As described above, when the manganese-titanium oxide pigment of the present invention is used to make up cosmetics for preventing makeup and burnout, it provides natural color expression and transparency and reduces whitening phenomenon (PWE) when taking pictures in dark places. It was confirmed that there is.

Claims (5)

A manganese-titanium oxide prepared by replacing a portion of titanium ions (Ti ⁴⁺ ) of ultrafine titanium dioxide with manganese ions (Mn ²⁺ ) by mixing titanium tetrachloride and manganese chloride in a weight ratio of 97.0: 3.0 to 96.0: 4.0. The oxide of claim 1, wherein the oxide is used as a cosmetic pigment. Method for preparing manganese-titanium oxide prepared by neutralization hydrolysis of Scheme 1, in which titanium tetrachloride (TiCl ₄ ) and manganese chloride (MnCl ₂ ) are dissolved in purified water and sodium hydroxide is added to the solution. Scheme 1

The method of claim 3, wherein the mixing ratio of titanium tetrachloride and manganese chloride is mixed in a weight ratio of 97.0: 3.0 to 96.0: 4.0. The cosmetic composition containing the manganese titanium oxide of Claim 1 in the quantity of 1-20 weight% with respect to the cosmetic composition total weight.

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