JPS6330407A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic having high safety and water-repellency and giving smooth feeling to the skin and durable make-up, by irradiating a mixture of a specific organosiloxane and powder with low-temperature plasma and compounding the obtained surface-treated powder to a cosmetic base. CONSTITUTION:A mixture of powder and one or more organosiloxanes of formula (R1-R5 are H or 1-30C hydrocarbon group which may be substituted with one or more halogen atoms provided that two H atoms are not bonded to one Si atom; m is integer of 1-250; n is 0, 1 or 2) is subjected to low- temperature plasma irradiation and the obtained surface-treated powder is compounded to a cosmetic base to improve the water-repellency, stability and applicability of conventional powder-compounded cosmetic and to obtain a cosmetic having the above effects. The low-temperature plasma irradiation can be carried out by the corona discharge or glow discharge of low-frequency or high-frequency range in vacuum or in the presence of nitrogen, oxygen, hydrogen, argon, helium or air.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to cosmetics, and particularly to cosmetics that have high water repellency, a smooth feeling on use, little makeup fading, and high stability.

[Prior Art] Among cosmetics, especially makeup cosmetics, a large amount of powder such as inorganic powder and organic powder is blended, and active sites are present on the surface of most of the powders. These active sites cause components such as fragrances contained in makeup cosmetics to decompose, causing problems such as odor and deterioration. As a method to solve these problems, treating powder with silicone has been used for some time.

In many conventional silicone treatments, a surface reaction is performed in a solvent while adding a catalyst, and this method involves complicated steps. Furthermore, when drying the surface-treated powder, problems such as agglomeration of the powder and residual catalyst occur. In particular, residual catalyst is undesirable because it causes deterioration of the coated silicone and decomposition and deterioration of cosmetic ingredients such as fragrances.

Also, JP-A-56-16404, JP-A-55-1
No. 36213 and Japanese Unexamined Patent Publication No. 56-29512 disclose a technique in which silicone and oil are added to powder and the surface of the powder is baked. However, these methods have the fatal drawback of impairing the color tone of heat-sensitive organic and inorganic powders, especially powders such as yellow iron oxide and dark blue, and are not suitable for makeup cosmetics.

Further, JP-A-56-16404 describes a method for treating powder with silicone using a mechanochemical reaction. Since this method does not require a baking treatment, it can also be applied to powders with poor temperature stability. However, this mechanochemical method inevitably involves crushing force, which may destroy the shape of the powder (particularly powders that are plate-shaped or spherical), which can significantly change usability. There was a drawback.

In addition, conventional silicone treatments often use methylhydrogen polysiloxane, which enhances the treatment effect due to the reactivity of its 5i-H group, but the 5f-H group becomes unstable over time, and water, ethanol, etc. This has the disadvantage that when it comes into contact with the product, hydrogen gas is generated, which impairs the stability of the product.

[Problems to be Solved by the Invention] As described above, conventional powdered cosmetics have many problems and do not satisfy water repellency, stability, and usability. That is, with conventional silicone coatings, it has not always been possible to obtain coated powders with sufficient water repellency and stability.

In view of these circumstances, the inventors of the present invention have conducted extensive research in order to obtain a cosmetic that has sufficient water repellency, is highly stable, and has an excellent feel when used. It was discovered that an excellent cosmetic that solved the above problems could be obtained by blending the resulting powder, and the present invention was completed.

[Means for Solving the Problems] That is, the present invention provides a surface-treated powder obtained by irradiating a mixture of powder and one or more organosiloxanes represented by the following formula (a) with low-temperature plasma. This cosmetic is characterized by containing:

Formula (a) (R+R2SiO)m(R3R4RsSiOo, 5)n
(In the formula, R1, R2, R3, R4 and R5 each represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. However, no two hydrogen atoms bond to the same silicon atom. In addition, the number of hydrocarbon groups is small (both may be substituted with one or more halogen atoms, m is an integer of 1 to 250, and n is O or 2).Hereinafter, the present invention will be explained in detail. .

The organosiloxane used in the present invention has the above formula (
a), more specifically, a linear organosiloxane represented by the following formula (b) or a cyclic organosiloxane represented by the formula (C).

(Blank below) (b) (In the formula, R6 and R7 may be the same or different and are selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a phenyl group, and a halogen group, but hydrogen atoms are the same (It does not exist with two atoms bonded to a silicon atom, and x is a value of 1 to 250, and y is a value of 3 to 250.) The smaller the number of y in formula (c), the lower the boiling point and the more volatile it is. Trimers are preferred because a large amount of them can be adsorbed onto the powder, and trimers are particularly preferred because they are easily polymerized due to their steric properties. However, even those with a high boiling point can be added and processed in liquid form.

In the present invention, one or more of the above organosiloxanes can be selected and applied. The amount of organosiloxane used is generally preferably 0.1 to 20% by weight based on the powder. If it is less than 0.1% by weight, the treatment effect is insufficient, and if it exceeds 20% by weight, it is not preferable because it is too much and the powder tends to agglomerate.

The powder used in the present invention is a powder normally used in cosmetics, such as talc, kaolin, sericite,
Muscovite, synthetic sea urchin, phlogopite, rhodotite, biotite, Lithia B
Mother, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, bitroxyapatite, zeolite , boron nitride, inorganic powders such as ceramic powders, nylon powders, polyethylene powders, benzoguanamine powders, tetrafluoroethylene powders, distyrene benzene vinyl polymer powders, organic powders such as microcrystalline cellulose, titanium oxide, zinc oxide, etc. Inorganic white pigments, inorganic red pigments such as iron oxide (red iron oxide), iron titanate, inorganic brown pigments such as 7-iron oxide, inorganic yellow pigments such as yellow iron oxide, ocher, black iron oxide, carbon black, etc. Inorganic black pigments, inorganic purple pigments such as mango violet and cobalt violet, inorganic edge color pigments such as chromium oxide, chromium hydroxide, and cobalt titanate, inorganic blue pigments such as ultramarine and deep blue, titanium oxide coated mica, titanium oxide coated Pearl pigments such as bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, fish scale foil, colored titanium oxide coated tarad mica, metal powder pigments such as aluminum powder, copper powder, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226
No., Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue 404
Organic pigments such as No. 3, Red No. 3, Red No. 104, Red No. 106
No., Red No. 227, Red No. 203, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 2
Organic pigments such as zirconium, barium, or aluminum lake of No. 02, yellow No. 203, green No. 3, and blue No. 1, natural pigments such as chlorophyll, β-carotene, etc. are used, but are not limited thereto.

Next, in the present invention, the organosiloxane and the powder are irradiated with low-temperature plasma, but the plasma used at this time can be generated by corona discharge, glow discharge, etc. in the low frequency and high frequency ranges. can.

This low-temperature plasma irradiation has made it possible to use dimethyl-type organosiloxane, which could hardly be treated in the past. Not only does it show better water repellency than treatment with the methyl hydrogen type, it also makes it possible to produce a powder that is surprisingly stable against water and methanol.

The irradiation atmosphere is under vacuum, nitrogen, oxygen, hydrogen, argon,
Either in the presence of helium or air may be used.The treatment time is preferably within a range that does not adversely affect the hue change or weather resistance of the powder, and the type of gas used for rinsing, the output of the plasma, the type of powder to be treated, etc. Although an appropriate treatment time can be selected according to the following, it is preferably 20 seconds to 60 minutes.

Specifically, low-temperature plasma irradiation may be performed using, for example, Practical Line (manufactured by Sankyo Dengyo ■). Practical lines can be processed either directly in the atmosphere or with specific gases in contact with the powder. It is particularly suitable for processing on an industrial scale.

By blending 0.5 to 100% by weight of the treated powder obtained as above, it can be used to create makeup cosmetics such as foundation, pressed powder, nail enamel, eye shadow or lipstick, as well as skin cosmetics and hair cosmetics. Cosmetics such as cosmetics can be manufactured.

In addition to the organosiloxane of the formula (a) and the treated powder that has been subjected to low-temperature plasma treatment, the cosmetic composition of the present invention may contain ingredients that are generally added to cosmetic compositions, such as squalane, liquid paraffin, petrolatum, etc., if necessary. Microcrystalline wax, osikelite, ceresin, myristic acid, valmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, hexadecyl alcohol, oleyl alcohol, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, 2-octyldodecyl gum ester, neopentyl glycol-2-ethylhexanate, isooctyl triglyceride, 2-octyl dodecyl oleate, isopropyl myristate, isostearic triglyceride, coconut oil fatty acid triglyceride, olive oil, Avocado oil, beeswax, myristyl myristate, mink oil, lanolin, various hydrocarbons such as dimethylpolysiloxane, higher fatty acids, fats and oils, esters, higher alcohols, waxes, oils such as silicone oil, acetone, toluene, butyl acetate. , organic solvents such as ethyl acetate, resins such as alkyd resins and urea resins, plasticizers such as camphor and acetyltributyl citrate, ultraviolet absorbers, antioxidants, preservatives, surfactants, humectants,
Flavors, water, alcohol, thickeners, etc. can be added.

[Example] Next, the present invention will be explained in more detail by giving examples. However, the present invention is not limited thereto.

The blending amount is in weight%. Prior to examples, evaluation methods will be explained.

(Evaluation method) A sensory test was conducted by 20 expert panelists regarding spread and makeup durability. Ratings were expressed on a 5-point scale from 1 to 5 points.

1 Bad 2　　　　　　　　Slightly bad 3 Normal 4 Somewhat good 5 Good The results are expressed as average values as shown below.

o 4.5-5.0 o 3.5-4.4 △ 2.5-3.4 xx 1.0-1.4 × 1.5-2.4 For water repellency, press-molded powder makeup 0.5 ml of water was gently dropped onto the material, and the time for the water to soak in was measured.

The results are expressed as follows.

o Does not soak in 0 2 hours to 6 hours △ 30 minutes to 2 hours x 10 minutes to 30 minutes A sensory comparison was made between the

The results are expressed as follows.

0 It is almost the same as control.

Q: There is a strange odor compared to the control.

×　The odor is quite strange compared to the control.

Example 1 Pressed powder muscovite 20g and dimethylsiloxane (n=3) 0.3
Mix 7g evenly and apply a practical line (
Treated mica was obtained by plasma irradiation for 10 minutes under low frequency (5 kHz) and output 30 W conditions using a Sankyo Dengyo ■Rie) while flowing nitrogen at 200 ml/win.

Talc was similarly treated to obtain treated talc. Using this treated powder, pressed powder shown below was manufactured.

(1) Treated muscovite $30.0 (2
) Treated talc 65.8X (3)
Iron oxide pigment 0.1% (4)
Squalane 2.0χ(5)2
-Ethylhexyl palmitate 2.0z (6) Fragrance
0.1z (1) to (3) were mixed in a Henschel mixer, and a heated mixture of (4) and (5) was sprayed thereon, and after mixing, the mixture was crushed and molded into a medium plate to obtain a pressed powder.

Comparative Example 1 Comparative Example 1 was obtained in the same manner as in Example 1, except that the treated muscovite and talc in the formulation of Example 1 were replaced with untreated muscovite and talc.

The evaluation results are shown in Table 1. The results show that Example 1 is superior.

(Margin below) Table 1 Example 2 Dual use foundation 13 parts titanium oxide, 13 parts muscovite, 45 parts sericite,
10 parts of octamethyltetracyclosiloxane (n=4) were mixed uniformly with 25 parts of talc and 4 parts of iron oxide pigment, and the mixture was vacuum-treated using a plasma ashing device LTA-4SN model (Yanagimoto Seisakusho @Cabi). High frequency (13,56 mmHg)
MHz) and output power of 20 W for 10 minutes to obtain a mixed treated powder. The following foundation was manufactured using this mixed powder.

(1) Mixed processed powder 84.0X
(2) 2-ethylhexyl palmitate 5.5X (3)
Liquid paraffin 5.0x (4)
Sorbitan Sesquiolate 5.0x (5)
Preservative 0.3x (6) Fragrance 0.2z (1) (2
) to (6) were added and mixed by heating and melting, and then pulverized, and the mixture was filled into a medium dish to obtain a dual-purpose foundation that could be used with or without water. Comparative Example 2 Comparative Example 2 was obtained in the same manner as Example 2, except that the mixed treated powder of Example 2 was replaced with a metal soap treated powder of the same powder composition.

The evaluation results are shown in Table 2. The results show that Example 2 is superior.

Table 2 Example 3 Powder eyeshadow ultramarine 10g and phenylmethylpolysiloxane (n=30
) 0.5g was mixed uniformly, and using a practical line (manufactured by Sankyo Dengyo ■), low frequency (5g
A treated powder was obtained by plasma irradiation for 10 minutes under conditions of 30 W (kHz) and 30 W output.

In the same manner, talc, Burr pigment, and iron oxide pigment were treated to obtain treated powders. The eye shadow shown below was manufactured using this treated powder.

(1) Treated talc 20.0% (2
) Treated Burr Pigment 18.5 pieces (3
) Processed Gunjo 50.0! (4)
Treated iron oxide 4.0x (5)
Squalane 4.0 pieces (6)
Cetyl-2-ethylhexanoate 2.0z(7)
Sorbitan sesquiolate 1.0 units (8)
Preservative 0.3z (9)
Fragrance 0.2x (1) ~ (4
) in a Henschel mixer, and add (5) to (9) to this.
) was heated, melted, mixed, pulverized by spraying, and molded into a medium plate to obtain an eye shadow.

Comparative Example 3.4 Comparative Example 3 was obtained in the same manner as in Example 3, except that the treated powder of Example 3 was replaced with silica-treated ultramarine and the other powders were replaced with untreated powder.

Comparative Example 4 was also prepared in the same manner as Example 3, except that all of the treated powder in Example 3 was replaced with untreated powder.

Table 3 shows the evaluation results of Example 3, Comparative Example 3, and Comparative Example 4. The results show that Example 3 is superior. In addition,
When products containing ultramarine blue are mixed in a Henschel mixer, there is usually a hydrogen sulfide odor, but in Example 3 of the present invention, there was no hydrogen sulfide odor. It was also excellent in gloss.

Example 4 10 g of emulsified foundation yellow iron oxide and 0.4 g of methylhydrogen polysiloxane (molecular weight 2600) were mixed uniformly, and 20 g of argon was added using a practical line (manufactured by Sankyo Dengyo ■).
Low frequency (5k) Iz) through 0m1/win, output 3
Plasma irradiation was performed for 10 minutes under 0W conditions to obtain treated powder.

In the same manner, treated black iron oxide, treated red iron oxide, and treated talc were obtained. Using these, the emulsified foundation shown below was manufactured.

(1) Stearic acid 0.4X (
2) Isostearic acid 0.3χ(3
) Cetyl-2-ethylhexanoate 4.0% (4
) Liquid paraffin 11.0% (5)
P OE (10) Stearyl ether 2.0% (
6) Treated talc 18.0% (
7) Treated yellow iron oxide 2. Og(8)
Treated red iron oxide 0.8% (9)
Treated black iron oxide 0.2x (10) Cetyl alcohol 0.3x (11) Preservative
0.09X (12) Triethanolamine 0.42% (13) Propylene glycol 5.0% (14) Ion exchange water 54.19% (15) Fragrance
0.3% (1) to (11) to 8
The mixture was heated to 5°C and mixed. A mixture of (12) to (14) heated and mixed at 85° C. was gradually added to the mixture to emulsify it, and the mixture was stirred and cooled. While cooling, (15) was added and filled into a container to obtain an emulsified foundation.

Comparative Example 5 Comparative Example 5 was obtained in the same manner as in Example 4, except that each of the treated powders in Example 4 was replaced with untreated powder.

In Example 4, the pigment dispersion stability was better than in Comparative Example 5, and the coating color was close to the external color.

Example 5 10 g of nail enamel red iron oxide and 0.2 g of hexamethyltricyclosiloxane (n = 3) were mixed uniformly and treated using a plasma ashing device LTA-4SN model (specially manufactured by Ikumoto Seisakusho). Oxygen 100m to maintain vacuum level 1.0mmHg
Plasma irradiation was performed for 10 minutes at a high frequency (13.56 MHz) and an output of 20 W at a rate of 1/min to obtain treated red iron oxide. A treated titanium dioxide and a treated pearl pigment were obtained in the same manner. Using these, the nail enamel shown below was manufactured.

(1) Nitrocellulose 12.0%
(2) Modified alkyd resin 12.0X
(3) Acetyltributyl citrate 5.0χ(
4) Butyl acetate 38.4X (
5) Ethyl acetate 6.0% (6)n
-Butyl alcohol 2.0x(7) Toluene 21.0%(8) Treated red iron oxide 0.5x(9) Treated titanium dioxide 0.1x(10) Treated pearl pigment
2.0X (11) Organically modified montmorillonite 1.0% (1) to (3), (5) to (7)
A part of (4) is dissolved, a gel-like mixture of (11) and the remainder of (4) is added and mixed, and (8) to (10) are added and mixed, The mixture was filled into a container to obtain nail enamel.

Comparative Example 6 Nail enamel was produced in the same manner as in Example 5, except that each treated powder in Example 5 was replaced with untreated powder.

Example 5 had better pigment dispersion stability than Comparative Example 6,
There was no powder adhesion to the bottle, and the product had good stability.

Example 6 UV Protection Stick Treated titanium dioxide, treated talc, treated mica and treated iron oxide were obtained according to the method of Example 5. A UV protection stick was manufactured using this treated powder.

(1) Treated titanium dioxide 20.0%
(2) Talc 10.0 pieces (3) Mica 11. Oχ
(4) Iron oxide 0.5x (
5) Carnauba wax 1.0% (6
) Solid paraffin 3.0% (7
) Liquid paraffin 45.0% (8
) Isopropyl myristate 8.0% (9) Sorbitan sesquiolate 1.5X (10) Fragrance
Pour appropriate amounts (7) and (8) into the pot,
Heat to 80-90°C and add 5) and (6) to dissolve. (1) to (4) were added thereto and dispersed uniformly, and after degassing, (10) was added and gently stirred. This was poured into a container at 80°C and cooled to room temperature to obtain an ultraviolet protection stick.

Comparative Example 7 Comparative Example 7 was prepared in the same manner as in Example 6, except that the treated powder was replaced with each untreated powder in the formulation of Example 6.
I got it.

In Example 6, the dispersibility of titanium dioxide was better than in Comparative Example 7, the finish was clean, and the sunburn prevention effect was high.

[Effects of the Invention] As is clear from the above, the treated powder blended into the cosmetic of the present invention is subjected to low-temperature plasma treatment with a specific organosiloxane, so that the powder surface is uniformly, firmly, and densely coated with silicone. Therefore, it is possible to obtain a cosmetic that has high water repellency, spreads well on the skin, is less prone to makeup smearing, and has good stability.

For example, fragrances blended into cosmetics are easily decomposed due to the activity of the powder and often cause odor, but this does not occur with the cosmetics of the present invention.

In addition, since the treated powder of the present invention exhibits excellent dispersibility in powder, oil, or solvent, when pearl pigment is used as the powder to be treated, it becomes a cosmetic with excellent gloss. When titanium dioxide is used as the powder to be treated, it is possible to obtain a cosmetic that does not aggregate, has excellent UV protection ability, and has a good makeup effect.

Red No. 202 has two crystal systems, α-type and β-type, and the β-type changes to the α-type in the presence of water, changing its color. Since the surface of such organic pigments is completely covered by the treatment according to the present invention, they do not change to the α-type even in the presence of water, resulting in stable cosmetics.

Ultramarine blue decomposes with acid and releases hydrogen sulfide, but the treatment of the present invention eliminates this problem.

Claims (4)

[Claims] (1) A cosmetic comprising a surface-treated powder obtained by irradiating a mixture of powder and one or more organosiloxanes represented by the following formula (a) with low-temperature plasma. Formula (a) (R_1R_2SiO)_m(R_3R_4R_5Si
O_0_. _5)_n (in the formula, R_1, R_2, R_3
, R_4 and R_5 each represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. However, two hydrogen atoms cannot exist bonded to the same silicon atom. Further, the hydrocarbon group may be substituted with at least one halogen atom. m is an integer from 1 to 250,
n is 0 or 2. ) (2) The cosmetic according to claim (1), wherein the low-temperature plasma irradiation is a low-temperature plasma irradiation generated by corona discharge or glow discharge in a low frequency or high frequency region. (3) Low-temperature plasma irradiation under vacuum, nitrogen, oxygen, hydrogen,
The cosmetic according to claim 1 or 2, which is prepared in an atmosphere of argon, helium, or air. (4) Claim No. 1, wherein the total amount of organosiloxane is 0.1 to 20% by weight based on the powder.
Cosmetics according to any one of paragraphs to (3).