JPH0586820B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a surface-treated powder using organosiloxane (hereinafter referred to as silicone). More specifically, the present invention relates to a powder whose color separation, active site blocking, and dispersibility are improved by silicone treatment using plasma irradiation. [Prior Art] Among cosmetics, especially makeup cosmetics, large amounts of powders such as inorganic powders and organic powders are blended, but active sites exist 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. In addition, powders are often blended into the oil phase of makeup cosmetics in order to reduce makeup discoloration, but it is extremely difficult to uniformly disperse inorganic powders in the oil phase. Have difficulty. To solve these problems, treating powders with silicone has been practiced for some time. However, in conventional silicone treatments, surface reactions are often carried out in a solvent while adding a catalyst, making the process complicated. Furthermore, when drying the surface-treated powder, problems such as agglomeration of the powder and residual catalyst may occur. Remaining catalyst is undesirable because it causes cooling of the coated silicone and decomposition and deterioration of cosmetic ingredients such as fragrances. Also, JP-A-56-16404, JP-A-55-
In Publication No. 136213 and Japanese Patent Application Laid-open No. 56-29512,
A technique is disclosed in which silicone and oil are added and the powder surface is baked. However, these methods have the fatal drawback of impairing the color tone of heat-sensitive organic and inorganic powders, such as yellow iron oxide and deep blue. Further, JP-A-56-16404 describes a method for treating powder with silicone using a mechanochemical reaction. Since this method does not require baking, it can also be applied to powders with poor temperature stability. However, since the mechanochemical method inevitably involves crushing force, it has the disadvantage that it destroys some powder shapes (particularly powders characterized by plate-like or spherical shapes). Furthermore, it is difficult to treat powders such as titanium dioxide, which tend to aggregate when stirred, alone. [Problems to be Solved by the Invention] In view of these circumstances, the present inventors have discovered that the process is simple, there is no agglomeration of powder or residual catalyst, there is no deterioration of the powder due to heat, and the surface of the powder can be effectively improved. As a result of extensive research into whether there is a way to coat this with silicone, we have completed the present invention. [Means for Solving the Problems] That is, the present invention provides powders with one or more of the following linear organosiloxanes represented by (a) and cyclic organosiloxanes represented by (b). It is a powder surface-treated with organosiloxane obtained by plasma irradiation.

[ka]

[Chemical formula] {R ₁ represents a methyl group or an ethyl group. R ₂ may be the same or different and represent a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. However, two hydrogen atoms do not exist bonded to the same silicon atom. m represents a value of 1 to 250, and n represents a value of 3 to 250. } Hereinafter, the configuration of the present invention will be explained in detail. The plasma used in the present invention belongs to low-temperature plasma, and the plasma can be generated by corona discharge, glow discharge, etc. in low frequency and high frequency regions. The atmosphere may be under vacuum or in the presence of nitrogen, oxygen, hydrogen, argon, helium, or air. The processing time must be within a range that does not adversely affect the hue change or weather resistance of the powder, and the appropriate processing time should be selected depending on the type of plasma gas used, plasma output, type of powder being processed, etc. There is a need. Specifically, the Practical Line (Sankyo Dengyo Co., Ltd.)
Plasma irradiation can be carried out using a commercially available product such as a commercially available product. 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. The silicone used in the present invention is a linear or cyclic organosiloxane and is represented by the above formula (a) or (b). One or a combination of two or more of these may be selected and applied. The smaller the number of n in the formula, the lower the boiling point and the greater the amount that is volatilized and adsorbed to the powder. In particular, trimers are most suitable because they are easier to polymerize due to their steric properties. The amount of silicone used in the present invention is generally 0.1 to 20% by weight based on the powder.
If it is less than 0.1% by weight, it is insufficient to produce a treatment effect, and if it exceeds 20% by weight, it is undesirable because the powder tends to agglomerate if it is excessive. The powders used in the present invention are inorganic and organic powders commonly used in cosmetics. For example, inorganic powders include talc, kaolin, bentonite, silicic anhydride, mica, titanium mica,
Zirconium oxide, magnesium oxide, zinc oxide, titanium dioxide, calcium carbonate, magnesium carbonate, yellow iron oxide, red iron oxide, black iron oxide, ultramarine blue, chromium oxide, chromium hydroxide, deep blue, alumina, etc. Organic powders include: Red No. 2, No. 3,
No. 102, No. 104 (1), No. 105, No. 106, No. 226, 227
No., No. 230, No. 240 (2), No. 231, No. 232, No. 401,
No. 502, No. 503, No. 504, No. 506, Orange No. 205,
No. 207, No. 402, Yellow No. 4, No. 5, No. 202, No. 203,
No. 402, No. 403, No. 406, No. 407, Green No. 3, No. 201,
No. 204, No. 205, No. 402, Blue No. 1, No. 2, No. 205,
Brown No. 201, purple No. 401 and black No. 401 aluminum lake, red No. 104 (1), orange 205
No. 402, Yellow No. 4, No. 5, No. 203, Green No. 402,
Blue No. 1 and 202 Barium Lake, Amber No. 205, Yellow No. 4, No. 5, 203, Green No. 205 and Blue No. 1 Zirconium Lake, Red 202
No. 203, 204, 205, 206, 207, 208
No. 219, 220, 221, 226, 228, 404
No. 405, orange No. 204, No. 204, and No. 404. These powders may be processed individually, or one type or two or more types may be mixed and processed. [Effects of the Invention] The treated powder obtained as described above has the following characteristics. Since there is no baking process, even powders that are sensitive to heat can be processed without discoloration. Since no mechanical force is used, particles of any shape can be processed without breaking them.
No aggregation occurs. The inorganic powder has almost perfect hydrophobicity and water repellency. The sequestration of surface activity is almost complete. [Example] The present invention will be described in more detail below with reference to Examples. The present invention is not limited thereby. Example 1 10 g of yellow iron oxide and dimethylcyclosiloxane (in structural formula (b), R ₂ is a methyl group, n = 3)
Mix 0.185g uniformly and add nitrogen 220g using a practical line (manufactured by Sankyo Dengyo Co., Ltd.).
Low frequency (5KHz), output while flowing ml/min
Plasma irradiation was performed for 10 minutes under 30W conditions. Comparative Example 1 25 g of a hexane solution containing 10 g of yellow iron oxide and 0.185 g of dimethylsiloxane (n=3) was added, stirred well, and then evaporated to dryness. After that, it was baked at 250℃. Comparative Example 2 Put 10 g of yellow iron oxide and 0.185 g of methylhydrogen polysiloxane (molecular weight 2600) into a ball mill, and
Mixing and milling was carried out for minutes. Regarding each of Example 1, Comparative Example 1, Comparative Example 2, and untreated yellow iron oxide, hydrophobicity, water repellency,
Activity against color change and fragrance was determined. -Hydrophobicity- Pour 5 ml of ion exchange water into a 10 ml sample tube, add 0.1 g of sample, and shake. The criteria for determining hydrophobicity are as follows. ×... Dispersed in the water. △...Although it was hydrophobic, some of it was dispersed in water. 〇... It is hydrophobic and the entire amount floated on top of water. The results are shown in Table-1.

[Table] Untreated yellow iron oxide was dispersed in water, but in Example 1 and Comparative Example 2 it was hydrophobic and floated on water, and in Comparative Example 1, the treatment was not complete and some of it was dispersed in water. did. -Hydrophobicity- 0.5g of the sample was molded into pellets using a tablet molding machine, and 50μ of distilled water was dropped onto the pellets. The measurement was carried out twice by measuring the contact angle using a microscope, once immediately after dropping and once 30 minutes later. The larger the contact angle, the higher the water repellency. -Degree of discoloration- A sample was filled into a cell for powder measurement, and measured in the range of 380 nm to 780 nm using a Color Analyzer Model 607 manufactured by Hitachi, Ltd. The measurement results are expressed as L, a, and b, and the color difference ΔE before and after treatment is shown in Table 1.
It can be seen that the dye ΔE of Example 1 is significantly smaller than that of the comparative example. - Decomposition of perfume - 20 mg of powder was fixed with quartz wool in a Pyrex glass tube with an inner diameter of 4 mm, and linalool, one of the perfume components, was passed through the pipe at 185°C to measure its decomposition behavior. Linalool injection volume: 0.3 μ, carrier gas: nitrogen flow rate of 50 ml/min. The analysis was carried out using a Shimadzu GC-7A.
PEG-20M, 0.31mm x 25mg, column temperature 80℃
(4 min) → 220°C, heating rate was 5°C/min. The indications in the table are as follows. Untreated yellow iron oxide △ Substances that decompose more rapidly than untreated yellow iron oxide
× Less decomposition than untreated yellow iron oxide
〇 The figure also shows the results of measuring the decomposition of linalool using GC. Figure 1 shows the GC pattern of linalool decomposition by untreated yellow iron oxide. a is the peak of linalool, and ~5 is the peak of decomposition products. Figure 2 is a GC pattern of linalool decomposition using the treated powder of Example 1. It can be seen that the amount of decomposed products decreased compared to the untreated product, and the linalool degrading activity was eliminated. Figure 3 shows the linalool decomposition pattern of the treated powder of Comparative Example 1.
There is no linalool peak, but peaks of decomposition products 1 to 8 are present. In other words, the decomposition activity of the powder of Comparative Example 1 was increased compared to the untreated powder, indicating that the fragrance stability was worsened. Figure-4 is Comparative Example 2
This is the decomposition pattern of linalool by treated powder. Although the activity is weaker than in Comparative Example 1, and unreacted linalool remains, it is clear that the activity is stronger than that of the untreated product. As described above, Comparative Examples 1 and 2 have stronger linalool decomposition activity and worse fragrance stability than untreated samples. On the other hand, in Example 1, the linalool decomposition activity was weakened and the fragrance stability was improved. Comprehensive evaluation of Table 1 shows that Example 1 maintains almost the same color as the untreated sample, and has hydrophobic and water-repellent properties. Furthermore, the stability of fragrances has been improved, and it is considered to be an extremely excellent treated powder when blended into cosmetics and the like. Example 2 5 g of ultramarine blue and 1.0 g of octamethyltetracyclosiloxane (n=4) were mixed uniformly,
Plasma ashing device LTA-4SN type (Yanagimoto Seisakusho Co., Ltd.)
(manufactured by Nitrogen Co., Ltd.) to maintain a vacuum level of 1.0 mmHg.
High frequency (13.56 MKz) was applied at 200 ml/min, output was 20 W, and plasma was irradiated for 10 minutes to obtain treated powder. The obtained powder had good hydrophobicity, water repellency and fragrance stability. Example 3 5 g of ultramarine blue and 0.5 g of phenylmethylcyclosiloxane (in structural formula (b), one of R ₂ is a phenyl group and the other is a methyl group, n = 30) were mixed uniformly, Using a line (manufactured by Sankyo Dengyo Co., Ltd.), low frequency (5KHz) is applied and output in the atmosphere.
Plasma irradiation was performed at 30 W for 10 minutes to obtain a powder with good hydrophobicity, water repellency, and fragrance stability. Example 4 5 g of Red No. 226 and methylhydrogen polysiloxane (structural formula (a), all R _1s are methyl groups, one R ₂ is a methyl group, the other is a hydrogen atom, average molecular weight
2600) 0.2g was mixed uniformly and heated with argon using a practical line (manufactured by Sankyo Dengyo Co., Ltd.).
Output by applying low frequency (5KHz) through 200ml/min
After plasma irradiation at 30W for 10 minutes, a powder with good hydrophobicity, water repellency, and fragrance stability was obtained. Example 5 5 g of kaolin and 0.1 g of trimethyltricyclosiloxane (n=3) were mixed uniformly,
Plasma ashing device LTA-4SN type (Yanagimoto Seisakusho Co., Ltd.)
Oxygen was used to maintain a vacuum level of 1.0 mmHg using
Plasma irradiation was performed for 10 minutes at a high frequency (13.56 MHz) output of 20 W at 100 ml/min to obtain a powder with good hydrophobicity, water repellency, and fragrance stability.

[Brief explanation of the drawing]

Figures 1 to 4 show the decomposition of a fragrance ingredient (linalool) by the powder coated with the organosiloxane of the present invention and other powders.
The results measured by GC are shown. Figure 1: Untreated yellow iron oxide, Figure 2: Treated powder of Example 1, Figure 3: Treated powder of Comparative Example 1, Figure 4: Treated powder of Comparative Example 2.

Claims (1)

[Scope of Claims] 1. An organosiloxane obtained by plasma irradiation of a powder together with one or more of a linear organosiloxane represented by (a) below and a cyclic organosiloxane represented by (b) below. Powder surface treated with siloxane. [C] [C] {R ₁ represents a methyl group or an ethyl group. R ₂ may be the same or different and represent a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. However, two hydrogen atoms do not exist bonded to the same silicon atom. m represents a value of 1 to 250, and n represents a value of 3 to 250. } 2. The powder according to claim 1, wherein the plasma irradiation is low temperature plasma irradiation. 3. Claim 2, 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.
Powder as described in section. 4. The powder according to any one of claims 1 to 3, wherein the irradiation atmosphere is any one of vacuum, nitrogen, oxygen, hydrogen, argon, helium, or air. 5. The powder according to any one of claims 1 to 4, wherein the amount of organosiloxane blended is 0.1 to 20% by weight based on the powder. 6 The powder is talc, kaolin, bentonite,
Silicic anhydride, mica, titanium mica, zirconium oxide, magnesium oxide, zinc oxide, titanium dioxide, calcium carbonate, magnesium carbonate, yellow iron oxide, red iron oxide, black iron oxide, ultramarine blue, chromium oxide, chromium hydroxide, navy blue or alumina. A powder according to any one of claims 1 to 5. 7 The powder is red No. 2, No. 3, No. 102, No. 104,
No. 105, No. 106, No. 226, No. 227, No. 230 (1), 240
No. 231, 232, 401, 502, 503, 504
No., No. 506, Orange No. 205, No. 207, No. 402, Yellow No. 4, No. 5, No. 202 (1), No. 202, No. 203, No. 402
No. 403, No. 406, No. 407, Green No. 3, No. 201,
No. 204, No. 205, No. 402, Blue No. 1, No. 2, No. 205,
Aluminum lake of brown No. 201, purple No. 401 and black No. 401, red No. 104, orange No. 205,
Barium Lake No. 402, Yellow No. 4, No. 5, No. 203, Green No. 402, Blue No. 1 and No. 202, Amber No. 205, Yellow No. 4, No. 5, No. 203, Green No. 205 and Blue No. 1 Zirconium lake, red No. 202,
No. 203, No. 204, No. 205, No. 206, No. 207, No. 208,
No. 219, No. 220, No. 221, No. 226, No. 228, No. 404,
405, Daidai-iro No. 204, No. 204, or No. 404. The powder according to any one of claims 1 to 5.