JP3014219B2 - Modified powder and cosmetics containing it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified powder obtained by mixing powders and methylhydrogenpolysiloxane having a specific average degree of polymerization and then subjecting the mixture to heat treatment, and a cosmetic comprising the same. About. More specifically, the present invention relates to a cosmetic containing a modified powder which has less secondary agglomeration, is excellent in water repellency, and has excellent catalytic activity blocking ability.

[0002]

2. Description of the Related Art
When the powders are coated with methyl hydrogen polysiloxane, those having the structures shown in Chemical formulas 3 and 4 are used as the structure of methyl hydrogen polysiloxane. After methylhydrogenpolysiloxane is coated on the pigment surface, by heat treatment, occur _{2Si-H + 1 / 2O 2} = Si-O-Si + H 2 reaction such as polymerization in the pigment surface, a film Form.

[0003]

Embedded image (However, a = 30-50)

[0004]

Embedded image (However, m = n, m + n = 30 to 50)

In the conventional methyl hydrogen polysiloxane, in order to carry out this polymerization reaction sufficiently,
A high-temperature and long-time reaction such as heating at 5 ° C. for 5 hours was required. However, depending on the pigment, under such heating conditions, quality deterioration such as alteration or discoloration occurs, so that it is necessary to lower the reaction temperature, and there has been a problem that the polymerization reaction is incomplete.

Accordingly, the present inventors have analyzed the factors affecting the polymerization of methyl hydrogen polysiloxane, and found that
It was found that 1) reaction conditions (reaction temperature and time), 2) average polymerization degree and structure of methyl hydrogen polysiloxane, and 3) catalytic activity of the pigment itself were main factors.

As a result of diligent studies on the relationship between the average polymerization degree and structure of 2) methylhydrogenpolysiloxane and the reaction conditions of 1), those having the structure shown in Chemical formula 5 have the highest reactivity. Was found.

[0008]

Embedded image (However, k is the average number, k = 7 to 30)

Japanese Patent Application Laid-Open No. Sho 59-76009 describes the use of methyl hydrogen polysiloxane having a degree of polymerization of 40 or less.
No. 4709 describes the use of methylhydrogenpolysiloxane having a degree of polymerization of 3 to 500, but there is no description on the properties recognized in the present invention, and only general expressions are made.

[0010] Further, a fine particle powder such as a fine particle titanium oxide having a characteristic of being easily aggregated is coated with the methyl hydrogen polysiloxane specified in the present invention by a dry method without using a solvent. Under the lower reaction conditions, the reforming was successfully performed while minimizing the aggregation of the powder.

The modified fine particle powder thus obtained has the same ultraviolet protection ability as the untreated powder, and does not increase the hiding power or decrease the ultraviolet protection ability due to aggregation of the powder. Even when blended in cosmetics, it has the same ultraviolet protection performance and color as untreated powder. In the conventional wet processing, air blender, and other treatments, since granulation of the fine particle powder occurs, a decrease in ultraviolet protection performance and an increase in hiding power were observed as compared with untreated powder.

That is, the object of the present invention is to obtain a modified powder having less secondary coagulation and excellent water repellency under milder reaction conditions, and to stabilize the quality by blending this modified powder. An object of the present invention is to provide cosmetics having excellent properties.

[0013]

SUMMARY OF THE INVENTION The present invention relates to a modified powder which is obtained by mixing powders and a specific methylhydrogenpolysiloxane described below and then surface-treating the mixture under specified heating conditions and a modified powder thereof. The present invention relates to cosmetics containing powder.

Hereinafter, the configuration of the present invention will be described in detail. Powders used in the present invention, for example, yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black,
Color pigments such as ultramarine blue, zinc oxide, titanium oxide, cerium oxide, white pigments such as zirconium oxide, talc, mica,
Body pigments such as sericite, kaolin, mica, montmorillonite, pearl pigments such as mica titanium, barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate,
Metal salts such as magnesium silicate, organic-coated pigments such as N-acyl aspartic acid-coated mica and metal soap-treated pigments, nylon powder, silk powder, urethane powder, Teflon powder, cellulose powder, silicone powder, gold-dyed silk powder, polyethylene powder And inorganic powders such as silica and alumina; dyes such as Blue No. 404; lake pigments such as Red No. 2 Al lake; bentonite; and amino acid organic pigments. Particularly, fine particle powders such as fine particle titanium oxide, fine particle zinc oxide, fine particle iron oxide, fine particle lower titanium oxide, alumina-coated fine particle titanium oxide, and silica-coated fine particle titanium oxide are preferable. Examples of the fine particle titanium oxide include those having a primary particle diameter of 5 to 50 nm and a crystalline form of a rutile type, an anatase type, or an amorphous type.
The amorphous type may or may not be subjected to treatment such as removal of impurities and reduction in catalytic activity.

The methylhydrogenpolysiloxane used in the present invention can be used alone or as a mixture of two or more of those having a structure represented by the following general chemical formula.

[0016]

Embedded image (However, k is the average number, k = 7 to 30)

Hereinafter, methylhydrogenpolysiloxane having this structure will be referred to as an MHPS treating agent.

In the present invention, the ratio of coating the powder with the MHPS treating agent is 100 parts by weight of the powder,
The S treating agent is 0.5 part by weight or more and less than 12 parts by weight , and more preferably, the MHPS treating agent is 1 part by weight or more and 12 parts by weight.
Parts .

The conditions for heating the mixture of the powders and the MHPS treating agent are as follows: heating at 80 to 200 ° C. for 0.5 to 5 hours, or primary heating at 60 to 120 ° C. For example, a method in which the heat treatment is performed for 0.5 to 4 hours, followed by performing a secondary heat treatment at 80 to 200 ° C. at a temperature higher than that of the primary heat treatment for 0.2 to 3 hours.

The coating method of the MHPS treating agent used in the present invention is as follows. A method in which powders and an MHPS treating agent are stirred and mixed without using a solvent. 2. A method in which a solution in which a MHPS treating agent is dissolved in a small amount of a solvent is stirred and mixed with powders. 3. A method of forming a slurry of a powder obtained by dissolving an MHPS treating agent in a large amount of a solvent and then distilling off the solvent. 4. A method of coating powders with an MHPS treating agent using a spray drier or an air blender. And the like. However, if a solvent is used in the step of coating the powder with the MHPS treating agent, it is necessary to pay attention to the fact that aggregation often occurs.

Further, when the MHPS treating agent is introduced, it is preferable to use an airbrush or the like to make the droplets of the MHPS treating agent as small as possible. Further, when handling the fine particle powder, since aggregation is likely to occur, a plate-like powder such as sericite or talc is mixed in a ratio of 10 to 60 parts by weight of the plate-like powder to 100 parts by weight of the fine-particle powder. When used, it is effective in preventing aggregation.

Examples of cosmetics of the present invention include white powder, foundation, pressed powder, foundation using water, oily foundation, emulsified foundation,
Lipstick, blush, eye shadow, eyebrows, eyeliner, mascara, nail color, cheek color, base foundation, sunscreen, emulsion, lotion and the like.

As cosmetics, oils, powders, and the like usually used in cosmetics are used as long as the object of the present invention is achieved.
Solvents, surfactants, ultraviolet absorbers, preservatives, bactericides, preservatives, antioxidants, hormones, vitamins, humectants, fragrances, and the like can be simultaneously added.

Examples of the oil agent in this case include higher fatty acids, higher alcohols, synthetic esters, waxes, vegetable oils and fats, animal oils and fats, hydrocarbons, fluorocarbons, perfluoropolyethers, and fluoroalkoxyphosphazenes. Examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, fluorine-modified silicone, methylcetyl-modified silicone, amino-modified silicone, and cyclic dimethylpolysiloxane. Examples of the powders include powders, resins, fibers, and the like that are usually used in cosmetics. These powders coupling agent treatment, bud present invention
Whether or not surface treatment such as silicone treatment other than chill hydrogen polysiloxane treatment , fluorine treatment, metal soap treatment, silica treatment, alumina treatment, amino acid treatment, metal coating treatment, plasma treatment, etc. is performed No problem. Examples of the solvent include water, alcohol, propylene glycol, and other solvents commonly used in cosmetics, as well as cyclic silicone and the like. Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

[0025]

The present invention will be described in detail below with reference to examples and comparative examples. The method for evaluating the polymerizability of methyl hydrogen polysiloxane used in the examples is as follows.

1. Method for evaluating the polymerizability of methylhydrogenpolysiloxane 7 g of methylhydrogenpolysiloxane having each average degree of polymerization was placed in a glass petri dish having a diameter of 9 cm.
It is put in a blow dryer set at 0 to 180 ° C for 1 to 8 hours, and the state of the formed film is observed. Then, the minimum heating condition for forming a film was examined. Table 5 shows the results.

Since the test method does not take into account the catalytic activity of the powder, the heating conditions for actually coating the powder with methyl hydrogen polysiloxane and heating are as follows:
It should be noted that in many cases the temperature is lower than the minimum heating condition obtained in this test.

The methods for evaluating the secondary aggregation, water repellency, and catalytically active closure described in the examples are as follows.

2. Evaluation method for secondary agglomeration of powders 2-1 Evaluation method for powders having an average particle diameter of 0.1 μm or more Particle size distribution analyzer (PRO-7000, PRO-
9000 (manufactured by Seishin Enterprise Co., Ltd.) and ethanol as a dispersion solvent, and the volume average particle diameter of the powders in an ultrasonic dispersion state was measured. The average particle size of the powders in the untreated state is D, and the average particle size of the processed powder is D1, (D1 / D)
Table 9 shows the results of evaluation based on the criterion shown in Table 1 using the cubic value of.

[0030]

[Table 1]

2-2 Evaluation method for powders having an average particle diameter of 0.1 μm or less Dimethylpolysiloxane (3
0000 cs), 150 mg of the fine particle powder was added to 50 g, and the mixture was stirred well and then dispersed using a roller. This sample was formed to a film thickness of 40 μm, and a spectrophotometer (MP
S-2000 type (manufactured by Shimadzu Corp.)
The spectral distribution at a wavelength between 0 and 190 nm was measured. When the transmittance (%) at 300 nm of the untreated fine particle powder is A and the transmittance (%) at 300 nm of the treated powder is B, the value of BA is C, and the value of C is shown in Table 2.
The evaluation was performed based on the criteria shown in (1). Table 8 shows the results.

[0032]

[Table 2]

3. Evaluation method of water repellency After weighing out 30 mg of the treated powder and placing it in a test tube containing 10 mL of an aqueous ethanol solution adjusted to a concentration of 0 to 100 vol%, an ultrasonic cleaner (BRANSON2200) was used.
Type BRANSON CLEANING EQUIPM
Ultrasonic wave was applied for 1 minute using ENT COMPANY). After the ultrasonic irradiation, the concentration of ethanol at which the treated powder started dispersing in the aqueous ethanol solution was measured. Table 8 and Table 9 show the results of evaluation based on the criteria shown in Table 3 where E is the concentration of ethanol at which dispersion starts. The higher the value of E, the better the water repellency.

[0034]

[Table 3]

4. Evaluation Method of Catalytic Activity Blocking State It is known that fine powder having a primary particle diameter of 0.1 μm or less has strong catalytic activity. In particular, titanium oxide, which has an anatase type or amorphous type structure, has a strong photocatalytic activity, and causes discoloration of titanium oxide due to migration to lower order titanium oxide and deterioration of flavors in cosmetics. In this evaluation method, the blocked state of catalytic activity was examined from the discolored state of titanium oxide when light was applied in the presence of water. Sample 0.03
g was dispersed in 1 g of ethanol, 10 g of glycerin was added, stirred, and transferred to a synthetic quartz cell. Then wavelength 25
Using a 4 nm black light (4 W tube), the discoloration of the solution was measured when the sample was irradiated with ultraviolet rays from a distance of 1 cm for 30 minutes. Table 8 shows the results of the evaluation based on the criteria shown in Table 4. It should be noted that the more discoloration occurs, the worse the catalytic activity is blocked.

[0036]

[Table 4]

The method for evaluating the sensory properties of the cosmetics described in the examples is as follows. 5. Using the examples and comparative examples work made by the cosmetics of the cosmetics of the sensory evaluation method of粧料, as the target of the men and women a total of 10 people of 22-36 years old, were evaluated in the rice cake of makeup. The results are shown in Table 1 0. Table 1 0
Oite, numerical values are those that indicate how many out of ten for the evaluation item is determined, 10 if 10 people everyone, indicating that the 1, then 1 out of 10 people were determined.

Hereinafter, the characteristics of methyl hydrogen polysiloxane will be described by evaluating the polymerizability of methyl hydrogen polysiloxane. Table 5 shows the relationship between the average degree of polymerization, the structure, and the minimum heating conditions determined according to the evaluation method.

[0039]

[Table 5]

[0040]

Embedded image (However, m = n, m + n = 30 to 50)

[0041]

Embedded image (However, a = 30-50)

[0042]

Embedded image (However, k = 21-30)

[0043]

Embedded image (However, k = 15-20)

[0044]

Embedded image (However, k = 7-10)

[0045]

Embedded image

According to Table 5, the conventional methyl hydrogen polysiloxanes represented by Chemical Formulas 7 and 8 are
It can be seen that the minimum heating conditions are stricter than the methyl hydrogen polysiloxane used in the present invention indicated by No. 1. Further, among the methylhydrogenpolysiloxanes used in the present invention, those having the average degree of polymerization shown in Chemical formulas 9 and 10 are more reactive. Chemical formulas 9, 10 and 11 are hereinafter referred to as MH, respectively.
PS treatment agent (A), MHPS treatment agent (B) and MHPS
Abbreviated as treating agent (C).

Hereinafter, a method for producing a modified powder will be described in Examples 1 to 8 . Example 1 300 g of sericite was mixed with 1000 g of fine particle titanium oxide (primary particle diameter 17 nm, amorphous type), and then 130 g of MHPS treating agent (A) was added. Speed of 1 ° C per minute from normal temperature to 95 ° C using a blow dryer (total 70 minutes)
, And then the temperature was increased to 130 ° C., followed by a 0.5 hour heat treatment.

Example 2 Fine particle titanium oxide (primary particle diameter 45 nm, rutile type) 5
35 g of the MHPS treating agent (A) was added to 00 g, and the mixture was stirred and mixed using a mixer. Then, a heat treatment was performed at 95 ° C. for 5 hours using a blow dryer.

Comparative Example 1 Fine particle titanium oxide (primary particle diameter 45 nm, rutile type) 5
00g, methyl hydrogen polysiloxane (KF
-99P, manufactured by Shin-Etsu Chemical Co., Ltd. )
Was dissolved in 100 g of isopropyl alcohol, and the mixture was stirred and mixed. After that, the solvent was distilled off, and then a heat treatment was performed at 95 ° C. for 5 hours using a blow dryer.

Example 3 1 kg of sericite and 20 g of MHPS treating agent (C) were mixed and stirred using a Henschel mixer. Then, after a heat treatment at 110 ° C. for 4 hours using a drier, 18
Heat treatment was performed at 0 ° C. for 3 hours.

Example 4 After mixing 100 g of yellow iron oxide (primary particle diameter 0.7 μm) and 25 g of sericite, 3.8 g of MHPS treating agent (B)
Was mixed using a spray. Then, using a blow dryer, the temperature was increased from 60 ° C. to 90 ° C. at a rate of 0.4 ° C./min (total of 75 ° C.).
Min), a primary heat treatment was performed, followed by heating to 105 ° C., and then a heat treatment was performed for 1 hour.

[0052] Comparative Example 2 Yellow iron oxide (primary particle diameter 0.7 [mu] m) were mixed 100g and sericite 25 g, methylhydrogenpolysiloxane (KF-9901, manufactured by Shin-Etsu Chemical) and (Formula 7m
n is 20) 3.8 g was mixed using a spray. Then, the air was dried at 60 ° C. to 90 ° C. using a blow dryer at 0.1 ° C./min.
The primary heat treatment was performed at a rate of 4 ° C. (total of 75 minutes), followed by heating to 105 ° C., and then performing the heat treatment for one hour.

Example 5 After mixing 100 g of red iron oxide (primary particle diameter 0.7 μm) and 25 g of sericite, 3.8 g of MHPS treating agent (B)
Was mixed using a spray. Next, heat treatment was performed at 120 ° C. for 1 hour using a blow dryer.

Example 6 After mixing 100 g of black iron oxide (primary particle diameter 0.6 μm) and 25 g of sericite, 3.8 g of MHPS treating agent (B)
Was mixed using a spray. Then, using a blow dryer, the temperature was increased from 60 ° C. to 90 ° C. at a rate of 0.4 ° C./min (total of 75 ° C.).
Min), and then the temperature was raised to 100 ° C., followed by a 1 hour heat treatment.

Example 7 100 g of sericite was mixed with 900 g of titanium oxide (primary particle diameter: 0.6 μm), and then MHPS treating agent (C) 4
0 g was added using an air spray, followed by stirring and mixing using a mixer. 60 ° C to 120 ° C using a blow dryer
The primary heat treatment was performed at a rate of 2 ° C. per minute (total 30 minutes), and then the temperature was increased to 130 ° C., and then the secondary heat treatment was performed for 0.4 hours.

[0056] Comparative Example 3 Titanium oxide were mixed sericite 100g (the primary particle size 0.6 .mu.m) 900 g, followed by methylhydrogenpolysiloxane (KF-9901, Shin-Etsu Chemical Co., Ltd.) (of
7 and m and n are 20) 40 g of isopropyl alcohol 1
A solution dissolved in 000 g was added, and the mixture was stirred and mixed using a mixer. After distilling off the solvent, a primary heat treatment was performed from 60 ° C. to 120 ° C. at a rate of 2 ° C./min (total 30 minutes) using a blow dryer, and then the temperature was raised to 130 ° C. The secondary heat treatment was performed for hours.

[0057] Example 8 mica titanium 100g and MHPS treating agent (A) 8 g was dispersed in trichlorethylene 120 g, then the solvent was distilled off. After the obtained powder was pulverized using a mixer, a heat treatment was performed at 180 ° C. for 1 hour using a blow dryer.

[0058] Comparative Example 4 mica titanium 100g and annular methylhydrogenpolysiloxane (KF-9902, Shin-Etsu Chemical Co., Ltd.) (Formula 1
2) 8 g was mixed using a mixer. The obtained powder was subjected to a heat treatment at 180 ° C. for 1 hour using a blow dryer.

[0059] Hereinafter, the work made by the modified powder in Example 1-8
Evaluation and an example of a cosmetic using the modified powder are described in Example 9.
It will be explained in. Incidentally,% of the amount shows Weight%.

Example 9 Sun oil

[0061]

[Table 6]

The component A was gradually added to the uniformly mixed and dissolved component B, and mixed using a sand mill to obtain a product. The obtained product was excellent in transparency. Also, it did not discolor even under sunlight.

Comparative Example 5 Sun Oil

[0064]

[Table 7]

The component A was gradually added to the uniformly mixed and dissolved component B, and mixed using a sand mill to obtain a product. The resulting product was excellent in transparency, but turned blue under sunlight.

[0066]

[Table 8]

[0067]

[Table 9]

[0068]

[Table 10]

From Table 8, it was confirmed that the modified fine particle powder of the present invention had little secondary agglomeration, was excellent in water repellency, and also blocked the catalytic activity of the fine particle titanium oxide. From Table 9 , the modified powder of the present invention has less secondary aggregation,
Excellent water repellency was observed. From the results in Tables 8 and 9 , it was found that the modified powder treated by the method of the present invention exhibited good performance regardless of the size of the powder.

Further, Example 2 , Comparative Example 1 , and Example
7 and Comparative Example 3 shows that the presence of the solvent has an adverse effect such as secondary aggregation. Further, from the results of Table 1 0, when the reforming powder of the present invention were formulated into cosmetics, it was found to have a good cosmetic can be obtained.

[0071]

As described above, according to the present invention, secondary agglomeration is achieved by coating powders with methylhydrogenpolysiloxane having a specific structure and then performing heat treatment under specific temperature conditions. It is clear that it is possible to provide a modified powder which is low in amount, excellent in water repellency, and furthermore has a blocked catalytic activity, and provides cosmetics excellent in quality stability and feel by blending this modified powder. is how et al.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁷ Identification code FI C09B 67/08 B01J 13/02 B

Claims (4)

(57) [Claims] After mixing 100 parts by weight of powders and 0.5 part by weight or more and less than 12 parts by weight of a compound represented by the following general chemical formula, heat treatment is carried out at 80 to 200 ° C. for 0.5 to 5 hours. A modified powder obtained by performing the method. Embedded image (However, k is the average number, k = 7 to 30) 2. After mixing 100 parts by weight of powders with 0.5 part by weight or more and less than 12 parts by weight of a compound represented by the following general chemical formula, a primary heat treatment at 60 to 120 ° C.
4 hours, followed by a second heat treatment at a temperature higher than that of the first heat treatment and at 80 to 200 ° C. for 0.2 to 3 hours.
A modified powder which is obtained after a long time. Embedded image (However, k is the average number, k = 7 to 30) 3. A fine titanium oxide powder such that the primary particle diameter of 5 to 50 nm, modification according to claim 1 or 2, characterized in that the particulate zinc oxide, particulate iron oxide, fine particles lower titanium oxide powder. 4. A cosmetic comprising the modified powder according to any one of claims 1 to 3.